JP7044565B2 - Resin composition and its uses - Google Patents

Description

The present invention relates to a resin composition and its use, and more particularly to a resin composition suitable as a raw material for a sealant film, a sealant film, and a laminated film using the sealant film.

The sealant film having easy peelability (easy peeling property) used for containers and packaging materials is required to simultaneously satisfy the contradictory performances of sealing property and easy peeling property. Among them, regarding the sealing property, it is required that the heat-sealing strength is always higher than the level that can protect the contents, and that the temperature dependence of the heat-sealing strength is small in order to cope with a wide variety of substrates. ing. On the other hand, regarding the easy peeling property, it is required to be heat-sealed to the extent that it can be easily peeled off by hand.

Many materials have been developed so far as resins for sealant films. Examples of such a material include a resin composition obtained by blending a polybutene resin with a polyethylene resin. For example, Patent Document 1 describes a resin mixture containing ethylene-vinyl acetate copolymers 50 to 90 and polybutylene. ing.

Patent Document 2 describes 60 to 95% by weight of an ethylene polymer having an MFR _PE of 0.2 to 30 g / 10 minutes and a density of 0.900 to 0.940 g / cm ³ and 0.1 to 25 g / of MFR _PB . A resin composition comprising 5 to 40% by weight of a 1-butene polymer having a 1-butene unit content of 60 to 100 mol% for 10 minutes and having an MFR _PE / MFR _PB of 1 or more is a sealant resin composition. Are listed.

Patent Document 3 describes a package containing a first sealant layer and a second sealant layer, wherein the first sealant layer is about 70 to 95% by weight of low density polyethylene and about 5 to 30% by weight of the first. The second sealant layer contains about 70 to 90% by weight of polyethylene (low density polyethylene, ethylene / α-olefin copolymer, etc.) and about 10 to 30% by weight. % A package containing a second contaminant (such as butene / ethylene copolymer) is described.

Further, Patent Document 4 is a composition composed of three layers in the order of a laminated resin layer (A), an adhesive layer (B) and a base material layer (C), and the layer (A) contains polyethylene and polybutene. Easy-to-open packaging materials are listed.

U.S. Pat. No. 4,189,579 Japanese Unexamined Patent Publication No. 2002-146343 International Publication No. 2015/178927 Japanese Unexamined Patent Publication No. 2016-175205

However, since the polybutene resin is expensive, even if the ratio of the polybutene resin to the polyethylene resin is reduced, the sealant film and the sealant film capable of exhibiting easy-opening property (particularly easy peeling property) equal to or higher than those of the conventional product and Development of laminated films and their materials is desired.

In view of such problems, the present invention provides a sealant film and a laminated film capable of exhibiting easy peelability equal to or higher than that of the prior art even if the ratio of the polybutene resin to the polyethylene resin is small, and materials thereof. The purpose is.

As a result of diligent research, the present inventors have found that the above problems can be solved by making improvements to the polybutene resin, and have completed the present invention.
The gist of the present invention is as follows.

[1]
5 to 30% by mass of the butene-based polymer (A) satisfying the following (a-1), (a-2) and (a-3), high-pressure low-density polyethylene, ethylene / α-olefin copolymer A resin composition containing 95 to 70% by mass of an ethylene-based polymer (B), which is one or more selected from the group consisting of an ethylene / vinyl acetate copolymer.
(A-1): The proportion of components having a molecular weight of 10,000 or less obtained from the integrated molecular weight distribution curve obtained by measurement by the GPC method is 2% or more.
(A-2): The melting point measured by a differential scanning calorimeter is 100 to 130 ° C.
(A-3): The melt flow rate ( 190 ° C., 2.16 kg load) is 0.3 to 10 g / 10 minutes.

[2]
The resin composition of the above [1], wherein the butene-based polymer (A) further satisfies the following (a-4).
(A-4): Mw / Mn, which is the ratio of the weight average molecular weight Mw measured by the GPC method to the number average molecular weight Mn, is 5 to 20.

[3]
The resin composition according to the above [1] or [2], wherein the melt flow rate ( 190 ° C., 2.16 kg load) of the butene-based polymer (A) is 0.3 to 1.5 g / 10 minutes.

[4]
The resin composition of the above [1], wherein the ethylene-based polymer (B) contains high-pressure low-density polyethylene.

[5]
The resin composition of the above [4], wherein the ethylene-based polymer (B) contains an ethylene / α-olefin copolymer.

[6]
The high-pressure method low-density polyethylene is 90 to 40% by mass, and the ethylene / α-olefin copolymer is 10 to 60% by mass (however, the amount of the ethylene-based polymer (B) is 100% by mass). The resin composition of the above [5] including.

[7]
The resin composition of the above [1], wherein the ethylene-based polymer (B) contains an ethylene-vinyl acetate copolymer.

[8]
A film comprising the resin composition according to any one of the above [1] to [7].

[9]
A laminated film in which the film of the above [8] and another layer are laminated.

[10]
The laminated film of the above [9], wherein the sealant layer and the base material layer are laminated, and the sealant layer is the film of the above [8].

[11]
The laminated film of the above [9], wherein the sealant layer, the intermediate layer, and the base material layer are laminated in this order, the sealant layer is made of an ethylene-based polymer, and the intermediate layer is made of the film of the above [8].

By using the resin composition of the present invention, it is possible to produce a sealant film and a laminated film that exhibit easy peelability equal to or higher than that of the prior art even if the proportion of the polybutene resin is small.

FIG. 1 is a differential molecular weight distribution curve of the butene-based polymer used in Examples and Comparative Examples. FIG. 2 is an integrated molecular weight distribution curve (partially enlarged) of the butene-based polymer used in Examples and Comparative Examples.

[Resin composition]
The resin composition according to the present invention contains 5 to 30% by mass of the butene-based polymer (A) and 95 to 70% by mass of the ethylene-based polymer (B) (the amount of the resin composition is 100% by mass). Contains.

<< Butene-based polymer (A) >>
Examples of the butene-based polymer (A) include a homopolymer of 1-butene and a copolymer of 1-butene and an α-olefin having 2 to 10 carbon atoms excluding 1-butene.

Examples of the α-olefin include ethylene, propylene, 1-pentene, 1-hexene, 1-hexene, 1-octene, 1-decene, 3-methyl-1-butene, 3-methyl-1-pentene and 4-. Examples thereof include methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene propylene, 1-hexene, 4-methyl-1-pentene and 1-octene, preferably ethylene and propylene. Examples thereof include 1-hexene, 4-methyl-1-pentene and 1-octene, and more preferably ethylene and propylene.

If necessary, the butene-based polymer (A) may be copolymerized with another comonomer in a small amount as long as the effects of the present invention are not impaired.
The 1-butene content of the butene-based polymer (A) is usually 90 to 100 mol%, preferably 95 to 100 mol%, more preferably 98 to 100 mol%, and the α-olefin content is 0 to 10 mol%. %, preferably 0-5 mol%, more preferably 0-2 mol% (provided that the total of the 1-butene content and the α-olefin content is 100 mol%).
The butene-based polymer (A) satisfies the following requirements (a-1) to (a-3).

Requirement (a-1);
In the integrated molecular weight distribution curve obtained by the measurement by the gel permeation (GPC) method under the conditions adopted in the examples described later, the proportion of the components having a molecular weight of 10,000 or less is 2% or more, preferably 2. It is 4% or more. Further, the upper limit value is mainly determined depending on the requirements (a-3) and (a-4).

When the ratio is in this range, the dispersibility when kneaded with the ethylene-based polymer is improved, so that the easy peelability is improved.
The ratio can be increased, for example, by polymerizing a low molecular weight butene polymer in one step of the multistage polymerization process, or by melt-kneading the low molecular weight butene polymer.

Requirement (a-2);
The melting point measured by the differential scanning calorimeter under the conditions adopted in the examples described later is 100 to 130 ° C., preferably 105 to 130 ° C., and more preferably 110 to 125 ° C.
When the melting point is in this range, the heat resistance of the film is improved, and it can be adapted to the packaging form for boil / retort sterilization, and heat sealing is possible at a wide sealing temperature.

Requirement (a-3);
The melt flow rate (ASTM D-1238, 190 ° C., 2.16 kg load) is 0.3 to 10 g / 10 minutes, preferably 0.35 to 5.0 g / 10 minutes, and more preferably 0. 45-1.5 g / 10 minutes.
When the melt flow rate is in this range, the balance between dispersibility and easy peelability when kneaded with the ethylene polymer is excellent.
The butene-based polymer (A) may satisfy one or more of the following requirements (a-4) to (a-9), and preferably satisfies the following requirement (a-4).

Requirement (a-4);
The ratio of the weight average molecular weight Mw measured by the gel permeation (GPC) method to the number average molecular weight Mn under the above conditions, that is, Mw / Mn is 5 to 20, preferably 6 to 18, and more preferably. It is 10 to 17.
When Mw / Mn is in this range, the dispersibility when kneaded with the ethylene-based polymer is improved, so that the easy peelability is improved.

The butene-based polymer (A) contains a predetermined amount of components having a molecular weight of 10,000 or less, has a specific melting point, and has a melt flow rate, so that it is easy to disperse when kneaded with an ethylene-based polymer. Excellent balance of peelability. Therefore, it exhibits lower heat-sealing strength at a wider sealing temperature than the conventional resin composition containing the same amount of butene-based polymer, and the conventional resin has a smaller amount of butene-based polymer (A) than the conventional resin composition. It is presumed that it is possible to achieve a low heat seal strength equal to or higher than that of the composition.

Requirements (a-5);
In the integrated molecular weight distribution curve obtained by the measurement by the gel permeation (GPC) method under the conditions adopted in the examples described later, the ratio of the components having a molecular weight of 1,000 or less is 0.1% or more, preferably 0. .2% or more.

Requirements (a-6);
The density measured under the conditions adopted in the examples described later is 0.880 to 0.925 kg / m ³ , preferably 0.885 to 0.920 kg / m ³ . When the density is in this range, the friction coefficient of the surface of the film formed from the resin composition is small, so that the contents can be filled at a high filling rate when the container is finally manufactured from the film.

Requirements (a-7);
The isotactic pentad fraction (mmmm fraction) measured under the conditions adopted in the examples described later is 85% or more, preferably 90 to 98%. When the mmmm fraction is in this range, a sealant film having excellent peelability can be produced.

Requirements (a-8);
The ultimate viscosity [η] measured in a decalin solvent at 135 ° C. is 1.8 to 3.0 dl / g, preferably 2.1 to 2.5 dl / g. When the ultimate viscosity [η] is in this range, the peelability is excellent.

Requirements (a-9);
Depending on the production method, phthalates used as electron donors may remain in the butene-based polymer, but the butene-based polymer (A) used in the present invention is a food product. From the viewpoint of hygiene required for the packaging material, it is preferably substantially free of phthalates.

Method for producing butene-based polymer (A);
Examples of the method for producing the butene-based polymer (A) include the methods described in International Publication No. 2002/002659. On pages 32 to 33 of this patent document, as an example of a method for producing a solid titanium catalyst (A') used for producing a butene-based copolymer,
(1) A halogen-containing magnesium compound (α) and a solubilizer (β) capable of dissolving the halogen-containing magnesium compound (α) are brought into contact with each other in a solvent (γ) to obtain a solution (I).
A first compound (δ) having two or more ether bonds existing via a plurality of atoms is added to the solution (I) to obtain a solution (II).
A method of contacting the solution (II) with a titanium compound (ε) in a liquid state to obtain a solution (III), or further separating a solid from the solution (III) (2) a halogen-containing magnesium compound (α) and a halogen. A solubilizer (β) capable of dissolving the contained magnesium compound (α) was brought into contact with the solvent (γ) to obtain a solution (I).
A first compound (δ) having two or more ether bonds existing via a plurality of atoms is added to the solution (I) to obtain a solution (II).
The liquid titanium compound (ε) is brought into contact with the solution (II) to obtain the solution (III).
A second compound (δ') having two or more ether bonds existing via a plurality of atoms is added to the solution (III) to obtain a solution (IV), or a solid is further separated from the solution (IV). How to do it is described. In the present invention, from the viewpoint of producing the butene-based polymer (A) having a high proportion of components having a molecular weight of 10,000 or less and a large Mw / Mn, the method (1) (that is, the solution (III)) is preferable. Does not include the step of adding a second compound (δ') having two or more ether bonds existing through multiple atoms to obtain a solution (IV) or further separating the solid from the solution (IV). In the presence of the solid titanium catalyst (A') produced in the method), 1-butene is (co) polymerized to produce a butene-based polymer (A).

Further, two or more kinds of butene-based polymers (however, each butene-based polymer may or may not satisfy all of the requirements (a-1) to (a-3)) are prepared. However, these may be mixed to prepare the butene-based polymer (A) so that the requirements (a-1) to (a-3) are satisfied as the whole mixture.

<< Ethylene polymer (B) >>
The ethylene-based polymer (B) is one or more ethylene-based polymers selected from the group consisting of high-pressure low-density polyethylene, ethylene / α-olefin copolymers, and ethylene / vinyl acetate copolymers.

The melt flow rate (ASTM D1238, 190 ° C., 2.16 kg load) of the high-pressure method low-density polyethylene, ethylene / α-olefin copolymer and ethylene / vinyl acetate copolymer is preferably 0.2 to 30 g. / 10 minutes, more preferably 0.5 to 2.5 g / 10 minutes, still more preferably 0.8 to 2.0 g / 10 minutes. When the melt flow rate is within this range, the resin composition of the present invention can be film-molded at a high molding speed using an existing molding machine.
The melting point measured by the ethylene polymer (B) DSC is preferably 90 to 130 ° C, more preferably 100 to 125 ° C.

High pressure method low density polyethylene;
The density of the high-pressure low-density polyethylene is usually 900 to 940 kg / m ³ , preferably 910 to 930 kg / m ³ .
As the high-pressure method low-density polyethylene, if it is a commercially available product, for example, NUC8160 (MFR = 2.4 g / 10 minutes, density = 922 kg / m ³ , manufactured by NUC Co., Ltd.), F218-0 (MFR = 1.0 g). / 10 minutes, density = 919 kg / m ³ , manufactured by Sumitomo Chemical Co., Ltd.

Ethylene / α-olefin copolymer;
Examples of the ethylene / α-olefin copolymer include an ethylene / α-olefin random copolymer. The α-olefin is an α-olefin having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, and examples thereof include propylene, 1-butene, 1-pentene, 1-hexene, 1-hexene, and 1 -Octen, 1-decene, 1-undecene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene and 4,4-dimethyl-1 -Hexene is mentioned. These may be used alone or in combination of two or more. Further, the ethylene / α-olefin copolymer may be a polymer obtained by further polymerizing a small amount of comonomer other than ethylene and α-olefin, if necessary.

The α-olefin content of the ethylene / α-olefin copolymer is preferably 0.1 to 15 mol%, more preferably 0.5 to 10 mol%. However, the total of the ethylene content and the α-olefin content is 100 mol%.

The density of the ethylene / α-olefin copolymer is preferably 900 to 940 kg / m ³ , and more preferably 905 to 930 kg / m ³ . When the density is in the above range, a film having excellent transparency and low temperature sealing property can be obtained.

As the ethylene / α-olefin copolymer, if it is a commercially available product, for example, Evolu SP2320 (MFR = 1.9 g / 10 minutes, density = 920 kg / m ³ , manufactured by Prime Polymer Co., Ltd.), Neozex 2512F (MFR). = 1.3 g / 10 minutes, density = 924 kg / m ³ , manufactured by Prime Polymer Co., Ltd.).

Ethylene-vinyl acetate copolymer;
The density of the ethylene-vinyl acetate copolymer is usually 930 to 970 kg / m ³ , preferably 930 to 945 kg / m ³ .
The amount of the structural unit derived from vinyl acetate in the ethylene-vinyl acetate copolymer is usually 5 to 330% by mass, preferably 10 to 20% by mass.

As the ethylene-vinyl acetate copolymer, if it is a commercially available product, for example, Evaflex (registered trademark) EV460 (density = 940 kg / m ³ , EVA content = 19% by mass), P1403 (density = 930 kg / m ³ ), EVA content = 14% by mass) (manufactured by Mitsui-Dupont Polychemical Co., Ltd.).

Preferred embodiments of ethylene polymers;
The ethylene-based polymer (B) preferably contains the high-pressure method low-density polyethylene and the ethylene / α-olefin copolymer, or contains the ethylene / vinyl acetate copolymer, and more preferably the high-pressure method. Contains only low density polyethylene and the ethylene / α-olefin copolymer, or contains only the ethylene / vinyl acetate copolymer.

In the case of (i), the amount of the high-pressure low-density polyethylene in the resin composition of the present invention is preferably 90 to 40% by mass, more preferably 80 to 50% by mass, and the ethylene / α-olefin co-weight. The amount of the coalescence is preferably 10 to 60% by mass, more preferably 20 to 50% by mass (however, the amount of the ethylene-based polymer (B) is 100% by mass).

When the ethylene-based polymer (B) contains the high-pressure method low-density polyethylene and the ethylene / α-olefin copolymer, the balance between moldability and mechanical strength, or moldability and hot tack strength is excellent.
Further, when the ethylene-based polymer (B) contains the ethylene-vinyl acetate copolymer, it is excellent in heat-sealing property and hot tack strength at low temperature.

<< Various additives >>
In the resin composition according to the present invention, the sealant layer (also referred to as “heat seal layer”) and the base material layer described later include any additive, for example, an antioxidant, a heat-resistant stabilizer, a weather-resistant stabilizer, and a protective material. A fogging agent, an anti-blocking agent, a slip agent, a lubricant, a crystal nucleating agent, an antistatic agent, a flame retardant, a pigment, a dye, a filler and the like may be contained within a range that does not impair the effects of the present invention.

<< Resin composition >>
The resin composition according to the present invention contains the butene-based polymer (A) in an amount of 5 to 30% by mass, preferably 5 to 20% by mass, more preferably 6 to 14% by mass, and the ethylene-based polymer ( B) is contained in an amount of 95 to 70% by mass, preferably 95 to 80% by mass, more preferably 94 to 86% by mass (however, the amount of the resin composition is 100% by mass).

The resin composition can be prepared by mixing the butene-based polymer (A), the ethylene-based polymer (B), and optionally various additives by a conventionally known method.

By using the resin composition of the present invention, it is possible to produce a sealant film and a laminated film that exhibit easy peelability equal to or higher than that of the prior art even if the proportion of the polybutene resin is small. By reducing the proportion of the polybutene resin, it is possible to improve the transparency and slipperiness of the film and the laminated film in addition to reducing the manufacturing cost.

[Film and laminated film]
The film according to the present invention comprises the above-mentioned resin composition according to the present invention, and is preferably used as a sealant film for a packaging material.

The thickness of the film is appropriately set according to the use of the film, and is preferably 3 to 100 μm when used as a sealant film, for example.
The film according to the present invention can be produced by molding the resin composition according to the present invention. Examples of the film molding method include a cast molding method and an inflation molding method. The temperature of the molten resin at the time of film molding is preferably 160 to 260 ° C.

Further, in the laminated film according to the present invention, the above-mentioned film according to the present invention and another layer are laminated, and as an example, (i) a sealant layer and a base material layer are laminated, and the sealant is said. The layer is a laminated film made of the film (sealant film) according to the present invention, and (ii) the sealant layer, the intermediate layer and the base material layer are laminated in this order, and the sealant layer is made of an ethylene polymer. Examples thereof include a laminated film in which the intermediate layer is a film according to the present invention.

If the adhesive strength between the layers of the laminated film is not sufficient, an adhesive layer may be provided between these two layers.
The laminated film is preferably used as a wrapping film or a wrapping sheet, and may be used as a container material or a container lid material.

Examples of the base material layer include a polyolefin film such as polyethylene or polypropylene, a styrene resin film, a polyester film such as polyethylene terephthalate or polybutylene terephthalate, a polyamide film such as nylon 6 or nylon 6,6, and a polyolefin. Examples include a laminated film of a film and a gas-barrier resin film such as a polyamide resin or an ethylene / vinyl alcohol copolymer resin, a metal foil such as aluminum, a vapor-deposited film on which aluminum or silica is vapor-deposited, or paper. Be done. The base material layer may be appropriately selected depending on the purpose of use of the packaging material, etc., and may be used alone or in combination of two or more.

As an example of the manufacturing method of the laminated film,
The raw material resins for the sealant layer, the raw material resins for the base material layer, and optionally the raw material resins for the intermediate layer are supplied to different extruders, and after melting, they are merged and laminated, and the sheets are laminated from the T die. Method of extruding into a shape (coextrusion method);
A method in which raw material resins for a sealant layer are put into an extruder and melt-extruded onto an intermediate layer of a pre-manufactured base material layer or a laminate consisting of a pre-manufactured base material layer and an intermediate layer (melting). Laminating method); and a method in which the sealant layer, the base material layer, and optionally the intermediate layer are prepared from the corresponding raw material resins and thermocompression bonded with a group of overheated rolls or the like (thermal laminating method).
And so on. Of these, the coextrusion method is preferable in that the time required for production is short and the adhesiveness between layers is good.

When the film or laminated film of the present invention is subjected to heat sealing, the sealing temperature is usually 100 to 180 ° C., and even if the proportion of the polybutene resin (butene-based polymer (A)) is small, it is equal to or higher than that of the prior art. The temperature is preferably 140 to 180 ° C. from the viewpoint of exerting the effect of exhibiting easy peelability more remarkably. The sealing pressure is usually 0.1 to 0.5 MPa.

When the sealant films (sealant layers) are overlapped with each other and a heat seal operation is applied, or when the sealant film (sealant layer) is overlapped with another film and a heat seal operation is applied, the adhesion of the sealant film (sealant layer) is performed. The film and the laminated film of the present invention can be used as a film having both heat-sealing property and easy peeling property because they can be firmly bonded to each other by force and can be separated from each other by an appropriate force. can.

Further, in the laminated film according to the present invention, the sealant layer, the intermediate layer and the base material layer are laminated in this order, the sealant layer is made of an ethylene polymer, and the intermediate layer is made of the film according to the present invention. In the case of the laminated film (ii), polyethylene is mentioned as an example of the raw material of the sealant layer, and examples of this polyethylene include high pressure method low density polyethylene, high pressure method low density polyethylene and an ethylene / α-olefin copolymer. The mass ratio of these two resins is, for example, high pressure method low density polyethylene: ethylene / α-olefin copolymer = 1: 0 to 70:30.

The density of the ethylene / α-olefin copolymer is preferably 870 to 920 kg / m ³ , and more preferably 880 to 905 kg / m ³ . In particular, by blending a low-density ethylene / α-olefin copolymer, the heat sealability at low temperature is improved, and the high-speed seal suitability (productivity) is improved. The melt flow rate (190 ° C., 2.16 kg load) of this ethylene / α-olefin copolymer is preferably 0.5 to 7.0 g / 10 minutes, more preferably 1.0 to 4.0 g / min. It is 10 minutes. Examples of the α-olefin include the α-olefin used in the ethylene / α-olefin copolymer used as the above-mentioned ethylene-based polymer (B), and Toughmer A-1085S (commercially available). MFR = 1.2 g / 10 minutes, density = 885 kg / m ³ , manufactured by Mitsui Kagaku Co., Ltd.).

Two laminated films according to the present invention are prepared so that the sealant layer surfaces face each other, or the laminated films according to the present invention are bent and arranged so that the sealant layers face each other, or with the sealant layer of the laminated film according to the present invention. A sealed, for example, bag-shaped container can be manufactured by facing the other film and then heat-sealing the periphery thereof from one of the outer surface sides so as to have a desired container shape. When this bag-shaped container molding process is combined with the content filling process, that is, the bottom and sides of the bag-shaped container are heat-sealed, the contents are filled, and then the top is heat-sealed, and the package is automatically packaged. Can be completed. Therefore, this laminated film can be supplied and used for an automatic packaging device for solids, powders, or liquid materials such as snack foods.

Further, the laminated film according to the present invention or another film is previously molded into a cup-shaped container by means such as vacuum molding or deep drawing, or a normal injection molding container is prepared and placed in the container. A package containing the contents can be obtained by filling the contents, then covering the laminate film or other film as a lid, and heat-sealing from the upper side of the container or along the periphery of the side portion. In this case, the sealant film according to the present invention can be used for either the sealant layer of the lid material, the sealant layer of the container body, or both. This container can be suitably used for packaging cup ramen, miso, ham, bacon, jelly, pudding, snacks and the like.

The structure and manufacturing method of the container are not limited to the above description, and can be arbitrarily changed. Further, as another film or container that can be used in combination with the film or laminated film according to the present invention, the conventionally used packaging materials molded from resins such as polyethylene, ethylene / vinyl acetate copolymer, and polypropylene can be used as they are. can. For example, a container-shaped molded body having a collar at the opening is formed from such a material, laminated so that the sealant layer surface is overlapped with the collar of the opening, and both sides are joined by heat sealing to join the container. A package can be formed. The sealant film or the sealant layer and the above-mentioned packaging material can be heat-sealed with sufficient adhesive strength, and can be easily opened because they are easily peeled off. Therefore, this container can be suitably used as a packaging container having a hermetically sealed and easy-peel property, particularly in the field of food packaging.

Hereinafter, the present invention will be described in more detail based on examples. However, the present invention is not limited to these examples.
[Molecular weight distribution (Mw / Mn), ratio of components with molecular weight of 10,000 or less, ratio of components with molecular weight of 1,000 or less]
Using a gel permeation chromatograph HLC-8321 GPC / HT type manufactured by Tosoh Corporation, the measurement was performed as follows. The separation column has two TSKgel GMH6-HT and two TSKgel GMH6-HTL, the column size is 7.5 mm in inner diameter and 300 mm in length, the column temperature is 140 ° C., and the mobile phase is ortho. Using dichlorobenzene (manufactured by Wako Pure Chemical Industries, Ltd.) and BHT (manufactured by Wako Pure Chemical Industries, Ltd.) 0.025% by weight as an antioxidant, the flow velocity is 1.0 mL / min, and the sample concentration is 30 mg / min. The sample injection volume was set to 20 mL, the sample injection volume was set to 0.4 mL, and a differential refractometer was used as a detector. As a standard sample, 16 TSK standard polystyrenes manufactured by Tosoh Corporation were used. For the molecular weight calculation, Emper3 manufactured by Waters, a data processing software, is used, and the weight average molecular weight Mw, the number average molecular weight Mn, the molecular weight distribution (Mw / Mn), the ratio of the components having a molecular weight of 10,000 or less, and the components having a molecular weight of 1,000 or less. The ratio of was calculated.

[Measurement of ethylene content in butene-ethylene copolymer]
The measurement was performed as follows using an AVANCE III500 (CryoProbe) type NMR measuring device manufactured by Bruker Biospin Co., Ltd.

A sample of 60 mg and 0.5 ml of orthodichlorobenzene were placed in an NMR tube having an inner diameter of 5 mm and dissolved by heating. 0.1 ml of deuterated benzene was added to this solution, and ¹³ C-NMR measurement was performed at 120 ° C. The total number of times was 128 or more. The composition of 1-butene and ethylene was quantified from the obtained ¹³ C-NMR spectrum.

[Isotactic pentad fraction (mmmm fraction)]
The ¹³ C-NMR spectrum was measured with an orthodichlorobenzene solution (butene side chain methylene signal: 27.5 ppm as a reference), and the ratio (%) of the mmmm peak area was determined using the following formula.
mmmm fraction (%) = (S1 / S2) x 100
[In the formula, S1 (mmmm peak area)
= (Peak area of 27.39 to 27.80 ppm) /0.995
S2 (total peak area of butene quintuplets)
= (Peak area of 26.24 to 27.80 ppm) -CH (EBB) x 2-CH (EBE)-(2 x γγ + γδ)
Is. ]
For the attribution of peaks such as CH (EBB), CH (EBE), and γγ + γδ, refer to JCRandall, JMS-Rev.Macromol.Chem.Phys., C29, 201 (1989).

[Melting point (Tm-I)]
A polymer containing a structural unit derived from 1-butene was used, and a 1 mm thick press sheet prepared under the following conditions was stored at room temperature for 10 days, and is described below by a differential scanning calorimeter (DSC). The melting point (Tm-I) was measured by the measuring method.
<Press molding conditions>
Press machine: Made by Kansai Roll Co., Ltd. (Model number: PEWE-70 / 50 35)
Heating time: 5 minutes Heating temperature: 200 ° C
Heating pressure: 5 MPa
Cooling rate: 40 ° C / min or more (pressurize at 5 MPa for 4 minutes with another press set at 30 ° C and cool to room temperature)
<DSC measurement conditions>
The largest peak among the crystal melting peaks when the temperature of a sample of about 5 mg was raised from room temperature to 200 ° C. at 10 ° C./min under a nitrogen atmosphere (20 ml / min) using DSC Pris 1 or DSC7 manufactured by PerkinElmer. It was defined as the melting point (Tm-I).

[density]
Using a polymer containing a structural unit derived from 1-butene, a 1 mm thick press sheet prepared under the following conditions was stored at room temperature for 10 days, and the density was measured by a measuring method compliant with ASTM D1505-68. It was measured.
<Press molding conditions>
Press machine: Made by Kansai Roll Co., Ltd. (Model number: PEWE-70 / 50 35)
Heating time: 5 minutes Heating temperature: 200 ° C
Heating pressure: 5 MPa
Cooling rate: 40 ° C / min or more (pressurize at 5 MPa for 4 minutes with another press set at 30 ° C and cool to room temperature)

[Melt flow rate (MFR)]
Measurements were performed at 190 ° C. under a load of 2.16 kg in accordance with ASTM D1238.

[Ultimate viscosity [η]]
The ultimate viscosity [η] of the polymer containing 1-butene-derived structural units is a value measured at 135 ° C. using a decalin solvent. That is, granulated pellets (about 20 mg) of a polymer containing a structural unit derived from 1-butene were dissolved in a decalin solvent (15 mL), and the specific viscosity ηsp was measured in an oil bath at 135 ° C. After adding a decalin solvent (5 mL) to this decalin solution and diluting it, the specific viscosity ηsp was measured in the same manner as described above. This dilution operation is repeated twice more, and the value of ηsp / C when the concentration (C) of the polymer containing the 1-butene-derived structural unit is extrapolated to 0 is the polymer containing the 1-butene-derived structural unit. The ultimate viscosity [η] of.

[Content of phthalates]
A polymer containing a structural unit derived from 1-butene is soxley-extracted (solvent: acetone / hexane = 50/50 VOL%, 6 hours), the extract is concentrated, filtered through a hydrophilic butyl filter, and then subjected to GC / MS. Di-iso-butyl phthalate (DiBP), di-n-butyl phthalate (DnBP), benzyl butyl phthalate (BBP), di- (2-ethylhexyl) phthalate (DEHP), di-butyl phthalate were measured. Quantification of n-octyl (DnOP), di-iso-nonyl phthalate (DiNP), and di-iso-decyl phthalate (DiDP) was performed.

[Preparation Example 1] -Preparation of solid titanium catalyst component (c-1)-
Anhydrous magnesium chloride 6.0 kg (63 mol), decan 26.6 L and 2-ethylhexyl alcohol 29.2 L (189 mol) were heated and reacted at 140 ° C. for 3.5 hours to prepare a uniform solution. Then, 1.59 kg (7.88 mol) of 2-isopropyl-2-isobutyl-1,3-dimethoxypropane was added to the solution, and the mixture was further stirred and mixed at 110 ° C. for 1.5 hours. After cooling the obtained uniform solution to room temperature, 37.0 kg of the solution obtained by the above method was added dropwise to 120 L (1080 mol) of titanium tetrachloride kept at -24 ° C. for 7 hours. Then, the temperature of the obtained solution was raised over 6 hours to reach 110 ° C., and then the solution was further stirred at 110 ° C. for 2 hours to react. Then, the solid part was collected from the reaction mixture by hot filtration, placed in 132 L of titanium tetrachloride to reslurry, and then the slurry was heated again at 110 ° C. for 2 hours to react.

A solid part was collected by hot filtration from the reaction mixture obtained by the above operation, and washed with decane and hexane at 90 ° C. When no titanium compound was detected in the washing liquid, washing was stopped to obtain a solid titanium catalyst component (c-1). A part of the hexane slurry of the solid titanium catalyst component (c-1) was collected and dried, and the dried product was analyzed. The mass composition of the solid titanium catalyst component (c-1) was 3.9% titanium, 17% magnesium and 15% 2-isopropyl-2-isobutyl-1,3-dimethoxypropane.

[Preparation Example 2] -Preparation of butene-based polymer (BER-1)-
In a continuous polymerizer with an internal volume of 200 L, hexane is 114 L / h, 1-butene is 21.4 kg / h, ethylene is 0.032 kg / h, hydrogen is 23.2 NL / h, and the solid titanium catalyst component (c-1) is titanium. Copolymerization of 1-butene and ethylene was carried out while supplying 0.97 mmol / h, triethylaluminum 48.5 mmol / h and cyclohexylmethyldimethoxysilane 2.4 mmol / h in terms of atoms, and 4.2 kg / h. The polymer BER-1 was obtained. The polymerization temperature was 60 ° C., the average residence time was 40 minutes, and the total pressure was 5 × 10 ^-1 MPa · G. Physical properties of polymer BER-1 (MFR, density, extreme viscosity [η], melting point Tm-I, ethylene content, isotactic pentad fraction, weight average molecular weight Mw, number average molecular weight Mn, molecular weight distribution Mw / Mn , The ratio of components having a molecular weight of 10,000 or less, the ratio of components having a molecular weight of 1,000 or less, and the content of phthalates) are shown in Table 1. The GPC measurement results are shown in FIG.

[Preparation Example 3] -Preparation of butene-based polymer (PB-1)-
In a continuous polymerizer with an internal volume of 200 L, hexane is 114 L / h, 1-butene is 21.4 kg / h, hydrogen is 10.0 NL / h, and the solid titanium catalyst component (c-1) is converted to titanium atom to 0 / h. Polymerization of 1-butene was carried out while supplying .97 mmol, triethylaluminum at 48.5 mmol / h and cyclohexylmethyldimethoxysilane at 2.4 mmol per hour to give 4.2 kg of polymer PB-1 per hour. The polymerization temperature was 60 ° C., the average residence time was 40 minutes, and the total pressure was 5 × 10 ^-1 MPa · G. Physical properties of polymer PB-1 (MFR, density, extreme viscosity [η], melting point Tm-I, ethylene content, isotactic pentad fraction, weight average molecular weight Mw, number average molecular weight Mn, molecular weight distribution Mw / Mn , The ratio of molecular weight of 10,000 or less, the ratio of molecular weight of 1,000 or less, and the content of phthalates) are shown in Table 1. The GPC measurement results are shown in FIG.

[Preparation Example 4] -Preparation of Butene Polymer Blend (BER-2)-
In a continuous polymerizer with an internal volume of 200 L, hexane is 114 L / h, 1-butene is 21.4 kg / h, ethylene is 0.032 kg / h, hydrogen is 97.2 NL / h, and the solid titanium catalyst component (c-1) is titanium. Copolymerization of 1-butene and ethylene was carried out while supplying 0.97 mmol / h, triethylaluminum 48.5 mmol / h and cyclohexylmethyldimethoxysilane 2.4 mmol / h in terms of atoms, and 4.2 kg / h. The polymer BER-2a was obtained. The polymerization temperature was 60 ° C., the average residence time was 40 minutes, and the total pressure was 5 × 10 ^-1 MPa · G. The MFR of the polymer BER-2a was 41 g / 10 min, and the melting point Tm-I was 115 ° C.

The polymer PB-1 obtained in Preparation Example 3 and the polymer BER-2a obtained here were supplied to a uniaxial extruder at a weight ratio of PB-1 / BER-2a = 85/15 to 200 ° C. The obtained butene-based polymer BER-2 was pelletized by melting and kneading with. Physical properties of polymer BER-2 (MFR, density, extreme viscosity [η], melting point Tm-I, ethylene content, isotactic pentad fraction, weight average molecular weight Mw, number average molecular weight Mn, molecular weight distribution Mw / Mn , The ratio of molecular weight of 10,000 or less, the ratio of molecular weight of 1,000 or less, and the content of phthalates) are shown in Table 1. The GPC measurement results are shown in FIG.

[Preparation Example 5] -Preparation of Butene Polymer Blend (BER-3)-
In a continuous polymerizer with an internal volume of 200 L, hexane is 114 L / h, 1-butene is 21.4 kg / h, ethylene is 0.046 kg / h, hydrogen is 25.1 NL / h, and the solid titanium catalyst component (c-1) is titanium. Copolymerization of 1-butene and ethylene was carried out while supplying 0.97 mmol / h, triethylaluminum 48.5 mmol / h and cyclohexylmethyldimethoxysilane 2.4 mmol / h in terms of atoms, and 4.2 kg / h. The polymer BER-3a was obtained. The polymerization temperature was 60 ° C., the average residence time was 40 minutes, and the total pressure was 5 × 10 ^-1 MPa · G. The MFR of the obtained polymer BER-3a was 1.2 g / 10 min, and the melting point Tm-I was 113 ° C.

The polymer BER-3a obtained here and the polymer PB-1 obtained in Preparation Example 3 are supplied to a uniaxial extruder at a weight ratio of BER-3a / PB-1 = 70/30 to 200 ° C. The obtained butene-based polymer BER-3 was pelletized by melting and kneading with. Physical properties of polymer BER-3 (MFR, density, extreme viscosity [η], melting point Tm-I, ethylene content, isotactic pentad fraction, weight average molecular weight Mw, number average molecular weight Mn, molecular weight distribution Mw / Mn , The ratio of molecular weight of 10,000 or less, the ratio of molecular weight of 1,000 or less, and the content of phthalates) are shown in Table 1. The GPC measurement results are shown in FIG.

[Preparation Example 6]
The butene-ethylene copolymer was polymerized by the production method described in JP-A-59-206416. Physical properties (MFR, density, extreme viscosity [η], melting point Tm-I, ethylene content, isotactic pentad fraction, weight average molecular weight Mw, number average molecular weight Mn, molecular weight distribution Mw / Mn, molecular weight 10,000 or less , The ratio of molecular weight of 1,000 or less, and the content of phthalates) are shown in Table 1. The GPC measurement results are shown in FIG.

In Examples and the like, the following commercially available products were used as they were as raw material components other than the polymers obtained in Preparation Examples 2 to 6.
・ MLLDPE-1:
Evolué SP2320 (manufactured by Prime Polymer Co., Ltd.), MFR (190 ° C, 2.16 kg load) = 1.9 g / 10 minutes, density 920 kg / m ³ )
・ MLLDPE-2:
Evolué SP1520 (manufactured by Prime Polymer Co., Ltd.), MFR (190 ° C, 2.16 kg load) = 2.0 g / 10 minutes, density 913 kg / m ³ )
・ LDPE-1:
NUC8160 (manufactured by NUC Co., Ltd.), MFR (190 ° C, 2.16 kg load) = 2.4 g / 10 minutes, density 922 kg / m ³ )
・ EVA-1:
EV460 (manufactured by Mitsui DuPont Polychemical Co., Ltd.), MFR (190 ° C, 2.16 kg load) = 2.5 g / 10 minutes, vinyl acetate content 19% by weight)
-AB agent-1 (anti-blocking agent):
EAZ-20 (Made by Prime Polymer Co., Ltd., a composition containing 20% by mass of synthetic zeolite and 80% by mass of low-density polyethylene)
・ EBR-1:
A-1085S (Mitsui Chemicals, Inc.) MFR (190 ° C, 2.16 kg load) = 1.2 g / 10 minutes, density 885 kg / m ³

[Example 1]
(Manufacturing of laminated film)
The resin composition for the heat seal layer and the resin composition for the base material layer shown below are supplied to each extruder, and an inflation molding die (die diameter 200 mmφ, lip gap 3.5 mm) is used, and the resin temperature is used. The extrusion amount of each extruder was set to 190 ° C. so that the thicknesses of the heat seal layer and the base material layer were 20 μm and 50 μm, respectively, and a laminated film having a thickness of 70 μm was obtained by coextrusion molding. The molding speed was 20 m / min.
-Resin composition for heat seal layer;
A resin composition obtained by blending mLLDPE-1, LDPE-1, BER-1 and AB agent-1 in a weight ratio of 42/50/8/1, respectively.
-Resin composition for base material layer;
A resin composition obtained by blending mLLDPE-1 and LDPE-1 in a weight ratio of 50/50, respectively.

(Manufacturing of adherend film)
The resin for the heat seal layer of the adherend film and the resin composition for the base material layer shown below are supplied to each extruder, and an inflation molding die (die diameter 10 mmφ, lip gap 2.5 mm) is used, and the resin temperature is used. The extrusion amount of each extruder was set so that the thicknesses of the heat seal layer and the base material layer were 20 μm and 80 μm, respectively, at 190 ° C., and an adherend film having a thickness of 100 μm was obtained by coextrusion molding. The molding speed was 8 m / min.
・ Resin for heat seal layer;
mLLDPE-2
-Resin composition for base material layer;
A resin composition obtained by blending mLLDPE-1 and LDPE-1 in a weight ratio of 50/50, respectively.

(Measurement of heat seal strength)
Next, the heat-sealing layer of the laminated film formed in Example 1 and the heat-sealing layer of the adherend film described above were laminated so that the MD directions were aligned, and both sides of the laminated film were Teflon (registered trademark) having a thickness of 50 μm. ) A test piece sandwiched between sheets was prepared. Next, a heat seal bar of a heat seal tester (TB-701B type manufactured by Tester Sangyo Co., Ltd.) was installed with a width of 5 mm and a length of 300 mm, and the lower seal bar was set at 70 ° C. The upper heat seal bar was set to a predetermined temperature, the test piece (Teflon sheet / laminated film / adherent film / Teflon sheet) was sandwiched between the seal bars, and heat sealing was performed at a pressure of 0.2 MPa for 1.0 second. .. The Teflon sheet was removed, and the heat-sealed film portion was left at about 23 ° C. for 1 day. A slit having a width of 15 mm was inserted so as to include the heat-sealed portion of the film, and the unsealed portion was chucked on a tensile tester (“IM-20ST manufactured by INTESCO”). The peel strength of the film was measured at a speed of 300 mm / min. The above operation was performed 5 times, and the average value was taken as the heat seal strength. The maximum peel strength was adopted as the peel strength. Table 2 shows each physical property value.

[Examples 2 to 7, Comparative Example 1]
A laminated film was produced in the same manner as in Example 1 except that the resin composition shown in Table 2 was used as the resin composition for the heat seal layer, and the heat seal strength was determined by the same evaluation method as in Example 1. It was measured. The results are shown in Table 2.

[Comparative Example 1 to Comparative Example 9]
A stretched laminated film was produced in the same manner as in Example 1 except that the resin composition shown in Table 2 was used as the resin composition for the heat seal layer, and the heat seal strength was evaluated by the same evaluation method as in Example 1. And the hot tack strength was measured. The results are shown in Table 3.

[Example 8]
(Manufacturing of laminated film)
The resin composition for the heat seal layer and the resin composition for the base material layer shown below are supplied to each extruder, and an inflation molding die (die diameter 200 mmφ, lip gap 3.5 mm) is used to adjust the resin temperature. The extrusion amount of each extruder was set at 190 ° C. so that the thicknesses of the heat seal layer and the base material layer were 20 μm and 50 μm, respectively, and a laminated film having a thickness of 70 μm was obtained by coextrusion molding. The molding speed was 20 m / min.
-Resin composition for heat seal layer;
A resin composition obtained by blending EVA, BER-1 and AB agent-1 in a weight ratio of 90/10/2, respectively.
-Resin composition for base material layer;
A resin composition obtained by blending mLLDPE-1 and LDPE-1 in a weight ratio of 50/50, respectively.

(Measurement of heat seal strength)
Next, the heat-sealed layers of the laminated film formed in Example 8 were laminated so that the MD directions were aligned, and a test piece was prepared in which both sides of the laminated film were sandwiched between Teflon sheets having a thickness of 50 μm. Next, a heat seal bar of a heat seal tester (TB-701B type manufactured by Tester Sangyo Co., Ltd.) was installed with a width of 5 mm and a length of 300 mm, and the lower seal bar was set at 70 ° C. The upper heat seal bar was set to a predetermined temperature, the test piece (Teflon sheet / laminated film / laminated film / Teflon sheet) was sandwiched between the seal bars, and heat sealing was performed at a pressure of 0.2 MPa for 1.0 second. The Teflon sheet was removed, and the heat-sealed film portion was left at room temperature of about 23 ° C. for 1 day. A slit having a width of 15 mm was inserted so as to include the heat-sealed portion of the film, and the unsealed portion was chucked on a tensile tester (“IM-20ST manufactured by INTESCO”). The peel strength of the film was measured at a speed of 300 mm / min. The above operation was performed 5 times, and the average value was taken as the heat seal strength. The maximum peel strength was adopted as the peel strength. Table 3 shows each physical property value.

[Examples 9 to 11, Comparative Examples 2 to 3]
A laminated film was produced in the same manner as in Example 8 except that the resin composition shown in Table 3 was used as the resin composition for the heat seal layer, and the heat seal strength was determined by the same evaluation method as in Example 8. It was measured. The results are shown in Table 3.

[Example 12]
(Manufacturing of laminated film)
The resin (composition) for the heat seal layer, the resin composition for the intermediate layer, and the resin composition for the base material layer shown below are supplied to each extruder, and an inflation molding die (die diameter 10 mmφ, lip gap 2) is supplied. .5 mm) was used, and the extrusion amount of each extruder was set so that the resin temperature was 190 ° C. and the thicknesses of the heat seal layer, the intermediate layer, and the base material layer were 10 μm / 20 μm / 30 μm in this order. A multilayer film having a thickness of 60 μm was obtained by coextrusion molding. The molding speed was 15 m / min.
・ Resin for heat seal layer;
LDPE-1
-Resin composition for intermediate layer;
A resin composition obtained by blending mLLDPE-1, LDPE-1 and BER-1 in a weight ratio of 42/50/8, respectively; a resin composition for a base material layer;
A resin composition obtained by blending mLLDPE-1 and LDPE-1 in a weight ratio of 50/50, respectively.

(Measurement of heat seal strength)
Next, using the film formed in Example 12, the heat seal strength was measured by the same method as in Example 8. The maximum peel strength was adopted as the peel strength. Table 4 shows each physical property value.

[Examples 13 to 16, Comparative Example 4]
A laminated film was produced in the same manner as in Example 12 except that the resin composition shown in Table 4 was used as the resin composition for the intermediate layer and the heat seal layer, and the laminated film was heated by the same evaluation method as in Example 12. The seal strength was measured. The results are shown in Table 4.

As shown in Table 2, the laminated films of Examples 1 to 4 showed lower heat-sealing strength than the laminated film of Comparative Example 1 containing the same amount of butene-based polymer in the heat-sealing layer. Further, although the laminated films of Examples 5 to 7 have a smaller amount of butene-based polymer in the heat-sealing layer than the laminated film of Comparative Example 1, the heat-sealing is about the same as that of the laminated film of Comparative Example 1. Shown the strength.

As shown in Table 3, in the laminated film of Comparative Example 2, the change in the heat-sealing strength was large depending on the heat-sealing temperature, whereas in the laminated films of Examples 8 to 11, the same amount was applied to the heat-sealing layer. Compared with the laminated film of Comparative Example 2 containing a butene polymer, it showed stable and low heat seal strength over a wide heat sheet temperature range.

As shown in Table 4, the laminated films of Examples 12, 13, 15 and 16 are laminated with Comparative Example 4 containing the same amount of butene-based polymer in the intermediate layer even when the heat sheet temperature is high. It showed lower heat seal strength than the film. In Example 14, the heat-sealing property at a low temperature was improved as compared with Example 13 by blending an ethylene / α-olefin copolymer with high-pressure low-density polyethylene as a heat-sealing layer.

Claims (12)

5 to 14 % by mass of the butene-based polymer (A) satisfying the following (a-1), (a-2) and (a-3), and high-pressure low-density polyethylene, ethylene / α-olefin copolymer. A resin composition containing 95 to 86 % by mass of an ethylene-based polymer (B), which is one or more selected from the group consisting of an ethylene / vinyl acetate copolymer.
(A-1): The proportion of components having a molecular weight of 10,000 or less obtained from the integrated molecular weight distribution curve obtained by measurement by the GPC method is 2% or more.
(A-2): The melting point measured by a differential scanning calorimeter is 100 to 130 ° C.
(A-3): The melt flow rate (190 ° C., 2.16 kg load) is 0.3 to 10 g / 10 minutes. The resin composition according to claim 1, wherein the butene-based polymer (A) further satisfies the following (a-4).
(A-4): Mw / Mn, which is the ratio of the weight average molecular weight Mw measured by the GPC method to the number average molecular weight Mn, is 5 to 20. The resin composition according to claim 1 or 2, wherein the melt flow rate (190 ° C., 2.16 kg load) of the butene-based polymer (A) is 0.3 to 1.5 g / 10 minutes. The resin composition according to claim 1, wherein the ethylene-based polymer (B) contains high-pressure low-density polyethylene. The resin composition according to claim 4, wherein the ethylene-based polymer (B) contains an ethylene / α-olefin copolymer. The high-pressure method low-density polyethylene is 90 to 40% by mass, and the ethylene / α-olefin copolymer is 10 to 60% by mass (however, the amount of the ethylene-based polymer (B) is 100% by mass). The resin composition according to claim 5, which comprises. The resin composition according to claim 1, wherein the ethylene-based polymer (B) contains an ethylene-vinyl acetate copolymer. The melt flow rates (ASTM D1238, 190 ° C., 2.16 kg load) of the high-pressure method low-density polyethylene, the ethylene / α-olefin copolymer and the ethylene / vinyl acetate copolymer are all 0.2 to 2. The resin composition according to claim 1, which is 0.0 g / 10 minutes. A film comprising the resin composition according to any one of claims 1 to 8 . A laminated film obtained by laminating the film according to claim 9 and another layer. The laminated film according to claim 10 , wherein the sealant layer and the base material layer are laminated, and the sealant layer is the film of claim 9 . The laminated film according to claim 10 , wherein the sealant layer, the intermediate layer, and the base material layer are laminated in this order, the sealant layer is made of an ethylene-based polymer, and the intermediate layer is made of the film of claim 9 .

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