JPH06218869A - Film and laminated material - Google Patents

Abstract

PURPOSE:To provide a film and a laminated material having high gas barrier properties and incineration aptitude and effectively blocking external light. CONSTITUTION:A shading material is added to a film based on polyethylene terephthalate and a membrane 3 composed of inorg. oxide is provided to at least one surface of the film. A shading/barrier layer is based on polyethylene terephthalate containing a shading material and the membrane 3 of inorg. oxide is provided on one surface of the shading/barrier layer and a resin layer such as a polyolefin resin layer, a polyester resin layer or a polyamide layer is laminated on the membrane 3 to obtain a laminated material.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a film and a laminate having excellent UV cut property and gas barrier property.

[0002]

2. Description of the Related Art As a container for containing liquid foods such as fruit juices, alcoholic beverages, yogurt, seasonings, etc., a container formed of a packaging material having a barrier property, a laminate in which various resin layers are laminated around a paper layer. There are containers and the like formed of materials. As a conventional packaging material, a packaging material having a laminated structure having an aluminum foil layer as a barrier layer has been used. As the laminated material, a polyolefin-based resin layer having a heat-fusible property is provided on the outermost surface and the innermost surface in consideration of the container forming property, and in order to prevent the contents from being oxidized and deteriorated, the laminated materials are laminated. An aluminum foil layer was provided as a barrier layer in the material.

[0003]

In a container formed by using a packaging material or a laminated material having the above-mentioned aluminum foil layer, the gas barrier property of the aluminum foil layer due to the heat at the time of sealing by the filling machine. Without deterioration,
Therefore, stable gas barrier properties can be obtained.

However, since such a container is inferior to incineration, there is a problem that it is difficult to dispose of the used container. In order to cope with this, a container provided with a barrier layer in which a thin film of silicon oxide is formed on a resin film has been developed (JP-A-63-281838). Such a container has excellent barrier properties and is suitable for incineration.

However, the above-mentioned barrier layer is inferior to the aluminum foil layer in light-shielding property, and in particular, there is a problem that ultraviolet rays (UV) reach the inside of the container to cause deterioration and deterioration of the contents. The present invention has been made in view of the above circumstances, and provides a film and a laminated material that have high gas barrier properties and incineration suitability, and that can effectively block ultraviolet rays (UV). To aim.

[0006]

In order to achieve such an object, the film of the present invention has a structure having a thin film of an inorganic oxide on at least one surface of a polyethylene naphthalate layer.

Further, the laminated material of the present invention is UV having a thin film of an inorganic oxide on one surface of the polyethylene naphthalate layer.
A structure in which a cuttability / barrier layer and a resin layer of any one of a polyolefin-based resin layer, a polyester-based resin layer, and a polyamide-based resin layer are laminated on the inorganic oxide thin film of the UV cuttability / barrier layer. Is.

[0008]

The polyethylene naphthalate film effectively blocks light, especially ultraviolet rays (UV), and the thin film of an inorganic oxide located on at least one surface of the film exhibits excellent barrier properties, and is a laminated material. The UV-cutting / barrier layer constituting the film has the same constitution as that of the film as described above. With this UV-cutting / barrier layer, the laminated material can obtain excellent gas barrier property and light can Penetration is effectively prevented.

[0009]

Embodiments of the present invention will be described below with reference to the drawings. FIG. 1 is a schematic sectional view showing an example of the film of the present invention. In FIG. 1, the film 1 is a substrate 2
And a thin film 3 of an inorganic oxide formed on at least one surface of the base material 2.

The substrate 2 is made of polyethylene naphthalate. This polyethylene naphthalate
Due to the effective blocking of light, particularly ultraviolet rays (UV) having a wavelength of 350 nm or less, the film 1 is excellent in U by the base material 2.
Has V-cut property. The polyethylene naphthalate constituting the base material 2 as described above is subjected to uniaxial or biaxial stretching treatment, corona discharge treatment, discharge treatment such as low temperature plasma treatment, silane coupling agent coating, primer coating, It may be one that has been subjected to a surface treatment such as sand plast treatment to improve the adhesiveness with the inorganic oxide thin film 3. Usually, about 2 to 30 μm is preferable.

The inorganic oxide thin film 3 formed on the substrate 2 is
For example, it is composed of a thin film of silicon oxide (SiO _x ) or aluminum oxide (Al ₂ O ₃ ). The method for forming the inorganic oxide thin film 3 is not particularly limited, and there are a vacuum deposition method such as an ion beam method and an electron beam method, a sputtering method and the like.

The thickness of such an inorganic oxide thin film 3 is usually 10 nm or more, and preferably 20 to 150 nm, in order to obtain sufficient barrier properties. When the thickness of the inorganic oxide thin film 3 exceeds 150 nm, the inorganic oxide thin film 3 is apt to be cracked, the gas barrier property may be deteriorated, and the material cost becomes expensive, which is not preferable.

The inorganic oxide thin film 3 may be, for example, a mixture of silicon monoxide and silicon dioxide, a mixture of silicon oxide and aluminum oxide, or the like. FIG. 2 is a schematic sectional view showing an example of the laminated material of the present invention. In FIG. 2, the laminated material 11 has a UV cut barrier layer 12 and a resin layer 15 formed on one surface of the UV cut barrier layer 12.

The UV cut barrier layer 12 is composed of a UV cut layer 13 which is polyethylene naphthalate and an inorganic oxide thin film 14 formed on the UV cut layer 13. The UV cut layer 13 is for effectively blocking light, especially ultraviolet rays, and has a thickness of 2 to 30 μm.
A degree is preferable. UV other than polyethylene naphthalate
Examples of the constituent resin of the cut 13 include polyester which is a condensate of dibasic acid and glycol such as polyethylene terephthalate and polybutylene terephthalate. The inorganic oxide thin film 14 is the same as the film 1 described above.
Similar to the inorganic oxide thin film 3 constituting the above, it can be formed as a thin film of, for example, silicon oxide (SiO _x ) or aluminum oxide (Al ₂ O ₃ ). Inorganic oxide thin film 1
The method of forming No. 4 and the thickness of the thin film can be the same as in the case of the inorganic oxide thin film 3, and the description thereof is omitted here.

The resin layer 15 is the UV cut barrier layer 1
2 is a resin layer formed on the inorganic oxide thin film 14 constituting the second resin layer and is any one of a polyolefin resin layer, a polyester resin layer, and a polyamide resin layer. The polyolefin resin layer is polyethylene, linear low density polyethylene, polypropylene, ethylene / vinyl acetate copolymer, ethylene / acrylic acid copolymer, ethylene / methacrylic acid copolymer, ethylene / methyl acrylate copolymer, ethylene. It can be formed from a methyl methacrylate copolymer, an ionomer, a propylene / ethylene copolymer, or the like. The polyester resin layer can be formed by a condensate of a dibasic acid such as polyethylene naphthalate, terephthalic acid, isophthalic acid and adipic acid, and a glycol such as ethylene glycol, propylene glycol and butylene glycol. The polyamide resin layer has 6
-Nylon, 6,6-Nylon, 6,10-Nylon,
Condensates of lactams such as 11-nylon or diamines such as ethylenediamine, pentamethylenediamine, hexamethylenediamine, P-xylylenediamine and dibasic acids such as adipic acid, sebacic acid and P-phenylenelenic acid. Can be formed by. The thickness of the resin layer 15 is preferably about 5 to 50 μm. Also,
The resin layer 15 may be stretched.
Further, the resin layer 15 may be printed in advance.

When the resin layer 15 is a polyolefin resin layer, the resin layer 15 can act as a seal layer. When the resin layer 15 is a polyester resin layer or a polyamide resin layer, as shown in FIG. 3, the light blocking layer 13 of the UV cut barrier layer 12 is used.
The polyolefin resin layer 16 may be laminated on the upper surface (the surface on which the inorganic oxide thin film 14 is not formed).

The laminated material 11 as described above can be used as a flexible packaging material for forming various containers. FIG. 4 is a schematic sectional view showing another example of the laminated material of the present invention. In FIG. 4, the laminated material 21 includes a paper layer 22, a polyolefin resin layer 23 formed on one surface of the paper layer 22, and a paper layer 22.
A polysand layer 24, an adhesive polyolefin resin layer 25, a UV cut barrier layer 26 formed on the other surface of the
It has a laminated structure including a polyolefin resin layer 27.

The paper layer 22 constituting the laminated material 21 has a basis weight of 1
About 100 to 500 g / m ² is preferable. The polyolefin resin layer 23 laminated on the paper layer 22 can be formed of a polyolefin resin such as polyethylene or polypropylene, particularly low density polyethylene, and the thickness thereof is preferably about 10 to 50 μm.

The polysand layer 24 is a layer for heat-sealing the paper layer 22 and the adhesive polyolefin resin layer 25, and is formed on the UV cut barrier layer 26 via an anchor agent layer. On the resin layer 25,
While extruding the adhesive polyolefin resin, the paper layer 2
It is formed by heat-sealing the two.

Here, the adhesive polyolefin resin is
For example, polyethylene, ethylene-α-olefin copolymers, poly-α-olefins such as polypropylene, polybutene and polyisobutylene, polydiolefins such as polybutadiene and polyisoprene, and copolymers thereof can be used. Further, ethylene and a carbonyl group based on a carboxylic acid, a carboxylic acid salt, a carboxylic acid anhydride, a carboxylic acid ester, a carboxylic acid amide or a carboxylic acid imide, an aldehyde, a ketone or the like, alone, or a cyano group, a hydroxy group, an ether group. , A copolymer with one or more ethylenically unsaturated monomers having a combination with an oxirane ring or the like can be used. More specifically, A. Ethylenically unsaturated carboxylic acids: acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, 5-norbornene 2,3-dicarboxylic acid, etc., B.I. Ethylenically unsaturated carboxylic anhydrides: maleic anhydride, citraconic anhydride, 5-norbornene 2,3-dicarboxylic anhydride, tetrahydrophthalic anhydride and the like, C.I. Ethylenic unsaturated esters: ethyl acrylate, methyl methacrylate, 2-ethylhexyl acrylate, mono- or diethyl maleate, vinyl acetate, vinyl propionate, γ-hydroxymethacrylate propyl, β-hydroxyethyl acrylate, glycidyl acrylate, Glycidyl methacrylate, β-N-ethylaminoethyl acrylate, etc., D.I. Ethylenically unsaturated amides or imides: acrylamide, methacrylamide, maleimide, etc. E. Ethylenically unsaturated aldehydes or ketones: Ethylenically unsaturated monomers such as acrolein, methacrolein, vinylmethylketone and vinylbutylketone are used, preferably ethylenically unsaturated carboxylic acid or ethylenically unsaturated anhydrous carboxylic acid. Acid is used. Further, a neutralized metal product can be used as a copolymer of ethylene and an ethylenically unsaturated carboxylic acid.

The thickness of the polysand layer 24 formed of the adhesive polyolefin resin as described above is 5 to 50 μm.
About m is preferable. The UV blocking / barrier layer 26 is the UV blocking / barrier layer 12 constituting the laminated material 11 described above.
UV made of polyethylene naphthalate as well as
It comprises a cut layer 26a and an inorganic oxide thin film 26b formed on the UV cut layer 26a. And, such a light-shielding / barrier layer 26 is UV-blocking /
Since it can be formed in the same manner as the barrier layer 12, description thereof is omitted here.

The polyolefin resin layer 27 can be formed of a polyolefin resin such as polyethylene or polypropylene, especially low density polyethylene, and its thickness is preferably about 30 to 150 μm. Such a polyolefin resin layer 27 and a UV cut / barrier layer 26
The lamination with the inorganic oxide thin film 26b can be performed by dry lamination using an isocyanate adhesive. Examples of the isocyanate-based adhesive include a polyester polyurethane-based adhesive and a two-component curing type adhesive in which a polyether polyurethane-based adhesive is used as a main component and a curing agent such as tolylene diisocyanate and xylene diisocyanate is added to this main component. .

As shown in FIG. 5, such a laminated material 21 is manufactured by box-making so that the polyolefin resin layer 23 constitutes the outer surface of the container and the polyolefin resin layer 27 constitutes the inner surface of the container. The transparent container 31 can be formed. The container 31 has a bottomed body portion 32 and a top portion 33 connected to the body portion 32.

Next, the present invention will be described in more detail with reference to experimental examples. (Experimental Example) Preparation of sample 1 A vapor-deposited thin film (thickness: 50 nm) of silicon oxide (SiO ₂ ) was formed on a biaxially stretched polyethylene naphthalate resin film (Q film 7 μm manufactured by Teijin Ltd.) by a vacuum vapor deposition method. Thus, the film of the present invention (Sample 1) was prepared. Preparation of Sample 2 A film having a silicon oxide thin film was prepared in the same manner as in Sample 1, and a linear low density polyethylene resin film (SR-X manufactured by Dainippon Resin Co., Ltd.) was formed on the silicon oxide thin film of this film. , And a thickness of 40 μm) was dry-laminated to prepare a laminated material (Sample 2) of the present invention. Preparation of Sample 3 A film having a silicon oxide thin film was prepared in the same manner as in Sample 1, and a biaxially stretched polyester film (T4100 manufactured by Toyobo Co., Ltd.) preprinted on the silicon oxide thin film of this film. , Thickness 12 μm), and a low density polyethylene resin (Mirason 16sp manufactured by Mitsui Petrochemical Industry Co., Ltd.) is extruded on the silicon oxide thin film non-formed side of the above film and laminated to form a polyethylene resin layer (thickness 30 μm). To form a laminated material of the present invention (Sample 3). Preparation of Sample 4 A film having a silicon oxide thin film was prepared in the same manner as in Sample 1, and a biaxially stretched nylon film (Emblem manufactured by Unitika Ltd.) preliminarily printed on the silicon oxide thin film of this film. ON, thickness 15 μm) by dry lamination, and polypropylene resin film (manufactured by Tohcello Co., Ltd.) on the silicon oxide thin film non-formed side of the above film.
WC-X, thickness 60 μm) was dry laminated to prepare a laminated material of the present invention (Sample 4). Preparation of Sample 5 First, a low density polyethylene resin (Mirason 16 manufactured by Mitsui Petrochemical Co., Ltd.) was attached to one side of a paper having a basis weight of 340 g / m ^2.
sp) was extruded and laminated to form a polyethylene resin layer (thickness: 30 μm) to form a first sheet having a two-layer structure.

On the other hand, a film having a silicon oxide thin film was prepared in the same manner as in Sample 1. Then, a low density polyethylene resin film (SKL manufactured by Dainippon Resin Co., Ltd., thickness 60 μm) was dry-laminated on the silicon oxide thin film of this film, and an isocyanate-based anchoring agent was formed on the silicon oxide thin film non-formed side of the film. A low-density polyethylene resin (Mirason 16sp, manufactured by Mitsui Petrochemical Industry Co., Ltd.) was extruded and laminated to form a polyethylene resin layer (thickness 15 μm) to form a second sheet. Next, a low-density polyethylene resin (Mirason 16sp manufactured by Mitsui Petrochemical Industry Co., Ltd.) was extruded on the polyethylene resin layer of the second sheet with a thickness of 15 μm to heat-seal (sand bond) the paper layer of the first sheet. After lamination, a laminated material (Sample 5) of the present invention as shown in FIG. 4 was prepared. Preparation of Comparative Sample 1 A polyethylene terephthalate film (E510 manufactured by Toyobo Co., Ltd.) was used instead of the polyethylene naphthalate film.
A film (Comparative Sample 1) was prepared in the same manner as Sample 1 except that 0) was used. Preparation of Comparative Sample 2 A polyethylene terephthalate film (E510 manufactured by Toyobo Co., Ltd.) was used instead of the polyethylene naphthalate film.
A laminated material (Comparative Sample 2) was prepared in the same manner as Sample 2 except that 0) was used. Preparation of Comparative Sample 3 Polyethylene terephthalate film (E510 manufactured by Toyobo Co., Ltd.) was used instead of the polyethylene naphthalate film.
A laminated material (Comparative Sample 3) was prepared in the same manner as Sample 5 except that 0) was used.

Each of the samples prepared as described above (Sample 1
4 to 4 and comparative samples 1 to 2), the transmittance at 370 nm was first measured by a spectrophotometer manufactured by Shimadzu Corporation. The results are shown in Table 1.

Further, using Samples 2 to 4, 100 mm × 1
A 20 mm pouch was molded and filled with edible oil. Furthermore,
Using Sample 5 and Comparative Sample 3, a 1.0 liter capacity Gobel Top Carton type container was prepared and filled with edible oil. Next, the presence or absence of alteration or deterioration of the contents by external light was evaluated as described below. For sample 5 and comparative sample 3,
The total light transmittance was measured using a color computer SM-5 manufactured by Suga Test Instruments Co., Ltd. (Quality evaluation of contents) With the fluorescent lamp of 1500 LUX irradiated, the container is placed in an atmosphere of 40 ° C and 80% RH for 120 hours.
It was stored for one day and then opened to measure the peroxide value.
Further, the sample was stored in an atmosphere of 40 ° C. and 80% RH for 120 days without being irradiated with ultraviolet rays, and then opened to measure the peroxide value. The results are shown in Table 1.

[0028]

[Table 1] As shown in Table 1, the film and the laminated material of the present invention have both excellent UV cut property and gas barrier property, but Comparative Sample 1 does not have a polyethylene naphthalate resin layer and therefore has a poor UV cut property. In addition, although Comparative Samples 2 and 3 have a good gas barrier property, the UV cut property is insufficient, and alteration of the contents due to ultraviolet rays was observed.

[0029]

As described in detail above, according to the present invention, light can be emitted by the polyethylene naphthalate resin forming the film or the polyethylene naphthalate resin contained in the UV-cutting / barrier layer forming the laminated material. Effectively preventing the penetration of films and laminated materials, and
The thin film of the inorganic oxide contained in the film or the thin film of the inorganic oxide contained in the light shielding / barrier layer constituting the laminated material imparts excellent gas barrier properties to the film and laminated material, and a container is formed from such laminated material. In this case, the container has incineration suitability, stable gas barrier property and high light-shielding property,
Deterioration of contents is prevented.

[Brief description of drawings]

FIG. 1 is a schematic sectional view showing an example of a film of the present invention.

FIG. 2 is a schematic sectional view showing an example of a laminated material of the present invention.

FIG. 3 is a schematic cross-sectional view showing another example of the laminated material of the present invention.

FIG. 4 is a schematic cross-sectional view showing another example of the laminated material of the present invention.

FIG. 5 is a perspective view showing an example of a container manufactured by using the laminated material of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Film 2 ... Substrate 3 ... Inorganic oxide thin film 11 ... Laminated material 12 ... UV cut barrier layer 13 ... UV cut layer 14 ... Inorganic oxide thin film 15 ... Resin layer 16 ... Polyolefin resin layer 21 ... Laminated material 22 ... Paper layer 23 ... Polyolefin resin layer 24 ... Polysand layer 26 ... UV cut barrier layer 26a ... UV cut layer 26b ... Inorganic oxide thin film 27 ... Polyolefin resin layer

Claims (4)

[Claims] 1. A film having a thin film of an inorganic oxide on at least one surface of a polyethylene naphthalate layer. 2. A UV cut barrier layer having a thin film of an inorganic oxide on one surface of a polyethylene naphthalate layer, and a polyolefin resin layer and a polyester resin on the inorganic oxide thin film of the UV cut barrier layer. A laminated material comprising a resin layer and a polyamide resin layer, which are laminated. 3. The laminated material according to claim 2, further comprising a polyolefin resin layer laminated on the surface of the UV cut barrier layer on which the inorganic oxide thin film is not formed. 4. A polyolefin resin layer is provided on the inorganic oxide thin film of the UV cut barrier layer,
The laminated material according to claim 2, wherein a paper layer and a polyolefin resin layer are provided in this order on the surface of the V-cut barrier layer on which the inorganic oxide thin film is not formed.