JP5574174B2 - Resin composition, sealant film, laminated film, packaging bag and tube container - Google Patents

Description

  The present invention relates to a resin composition that can constitute a sealant film by itself, a sealant film, a laminated film, a packaging bag, and the like.

  Conventionally, a laminated film for constituting a bag uses a heat-sealable sealant film as an innermost layer, and is gas-permeable, moisture-resistant, heat-resistant, impact-resistant by co-pressing lamination or dry lamination, Laminated with another film having excellent transparency.

  For the outer layer film, for example, nylon, polyethylene terephthalate, polyvinyl alcohol, or the like is used, and for the intermediate layer film, an aluminum foil, an aluminum or glass vapor deposition film, or a film made of ethylene-vinyl alcohol copolymer (EVOH) is used. Yes. The innermost sealant film includes low density polyethylene, medium density polyethylene, high density polyethylene, linear (linear) low density polyethylene, ethylene-α / olefin copolymer polymerized using a metallocene catalyst, polypropylene , Ethylene-vinyl acetate copolymers, ionomer resins and the like are used.

  The EVOH film is used for the intermediate layer film because the EVOH film is excellent in high gas barrier property, oil resistance, organic solvent resistance, and fragrance retention, but has low puncture strength and heat sealability. It is because of not having.

  Polyolefin sealant films are widely used because they can be sealed at low temperatures and can provide high heat seal strength regardless of adhesion of dust or the like. However, the polyolefin sealant film does not have barrier properties, absorbs menthol, diffuses and penetrates to the outer layer side, weakens the adhesive strength of the adhesive at the heat seal point, and causes delamination, so an article containing menthol It is not suitable for packaging of menthol, and because menthol and other fragrances are adsorbed, the fragrance is lost when the bag is opened, which leads to lowering the evaluation of the product. Exists.

  Conventionally, it has been desired to provide a sealant film having excellent gas permeation resistance.

  A conventional barrier sealant film is nylon (MXD6) obtained by polycondensation from a diamine component mainly composed of ethylene-vinyl alcohol copolymer (EVOH) or metaxylylenediamine and a dicarboxylic acid component mainly composed of adipic acid. An intermediate layer made of nylon) and a sealing olefin-based resin laminated on both sides with an adhesive resin. With this configuration, a sealant film having oxygen barrier properties and sealability is realized.

  However, this barrier-type sealant film has an adhesive resin layer interposed between the barrier layer and the seal layer, which raises concerns about cost increase, complicated layer structure, stable adhesive strength and impact resistance, etc. Therefore, Patent Document 1 proposes a gas barrier film without an adhesive layer.

  In the gas barrier film described in Patent Document 1, a polyolefin is laminated without using an adhesive layer on a resin layer having a gas barrier property made of a copolymer of an olefin macromonomer and a vinyl monomer having a polar group. With this configuration, a gas barrier film in which a gas barrier resin layer of a hydrophilic polymer and a polyolefin layer are directly laminated can be provided.

  However, the gas barrier film described in Patent Document 1 places importance on the barrier property by a copolymer such as a polar vinyl monomer or the chemical affinity with EVOH or the like, but the impact resistance is not considered. In addition, Patent Document 2 has been proposed as a copolymer such as a special polar vinyl monomer must be used and it is unlikely that the cost will be reduced.

  Patent Document 2 describes a resin composition and a sealant film. The resin composition is based on a barrier resin composed of EVOH or MXD nylon, an olefin resin (an example is an ethylene-α / olefin copolymer or functional polypropylene block copolymer polymerized using a metallocene catalyst), a rubber component And a compatibilizing agent. The barrier sealant film includes a first layer composed of an olefin resin, a barrier resin composed of an ethylene-vinyl copolymer or MXD nylon as a main resin, and further includes an olefin resin, a rubber component, and a compatibilizer. It consists of the 2nd layer which consists of a composition, and the 3rd layer which consists of olefin system resin, the 1st layer is laminated on the 2nd layer through the adhesive resin layer, and the 2nd layer is the adhesive resin layer on the 3rd layer It is laminated through. This sealant film is described as having excellent impact resistance and high oxygen barrier properties. Furthermore, a barrier film is dry laminated on the first layer side of the sealant film via a primer agent layer or a laminating adhesive layer to form a laminated film. According to this laminated film, it has excellent mechanical, physical, chemical and other properties, is excellent in strength, toughness, etc., and further has heat resistance, moisture resistance, pinhole resistance, puncture resistance, and transparency. It describes that a resin film excellent in properties and the like can be used. Patent Document 2 describes that if EVOH contains 50% by weight, it has a high oxygen barrier property, and if EVOH is less than 50% by weight, an extremely low oxygen barrier property is observed. ing.

  The multilayer sealant film described in Patent Document 3 is a three-layer film manufactured by inflation molding / coextrusion lamination. This film comprises an innermost layer comprising at least one resin selected from the group consisting of linear low-density polyethylene, low-density polyethylene, polypropylene, and polybuden-1, an amorphous polyolefin, an adhesive polyolefin, and ethylene / vinyl acetate. It is a three-layer sealant film consisting of an intermediate layer as an adhesive layer composed of a resin whose main component is at least one copolymer (EVA), and an outer layer composed of EVOH, and has excellent antifouling properties. It is described. However, from the viewpoint of gas barrier properties, it is not preferable in that EVOH having a low puncture strength is used in the outer layer of the sealant film.

  On the other hand, ethylene-vinyl alcohol copolymer (referred to as EVOH) has a problem in impact resistance and stretchability, and a mixed resin in combination with various resins has been proposed for improvement.

  For example, in Patent Document 4, in order to improve stretchability of an EVOH film, 3-8% by weight of ethylene-vinyl acetate copolymer (hereinafter referred to as EVA) is melt-mixed in EVOH by an extruder. A method for producing an EVOH resin composition is disclosed in which the specific energy at the time of molding is melt-mixed at 0.020 kW · h / kg or less.

  Further, in Patent Document 5, in order to improve the adhesion with EVOH resin, 2-40 wt% EVOH and 60-98 wt% acid-modified polyolefin resin are melt-mixed in an extruder, and extrusion molding is performed. A method for producing a modified polyolefin resin composition in which the specific energy at the time is melt-mixed at 0.3 kW · h / kg or more is described.

JP 2000-318102 A JP 2008-150539 A Japanese Patent Laid-Open No. 10-201822 Japanese Patent Laid-Open No. 9-40825 JP-A-6-136206

  The sealant film disclosed in Patent Document 2 is a five-layer or three-layer laminated film obtained by co-extrusion laminating a barrier film of an intermediate layer and a film having heat sealability on both outer layers. Ascent and complication of layer structure exist as challenges.

  The EVOH resin composition disclosed in Patent Document 4 is described as having improved stretchability, but there is no disclosure regarding adhesiveness. Further, it is described that the compatibility becomes poor when the content of EVA exceeds 10% by weight. In addition, in the follow-up survey by the present inventors, no improvement in the adhesion of EVOH was observed at an EVA content of less than 10%.

  In addition, as in Patent Document 5, many attempts have been made to improve the adhesion properties of EVOH by blending a polyolefin resin having excellent adhesion properties. However, as the content of the polyolefin resin increases, the properties of the polyolefin become surfaced, so that there is a problem that the excellent non-adsorbability of EVOH is lost.

  Patent Document 5 does not describe the non-adsorption property of the resin molded product, and the adhesive property described in this document uses the resin composition as an adhesive between EVOH and another resin. That is, the heat seal characteristics are not disclosed.

  The present invention has been devised in view of the above points, and its purpose is to have a heat sealing performance necessary for constituting a bag and the like, and to maintain the non-adsorption characteristics of the aroma component of EVOH, Provided are a resin composition suitable for food and pharmaceutical bags containing an aromatic component such as menthol, a sealant film comprising the resin composition, and a laminated film using the sealant film. There is to do.

  Furthermore, the objective of this invention is providing the packaging bag comprised from this laminated film, a bag packaging body, and a tube container.

  In order to obtain a resin composition and a sealant film that have a gas barrier property and a heat seal property, and do not adsorb an aromatic component such as menthol, the present inventors use a twin screw extruder and The inventors have eagerly investigated the characteristics of the mixed resin obtained by melt-kneading by the active processing method. As a result, when the EVA mixed with EVOH is a base resin and EVA is a blended resin, the heat seal strength required for the bag is 20% by weight when the EVA is 10-30% by weight with respect to the EVOH. When there is a peak, odor components such as menthol are not adsorbed regardless of the EVA content, while phase separation occurs when EVA is 40% by weight with respect to EVOH (film formation as a film). The inventor found out that the present invention has been completed.

  In order to achieve the above object, the resin composition of the present invention comprises an ethylene-vinyl alcohol copolymer (EVOH): 70% by weight to 90% by weight, and an ethylene-vinyl acetate copolymer (EVA): 10% by weight. % Or more and 30% by weight or less, and a melt-kneaded resin composition comprising two films formed by film-forming the resin composition under conditions of 140 ° C., 0.3 MPa, 0.7 sec. The seal strength measured by JIS Z0238 when heat-sealed is 50 gf / 15 mm or more.

  According to this structure, the sealant film of a resin composition simple substance can be comprised. This sealant film has a high oxygen barrier property and a heat seal property required as a bag.

  The proportions of EVOH and EVA are ethylene-vinyl alcohol copolymer: 80% by weight or more and 85% by weight or less, and ethylene-vinyl acetate copolymer: 15% by weight or more and 20% by weight or less. This range is preferable because it has heat sealability.

  The resin composition of the present invention can be used as a material for a sealant film suitable for packaging an article having fragrance such as menthol.

  The sealant film of the present invention is formed from the resin composition. As a molding method, T-die molding or the like can be used. Moreover, since it uses as a sealant film, it is more preferable that it is unstretched. And the laminated | multilayer film of this invention consists of the said sealant film used as an innermost layer at the time of bag formation, and the other single film or several film laminated | stacked with this sealant film.

  Moreover, this invention includes the laminated | multilayer film which has a sealant film which consists of a resin composition, and the other 1 or several film laminated | stacked on the outer side of this sealant film.

  This invention includes the packaging bag by which the said laminated | multilayer film was made for foodstuffs, a pharmaceutical, a detergent, an ink, another oily material, or for infusion bags. In the case of a packaging bag that requires light-shielding properties, it is preferred that the laminated film is composed of one or more of the other films made of the light-shielding resin composition.

  The present invention includes a packaging bag made of the laminated film and a bag package formed by packaging an article to be packaged in the packaging bag. Further, according to the present invention, the laminated film is a body part, the lower end of the body part is an opening for filling, and the upper end of the body part is covered with the periphery of the shoulder part of the mouth member into which the cap is fitted. A tube container.

  According to the present invention, since EVOH is contained in the base resin in an amount of 70% by weight to 90% by weight, the high oxygen barrier property and non-adsorptive property possessed by EVOH are completely impaired even when molded into a film. It is possible to provide a resin composition free from the above. Furthermore, the resin composition of the present invention is obtained by melt-mixing 10 wt% or more and 30 wt% or less of EVA to EVOH of the base resin by a reactive processing method using a multi-screw extruder, and has heat sealing performance. Therefore, it is a resin composition that can constitute a sealant film having a high oxygen barrier property and non-adsorptive property by itself.

  According to this invention, the laminated | multilayer film which made the sealant film which has a high oxygen barrier property with the single-piece | unit comprised with the said resin composition the innermost layer can be comprised. In this case, since the sealant film has a high oxygen barrier property, a packaging bag having a high oxygen barrier property without using an EVOH film for the intermediate layer and the outer layer, and other films having a high oxygen barrier property, It can constitute a bag package or tube container, and is suitable for packaging foods, drinks, fruit juices, cooked foods, marine products, frozen foods, meat products, boiled foods, seasonings and other various foods and drinks, Suitable for packaging.

  When a packaging bag is constituted by the laminated film having the sealant film of the present invention as the innermost layer and food containing aromatic components such as menthol is stored in the packaging bag, it is avoided that delamination due to menthol occurs, and when opening Can hold aromatic components such as menthol. This means that when a bag made of a conventional sealant film of polyethylene is applied to a bag of food that aromas menthol, delamination occurs, and when opened, the ingredients such as menthol do not aroma from the food, It is superior to

It is an expanded sectional view of the lamination film concerning the embodiment of the present invention. It is the front view which fractured | ruptured the tube container using the laminated film which concerns on embodiment of this invention partially.

Hereinafter, embodiments of the present invention will be described in detail.
[Embodiment of Resin Composition]
The resin composition of the present invention comprises an ethylene-vinyl alcohol copolymer (EVOH): 70% by weight to 90% by weight, and an ethylene-vinyl acetate copolymer (EVA): 10% by weight to 30% by weight. Is a resin composition formed by melt-kneading, and JIS is obtained by heat-sealing two films formed by forming the resin composition under the conditions of 140 ° C., 0.3 MPa, and 0.7 sec. The seal strength measured by Z0238 is 50 gf / 15 mm or more.

  In order to obtain a more preferable strength for the seal strength, the proportion of the EVOH and EVA content is such that the ethylene-vinyl alcohol copolymer is 80% by weight or more and 85% by weight or less, and the ethylene-vinyl acetate copolymer: 15 wt% or more and 20 wt% or less. With this blending ratio, a seal strength of 250 gf / 15 mm or more is obtained.

  The resin composition of the present invention has a high oxygen barrier property because EVOH is 70% by weight or more. EVOH is a saponified ethylene-vinyl acetate copolymer obtained by saponifying a copolymer obtained by copolymerizing ethylene and vinyl acetate. The saponification degree of the EVOH vinyl ester is preferably 90 mol% or more, more preferably 98 mol% or more. The higher the degree of saponification, the better the thermal stability and oxygen barrier properties. That is, when the ethylene molar concentration is lowered, the oxygen barrier property is improved.

  The resin composition of this embodiment is obtained by melt-kneading EVOH and EVA by a reactive processing method using a twin screw extruder. Reactive processing is a technology that is widely used industrially to create polymer alloys. However, reactive processing is a technique in which kneading and polymer / polymer chemical reaction are simultaneously performed, and the mechanism can only be imagined from the result of kneading. In the resin composition of the present invention, EVOH and EVA are generally low in compatibility, but when reactive kneading is used to melt and knead the resin with a certain amount of energy during extrusion molding, the EVA content Up to 30% by weight can be formed into a film having the required strength as a film without compromising EVOH's high oxygen barrier properties, oil resistance, organic solvent resistance, non-adsorption properties, etc. The result of expressing the heat seal property of EVA was obtained with the peak value when the content of EVA was 20% by weight. The extruder is not limited to a twin screw extruder, and a four screw extruder can be used.

  The specific energy given to the resin during extrusion molding by reactive processing is preferably 2.0 MJ / kg or more. In this embodiment, the screw of the extrusion molding machine gives a shearing force to the resin using a screw having a flight screw, a pineapple, and a kneading disk. Here, the specific energy is approximately expressed by the power consumption of the screw driving motor given to extrude the resin per kg when the resin is melt-mixed, and the larger the numerical value, the higher the degree of kneading. It will be. Specifically, an ammeter and a voltmeter are attached to the motor of the extruder, the power consumption of the motor is measured, and this is a value obtained by multiplying the power factor of the motor, usually 0.85.

  The resin composition of the present invention is not affected by the high oxygen barrier properties of EVOH, and as long as heat sealing properties are manifested by mixing EVA, unsaturated monomers such as propylene and isobutene, acrylic acid, and methacrylic acid Also included are those containing an unsaturated carboxylic acid such as maleic acid or a salt / ester thereof as a component to increase the mechanical properties.

  In addition to the ethylene-vinyl alcohol copolymer and the ethylene-vinyl acetate copolymer, the resin composition of the present invention includes a heat stabilizer, an antioxidant, a slip agent, an antiblocking agent, an antistatic agent, a colorant, Additives such as plasticizers, ultraviolet absorbers, antibacterial agents, molding aids, moisture absorbers, and gas absorbers may be included.

As a heat stabilizer and an antioxidant, about 1 to 10,000 ppm of one or more compounds selected from hindered phenol compounds, vitamin E compounds, carboxylic acid compounds, boron compounds and phosphoric acid compounds may be added.
The carboxylic acid compound is, for example, oxalic acid, succinic acid, benzoic acid, citric acid, acetic acid, propionic acid or lactic acid.
The boron compound is, for example, borax, orthoboric acid, metaboric acid, tetraboric acid, triethyl borate, trimethyl borate, a metal salt thereof, or an alkaline earth metal salt thereof.
The phosphoric acid compound is, for example, sodium dihydrogen phosphate, potassium dihydrogen phosphate, sodium dihydrogen phosphate or dipotassium hydrogen phosphate.

  The slip agent is, for example, a hydrocarbon, an alcohol, a higher fatty acid, an ester, a polyhydric alcohol obtained by esterifying a part of alcohol, a higher fatty acid metal salt, a natural wax, or a fatty acid amide, and the present invention is within a range of about 100 to 10,000 ppm. You may make it contain in this resin composition.

  The anti-blocking agent is, for example, silica, zeolite, polymer beads, fatty acid ester, or silicone powder, and may be contained in the resin composition of the present invention in the range of about 100 to 10000 ppm.

  The antistatic agent is, for example, glycerin, a surfactant or conductive fine particles, and may be contained in the resin composition of the present invention in a range of about 100 to 10,000 ppm.

  The colorant is, for example, an inorganic pigment, an organic pigment or a dye, and may be contained in the resin composition of the present invention in a range of about 1000 to 100,000 ppm.

  The plasticizer is, for example, a phthalate ester, a polyhydric alcohol or an amine compound, and may be contained in the resin composition of the present invention in a range of about 1000 to 100,000 ppm.

  An ultraviolet absorber is a benzotriazole type compound, a triazine type compound, a benzophenone type compound, or a hindered amine type compound, for example, and may be contained in the resin composition of the present invention in a range of about 1000 to 100,000 ppm.

  The antibacterial agent is, for example, silver zeolite, thiosulfite silver complex, nitrile derivative, imidazole derivative, triazine derivative, phenol ether derivative or pyrrole derivative, and is contained in the resin composition of the present invention in the range of about 1000 to 20000 ppm. Also good.

  The molding aid is, for example, a higher fatty acid salt and may be contained at a concentration depending on the application.

  The moisture absorbent is, for example, silica gel, zeolite, or calcium chloride, and may be contained in the resin composition of the present invention in a range of about 10,000 to 300,000 ppm.

The gas absorbent is, for example, activated carbon, zeolite, iron powder, or ascorbic acid, and may be contained in the resin composition of the present invention in a range of about 10,000 to 300,000 ppm.
[Embodiment of sealant film]
The film obtained from the resin composition of the present embodiment has a high oxygen barrier property, oil resistance, organic solvent resistance, non-adsorption property, etc., and heat seal properties required by the innermost layer film such as a packaging bag. It can be a sealant film having a high oxygen barrier property.

  In forming the film, a molding aid may be added to the resin composition of the present invention at an appropriate concentration.

  Specific heat seal strength as the sealant film will be described in Examples.

  This sealant film is a single film, and the cost can be greatly reduced as compared with a conventional five-layer or three-layer sealant film.

  The menthol adsorption amount of the sealant film of this embodiment is less than 1 mg per 1 g of the sealant film. The menthol adsorption amount is a value obtained by converting the amount of menthol contained in the acetone extract of the sealant film exposed in menthol vapor for one week per 1 g of the sealant film.

[Embodiment of laminated film]
The sealant film of this embodiment can be laminated as an innermost layer film by dry lamination, extrusion lamination or coextrusion lamination on a base film. The thickness of the sealant film can be about 10 μm to 100 μm. However, since the required packaging function is to maintain high oxygen barrier properties and non-adsorption properties, the thickness is preferably about 40 to 60 μm. When an EVOH film is used for the intermediate layer and the sealant film of the present embodiment is laminated on the intermediate layer using a T-die, the thickness may be 10 to 30 μm.

  A laminated film is composed of the sealant film of the present embodiment and one or more other films laminated with the sealant film. FIG. 1 is a schematic enlarged cross-sectional view of a laminated film A of this embodiment. 1 is a sealant film of the present embodiment, 2 is a film forming an intermediate layer, and 3 is an outer layer film. As the outer layer film, a biaxially stretched polyamide film or a biaxially stretched PET film having a high puncture resistance can be used, which is usually laminated with the film 2 that forms the intermediate layer by dry printing or the like by performing reverse printing. The The sealant film 1 can be laminated on the film 2 forming the intermediate layer by a known laminating method such as dry lamination, sand lamination, or extrusion lamination.

  In a laminated film that has a required function and has high oxygen barrier property and non-adsorption property, the film 2 forming the intermediate layer conventionally uses an EVOH film, aluminum foil, aluminum vapor deposition, or silicon vapor deposition film. It was. On the other hand, according to the present embodiment, when the sealant film 1 is about 40 to 80 μm, the above-mentioned EVOH film has sufficient oxygen barrier properties, oil resistance, organic solvent resistance, non-adsorption property and the like. And aluminum foil can be omitted. Therefore, the film 2 forming the intermediate layer can be provided to have a function of maintaining strength, stiffness, or light shielding, and can greatly reduce the overall cost when forming a laminated film. . As a film that retains light shielding properties, light shielding printing can be performed on the inner surface of the outer layer film or the intermediate film. However, when it is required to maintain a higher oxygen barrier property, oil resistance, organic solvent resistance, non-adsorption property, etc., if an EVOH film is used for the intermediate layer 2, the sealant film 1 of this embodiment is used. Together, this requirement is met. In this case, the EVOH film and the sealant film of this embodiment can be laminated by dry lamination, extrusion lamination, or coextrusion lamination.

[Embodiments of packaging bag and bag package]
A packaging bag or a bag package is produced from the laminated film of this embodiment. The laminated film of the present embodiment is rolled and provided in the form of a raw fabric roll, hung on a bag making machine to form a packaging bag, or hung on a bag filling and packaging machine to wrap an item to be packaged. It becomes a package.

  The packaging bag and bag package of this embodiment are a side seal type, a two-side seal type, a three-side seal type, a four-side seal type, an envelope-attached seal type, a palm-attached seal type (pillow seal type), a pleated seal type, It includes bags classified according to the form of heat seal, such as flat bottom seal type, square bottom seal type, standing pouch, etc., and also includes one-piece type, two-piece type and other bags attached with a spout or opening zipper.

  Since the packaging bag or package of this embodiment has high oxygen barrier properties, oil resistance, organic solvent resistance, non-adsorption property, etc., food and drink, cooked food, marine products, frozen food, meat products Suitable for packaging of simmered foods, seasonings and other foods and drinks. Furthermore, this packaging bag or package is suitable for packaging pharmaceuticals and other substances containing aromatic components such as menthol. That is, when a substance that fragrances menthol is packaged, since menthol does not diffuse and penetrate into the sealant film, menthol does not ooze out on the boundary surface between the sealant film and the base film laminated on the outside thereof. The adhesive function of the adhesive coated with dry laminate is not lost in menthol. Moreover, since there is no loss of menthol, there is no loss of medicinal effect. Furthermore, the fragrance of menthol can be confined in the bag, and menthol fragrances when opened, so that one condition for providing freshness can be ensured. The fragrance component is not limited to menthol, and limonene, methyl salicylate, and camphor are not adsorbed on the sealant film, packaging bag, and package of the present invention, so that these components are not lost. Furthermore, the sealant film, packaging bag and package of the present invention do not adsorb chemical components other than fragrance components such as tocopherol.

The adsorption amount of at least one compound of menthol, limonene, methyl salicylate, camphor and tocopherol in the sealant film, packaging bag and package of this embodiment is less than 1 mg per 200 m ³ of the sealant film.
The adsorption amount of the above-mentioned compound is such that a MEK solution containing at least one compound having a concentration of 10% by mass is sealed for one week, the MEK solution containing one compound is removed, and the sealant film of the packaging bag is sufficiently bonded to the MEK. Then, the weight of at least one compound of menthol, limonene, methyl salicylate, camphor or tocopherol contained in the eluate obtained from MEA as a solvent from the sealant film is measured. During the sealing period, the MEK solution containing at least one compound comes into contact with the sealant.

[Embodiments of packaging bag / tube container]
Since the packaging bag or package of the present embodiment uses a laminated film including a sealant film having a high oxygen barrier property, it is self-supporting for packaging photosensitive materials as industrial materials, such as films, photosensitive agents and other articles. It is also useful as a bag.
The resin composition of this embodiment is formed into a laminated film of two layers or three or more layers as a sealant film of the innermost layer by dry lamination, extrusion lamination, coextrusion lamination, etc., and has high oxygen barrier properties, oil resistance, organic resistance Solvent and non-adsorption properties. The laminated film is used as a packaging bag for foods, pharmaceuticals, detergents, inks, other oily materials, or infusion bags.

  As shown in FIG. 2, a tube container for packaging toothpaste, kneaded medicine, kneaded ink, and kneaded food can be configured using the laminated film of the present embodiment. The tube container B includes a body portion 4, a mouth shoulder member 5 that is integrally provided on the upper end of the body portion 4 by heat sealing, and a cap 6 that is fitted to the mouth portion 5 a of the mouth shoulder member 5. The lower end of the body 4 is open. The mouth-shoulder member 5 includes a mouth portion 5a to which the cap 6 is fitted, and a generally circular cone-shaped shoulder portion extending from the mouth portion 5a to the trunk portion 4 so that the mouth-shoulder member 5 can be easily understood from the form of a toothpaste tube and a paint tube. 5b is an integrally formed body. The mouth portion 5a and the cap 6 may have any configuration such as a screwing type or a forced fitting type.

  In the tube container B of this embodiment, the body 4 is configured using the laminated film of this embodiment, the innermost layer film 4a is the sealant film of this embodiment, the intermediate layer film 4b is an EVOH film, and the outer layer The film 4c is made of polyamide or the like.

  The mouth shoulder member 5 is molded using the resin composition of the present embodiment. And the lower end of the trunk | drum 4 is opened as an opening for filling to-be-packaged goods, the mouth-shoulder member 5 is inserted in the upper end of the trunk | drum 4, and the upper end of the trunk | drum 4 is bend | folded, and a shoulder It is covered on the periphery of the shoulder portion 5b of the member 5 and is heat-sealed all around. That is, since the innermost sealant film 4a and the shoulder member 5 of the body part 4 are both made of the resin composition of the present embodiment, heat sealing is realized. The tube container B of the present embodiment is heat-sealed in a palm-like shape after filling a packaged object from the lower end of the body part 4.

  In addition, although it is preferable that the tube container of this embodiment shall be 3 layers or more, a 2 layer structure may be sufficient.

  The characteristics of the resin composition / sealant film of the present invention will be further clarified by the following experimental examples.

  First, the heat seal strength was examined when melt mixing was performed using EVOH resin as a base resin and varying the content of EVA resin.

  Table 1 shows 7 to 40 parts by weight of EVOH resin (Eval F104B, Kuraray Co., Ltd .; the same in the following examples) as a base resin, EVA resin (Mersen MX02, Tosoh Corporation; the same in the following examples). The mixture was blended and melt-mixed using a twin screw extruder of L / D = 30 (lab blast mill, Toyo Seiki Seisakusho; the same in the following examples) at a specific energy of 4.0 MJ / kg. A polymer alloy obtained by kneading was formed into a film with a T-die to obtain a sealant film having a thickness of 40 μm. The twin screw extruder includes a screw made up of a flight screw, a pineapple, and a kneading disk.

  Two laminated films obtained by dry laminating the above sealant film and a biaxially stretched PET film having a thickness of 12 μm are heat-sealed under the conditions of 140 ° C., 0.2 MPa, 0.7 seconds with the sealant films facing each other. Each of the heat-sealed part and the non-heat-sealed part was cut out to a width of 15 mm so as to have half in the length direction.

  And seal strength was measured by the T-type peel test based on JISZ0238. That is, the portion not heat-sealed was opened and held in a T shape, and the tensile strength when the tensile portion was applied to peel off the heat-sealed portion was used as the seal strength. The seal strength is shown in Table 1.

  In addition, the sealant film 100 mm × 100 mm was exposed in menthol vapor generated at 40 ° C. for one week, menthol adsorbed on the sealant film was extracted with acetone, and the value determined by gas chromatography was measured as the menthol adsorption amount. The amount of menthol adsorbed is shown in Table 1.

[Evaluation]
When the seal strength is lower than 50 gf / 15 mm, the heat seal strength necessary for a packaging bag is not reached. According to Table 1, when the EVA content is less than 10% by weight, the seal strength cannot be obtained. When the EVA content is in the range of 10 to 30% by weight, the heat seal strength necessary for the packaging bag is reached. When the EVA content is in the range of 15 to 20% by weight, the seal strength is 200 gf / 15 mm or more, and the heat seal strength necessary for a packaging bag is obtained. The seal strength peaks when the EVA content is around 20% by weight. When the content of EVA was 40% by weight, phase separation between EVOH and EVA occurred, and a film having the strength required for a packaging film could not be formed.

  From the above, the content of EVA needs to be in the range of 10% by weight to 30% by weight.

  Since it was found from Example 1 that the EVA content was in the range of 15 wt% or more and 20 wt% or less, a large sealing strength was obtained. Therefore, as Experimental Example 1, the content of EVA was 85 wt%, and EVA When the specific energy was varied by fixing the content to 15% by weight, as Experimental Example 2, the specific energy was varied by fixing the EVOH content to 80% by weight and the EVA content to 20% by weight. In each case, the heat seal strength was examined and summarized in Tables 2 and 3 below.

  EVOH resin and EVA resin are manufactured by the same manufacturer as in the first embodiment.

[Evaluation]
According to the results in Table 2, the seal strength when giving a specific energy of 0.7 MJ / kg is 48 gf / 15 mm, which is lower than 50 gf / 15 mm. Further, according to the results in Table 2, the seal strength when the specific energy of 2.3 MJ / kg is given is 98 gf / 15 mm. From the two results, it is expected that the seal strength when the specific energy of 2.0 MJ / kg is applied exceeds the 50 gf / 15 mm required for the packaging bag.

  From the above, the resin composition of the present invention needs to be melt kneaded by applying a specific energy of 2.0 MJ / kg by a reactive processing method using a multi-screw extruder.

  A sealant film having an EVOH content of 90% and an EVA content of 10% was prepared, and the oxygen permeability was measured. In addition, the oxygen permeability of the EVOH 100% film and the low-density polyethylene 100% sealant film was measured. Was measured. The results are shown in Table 4.

(Evaluation)
From the results shown in Table 4, the sealant film having an EVOH content of 90% and an EVA content of 10% obtained values not different from those of an EVOH 100% film. From this, it is expected that there is sufficient oxygen impermeability even when the EVA content is 15 to 20% of the best mode.

  About the sealant film of the following Experimental examples 1-3 and Comparative Examples 1-3, the menthol adsorption amount was measured on the same conditions as Example 1. FIG.

In addition, if the menthol adsorption amount per 1g is less than 1 mg, it can be said that it is excellent in non-adsorption property.
(Experimental example 1)
80% by weight of EVOH resin and 20% by weight of EVA resin were dry blended and kneaded at a specific energy of 6.3 MJ / kg using a twin screw extruder. A polymer alloy obtained by kneading was formed into a film with a T-die to obtain a sealant film having a thickness of 40 μm.
[Experiment 2]
EVOH resin 85% by weight and EVA resin 15% by weight were dry blended and kneaded using a twin screw extruder at a specific energy of 6.2 MJ / kg. A polymer alloy obtained by kneading was formed into a film with a T-die to obtain a sealant film having a thickness of 40 μm.
[Experimental Example 3]
EVOH resin 80% by weight and EVA resin 20% by weight were dry blended and kneaded at a specific energy of 1.8 MJ / kg using a twin screw extruder. The kneaded polymer alloy was discharged from a nozzle to produce a strand, and was cut with a rotary knife to produce a pellet. The obtained polymer alloy pellets were again kneaded with a specific energy of 3.5 MJ / kg by a twin screw extruder, and formed into a film with a T die to obtain a sealant film having a thickness of 40 μm (the total specific energy was 5. 3MJ / kg).
(Comparative Example 1)
EVOH resin 80% by weight and EVA resin 20% by weight were dry blended and kneaded at a specific energy of 0.4 MJ / kg using a twin screw extruder. A polymer alloy formed by kneading was formed into a film with a T-die to obtain a sealant film having a thickness of 40 μm.
(Comparative Example 2)
Only EVOH resin was kneaded with a specific energy of 9.4 MJ / kg using a twin screw extruder, and a film was formed with a T-die to obtain a sealant film having a thickness of 40 μm. The comparative example 2 is added to confirm whether or not the heat sealability is exhibited by giving a sufficiently large specific energy to the EVOH resin which is known not to have the heat sealability.
(Comparative Example 3)
Only the LDPE resin was kneaded using a twin screw extruder and formed into a film with a T-die to obtain a sealant film having a thickness of 40 μm.

  Two laminated films obtained by dry laminating each sealant film obtained in Experimental Examples 1 to 3 and Comparative Examples 1 to 3 and a biaxially stretched PET film having a thickness of 12 μm are laminated with the sealant films facing each other. Half of the area of the surface is heat-sealed under the conditions of 140 ° C., 0.2 MPa, 0.7 seconds, and the width is 15 mm so that the heat-sealed part and the non-heat-sealed part have half in the length direction. The seal strength and menthol adsorption were measured in the same manner as in Example 1. The results are shown in Table 5. For Comparative Example 3, only the menthol adsorption amount was measured.

[Evaluation]
From Table 5, it was found that when a specific energy of approximately 5.0 MJ / kg was given and melt-mixed, the seal strength reached 360 gf / 15 mm, so that sufficient seal strength was obtained. It has also been found that a smaller specific energy is sufficient to obtain 50 gf / 15 mm as the sealing strength required for the bag.

  It was found that when a specific energy of 0.4 MJ / kg was applied from Comparative Example 1, sufficient seal strength could not be obtained.

  In addition, menthol was adsorbed as much as 86 mg / g with the LDPE resin alone, whereas no adsorption of menthol was observed in Experimental Examples 1 to 3 in which the present invention was carried out.

  A laminated film having a structure of PET (thickness 12 μm) / aluminum sheet (thickness 9 μm) / sealant film (thickness 40 μm) was dry-laminated using the sealant film having a thickness of 40 μm produced under the conditions of Experimental Example 1 in Example 4. Produced. Next, the sealant films of the laminated film were heat-sealed to produce a bag with three sides closed.

20 ml of MEK solution having a 10% mass concentration of menthol, limonene, methyl salicylate, camphor and tocopherol was filled in a bag and sealed to prepare a sample having a solution contact area of 200 cm ² .

Also, a laminated film using LDPE (tinlon L N-280) instead of the sealant film: a bag made of PET (thickness 12 μm) / aluminum sheet (thickness 9 μm) / LDPE (thickness 40 μm) was prepared, menthol, limonene, 20 ml of MEK solution having a 10% mass concentration of each of methyl salicylate, camphor and tocopherol was filled in a bag and sealed to prepare a control sample having a solution contact area of 200 cm ² .

  After storing the sample and the control sample at 40 ° C. for 1 week, the solution was taken out from the bag, and the sealant surface and LDPE surface of the bag were washed with MEK, and then the chemical components adsorbed on the sealant or LDPE were eluted using MEK as a solvent. . The eluate was analyzed by gas chromatography, and the collected components were quantified. The results are shown in Table 6.

  It can be seen from Table 6 that the sample sealant does not adsorb or permeate odor components such as menthol, limonene, methyl salicylate, camphor, and chemical components such as tocopherol contained in food. Since the resin composition and sealant film of the present invention do not adsorb or permeate the package contents, they are excellent materials as packaging materials.

A laminated film,
1 sealant film,
2 a film forming an intermediate layer,
3 outer layer film,
B tube container 4 trunk 4a sealant film 4b intermediate layer film 4c outer layer film 5 mouth shoulder 5a mouth part 5b shoulder part 6 cap

Claims (9)

A sealant film for a sachet or tube container obtained by film-forming a resin composition obtained by melt-kneading a binary mixed resin containing an ethylene-vinyl alcohol copolymer and an ethylene-vinyl acetate copolymer There,
In the two-mixed resin constituting the sealant film,
The ethylene-vinyl alcohol copolymer is 70% by weight or more and 90% by weight or less,
Ethylene-vinyl acetate copolymer is 10 wt% or more and 30 wt% or less,
When the two sealant films are heat-sealed under the conditions of 140 ° C., 0.3 MPa, 0.7 sec, the seal strength measured by JIS Z0238 is 50 gf / 15 mm or more,
After sealing a MEK solution containing at least one compound selected from the group consisting of 10% mass concentration of menthol, limonene, methyl salicylate, camphor and tocopherol for one week in a packaging bag made of the sealant film, At least one compound selected from the group consisting of menthol, limonene, methyl salicylate, camphor and tocopherol contained in an eluate obtained from the sealant film constituting the packaging bag using MEK as a solvent is 200 m ^{2 of} sealant film. A sealant film that is less than 1 mg. In the two-mixed resin constituting the sealant film,
The ethylene-vinyl alcohol copolymer is 80% by weight or more and 85% by weight or less,
The sealant film according to claim 1, wherein the ethylene-vinyl acetate copolymer is 15 wt% or more and 20 wt% or less. The sealant film according to claim 1 or 2 , wherein an amount of menthol contained in an acetone extract of the sealant film exposed for one week in menthol vapor is less than 1 mg per 1 g of the sealant film. The articles to be packaged in wrappers or in a tube container, menthol, limonene, methyl salicylate, at least one compound selected from the group consisting of camphor and tocopherol, as claimed in any one of claims 1 to 3 Sealant film. A laminated film comprising the sealant film according to any one of claims 1 to 4 and one or more other films. A packaging bag made of the laminated film according to claim 5 . A bag package, which is packaged and packaged with the laminated film according to claim 5 . A body portion is formed of the laminated film according to claim 5, a lower end of the body portion is an opening for filling, and an upper end of the body portion covers a shoulder portion periphery of a mouth shoulder member into which a cap is fitted. A tube container that is heat sealed. Step 1 for obtaining a resin composition obtained by melt-kneading a binary mixed resin containing an ethylene-vinyl alcohol copolymer and an ethylene-vinyl acetate copolymer;
A process for producing a sealant film for a sachet or tube container, comprising the step 2 of obtaining a sealant film by forming a film of the resin composition obtained in the step 1;
The melt kneading gives a specific energy of 2.0 MJ / kg or more to the mixture of the ethylene-vinyl alcohol copolymer and the ethylene-vinyl acetate copolymer by a reactive processing method using a multi-screw extruder. Done,
In the two-mixed resin constituting the sealant film,
The ethylene-vinyl alcohol copolymer is 70% by weight or more and 90% by weight or less,
Ethylene-vinyl acetate copolymer is 10 wt% or more and 30 wt% or less,
When the two sealant films are heat-sealed under the conditions of 140 ° C., 0.3 MPa, 0.7 sec, the seal strength measured by JIS Z0238 is 50 gf / 15 mm or more,
After sealing a MEK solution containing at least one compound selected from the group consisting of menthol, limonene, methyl salicylate, camphor and tocopherol at a concentration of 10% in a packaging bag made of the sealant film for one week. At least one compound selected from the group consisting of menthol, limonene, methyl salicylate, camphor and tocopherol contained in the eluate obtained from MEK as a solvent from the sealant film constituting the packaging bag is a sealant film 200 m ^2. The manufacturing method of the sealant film which is less than 1 mg per.

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