JPH0592528A - Laminate, cover and container - Google Patents

Abstract

PURPOSE:To improve easily unsealable properties and shelf stability of a content, make the same inexpensive and utilize the same for the fields of various kinds of foodstuffs, pharmaceuticals and non-foodstuffs by forming a laminate composed of a copolymer saponification layer in which the degree of saponification of ethylene content and vinyl ester component are controlled within the specified range and an EVA wax layer. CONSTITUTION:A laminate is composed of an ethylene - vinyl ester copolymer saponification A layer containing ethylene of 20-65mol% and provided with the saponification degree of 90mol% or more, and a composition B layer composed of an ethylene - hydrochloric acid vinyl ester copolymer or an ethylene unsaturated carboxylic acid ester copolymer, a viscosity imparting agent and wax. The A layer can be two or more vinyl ester copolymer saponification materials containing different contents of ethylene. The materials in which the contents of ethylene and the degree of vinyl ester being in the range similar to above-mentioned are laminated in a plurality of layers.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a saponified product of an ethylene-vinyl ester copolymer (A) layer and an ethylene-vinyl acetate copolymer, or an ethylene-unsaturated carboxylic acid ester copolymer, and a tackifier. Also, the present invention relates to a laminate, a lid and a container which are less likely to block when a laminate comprising the composition (B) layer made of wax is wound up in a roll shape, are easy to open, and have excellent storage stability of contents, and are inexpensive.

[0002]

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

JP-A No. 53-129271 discloses an ethylene-vinyl acetate copolymer saponified product layer having an ethylene content of 20 to 50 mol% and a saponification degree of 90% or more, and the ethylene-vinyl acetate copolymer saponified product. And a coextrusion multilayer film comprising 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 product of an ethylene-vinyl acetate copolymer and an ethylene-vinyl acetate copolymer,
A layer containing a tackifier, or further, a polyolefin resin layer is melted by a co-extrusion method to obtain a multilayer film having very excellent interlaminar strength between the resins by fusion in a die. Yes, description regarding easy-opening property (moderate interlaminar strength) and non-blocking property, ethylene-vinyl acetate copolymer saponified layer, ethylene-vinyl acetate copolymer, or ethylene-
There is no description about coating a composition comprising an unsaturated carboxylic acid ester copolymer, a tackifier and a wax (hereinafter abbreviated as EVA wax), and no description about blending 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. With such a high viscosity, it is difficult to laminate with a hot melt applicator described later.

JP-A-60-239233 discloses a vinyl chloride copolymer layer containing 60 to 99 mol% of vinyl chloride component and 40 to 1 mol% of vinyl acetate and / or (meth) acrylic acid ester ( Ethylene-containing, which is composed of A) and a reactive polyurethane polymer layer (B) containing an isocyanate group, and is covered with an adhesive layer having a mixing ratio (weight) of A / B = 2/3 to 6 Ethylene with an amount of 20 to 60 mol% and a saponification degree of the vinyl acetate component of 95% or more
A film for thermal lamination comprising a saponified vinyl acetate copolymer is described. In addition, JP-A-60
No. 242053 discloses an ethylene content of 20-60.
60% to 99% by mol of an ethylene-vinyl acetate copolymer saponification product (A) having a saponification degree of 95% or more of a vinyl acetate component, a reactive polyurethane-based polymer layer (B) containing an isocyanate group, and a vinyl chloride component. And a vinyl chloride-based 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 composition of / B / C is described. However, in these publications, E
There is no description about VA wax.

In Japanese Utility Model Application Laid-Open No. 2-39973, a laminated material 1 having a high-barrier plastic layer 1A on the inner surface and a polyolefin layer 1B on the inner side thereof is disclosed as a flange portion 3.
A container body 3 is formed by molding into a cup shape and has a lid 4 heat-sealed thereto, and the lid 4 penetrates the high barrier plastic layer 1A to reach the polyolefin layer 1B. A high-barrier easy opening container characterized by being sealed by heat sealing is described. However, E
There is no description about VA wax, and the high barrier plastic is polyacrylonitrile, ethylene-
It does not relate to saponified vinyl ester copolymers.

As described above, there is still no sufficient easy-opening property which has the contradictory characteristics of having a sufficient adhesive force during transfer and being easily opened at the time of opening.
It has been desired for many years to develop an easily-openable lid material that has the above-mentioned characteristics, is hard to block when wound into a roll, and has excellent transparency. Further, in order to satisfy both the easy opening property and the gas barrier property, it is necessary to laminate a resin having an easy opening property and a resin or a metal foil having a gas barrier property, which is disadvantageous in terms of cost and reduces the cost. Was wanted. The easy-open property is JIS Z 0.
238 regulates 0.3 to 0.6 kgf / 15 mm, but here the pressure of 2 kg /
The value measured by heat sealing under conditions of cm ↑ 2 and time of 1 second, peeling at 180 degrees, and peeling speed of 300 mm / min was 6
It refers to a width of 00 to 1500 g / 15 mm.

[0007]

As described above, the prior art has both the easy-open property and the storability of the contents.
When the laminated film having the structure (/ B) is wound up in a roll, it is difficult to obtain an inexpensive lid material and container which are difficult to block.

[0008]

Means for Solving the Problems The present inventor has conducted earnest research based on the recognition of the above problems, and as a result, found that the ethylene content was 20
~ 65 mol%, saponification degree of vinyl ester component 90 mol% or more saponification product of ethylene-vinyl ester copolymer (hereinafter abbreviated as EVOH) (A) layer and EVA wax (B) layer, and ( A) layer, (B)
A laminate having a constitution of (C) layer / (A) layer / (B) layer, which is composed of a layer and a base material (C) layer, has easy opening property, storability of contents, and transparency. They have found that the laminated film of (A) / (B) structure is useful for an inexpensive lid material and container that are difficult to block when wound in a roll shape, and completed the present invention.

The present invention will be described in more detail below. In the present invention, EVOH (A) is a polymerization initiator such as benzoyl peroxide or azobisisobutyronitrile obtained by pressurizing ethylene and vinyl ester in a solvent such as methanol, t-butanol or dimethyl sulfoxide under pressure. It is obtained by polymerizing by a known method, followed by saponification with an acid or alkali catalyst. Examples of the vinyl ester include fatty acid vinyl esters such as vinyl acetate, propionic acid vinyl ester, versatic acid vinyl ester, pivalic acid vinyl ester, etc. Also, aromatic carboxylic acid vinyl ester etc. can be used, but the price is low. Therefore, vinyl acetate is preferable, and pivalic acid vinyl ester is preferable from the viewpoint of gas barrier property. The ethylene content of EVOH is 20 to 65 mol%, preferably 20 to 5
0 mol%, saponification degree of vinyl ester component is 90 mol%
Or more, preferably 95 mol% or more. The EVOH layer may be biaxially stretched or unstretched.
When the ethylene content is less than 20 mol%, the gas barrier property at high humidity is deteriorated, and when it exceeds 65 mol%, sufficient gas barrier property cannot be obtained. On the other hand, the degree of saponification is 90 mol%
When the amount is less than 3, not only the gas barrier property at high humidity is deteriorated, but also the thermal stability of EVOH is deteriorated, and gel is apt to be generated on the obtained film surface.

Further, EVOH (A) contains a smaller amount of α-olefins such as propylene, isobutene, 4-methylpentene-1, hexene and octene, and unsaturated compounds such as itaconic acid, methacrylic acid, acrylic acid and maleic anhydride. Carboxylic acid, its salt, its partial or complete ester, its nitrile, its amide, its anhydride, vinylsilane compounds such as vinyltrimethoxysilane, unsaturated sulfonic acid,
It does not matter even if it contains a copolymer component such as its salt or alkyl thiols.

EVOH (A) may be a mixture of two or more kinds of EVOH having different ethylene contents,
Also, two or more types of EVOH with different degrees of polymerization and saponification
May be a mixture of. Further, 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 kinds of EVOH having different ethylene contents. In such cases, the water activity value of the contents should be 1
Comparing the value multiplied by 00 with the relative humidity value of the storage environment, the EVOH having a smaller ethylene content is arranged in the smaller value, the better the gas barrier property of the packaging material. In the plural layers of EVOH, all layers may be biaxially stretched, only specific layers may be biaxially stretched, or all layers may be unstretched.

Further, EVOH (A) includes, as long as it does not hinder the present invention, an antioxidant, a colorant, an ultraviolet absorber, a slip agent, an antistatic agent, a plasticizer, a cross-linking agent such as boric acid, and an inorganic filler. Various additives such as an inorganic desiccant and various resins such as polyamide, polyolefin and super absorbent resin may be blended.

In the present invention, the composition (B) comprising an ethylene-vinyl acetate copolymer or an ethylene-unsaturated carboxylic acid ester copolymer, a tackifier and a wax 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 adheres to adherend and EVOH And a wax for improving the fluidity of the EVA wax and for accelerating the dissolution of the EVA wax.
Preferably ethylene-vinyl acetate copolymer or ethylene-unsaturated carboxylic acid ester copolymer 10-
90% by weight, preferably 20-70% by weight, tackifier 5
-60% by weight, preferably 10-50% by weight, wax 1
To 60% by weight, preferably 5 to 45% by weight, and more preferably 0.001 of an antioxidant such as 4-4'-thiobis (6-tert-butyl-m-cresol) or BHT. ~ 20% by weight, preferably 0.005
10% by weight of composition, viscosity at 150 ° C., preferably 100 to 20000 cps, more preferably 5
It is a composition showing 100-8000 cps.

In the EVA wax, ethylene-vinyl ester copolymers such as ethylene-propionic acid vinyl ester copolymer and ethylene-butyric acid vinyl ester copolymer, dibutyl phthalate,
Plasticizers such as di-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, colorants, ultraviolet absorbers, slip agents, Various additives such as antistatic agents, crosslinking agents, inorganic desiccants,
You may mix | blend various resins, such as polyamide, polyester, polyethylene, polypropylene, polyvinyl acetate, a super absorbent resin.

In the present invention, the ethylene-vinyl acetate copolymer in EVA wax has a vinyl acetate content of preferably 10 to 50% by weight, more preferably 15 to 45% by weight. is there. If desired, those obtained by graft-modifying unsaturated carboxylic acids such as (meth) acrylic acid, maleic acid, maleic anhydride, itaconic acid, and itaconic anhydride can also be used. The MI of the ethylene-vinyl acetate copolymer at a load of 2160 g and 190 ° C. is preferably 16 g / 10 minutes or more, and more preferably 20 to 700 g / 10 minutes. Further, in order to satisfy the high adhesive strength, low viscosity, high compatibility, and low stringiness of EVA wax, ethylene-vinyl acetate copolymers having different vinyl acetate contents and MIs, and their parts It may be a saponified composition.

In the present invention, the ethylene-unsaturated carboxylic acid ester copolymer in EVA wax is ethylene- (meth) acrylic acid methyl ester copolymer,
Ethylene- (meth) acrylic acid ethyl ester copolymer, ethylene-itaconic acid dimethyl ester copolymer,
Examples of the ethylene-itaconic acid diethyl ester copolymer include ethylene-acrylic acid ethyl ester copolymers having an acrylic acid ethyl ester content of 10 to 40.
Weight% is preferable, and a product obtained by graft-polymerizing an unsaturated carboxylic acid such as (meth) acrylic acid, maleic anhydride or itaconic acid may be used if necessary.

In the present invention, the tackifier means rosins such as gum rosin, wood rosin and tall oil, and modified rosins and α-pinene modified by hydrogenation, disproportionation, dimerization, esterification and the like. Pinene resins such as polymers, β-pinene polymers, dipentene polymers, terpene-phenol copolymers, α-pinene-phenol copolymers, 1-butene, isobutylene, butadiene, 1,3-
C4 to C5 such as pentadiene, isoprene and piperylene
Of aliphatic resins such as polymers containing mono- and diolefins as main components, resins obtained by polymerizing diene components in spent C4 to C5 fractions after cyclization dimerization, and aromatic hydrocarbon resins Alicyclic resins such as internally hydrogenated resins, aromatic resins such as vinyltoluene, indene, α-methylstyrene, and other C9-C10 vinyl aromatic hydrocarbon-based polymers, and styrene. , Vinyltoluene, α-methylstyrene, isopropenyltoluene and other polymers such as styrene resins, coumarone-indene resins, phenolic resins and other petroleum resins, and the like (meta) It may be graft-polymerized and modified with an unsaturated carboxylic acid such as acrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, or a maleic acid ester.

In the present invention, the waxes are liquid at room temperature or have a low melting temperature or a (semi) solid state with a low melt viscosity, and have an average molecular weight of 300 to 10,000.
It is a petroleum wax or modified petroleum wax of a certain degree, and examples thereof include paraffin wax, microcrystalline wax, castor wax, and chlorinated paraffin, and further, low molecular weight polyethylene wax and the like. Furthermore, waxes (vegetable wax, animal wax, etc.) composed 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 EVA wax (B) layer and the EVOH (A) layer can be variously selected depending on the cost and the target heat-sealing strength for easy opening. The EVA wax (B) layer is preferably 1 to 50 μm, and the EVOH (A) layer is preferably 1 to 100 μm.

In the present invention, when a laminated film comprising an EVA wax (B) layer and an EVOH (A) layer is wound into a roll, the property that blocking is difficult is exhibited. When a layer other than EVOH, for example, a laminated film made of EVA wax and an ethylene-vinyl acetate copolymer is wound into a roll, blocking is likely to occur, and it becomes difficult to laminate with the base material (C) layer. Often.

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

In the present invention, the thermoplastic resin used in the base material (C) layer includes polyesters such as polyethylene terephthalate, polyolefins such as polyethylene, polypropylene, polybutene-1, polymethylpentene, nylon 6, nylon 66, MXD6. Examples include polyamides such as (polyamides consisting of metaxylylenediamine and adipic acid), polyvinyl chloride, polystyrene, polyacrylonitrile, polycarbonate, poly (meth) acrylate, polysulfone, polydiene compounds (polybutadiene, polyisoprene, etc.), and lids. When used as a material, a biaxially stretched film of polyethylene terephthalate, nylon 6, nylon 66, MXD6, or polypropylene is suitable in terms of good easy-opening property, printability, and aesthetics. Beam may be coated with a polyvinylidene chloride. When used as a molding container such as a cup or tray obtained by thermoforming or injection molding from a sheet or a film, or a blow molding container such as a direct blow bottle or a stretch blow bottle, polyester, polyethylene, polypropylene, or polyvinyl chloride. , Polystyrene, polycarbonate, and polyacrylonitrile are preferable in terms of good easy-opening property, strength of the molding container, and aesthetics, and the base material (C) layer may be a multilayer body.

In the present invention, the cellulosic film used for the substrate (C) layer includes cellophane, cellulose acetate, moisture-proof cellophane, vinylidene chloride copolymer-coated cellophane, cellulose acetate and the like. Cellophane coated with a vinylidene chloride-based copolymer is preferable.

In the present invention, a metal-deposited thermoplastic resin,
As the paper and the cellulose-based film, the above thermoplastic resin, paper and the above-mentioned cellulose-based film are metal-deposited. Examples of 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, but aluminum vapor deposition, aluminum oxide vapor deposition in view of price and gas barrier properties. Vapor deposition and silicon oxide vapor deposition are preferred.

In the present invention, examples of the metal foil include aluminum foil, iron foil, stainless steel foil, gold foil, copper foil and the like, but aluminum foil and iron foil are preferable in terms of price, aesthetics and formability. ..

In the present invention, paper, cellulosic film,
Base material (C) layer and EVA wax (B) layer and EVOH (A) consisting of at least one selected from thermoplastic resin, metal vapor-deposited thermoplastic resin, metal vapor-deposited paper, metal vapor-deposited cellulosic film, and metal foil. Consisting of layers (C) /
The laminate having the structure of (A) / (B) is used for a lid material, a molding container, and the like. To laminate the base material (C) layer and the EVOH (A) layer, a known lamination method, for example, A coextrusion laminating method, a dry laminating method, an extrusion laminating method, a coextrusion coating method, a solution coating method and the like can be adopted. Further, in order to stack the EVOH (A) layer and the EVA wax (B) layer, not only a known hot melt applicator, for example, a nozzle type, a foil type, a roll type, a jet type method or the like can be adopted, It is also possible to employ a method such as gravure coater, reverse roll coater, spin coater, knife coater, spray coater, dipping method, etc. by dissolving in an organic solvent such as toluene.

In adopting these laminating methods,
If a sufficient adhesive force can be obtained between the (C) layer and the (A) layer, they may be directly laminated, but there are cases where sufficient adhesive force cannot be obtained. When sufficient cohesive strength cannot be obtained, when using the coextrusion laminating method, the adhesive properties of polyolefins graft-modified with unsaturated carboxylic acids or copolymers of olefins and unsaturated carboxylic acids, etc. It is necessary to use a resin. When the dry laminating method or extrusion laminating method is adopted, polyester, polyether,
It is necessary to use a two-component curing type adhesive or anchor coating agent containing polyurethane as the main ingredient and isocyanate as the curing agent. When using the solution coating method,
It is necessary to use the anchor coating agent as appropriate. Furthermore, when the coextrusion coating method is adopted, it is necessary to appropriately use the anchor coating agent or the adhesive resin.

In addition, the procedure for laminating a laminate having a structure of (C) layer / (A) layer / (B) layer is as follows. First, layer (C) and layer (A) are laminated, and then layer (B) is laminated. Alternatively, the (A) layer and the (B) layer may be laminated first, and then the (C) layer may be laminated. It is also useful to print on the front surface or the back surface of the base material (C) layer in order to enhance aesthetics and commercial value.

The laminated body obtained by the present invention has excellent gas barrier properties, and also from the viewpoint of ensuring excellent gas barrier properties of the hermetically sealed container formed by sealing at the peripheral portion of the opening of the container, the adherend is also adhered. It is desirable that the molding container or the lid material to be the same also contains a resin, a metal foil, a metal vapor deposition, or the like having excellent gas barrier properties as constituent elements.

As the adherend, polyesters such as polyethylene terephthalate, polyolefins such as polyethylene, polypropylene, polybutene-1, polymethylpentene, polyamides such as nylon 6, nylon 66 and MXD6, polyvinyl chloride, polystyrene, polyacrylonitrile, Examples include polydiene compounds such as polycarbonate, poly (meth) acrylate, polysulfone, polybutadiene, and polyisoprene. Cups, trays, etc. obtained by thermoforming and injection molding of adherends from sheets and films, and direct blow bottles. In the case of molded containers such as blow molded containers such as stretch blow bottles, polyester, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polycarbonate, polyacryloni Lil is good easy-open, the strength of the molded container is suitable in terms of aesthetics, the molding container may be a multilayer body. If the adherend is a lid, polyethylene terephthalate, nylon 6, nylon 66, MXD
6, biaxially stretched film such as polypropylene, paper, cellulosic film, and metal foil are preferable in terms of good easy-opening property, printability, and aesthetics, and biaxially stretched film, paper, and cellulosic film are It may be coated with vinylidene chloride, or may be vapor-deposited with metal, and of course, may be a multilayer body.

The easily openable container obtained by the present invention includes cherries, cherry tomatoes, shimeji mushrooms, cut vegetables, salads,
Fresh foods such as clams, sashimi, and mozuku, enamel, sushi,
Gyoza, sushi, side dishes such as koko soba, kelp, seaweed, boiled fish such as small fish, radish, nozawana, eggplant, red turnip, ginger, umeboshi,
Pickled vegetables such as Rakkyo, kimchi, miso such as red soup, white miso, Kanayama Toki miso, moromi, tofu such as tofu and egg tofu,
Processed meat products such as sliced ham, bacon, wiener sausages, fish paste products such as bamboo shoots, bamboo rings, hanpen, etc.
Jam such as strawberry jam and marmalade, processed egg products such as salmon roe, cod roe, mentaiko, mustard, pudding, fruit jelly, cakes, candies, chocolate, biscuits desserts, grains such as white rice and non-washed rice Suitable for non-food items such as seafood, crocodile fish, dried shirako, dried bonito flakes, frozen foods such as fried shrimp, dumplings, dumplings, audio parts, non-foods such as stationery, pharmaceuticals, etc. Used.

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. All parts and% are based on weight unless otherwise specified.

The evaluation method is as follows, and the evaluation criteria are as follows. ◎: Very good ○: Good △: Slightly bad ×: Bad

(1) Preservation of contents After filling the seal with miso, the seal is left for 90 days at the window on the south side of the room where it is not exposed to direct sunlight but sufficiently reflected light.
Then, the package was opened, and the color tone and taste of the miso were judged by 10 panelists and the average value was taken.

(2) Transparency [0038] Miso is filled and the (C) layer / (A) layer / (B) layer of the package is seen through. It was

[0037]

【Example】

Example 1 Obtained by saponifying an ethylene-vinyl acetate copolymer as an EVOH (A) layer, the ethylene content was 32 mol%, and the degree of saponification of the vinyl acetate component was 99.5 mol%.
The resin was melt-extruded at 230 ° C. to obtain an unstretched film having a thickness of 15 μm.

A 50 μm biaxially oriented polyethylene terephthalate film of Lumirror manufactured by Toray Industries, Inc. was selected as the base material (C) layer, and A-385 / A manufactured by Takeda Pharmaceutical Co., Ltd. was used as an adhesive for dry lamination. 3 g / m ↑ 2 was applied as -50 as a solid content, the solvent was evaporated at 80 ° C., the EVOH film was attached, and aging was performed at 40 ° C. for 3 days to obtain a composite film.

Ethylene-as the EVA wax (B) layer
As vinyl acetate copolymer, vinyl acetate content 28 parts by weight, MI 400 g / 10 min resin 30
% By weight, 35 parts by weight of hydrogenated rosin glycerin ester as a tackifier, 35 parts by weight of 120 ° F. paraffin wax as a wax, and 80 parts of BHT as an antioxidant.
A composition consisting of 0 ppm was selected and adjusted to a toluene solution having a concentration of 15% by weight. EVO of the solution into the composite film
The H (A) layer surface was coated with 2 g / m 2 and the solvent was evaporated at 130 ° C. to obtain a laminate having a structure of (C) layer / (A) layer / (B) layer.

As the adherend, a 500 μm sheet of KLUPET sheet KS750R manufactured by Kuraray Co., Ltd. was used.
Using a heat sealer manufactured by Yasuda Seiki Co., Ltd., the laminate was heat-sealed with the (C) face of the laminate at a pressure of 2 kg / cm 2 for 1 second at a temperature of 140 ° C. When the heat sealing strength was measured using an autograph manufactured by Shimadzu Corporation, it was 0.7 kg /
It showed a good easy opening property of 15 mm.

Separately 1m of krapet sheet KS750R
A container having a thickness of m was formed by vacuum forming. After filling with the miso, the laminate and the peripheral edge of the opening of the container were heat-sealed. The results are shown in Table 1.

Comparative Example 1 In Example 1, the EVA wax (B) layer was a maleic anhydride graft-modified ethylene-vinyl acetate copolymer Admer V manufactured by Mitsui Petrochemical Industry Co., Ltd.
F600 (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 a toluene solution of EVOH and an adhesive resin for coextrusion for PET and PS) was used. The heat sealing strength was only 0.2 kg / 15 mm, which was extremely inferior to that of Example 1. The results are shown in Table 1.

Comparative Example 2 In Example 1, the EVOH (A) layer had an ethylene content of 89 mol% and a vinyl acetate component saponification degree of 9
2 mol% resin was melt extruded at 200 ° C.
A similar laminate was obtained in the same manner as in Example 1. The storability of the miso was extremely inferior to that of Example 1. The results are shown in Table 1.

Example 2 As an EVOH (A) layer, an ethylene-vinyl acetate copolymer was saponified to obtain an ethylene content of 44 mol% and a vinyl acetate component saponification degree of 99.5 mol%.
The resin was melt-extruded at 220 ° C. to obtain an unstretched 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 base material (C) layer, and A-385 / A manufactured by Takeda Pharmaceutical Co., Ltd. was used as an adhesive for dry lamination. 3 g / m ↑ 2 was applied as -50 as a solid content, the solvent was evaporated at 80 ° C., the EVOH film was attached, and aging was performed at 40 ° C. for 3 days to obtain a composite film.

As the EVA wax (B) layer, a resin containing 28 parts by weight of vinyl acetate as an ethylene-vinyl acetate copolymer and a MI of 150 g / 10 min was used as a resin.
0% by weight, 40 parts by weight of gum rosin as a tackifier,
As a wax, 20 parts by weight of 145 ° F paraffin wax and 1000 ppm of 4-4'-thiobis (6-tert-butyl-m-cresol) as an antioxidant were selected and melted at 150 ° C. Apply 25g / m ↑ 2 onto the EVOH (A) side of the film,
A similar laminate was obtained in the same manner as in Example 1 except that a laminate having a structure of (C) layer / (A) layer / (B) layer was obtained. When heat sealing strength is measured, it is 1.2 kg / 15 mm
And showed a good easy opening property. The results are shown in Table 2.

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

As the EVA wax (B) layer, an ethylene-vinyl acetate copolymer as vinyl acetate content of 33 parts by weight, MI 40 g / 10 min of resin 15
Wt% and vinyl acetate content 25 parts by weight, MI4
A composition comprising 25% by weight of a resin of 00 g / 10 minutes, 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 is selected. , 15 wt% concentration toluene solution. 2 g / m ↑ 2 of the solution on the EVOH (A) surface of the composite film
After coating, the solvent was evaporated at 130 ° C. to obtain a laminate having a structure of (C) layer / (A) layer / (B) layer.

As the adherend, a 12 μm polyvinylidene chloride-coated biaxially oriented polyethylene terephthalate film of Emblet KPW manufactured by Unitika Ltd. was selected,
Using a heat sealer manufactured by Yasuda Seiki Co., Ltd., the laminate was heat-sealed with the (C) face of the laminate at a pressure of 2 kg / cm 2 for 1 second at a temperature of 140 ° C. When the heat sealing strength was measured using an autograph manufactured by Shimadzu Corporation, it was 0.8 kg /
It showed a good easy opening property of 15 mm. The results are shown in Table 2.

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

A 25 μm biaxially oriented polyethylene terephthalate film of Lumirror manufactured by Toray Industries, Inc. was selected as the base material (C) layer, and A-385 / A manufactured by Takeda Pharmaceutical Co., Ltd. was used as an adhesive for dry lamination. 3 g / m ↑ 2 was applied as -50 as a solid content, the solvent was evaporated at 80 ° C., and then it was laminated on the side of ethylene content 27 mol% of the EVOH film and aged at 40 ° C. for 3 days to obtain a composite film. A similar laminate was obtained in the same manner as in Example 1 except that the above was obtained. When the heat sealing strength was measured, it was 1.2 kg /
It showed a good easy opening property of 15 mm. The results are shown in Table 3.

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

As an EVA wax (B) layer, a resin containing 28 parts by weight of vinyl acetate as an ethylene-vinyl acetate copolymer and a resin of MI 400 g / 10 min was used as 4 parts.
0% 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'-as an antioxidant.
Thiobis (6-tert-butyl-m-cresol)
Was selected to prepare a toluene solution having a concentration of 10% by weight. 2 g / m ↑ 2 of the solution was applied to the side of 44 mol% ethylene content of the EVOH film, and the solvent was evaporated at 130 ° C. to obtain a laminated film having a structure of (A) / (B). The film roll at 42 ° C
It was allowed to stand for 1 day, but no blocking occurred.

A 25 μm biaxially stretched polyethylene terephthalate film of Lumirror manufactured by Toray Industries, Inc. was selected as the base material (C) layer, and A-385 / A manufactured by Takeda Pharmaceutical Co., Ltd. was used as an adhesive for dry lamination. After applying -50 as a solid content of 3 g / m ↑ 2 and evaporating the solvent at 80 ° C, the solvent is evaporated, and then the laminated film is attached to the EVOH film side having an ethylene content of 27 mol% and aged at 40 ° C for 3 days. A similar laminate was obtained in the same manner as in Example 1 except that the laminate was obtained. When the heat sealing strength was measured, 1.
It exhibited a good easy opening property of 1 kg / 15 mm. The results are shown in Table 3.

COMPARATIVE EXAMPLE 3 In Example 5, instead of the EVOH (A) layer, SB-10 manufactured by Tama Poly Co. (vinyl acetate content 1) was used.
(0% by weight) except that a 40 μm film was used, and a laminated film having a configuration of (A) / (B) was obtained in the same manner as in Example 5. When the film roll was left at 42 ° C. for 1 day, it was blocked, which hindered the bonding with the substrate (C) layer, and the subsequent experiments were stopped. The results are shown in Table 3.

[0056]

[Table 1]

[0057]

[Table 2]

[0058]

[Table 3]

[0059]

Industrial Applicability As described above, the package using the lid and container of the present invention is excellent in easy-opening property and storability of contents, and inexpensive, and suitable for various foods, pharmaceuticals, and non-foods. Applicable to

Claims (7)

[Claims] 1. An ethylene having an ethylene content of 20 to 65 mol% and a saponification degree of a vinyl ester component of 90 mol% or more.
A laminate comprising a saponified vinyl ester copolymer (A) layer and a composition (B) layer comprising an ethylene-vinyl acetate copolymer or an ethylene-unsaturated carboxylic acid ester copolymer, a tackifier and a wax. 2. A laminate comprising a layer (A), a layer (B) and a base material (C), and having a structure of layer (C) / layer (A) / layer (B). 3. An ethylene-vinyl ester copolymer saponified product (A) layer is made of two or more kinds of ethylene-vinyl ester copolymer saponified products having different ethylene contents, and each of them has an ethylene content of 20 to 65. The laminate according to claim 1 or 2, which is a plurality of layers of a saponification product of an ethylene-vinyl ester copolymer having a mol% and a saponification degree of a vinyl ester component of 90 mol% or more. 4. A lid member made of the laminated body according to any one of claims 1 to 3. 5. A container made of at least one selected from a thermoplastic resin, a metal and glass, and the lid member according to claim 4, wherein the layer (B) of the lid member and the container are the opening of the container. A sealed container that is sealed at the peripheral edge. 6. A molded container comprising the laminate according to any one of claims 1 to 3. 7. A lid member made of at least one selected from paper, a cellulosic film, a thermoplastic resin, a metal-deposited thermoplastic resin, a metal-deposited paper, a metal-deposited cellulosic film, and a metal foil. A hermetically sealed container comprising the above described molded container, wherein the lid member and the molded container are sealed at the peripheral edge portion of the opening.