JP3121395B2 - Sealed container - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a saponified ethylene-vinyl ester copolymer (A) layer and an ethylene-vinyl acetate copolymer or an ethylene-unsaturated carboxylic acid ester copolymer, and a tackifier. The present invention relates to an inexpensive laminate, a lid material and a container which are hardly blocked when wound up in a roll, and which are excellent in easy-opening properties and preservability of contents, when the laminate comprising a composition (B) layer composed of a wax and a composition is wound into a roll.

[0002]

2. Description of the Related Art Conventionally, many lids having easy-opening properties have been introduced. For example, the innermost layer of a lid made of polypropylene and a heat-sealed lid is mainly composed of polypropylene, high-density polyethylene, A method of blending low-density polyethylene, linear low-density polyethylene, ethylene-vinyl acetate copolymer, or the like to reduce the cohesive force of the sealant or a method of filling polypropylene with an inorganic filler such as talc has been adopted. However, these methods do not yet have sufficient openability, which has a contradictory property of having a sufficient adhesive force during transport and being easily opened at the time of opening.

JP-A-53-129271 discloses a saponified ethylene-vinyl acetate copolymer layer having an ethylene content of 20 to 50 mol% and a saponification degree of 90% or more, and a saponified ethylene-vinyl acetate copolymer. And a coextruded multilayer film composed of at least two mixed resin layers in which a tackifier is added to a resin having excellent adhesiveness.
However, the publication is based on a saponified ethylene-vinyl acetate copolymer and an ethylene-vinyl acetate copolymer,
A layer containing a tackifier, or further, a polyolefin resin layer and a co-extrusion method are melted by a co-extrusion method to obtain a multilayer film having an extremely excellent interlayer strength between the respective resins by fusing in a die. Yes, description on easy-opening property (moderate interlayer strength) and non-blocking property, ethylene-vinyl acetate copolymer saponified layer, ethylene-vinyl acetate copolymer or ethylene-
There is no description relating to coating a composition comprising an unsaturated carboxylic acid ester copolymer, a tackifier and a wax (hereinafter , abbreviated as the present resin composition ), and no description relating to compounding a wax. Furthermore, the specification of this publication describes that an ethylene-vinyl acetate copolymer having a melt index (hereinafter abbreviated as MI) of about 1.5 to 15 is effective. If the viscosity is too high, lamination using a hot melt applicator, which will be described later, is difficult.

JP-A-60-239233 discloses a vinyl chloride copolymer layer containing 60 to 99 mol% of a vinyl chloride component and 40 to 1 mol% of vinyl acetate and / or (meth) acrylate. A) and a reactive polyurethane polymer layer (B) containing an isocyanate group, the ethylene-containing layer being coated with an adhesive layer having a mixing ratio (weight) of A / B = 2/3 to 6. Ethylene having an amount of 20 to 60 mol% and a saponification degree of the vinyl acetate component of 95% or more.
A heat lamination film comprising a saponified vinyl acetate copolymer is described. In addition, JP
No. 242053 discloses that the ethylene content is 20 to 60.
Mol%, saponified ethylene-vinyl acetate copolymer (A) having a degree of saponification of vinyl acetate component of 95% or more, reactive polyurethane polymer layer containing isocyanate group (B) and 60 to 99 mol% of vinyl chloride component. And a vinyl chloride copolymer layer (C) containing 40 to 1 mol% of vinyl acetate and / or (meth) acrylic acid ester, and A
A composite film for thermal lamination having a configuration of / B / C is described. However, the present is to this, such as publications
There is no description about the resin composition .

Japanese Utility Model Laid-Open Publication No. 2-39973 discloses that a laminated material 1 having a high barrier plastic layer 1A on the inner surface and a polyolefin layer 1B inside the laminated material 1 is provided on a flange portion 3.
Is a container formed by forming a cup-shaped body having a container body 3 and a lid body 4 heat-sealed to the container body 3, and the lid body 4 reaches the polyolefin layer 1B through the high barrier plastic layer 1A. A high barrier easy opening container characterized by being sealed by heat sealing is described. However, the present also in the publication
There is no description about the resin composition , and the high barrier plastic is polyacrylonitrile, not a saponified ethylene-vinyl ester copolymer.

As described above, there is no sufficient easy-opening property which has a contradictory property that it has a sufficient adhesive force during transportation and can be easily opened at the time of opening.
For many years, there has been a long-felt need to develop an easily-openable lid material having both of these properties, being less likely to be blocked when wound into a roll, and having excellent transparency. In addition, in order to satisfy both easy-opening properties and gas barrier properties, it is necessary to laminate a resin having easy-opening properties and a resin or metal foil having gas-barrier properties. Was desired. It should be noted that the easy-opening property refers to JIS Z 02
38 specifies 0.3 to 0.6 kgf / 15 mm, but here, a pressure of 2 kg / c, which is widely used in the industry, is used.
m ² , heat-sealed under the conditions of 1 second and 180 ° peeling, the value measured under the condition of peeling speed 300 mm / min is 600 to
It refers to 1500 g / 15 mm width.

[0007]

As described above, the prior art has both easy opening property and preservability of contents.
Inexpensive lids and containers that are difficult to block when the laminated film having the configuration (B) are wound into a roll cannot be obtained.

[0008]

Means for Solving the Problems The present inventor has conducted intensive studies based on the recognition of the above problems, and as a result, has found that the ethylene content is 20%.
(A) layer of a saponified ethylene-vinyl ester copolymer (hereinafter abbreviated as EVOH) having a saponification degree of at least 90 mol% of the vinyl ester component and the present resin composition
A laminate comprising the product (B) layer, and a layer (A), a layer (B) and a substrate (C) layer, and a layer (C) / layer (A) /
(B) The laminated body having the layer configuration has both easy-opening properties, preservability of contents, and transparency, and is less likely to be blocked when the laminated film (A) / (B) is wound into a roll. They have found that they are useful for inexpensive lids and containers, and have completed the present invention.

Hereinafter, the present invention will be described in more detail. In the present invention, EVOH (A) refers to a polymerization initiator such as benzoyl peroxide or azobisisobutyronitrile obtained by converting ethylene and a vinyl ester under pressure in a solvent such as methanol, t-butanol or dimethyl sulfoxide. It is a product obtained by polymerization by a known method and then saponification with an acid or alkali catalyst. Examples of the vinyl ester include fatty acid vinyl esters such as vinyl acetate vinyl ester, vinyl propionate ester, vinyl versatate ester and vinyl pivalate ester.Although vinyl esters of aromatic carboxylic acids and the like can be used, the price point is low. From the viewpoint of gas barrier properties, vinyl acetate pivalate is preferred. EVOH has an ethylene content of 20 to 65 mol%, preferably 20 to 5 mol%.
0 mol%, saponification degree of vinyl ester component is 90 mol%
It is at least 95 mol%. The EVOH layer may be biaxially stretched or non-stretched.
If the ethylene content is less than 20 mol%, the gas barrier property at high humidity decreases, and if it exceeds 65 mol%, a sufficient gas barrier property cannot be obtained. On the other hand, the degree of saponification is 90 mol%
If it is less than 1, the gas barrier property at high humidity is not only lowered, but also the thermal stability of EVOH is deteriorated, and a gel is easily generated on the obtained film surface.

Further, EVOH (A) further contains a small amount of unsaturated olefins such as α-olefins such as propylene, isobutene, 4-methylpentene-1, hexene and octene, itaconic acid, methacrylic acid, acrylic acid and maleic anhydride. Carboxylic acids, salts thereof, partial or complete esters thereof, nitriles thereof, amides thereof, anhydrides thereof, vinylsilane compounds such as vinyltrimethoxysilane, unsaturated sulfonic acids,
A copolymer component such as a salt thereof or an alkyl thiol may be contained.

The EVOH (A) may be a mixture of two or more EVOHs having different ethylene contents.
In addition, two or more types of EVOH having different degrees of polymerization and saponification are used.
May be used. Furthermore, both the ethylene content and the degree of polymerization or the degree of saponification may be different.

Furthermore, the EVOH (A) layer may be a plurality of layers of two or more EVOHs having different ethylene contents. In such a case, the water activity value of the contents should be 1
When the value multiplied by 00 is compared with the relative humidity value of the storage environment, the gas barrier property of the packaging material becomes better when the EVOH having a smaller ethylene content is arranged in the smaller value. In the plurality of layers of the EVOH, all the layers may be biaxially stretched, only specific layers may be biaxially stretched, or all the layers may be non-stretched.

The EVOH (A) may contain an antioxidant, a coloring agent, an ultraviolet absorber, a slip agent, an antistatic agent, a plasticizer, a crosslinking agent such as boric acid, and an inorganic filler within a range not to impair the present invention. And various additives such as an inorganic desiccant and various resins such as polyamide, polyolefin and superabsorbent resin.

In the present invention, a composition comprising the ethylene-vinyl acetate copolymer or the ethylene-unsaturated carboxylic acid ester copolymer, a tackifier and a wax (the present resin composition) (B) is 1 ) Ethylene-vinyl acetate copolymer or ethylene-unsaturated carboxylic acid ester copolymer, 2) compatible with ethylene-vinyl acetate copolymer or ethylene-unsaturated carboxylic acid ester copolymer, and A tackifier having tackiness to the adherend and EVOH, and 3) a wax for improving the fluidity of the resin composition and accelerating dissolution. 10 to 90% by weight of a polymer or an ethylene-unsaturated carboxylic acid ester copolymer, preferably 20 to 70% by weight,
5 to 60% by weight of a tackifier, preferably 10 to 50% by weight, 1 to 60% by weight of a wax, preferably 5 to 45% by weight
And more preferably 0.001 to 20% by weight of an antioxidant such as 4-4'-thiobis (6-tert-butyl-m-cresol) or BHT, and more preferably 0.005 to 10%. % By weight of a composition having a viscosity at 150 ° C., preferably 100 to 20,000 cps.
More preferably, the composition exhibits 500 to 8000 cps.

In the present resin composition , ethylene-vinyl propionate copolymer,
Ethylene-vinyl ester copolymer such as ethylene-butyric acid vinyl ester copolymer, dibutyl phthalate, di-
Plasticizers such as 2-ethyl-hexyl phthalate and dioctyl phthalate, inorganic fillers such as barium sulfate, calcium carbonate, titanium oxide, magnesium carbonate, magnesium oxide, and hydrous silicic acid, coloring agents, ultraviolet absorbers, slip agents,
Various additives such as an antistatic agent, a cross-linking agent, and an inorganic drying agent, and various resins such as polyamide, polyester, polyethylene, polypropylene, polyvinyl acetate, and superabsorbent resin may be blended.

In the present invention, the ethylene-vinyl acetate copolymer in the resin composition preferably has a vinyl acetate content of 10 to 50% by weight, more preferably 15 to 45% by weight. Things. If necessary, an unsaturated carboxylic acid such as (meth) acrylic acid, maleic acid, maleic anhydride, itaconic acid, and itaconic anhydride may be graft-modified to be used. The MI of the ethylene-vinyl acetate copolymer at a load of 2160 g and 190 ° C. is preferably 16 g / 10 min or more, more preferably 20 to 700 g / 10 min. In addition, in order to satisfy the high adhesive strength, low viscosity, high compatibility, and low stringability of the resin composition, ethylene-vinyl acetate copolymers having different vinyl acetate contents and MIs and Or a partially saponified composition thereof.

In the present invention, the ethylene-unsaturated carboxylic acid ester copolymer in the present resin composition includes ethylene- (meth) acrylic acid methyl ester copolymer and ethylene- (meth) acrylic acid ethyl ester copolymer. Coalescing,
Examples include an ethylene-itaconic acid dimethyl ester copolymer and an ethylene-itaconic acid diethyl ester copolymer, which are ethylene-acrylic acid ethyl ester copolymers having an acrylic acid ethyl ester content of 10 to 40% by weight. Preferably, a product obtained by graft polymerization modification of an unsaturated carboxylic acid such as (meth) acrylic acid, maleic anhydride, and itaconic acid can also be used.

In the present invention, the tackifier includes rosins such as gum rosin, wood rosin and tall oil, and modified rosins obtained by modifying them by hydrogenation, disproportionation, dimerization, esterification, etc., α-pinene Polymers, β-pinene polymers, dipentene polymers, terpene-phenol copolymers, α-pinene-phenol copolymers and other pinene resins, 1-butene, isobutylene, butadiene, 1,3-
C4-C5 such as pentadiene, isoprene and piperylene
Aliphatic resins such as polymers having mono- and diolefins as main components, resins obtained by cyclizing and dimerizing diene components in spent C4 to C5 fractions, and aromatic hydrocarbon resins as nuclei Alicyclic resins such as internally hydrogenated resins, aromatic resins such as vinyltoluene, indene, α-methylstyrene, etc., which are polymers mainly composed of C9-C10 vinyl aromatic hydrocarbons, styrene And petroleum resins such as styrene-based resins, cumarone-indene-based resins, and phenol-based resins, which are polymers such as vinyl toluene, α-methylstyrene, and isopropenyltoluene. It may be graft-polymerized with an unsaturated carboxylic acid such as acrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, or a maleic ester.

In the present invention, the wax is a liquid at room temperature or a solid (semi) solid having a low melting temperature or a low melt viscosity, and has an average molecular weight of 300 to 10,000.
Petroleum wax or modified petroleum wax, such as paraffin wax, microcrystalline wax, castor wax, chlorinated paraffin, and low molecular weight polyethylene wax. Furthermore, waxes (eg, vegetable waxes and animal waxes) made of esters of fatty acids and water-insoluble higher monohydric alcohols or dihydric alcohols are also included.

In the present invention, the thickness of the laminate comprising the resin composition (B) layer and the EVOH (A) layer can be variously selected depending on the cost and the target heat-sealing strength of the easy-open property. However, the thickness of the resin composition (B) layer is preferably 1 to 50 μm , and the thickness of the EVOH (A) layer is preferably 1 to 100 μm .

In the present invention, when a laminated film comprising the present resin composition (B) layer and the EVOH (A) layer is wound into a roll, a property of being hardly blocked is exhibited. When a layer other than EVOH, for example, a laminated film composed of the present resin composition and an ethylene-vinyl acetate copolymer is wound into a roll, blocking is likely to occur, and it is difficult to laminate the layer with the substrate (C) layer. Often becomes.

In the present invention, the substrate (C) layer
Examples thereof include paper, cellulose-based film, thermoplastic resin, metal-deposited thermoplastic resin, metal-deposited paper, metal-deposited cellulose-based film, and metal foil, and these can be used as one or more layers.

In the present invention, the thermoplastic resin used for the substrate (C) layer includes polyester such as polyethylene terephthalate, polyolefin such as polyethylene, polypropylene, polybutene-1 and polymethylpentene, nylon 6, nylon 66, and MXD6. Polyamides such as (polyamide composed of meta-xylylenediamine and adipic acid), polyvinyl chloride, polystyrene, polyacrylonitrile, polycarbonate, poly (meth) acrylate, polysulfone, and polydiene compounds (polybutadiene, polyisoprene, etc.). When used as a material, biaxially stretched films of polyethylene terephthalate, nylon 6, nylon 66, MXD6, and polypropylene are preferred in terms of good easy-openability, printability, and aesthetic appearance. Beam may be coated with a polyvinylidene chloride. When used as molding containers such as cups and trays obtained by thermoforming and injection molding from sheets and films, and blow molding containers such as direct blow bottles and stretch blow bottles, polyester, polyethylene, polypropylene, and polyvinyl chloride , Polystyrene, polycarbonate, and polyacrylonitrile are preferable in terms of good easy-openability, strength of the molded container, and aesthetic appearance, and the substrate (C) layer may be a multilayer.

In the present invention, examples of the cellulose-based film used for the substrate (C) layer include cellophane, cellulose acetate, moisture-proof cellophane, cellophane coated with a vinylidene chloride copolymer, and cellulose acetate. Cellophane coated with a vinylidene chloride-based copolymer is preferred.

In the present invention, a metal-deposited thermoplastic resin,
The paper and the cellulose-based film are obtained by metal-depositing the above-mentioned thermoplastic resin, paper and the above-mentioned cellulose-based film. Examples of the metal vapor deposition include aluminum vapor deposition, gold vapor deposition, silver vapor deposition, aluminum oxide vapor deposition, silicon oxide vapor deposition, magnesium oxide, indium oxide / zinc oxide vapor deposition, and the like. Vapor deposition and silicon oxide deposition are preferred.

In the present invention, examples of the metal foil include aluminum foil, iron foil, stainless steel foil, gold foil, and copper foil. Aluminum foil and iron foil are preferred in terms of price, appearance and formability. .

In the present invention, paper, cellulosic film,
Thermoplastic resin, metal-deposited thermoplastic resin, metal-deposited paper, gold
Selected from metallized cellulosic film and metal foil
And a substrate (C) layer comprising at least one kindThe resin composition
(C) / (B) layer and EVOH (A) layer
(A) / (B) for use as a lid, molded container, etc.
The base (C) layer and the EVOH (A) layer
For lamination, a known lamination method, for example, co-extruded laminating
Coating method, dry laminating method, extrusion laminating method,
Extrusion coating, solution coating, etc. can be used
Noh. In addition, the EVOH (A) layerThe resin composition
(B) The lamination of the layers may also be performed using a known hot melt application.
For example, nozzle type, wheel type, roll type,
Not only can the method such as
Gravure coater, reverse throw
Le coater, spin coater, knife coater, spray
-Coater, dipping and other methods can also be adopted.

In adopting these lamination methods,
As long as a sufficient adhesive force can be obtained between the layer (C) and the layer (A), the layers may be directly laminated, but there is a case where a sufficient adhesive force cannot be obtained. When a sufficient adhesive strength cannot be obtained, when the co-extrusion laminating method is employed, the adhesive property of a polyolefin graft-modified with an unsaturated carboxylic acid or a copolymer of an olefin and an unsaturated carboxylic acid is used. It is necessary to use a resin. When using the dry lamination method or the extrusion lamination method, polyester, polyether,
It is necessary to use a two-part curable adhesive or anchor coat agent containing polyurethane as a main component and isocyanate as a curing agent. When using the solution coating method,
It is necessary to appropriately use the above-mentioned anchor coating agent. Furthermore, when the co-extrusion coating method is employed, it is necessary to appropriately use the anchor coating agent or the adhesive resin.

The procedure for laminating the laminate having the layer (C) / layer (A) / layer (B) is as follows. First, the layer (C) and the layer (A) are laminated, and then the layer (B) is laminated. Alternatively, the (A) layer and the (B) layer may be stacked first, and then the (C) layer may be stacked. Printing on the front surface or the back surface of the base (C) layer is also useful for enhancing aesthetics and commercial value.

The laminate obtained according to the present invention is excellent in gas barrier properties, and also from the viewpoint of ensuring excellent gas barrier properties of a sealed container sealed at the periphery of the opening of the container. It is desirable that the molding container or the lid material to be formed also includes a resin, a metal foil, a metal vapor deposition, or the like, which is excellent in gas barrier properties.

Examples of the adherend include polyester such as polyethylene terephthalate, polyethylene, polypropylene, polyolefin such as polybutene-1, polymethylpentene, polyamide such as nylon 6, nylon 66 and MXD6, polyvinyl chloride, polystyrene, polyacrylonitrile, and the like. Examples thereof include polydiene compounds such as polycarbonate, poly (meth) acrylate, polysulfone, polybutadiene, and polyisoprene ; metals and glass ; and cups and trays whose adherends are obtained by thermoforming and injection molding from sheets and films. For molded containers such as blow molded containers such as direct blow bottles and stretch blow bottles, polyester, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polycarbonate , Polyacrylonitrile, good easy-open, the strength of the molded container is suitable in terms of aesthetics,
The molded container may be a multilayer body.

The easily-openable container obtained by the present invention includes cherries, mini tomatoes, shimeji, cut vegetables, salads,
Fresh foods such as clams, sashimi, mozuku, etc.
Gyoza, sushi, side dishes such as Wariko soba, kelp, seaweed, boiled fish such as small fish, radish, nozawana, eggplant, red turnip, ginger, plum dried,
Pickles such as raccoon, kimchi, reddish paste, white miso, miso such as Kanayama time, moromi, tofu such as tofu, egg tofu,
Processed meat products such as sliced ham, bacon, and vienna sausage; fishery products such as bamboo grass, bamboo rings, and hampen;
Jams such as strawberry jam and marmalade, processed fish and egg products such as salmon roe, cod, mustard mentaiko, soda noodles, pudding, fruit jelly, cakes, candy, chocolate, biscuits and other desserts, white rice, unwashed rice and other grains Suitable for dried foods such as varieties, crepe small fish, dried milt, dried bonito cut-off knives, frozen foods such as fried shrimp, fried rice, dumplings, audio parts, non-foods such as stationery, pharmaceuticals, etc. Used.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. All parts and percentages are by weight unless otherwise specified.

The evaluation method is as follows, and the evaluation criteria are as follows. ◎: extremely good ○: good △: slightly poor ×: bad

(1) Preservability of contents The miso is filled in the hermetic seal, and after sealing, it is allowed to stand for 90 days near the south side window of the room where direct sunlight does not shine but sufficient reflected light shines.
Next, the package was opened, and the color tone and taste of the miso were judged by ten panelists and averaged.

(2) Transparency The miso was filled, the package (C) layer / (A) layer / (B) layer was seen through, and the transparency was judged by 10 panelists, and the average value was taken. Was.

[0037]

EXAMPLES Example 1 As an EVOH (A) layer, an ethylene-vinyl acetate copolymer was saponified to obtain an ethylene content of 32 mol% and a saponification degree of a vinyl acetate component of 99.5 mol%.
Was extruded at 230 ° C. to obtain a non-stretched film having a thickness of 15 μm.

A 50 μm biaxially stretched polyethylene terephthalate film of Lumirror manufactured by Toray Industries, Inc. was selected as the substrate (C) layer, and A-385 / A manufactured by Takeda Pharmaceutical Co., Ltd. was used as an adhesive for dry lamination. After applying 3 g / m ² as a solid content of -50 and evaporating the solvent at 80 ° C., the EVOH film was laminated and aged at 40 ° C. for 3 days to obtain a composite film.

As the resin composition (B) layer, a vinyl acetate ester content of 28 parts by weight as an ethylene-vinyl acetate copolymer, a resin of MI 400 g / 10 min, 30% by weight, and a hydrogenated rosin glycerin ester as a tackifier 35 parts by weight, 35 parts by weight of 120 ° F paraffin wax as a wax, and 800 BHT as an antioxidant
A composition consisting of ppm was selected and adjusted to a toluene solution having a concentration of 15% by weight. The solution is mixed with the EVOH of the composite film.
(A) 2 g / m ^{2 was} applied to the layer surface, and the solvent was evaporated at 130 ° C. to obtain a laminate having the structure of (C) layer / (A) layer / (B) layer.

A Kuraray Co., Ltd. KS750R 500 μm sheet manufactured by Kuraray Co., Ltd. was used as the adherend.
Using a heat sealer manufactured by Yasuda Seiki Seisaku-sho, pressure of 2 kg / cm ² , time of 1 second, temperature of 140 ° C.
(B) The surface was heat-sealed. When the heat sealing strength was measured using an autograph manufactured by Shimadzu Corporation, it was 0.7 kg / 1.
It showed a good openability of 5 mm.

Separately, 1m of clappet sheet KS750R
A container was formed from a sheet having a thickness of m by vacuum forming. After filling the miso, the laminate and the peripheral edge of the opening of the container were sealed by heat sealing. Table 1 shows the results.

Comparative Example 1 In Example 1, this resin composition (B) layer was treated with male-anhydride graft-modified ethylene-vinyl acetate copolymer Admer VF manufactured by Mitsui Petrochemical Industries, Ltd.
600 (vinyl acetate content 20 parts by weight, MI
2.4 g / 10 min: A similar laminate was obtained in the same manner as in Example 1, except that the toluene solution of EVOH and coextrusion resin for PET or PS) was changed to a toluene solution. The heat sealing strength was only 0.2 kg / 15 mm, which was extremely inferior to Example 1. Table 1 shows the results.

Comparative Example 2 In Example 1, the EVOH (A) layer had an ethylene content of 89 mol% and a degree of saponification of the vinyl acetate ester component of 9
Except that 2 mol% of the resin was melt extruded at 200 ° C.
A similar laminate was obtained in the same manner as in Example 1. The storage stability of the miso was very poor as compared with Example 1. Table 1 shows the results.

Example 2 As an EVOH (A) layer, an ethylene-vinyl acetate copolymer was saponified to obtain an ethylene content of 44 mol% and a saponification degree of the vinyl acetate ester component of 99.5 mol%.
Was extruded at 220 ° C. to obtain a non-stretched film having a thickness of 25 μm.

A 25 μm biaxially stretched polyethylene terephthalate film of Lumirror manufactured by Toray Industries, Inc. was selected as the substrate (C) layer, and A-385 / A manufactured by Takeda Pharmaceutical Co., Ltd. was used as an adhesive for dry lamination. After applying 3 g / m ² as a solid content of -50 and evaporating the solvent at 80 ° C., the EVOH film was laminated and aged at 40 ° C. for 3 days to obtain a composite film.

As the resin composition (B) layer, ethylene-
As a vinyl acetate ester copolymer, a vinyl acetate ester content of 28 parts by weight and MI
% By weight, 40 parts by weight of gum rosin as a tackifier, 20 parts by weight of 145 ° F. paraffin wax as a wax, and 1000 ppm of 4-4′-thiobis (6-tert-butyl-m-cresol) as an antioxidant. The composition was selected, melted at 150 ° C., and applied to the EVOH (A) surface of the composite film at 25 g / m ² to obtain a laminate having a (C) layer / (A) layer / (B) layer configuration. The same procedure as in Example 1 was carried out except for the above, to obtain a similar laminate. The heat sealing strength was measured and found to be 1.2 kg / 15 mm, indicating a good easy-openability. Table 2 shows the results.

Example 3 As an EVOH (A) layer, an ethylene-vinyl acetate copolymer was saponified to obtain an ethylene content of 44 mol% and a saponification degree of the vinyl acetate ester component of 99.5 mol%.
And a polypropylene resin MA-6 manufactured by Mitsubishi Yuka Co., Ltd. as a base (C) layer at 230 ° C. through an adhesive polypropylene resin Admer QF550 manufactured by Mitsui Petrochemical Industry Co., Ltd. Thus, a three-layer coextruded composite sheet having a thickness of the EVOH (A) layer of 70 μm, a thickness of the admer layer of 70 μm, and a thickness of the substrate (C) layer of 360 μm was obtained.

As the resin composition (B) layer, ethylene-
A vinyl acetate ester copolymer having a vinyl acetate ester content of 33 parts by weight, a resin of MI 40 g / 10 min of 15% by weight, a vinyl acetate ester content of 25 parts by weight, MI40
A composition comprising 25% by weight of a resin of 0 g / 10 min, 35 parts by weight of hydrogenated rosin glycerin ester as a tackifier, 20 parts by weight of 120 ° F paraffin wax as a wax, and 800 ppm of BHT as an antioxidant was selected. , A 15% by weight toluene solution. The solution was applied to the EVOH (A) surface of the composite film at 2 g / m ² , and the solvent was evaporated at 130 ° C. to form a layer (C) / layer (A) /
(B) A laminate having a layer configuration was obtained.

As an adherend, a 12 μm polyvinylidene chloride-coated biaxially stretched polyethylene terephthalate film of ENBLET KPW manufactured by Unitika Ltd. was selected.
Using a heat sealer manufactured by Yasuda Seiki Seisaku-sho, pressure of 2 kg / cm ² , time of 1 second, temperature of 140 ° C.
(B) The surface was heat-sealed. When the heat sealing strength was measured using an autograph manufactured by Shimadzu Corporation, it was 0.8 kg / 1.
It showed a good openability of 5 mm. Table 2 shows the results.

Example 4 As an EVOH (A) layer, an ethylene-vinyl acetate copolymer was saponified to obtain an ethylene content of 27 mol% and a saponification degree of the vinyl acetate component of 99.5 mol%.
And a resin having an ethylene content of 44 mol% and a saponification degree of the vinyl acetate ester component of 99.5 mol% obtained by saponifying an ethylene-vinyl acetate copolymer.
Melt coextrusion at 40 ° C., each thickness 15 μm,
A co-extruded unstretched film of two types and two layers with a total thickness of 30 μm was obtained.

A 25 μm biaxially stretched polyethylene terephthalate film of Lumirror manufactured by Toray Industries Co., Ltd. was selected as the substrate (C) layer, and A-385 / A manufactured by Takeda Pharmaceutical Co., Ltd. was used as an adhesive for dry lamination. After applying 3 g / m ^{2 of} -50 as a solid content and evaporating the solvent at 80 ° C., the ethylene content of the EVOH film was 27 mol%.
The same lamination was obtained in the same manner as in Example 1 except that the composite film was obtained by laminating on the side and aging at 40 ° C. for 3 days. When the heat sealing strength was measured, it was 1.2 kg / 1.
It showed a good openability of 5 mm. Table 3 shows the results.

Example 5 As an EVOH (A) layer, an ethylene-vinyl acetate copolymer was saponified to obtain an ethylene content of 27 mol% and a saponification degree of the vinyl acetate ester component of 99.5 mol%.
And a resin having an ethylene content of 44 mol% and a saponification degree of the vinyl acetate ester component of 99.5 mol% obtained by saponifying an ethylene-vinyl acetate copolymer.
Melt coextrusion at 40 ° C., each thickness 15 μm,
A co-extruded unstretched film of two types and two layers with a total thickness of 30 μm was obtained.

As the resin composition (B) layer, ethylene-
As a vinyl acetate copolymer, a resin having a vinyl acetate content of 28 parts by weight and an MI of 400 g / 10 min was used as a resin.
% By weight, 40 parts by weight of hydrogenated rosin glycerin ester as a tackifier, 20 parts by weight of 145 ° F. paraffin wax as a wax, and 4-4′-thiobis (6-tert-butyl-m-cresol) as an antioxidant Of 700 ppm was selected and adjusted to a 10% by weight concentration toluene solution. 2 g / m ^{2 of the} solution was applied to the ethylene content 44 mol% side of the EVOH film,
The solvent was evaporated at 130 ° C. to obtain a laminated film having the configuration of (A) / (B). Bring the film roll to 42 ° C for 1
After standing for a day, no blocking occurred.

A 25 μm biaxially stretched polyethylene terephthalate film of Lumirror manufactured by Toray Industries Co., Ltd. was selected as the substrate (C) layer, and A-385 / A manufactured by Takeda Pharmaceutical Co., Ltd. was used as an adhesive for dry lamination. After applying 3 g / m ² as a solid content of -50 and evaporating the solvent at 80 ° C., E of the above laminated film having an ethylene content of 27 mol% was used.
A similar laminate was obtained in the same manner as in Example 1 except that the laminate was laminated on the VOH film side and aged at 40 ° C. for 3 days to obtain a laminate. When the heat sealing strength was measured, it was 1.1.
kg / 15 mm, showing good easy-openability. Table 3 shows the results
Shown in

Comparative Example 3 In Example 5, the EVOH (A) layer was replaced with SB-10 (vinyl acetate content: 1) manufactured by Tamapoli Corporation.
(A) / (B) to obtain a laminated film having the structure of (A) / (B), except that a 40 μm (0% by weight) film was used. When the film roll was left at 42 ° C. for 1 day, it was blocked, and hindered the lamination with the substrate (C) layer, and the subsequent experiments were stopped. Table 3 shows the results.

[0056]

[Table 1]

[0057]

[Table 2]

[0058]

[Table 3]

[0059]

As described above, according to the present invention,Sealed container
Is easy to open and easy to store
Yes, it can be suitably applied to various foods, pharmaceuticals, and non-foods.

Continuation of front page (56) References JP-A-1-58675 (JP, A) JP-A-53-129271 (JP, A) JP-A-58-1541 (JP, U) JP-A-57-88544 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) B32B 1/00-35/00 B65D 53/00-53/10

Claims (3)

(57) [Claims] 1. From polyester or polypropylene
A container comprising an ethylene content of 20 to 65 mol%, saponification degree 90 mol% or more of ethylene vinyl ester component - vinyl ester copolymer saponified (A) layer, an ethylene - vinyl ester copolymer or ethylene - unsaturated Carboxylic acid ester copolymer, tackifier , wax and oxidation
Composition (B) layer comprising an inhibitor and polyester or
Is a base (C) layer made of polypropylene (C)
A lid material having a layer / (A) layer / (B) layer configuration ,
The layer (B) of the lid material and the opening of the container are heat-sealed at the periphery of the opening of the container, and the heat sealing strength is 600 to 150.
A sealed container having a width of 0 g / 15 mm. 2. To obtain a cover material having a constitution of (C) layer / (A) layer / (B) layer, after laminating (A) layer and (C) layer, apply (B) layer with a solution. The method for producing a sealed container according to claim 1, wherein the container is laminated. 3. To obtain a cover material having a constitution of (C) layer / (A) layer / (B) layer, after laminating the (A) layer and the (C) layer, the (B) layer is melt- coated. The method for producing a sealed container according to claim 1, wherein the container is laminated.