JPH06218868A - 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 light-shielding 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 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 an object thereof is to provide a film and a laminated material which have high gas barrier properties and incineration suitability, and can effectively block external light. To do.

[0006]

In order to achieve such an object, the film of the present invention is mainly composed of polyethylene terephthalate, contains a light-shielding material and has a thin film of an inorganic oxide on at least one surface. It is a composition.

Further, the laminated material of the present invention is mainly composed of polyethylene terephthalate, contains a light-shielding material and has a thin film of an inorganic oxide on one surface, and the inorganic oxide of the light-shielding / barrier layer. The resin layer is any one of a polyolefin resin layer, a polyester resin layer, and a polyamide resin layer laminated on the thin film.

[0008]

The light-shielding material contained in the film mainly composed of polyethylene terephthalate effectively shields light, particularly ultraviolet rays, and the inorganic oxide thin film located on at least one surface of the film exhibits excellent barrier properties.
The light-shielding / barrier layer constituting the laminated material has the same constitution as that of the film as described above. With this light-shielding / barrier layer, the laminated material has excellent gas barrier properties, and light transmits through the laminated material. 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 base material 2 is mainly composed of polyethylene terephthalate, and contains 0.2 to 30% by weight of carbon black, preferably 1 to 2 in order to effectively block light, especially ultraviolet rays.
It is contained in the range of 0% by weight. In addition, the above-mentioned base material 2 is uniaxially or biaxially stretched, corona discharge treated,
It may be subjected to discharge treatment such as low-temperature plasma treatment, or may be subjected to surface treatment such as silane coupling agent coating, primer coating, and sand plast treatment to improve adhesion with the inorganic oxide thin film 3. The thickness of this substrate 2 is 5
About 50 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 includes a light shielding / barrier layer 12 and the light shielding / barrier layer 12.
The resin layer 15 formed on one surface of the barrier layer 12.

The light-shielding / barrier layer 12 is mainly composed of polyethylene terephthalate and contains carbon black of 0.2 to 3.
The light shielding layer 13 is contained in an amount of 0% by weight, preferably 0.5 to 20% by weight, and the inorganic oxide thin film 14 is formed on the light shielding layer 13. The light shielding layer 13 is
It is for effectively blocking light, especially ultraviolet rays, and the thickness is preferably about 5 to 50 μm. In addition, the inorganic oxide thin film 14 may be formed as a thin film of, for example, silicon oxide (SiO _x ), aluminum oxide (Al ₂ O ₃ ), or the like, like the inorganic oxide thin film 3 that constitutes the film 1. it can. The method of forming the inorganic oxide thin film 14 and the thickness of the thin film can be the same as in the case of the inorganic oxide thin film 3,
The description here is omitted.

The resin layer 15 is formed on the inorganic oxide thin film 14 constituting the light shielding / barrier layer 12 and is any one of a polyolefin resin layer, a polyester resin layer and a polyamide resin layer. The polyolefin resin layer includes polyethylene, linear polyethylene, polypropylene, ethylene / vinyl acetate copolymer, ethylene / acrylic acid copolymer, ethylene / methacrylic acid copolymer, ethylene / methyl acrylate copolymer, ethylene / methacrylic acid. It can be formed of an acid copolymer or the like. The polyester resin layer is polyethylene terephthalate,
It can be formed by a condensate of a dibasic acid such as terephthalic acid, isophthalic acid and adipic acid with a glycol such as ethylene glycol, propylene glycol and butylangcol. The polyamide resin layer is 6-nylon,
Condensates of lactams such as 6 / 6-nylon, 6 / 10-nylon and 11-nylon or diamines such as ethylenediamine, pentamethylenediamine, hexamethylenediamine, P-xylylenediamine and adipic acid, sebacic acid, P-phenylylene It can be formed by a condensate with a dibasic acid such as an acid. The thickness of the resin layer 15 is preferably about 5 to 50 μm. In addition, 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, a polyolefin resin is formed on the light shielding layer 13 of the light shielding / barrier layer 12 (the surface on which the inorganic oxide thin film 14 is not formed). The resin layer 16 may be laminated.

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.
Has a laminated structure including a polysand layer 24, an adhesive polyolefin-based resin layer 25, a light-shielding / barrier layer 26, and a polyolefin-based resin layer 27 formed on the other surface.

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 the adhesive polyolefin resin formed on the light shielding / barrier layer 26 via the anchor agent layer. It is formed by heat-bonding the paper layer 22 onto the layer 25 while extruding the adhesive polyolefin resin.

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 light-shielding / barrier layer 26, like the light-shielding / barrier layer 12 constituting the above-mentioned laminated material 11, is mainly composed of polyethylene terephthalate and contains carbon black in an amount of 0.2 to 30% by weight, preferably 0.5 to 20% by weight. And the light-shielding layer 26a contained in the range of
It is composed of an inorganic oxide thin film 26b formed above. Since such a light blocking / barrier layer 26 can be formed in the same manner as the light blocking / barrier layer 12, the 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 lamination of the polyolefin resin layer 27 and the inorganic oxide thin film 26b of the light shielding / barrier layer 26 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 polyethylene terephthalate resin containing 0.8% by weight of carbon black was extruded and then biaxially stretched to form a film having a thickness of 12 μm. Next, a vapor-deposited thin film of silicon oxide (SiO ₂ ) (thickness: 50 nm) was formed on this film by a vacuum vapor deposition method to prepare a film of the present invention (Sample 1). Preparation of Sample 2 Except that the content of carbon black was 5.0% by weight,
A film of the present invention (Sample 2) was prepared in the same manner as Sample 1. Preparation of Sample 3 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. , 40 μm in thickness) was dry-laminated to prepare a laminated material (Sample 3) of the present invention. 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 polyester film (T4100 manufactured by Toyobo Co., Ltd.) preprinted on the film was prepared. , 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 (Sample 4) of the present invention. Preparation of Sample 5 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 a 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 5). Preparation of Sample 6 First, on one side of a paper having a basis weight of 340 g / m ² , a low-density polyethylene resin (Mirason 16 manufactured by Mitsui Petrochemical Industry Co., Ltd.) was used.
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 (Mitsui Petrochemical Industry Co., Ltd.) was formed on the polyethylene resin layer of the second sheet.
The paper layer of the above-mentioned first sheet was heat-sealed (sand lamination) while extruding a manufactured Mirason 16 sp) with a thickness of 15 μm to prepare a laminated material (Sample 6) of the present invention as shown in FIG. Preparation of Comparative Sample 1 A film (Comparative Sample 1) was prepared in the same manner as Sample 1 except that the content of carbon black was 35% by weight. Preparation of Comparative Sample 2 A laminated material (Comparative Sample 2) was prepared in the same manner as Sample 3 except that the content of carbon black was 0% by weight. Preparation of Comparative Sample 3 A laminated material (Comparative Sample 3) was prepared in the same manner as Sample 6 except that the content of carbon black was 0% by weight.

Each of the samples prepared as described above (Sample 1
6 to 6 and comparative samples 1 to 3), the total light transmittance was first measured using a color computer SM-5 manufactured by Suga Test Instruments Co., Ltd. The results are shown in Table 1.

Further, using the samples 3 to 5 and the comparative sample 2, 100 mm × 120 mm pouches were molded and filled with edible oil. Further, using a sample 6 and a comparative sample 3, a container having a volume of 1.0 l and having a Goebel top carton type was prepared and filled with edible oil. Next, the presence or absence of alteration or deterioration of the contents due to external light was evaluated. The results are shown in Table 1. (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.

[0029]

[Table 1] As shown in Table 1, the film and laminated material of the present invention have both excellent light-shielding property and gas barrier property, but Comparative Sample 1 had a high carbon black content and was difficult to form into a film. . Further, although Comparative Samples 2 and 3 have good gas barrier properties, their light-shielding properties are insufficient, and alteration of the contents due to ultraviolet rays was observed.

[0030]

As described above in detail, according to the present invention, the light or the light-shielding material contained in the film or the light-shielding / barrier layer constituting the laminated material allows the light to pass through the film or the laminated material. Permeation is effectively prevented, and the thin film of the inorganic oxide of the film or the thin film of the inorganic oxide of the light-shielding / barrier layer constituting the laminated material imparts excellent gas barrier properties to the film and laminated material. When a container is formed of such a laminated material, the container has incineration suitability, stable gas barrier property, and high light-shielding property, and deterioration of the 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 ... Light-shielding / barrier layer 13 ... Light-shielding 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 ... Light-shielding / barrier layer 26a ... Light-shielding layer 26b ... Inorganic oxide thin film 27 ... Polyolefin resin layer

Claims (6)

[Claims] 1. A film comprising polyethylene terephthalate as a main component, containing a light-shielding material and having a thin film of an inorganic oxide on at least one surface. 2. The film according to claim 1, wherein carbon black is contained in the range of 0.2 to 30% by weight as the light shielding material. 3. A light-shielding / barrier layer mainly composed of polyethylene terephthalate, containing a light-shielding material and having a thin film of an inorganic oxide on one surface, and a polyolefin resin on the inorganic oxide thin film of the light-shielding / barrier layer. layer,
A laminated material comprising a laminated resin layer of either a polyester resin layer or a polyamide resin layer. 4. The laminated material according to claim 3, wherein a polyolefin resin layer is laminated on the surface of the light shielding / barrier layer on which the inorganic oxide thin film is not formed. 5. A polyolefin resin layer is provided on the inorganic oxide thin film of the light shielding / barrier layer, and a paper layer and a polyolefin resin layer are provided on the surface of the light shielding / barrier layer on which the inorganic oxide thin film is not formed. The laminated material according to claim 3, wherein the laminated material is provided in this order. 6. The laminated material according to claim 3, wherein the light shielding / barrier layer contains carbon black as the light shielding material in an amount of 0.5 to 30% by weight.