JP6531444B2 - Easy-open packaging material - Google Patents

Description

  The present invention relates to an easy-to-open packaging material excellent in oil resistance without using a polypropylene film for the innermost layer of the packaging material.

  Packaging materials such as foods, beverages, and pharmaceuticals are generally a resin composition-based resin film for laminating which is a sealant layer through an anchor coating agent on one side of a barrier film such as polyester or nylon excellent in film strength. Among them, laminates obtained by laminating polypropylene, high-pressure low density polyethylene, ethylene homopolymer, ethylene-vinyl acetate and the like are widely used.

  Such packaging materials are mainly manufactured by an extrusion laminating method, a solvent type dry laminating method, a non-solvent type dry laminating method or the like.

  Among them, since the extrusion laminating method exhibits excellent productivity, it is used as a manufacturing method of various packaging materials, and a high pressure low density polyethylene (hereinafter referred to as LDPE) excellent in extrusion laminating processability is widely used.

  However, in oil-based food packaging fields such as snack foods and instant noodles, LDPE has not been used up to now because of low oil resistance. Therefore, in the field of oil-based food packaging, packaging materials made of polypropylene film having excellent oil resistance are currently used.

  Further, in recent years, in the food packaging field, easy openability is sometimes required, but a laminate obtained by extrusion lamination of LDPE alone can not exhibit excellent easy openability. Because of this background, polypropylene films have been used for many years in the field of oily food packaging.

  As described above, polypropylene film is excellent as an inner surface material for oil-based food packaging, but polypropylene film alone has poor adhesion to the barrier film, and the barrier film and non-oriented polypropylene film are sandwich laminated using LDPE. The method is generally used (see, for example, Patent Document 1). Therefore, it was difficult to thin the packaging material.

Japanese Patent Application Laid-Open No. 4-128040

  This invention is made in view of the above situations, Comprising: It aims at providing the easily openable packaging material excellent in oil resistance, without using a polypropylene film.

The present invention comprises a resin composition for lamination comprising at least three layers, in the order of (A) layer, (B) layer, and (C) layer, wherein the (A) layer satisfies the following requirements (a) to (d), The present invention relates to an easily openable packaging material characterized in that the B) layer comprises an adhesive satisfying the following requirements (e) to (g), and the (C) layer comprises at least one or more base materials.
(A) Composition containing polyethylene and polybutene (b) The density measured based on JIS K 6922-1 is 910 to 947 kg / m ³
(C) Melt mass flow rate measured according to JIS K6922-1: 2 to 30 g / 10 min (d) Film thickness: 5 to 25 μm
(E) The film thickness is 0.01 to 1.0 μm
(F) Glass transition point measured based on JIS K7121 is -30 to + 10 ° C
(G) Storage modulus E 'at 20 ° C. is 1.0 × 10 ^{6 to} 2.5 × 10 ⁷ Pa
The present invention will be described in detail below.

The resin composition for lamination (A) constituting the layer (A) of the present invention is a composition containing polyethylene and polybutene. The polyethylene contained in the resin composition for lamination (A) is, for example, a linear ethylene homopolymer, an ethylene / α-olefin copolymer, a high pressure low density polyethylene, an ethylene / vinyl acetate copolymer, ethylene / methyl Acrylate copolymer, ethylene / ethyl acrylate copolymer, ethylene / butyl acrylate copolymer, ethylene / methacrylic acid copolymer, ethylene / acrylic acid copolymer, ethylene / methacrylic acid copolymer ionomer, maleic anhydride modified Polyethylene is mentioned.
The method for producing such linear ethylene homopolymer (1) and ethylene / α-olefin copolymer (2) is not particularly limited, but Ziegler-Natta catalyst, Phillips catalyst, metallocene catalyst are used. Examples thereof include high, medium and low pressure ionic polymerization methods, and such resins can be conveniently selected from commercially available products. For example, commercially available from Tosoh Corporation under the trade names Nipolon Hard, Nipolon-L, and Nipolon-Z. In addition, high pressure method low density polyethylene (3) production method can illustrate high pressure radical polymerization, such a resin can be conveniently selected from commercially available products, for example, Tosoh Corp. to Petrocene It is marketed under the trade name.

  Such polyethylene may be used singly or in combination of two or more. Among them, linear ethylene homopolymer (1), ethylene / α-olefin copolymer (2), or high pressure low density polyethylene (3) are preferable from the viewpoint of adhesion to the (B) layer, The composition which mix | blends 2 or more types is also preferable, since it is excellent also in extrusion lamination processability.

  The compounding ratio of the composition is such that from 10% to 90% by weight of linear ethylene homopolymer (1) and / or ethylene / α-olefin copolymer (2) from the viewpoint of extrusion laminating processability, high pressure Low density polyethylene (3) 10 to 90% by weight (3) (the total of (1), (2) and (3) is 100% by weight), more preferably a linear ethylene homopolymer (1) Or 20 to 80% by weight of ethylene / α-olefin copolymer (2), 20 to 80% by weight of high pressure method low density polyethylene (3) (3) ((1), (2) and (3) 100% by weight), most preferably 20 to 50% by weight of linear ethylene homopolymer (1) or ethylene / α-olefin copolymer (2), 50 to 80% by weight of high pressure low density polyethylene (3) (The sum of (1), (2) and (3) is 100 times Percent).

  The polybutene (4) constituting the resin composition for lamination (A) is a polymer of 1-butene, and is not particularly limited as long as the object of the present invention is achieved. For example, butene homopolymer, ethylene, propylene and the like And random polybutenes obtained by copolymerizing olefins other than 1-butene. Such polybutenes (4) are commercially available from Mitsui Chemicals, Inc. under the tradename Tafmer, from Lyondell Bassel, Polybutene-1, and from Idemitsu Kosan Co., for example, from Idemitsu Polybutene. Such polybutenes may be used singly or in combination of two or more.

  The compounding ratio of the resin composition for lamination (A) constituting the layer (A) of the present invention is preferably polyethylene ((1), (2) and (3), from the viewpoint of easy opening property and extrusion laminate formability. 80 to 98% by weight, and 2 to 20% by weight of polybutene (4) (the total of (1), (2), (3) and (4) is 100% by weight), more preferably polyethylene (((1) 1), (2) and (3) 85 to 98% by weight, polypropylene (4) 2 to 15% by weight ((1), (2), (3) and (4) total 100% by weight) And most preferably 90 to 95% by weight of polyethylene ((1), (2) and (3), 5 to 10% by weight of polypbutene (4) ((1), (2), (3) And the sum of (4) is 100% by weight).

Laminating resin composition constituting the layer (A) (A) of the present invention, JIS K6922-1 (1997 years) density 910~947kg / ^{m 3} as measured by, preferably 920~942kg / ^{m 3,} further It is preferably in the range of 927 to 942 kg / m ³ , most preferably 930 to 940 kg / m ³ . If the density is less than 910 kg / m ³ , it is not preferable because the easy openability is inferior. On the other hand, when the density exceeds 947 kg / m ³ , it is not preferable because the adhesiveness with the layer (C) and the extrusion laminate formability are inferior.

  Moreover, such a resin composition for lamination (A) has a melt mass flow rate of 2 to 30 g / 10 min, preferably 5 to 30 g / 10 min, more preferably 5 to 30 g / 10 min, as measured according to JIS K 6922-1 (1997). 10 to 30 g / 10 min. When the melt mass flow rate is less than 2 g / 10 min, it is not preferable because the ease of opening is inferior, and when it exceeds 30 g / 10 min, the extrusion laminate formability is inferior, which is not preferable.

In addition, the resin composition for lamination (A) constituting the layer (A) of the present invention may be, as required, an antioxidant, a lubricant, a neutralizing agent, an antiblocking agent, a surfactant, a slip agent, etc. Additives used in the above and thermoplastic resins such as other polyolefins may be added.
The resin composition (A) for lamination which comprises (A) layer of this invention can be manufactured with the mixing apparatus of resin used normally. Examples thereof include a single-screw extruder, a twin-screw extruder, a Banbury mixer, a pressure kneader, a melt-kneading apparatus such as a rotating roll, a Henschel mixer, a V blender, a ribbon blender, a tumbler and the like. When using a melt-kneading apparatus, the melting temperature is preferably about the melting point of polyolefin to about 350 ° C.

  In addition, a molded product (about 20 g) obtained by press-molding the resin composition for lamination (A) constituting the layer (A) of the present invention in a size of 150 mm × 150 mm × 1 mm into food oil (salad oil) at 60 ° C. for 24 hours When the weight change rate after immersion is 1.2% or less, when the packaged material contains an edible oil, it is difficult to cause delamination by the edible oil, which is preferable.

  The adhesive constituting the layer (B) of the present invention has a glass transition temperature of −30 to + 10 ° C., preferably −25 to + 5 ° C., most preferably −20 to 0 ° C., still more preferably − when measured according to JIS K7121. 20 to -5 ° C. When the glass transition temperature is less than -30 ° C, the unsealing strength is unfavorably low, and when it exceeds + 10 ° C, the peel appearance is inferior, which is not preferable.

In addition, the adhesive constituting the layer (B) of the present invention has a storage modulus of 1.0 × 10 ^{6 to} 2.5 × 10 ⁷ Pa, preferably 4.0 × 10 ^{6 at} 20 ° C. and a frequency of 10 Hz. It is in the range of 2.0 × 10 ⁷ , more preferably 8.0 × 10 ^{6 to} 2.0 × 10 ⁷ . If the storage elastic modulus is less than 1.0 × 10 ⁶ Pa, the unsealing strength is unfavorably low, and if it exceeds 2.5 × 10 ⁷ Pa, the peel appearance is inferior, which is not preferable.

  The compound which comprises such an adhesive agent will not be specifically limited if glass transition temperature and storage elastic modulus exist in said range, A polyurethane adhesive, a polyisocyanate adhesive, a polyurea adhesive, an epoxy adhesive, Although an acrylic adhesive, a polyamide adhesive, a polybutadiene type adhesive etc. can be illustrated, The polyurethane adhesive which control of adhesiveness and an elastic modulus is easy is preferable.

  Such polyurethane adhesives include a two-component curable polyurethane adhesive comprising a main component polyol component and a curing agent isocyanate component, and the polyol component having at least two or more hydroxyl groups in the molecule and the molecule It is composed of an isocyanate component having at least two or more isocyanate groups. The polyol component may, for example, be a polyurethane polyol, a polyester polyol, a polyether polyol, an acryl polyol or a polyolefin polyol, and two or more of such polyol components may be mixed and used. Among them, polyurethane polyols, polyester polyols and polyether polyols, which allow easy control of the glass transition temperature and storage elastic modulus, are preferable. Further, it is preferable that 30% by weight or more of the dicarboxylic acid component, the diol component, and the diester component constituting the polyurethane polyol or the polyester polyol is aliphatic because it is excellent in easy opening property.

  On the other hand, as an isocyanate component, aromatic aliphatic diisocyanate, aliphatic diisocyanate, alicyclic diisocyanate etc. are mentioned. Specific examples of the aromatic aliphatic diisocyanate include 1,3- or 1,4-xylylene diisocyanate or a mixture thereof, 1,3- or 1,4-bis (1-isocyanato-1-methylethyl) benzene or a mixture thereof , Ω, ω′-diisocyanato-1,4-diethylbenzene and the like can be mentioned. Specific examples of aliphatic diisocyanates include hexamethylene diisocyanate, tetramethylene diisocyanate, 2-methyl-pentane-1,5-diisocyanate, 3-methyl-pentane-1,5-diisocyanate, lysine diisocyanate, trioxyethylene diisocyanate, etc. It can be mentioned. Specific examples of alicyclic diisocyanates include isophorone diisocyanate, cyclohexyl diisocyanate, hydrogenated diphenylmethane diisocyanate, norbornane diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate, hydrogenated tetramethylxylene diisocyanate and the like.

  In addition, as an isocyanate component, it can be obtained by the reaction of a biuret, dimer, trimer, dimer-trimer, uretone imine modified product, etc. of a biislet of the above-mentioned diisocyanate, or a polyol having two or more functions with the above diisocyanate or its polymer. And modified polyisocyanates such as adducts of polyisocyanates.

  These can be used alone or in combination of two or more.

  Among these, aliphatic isocyanate modified products and / or alicyclic isocyanate modified products, and further aliphatic isocyanate modified products are preferable because they are excellent in easy opening property.

  Such polyurethane adhesives can be appropriately selected from commercially available products, and are commercially available from Tosoh Corporation under trade names such as Nipporan and Coronate.

  The adjustment of the glass transition temperature and the storage elastic modulus can be adjusted by the selection of the polyol component and the isocyanate component, and the compounding ratio of the polyol component and the isocyanate component. In addition, when the ratio (NCO / OH) of the number of hydroxyl groups of the polyol component and the number of isocyanate groups of the isocyanate component constituting the polyurethane adhesive is in the range of 0.5 to 2.5, easy openability, in particular, the open appearance is excellent. It is particularly preferable, preferably in the range of 0.7 to 2.0, and most preferably 0.8 to 1.6.

  The film thickness of the adhesive (B) of the layer (B) is in the range of 0.01 to 1.0 μm, preferably in the range of 0.1 to 0.7 μm. When the thickness of the adhesive (B) is less than 0.01 μm, it is not preferable because the adhesion is inferior and when it exceeds 1 μm, the easy opening property is inferior, which is not preferable.

  The solvent used for dilution of the adhesive is not particularly limited, but esters such as ethyl acetate, butyl acetate and cellosolve acetate, ketones such as acetone, methyl ethyl ketone, isobutyl ketone and cyclohexanone, tetrahydrofuran, dioxane and the like And aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as methylene chloride and ethylene chloride, dimethyl sulfoxide, dimethyl sulfoamide, alcohols such as methanol, ethanol and isopropanol, water and the like. be able to.

  Such an adhesive can be applied to the base of layer (C) with a coater attached to a known laminator. In particular, the prene roll is preferable because it is excellent in application accuracy when the thickness of the urethane adhesive is small.

  The base material constituting the (C) layer of the present invention is not particularly limited, and examples thereof include polyesters such as polyethylene terephthalate and polybutylene terephthalate, polyamides such as nylon 6 and nylon 66, ethylene-vinyl acetate copolymer Examples include films made of high polymers such as combined saponified polyvinyl alcohol, polypropylene resin, acrylic resin, polymethylpentene, polyvinyl chloride, polyvinylidene chloride, polycarbonate, cellulose resin, cellophane, polyester, polyamide The film is preferably at least one film selected from the group consisting of polypropylene, ethylene-vinyl acetate copolymer saponified product, and polyvinyl alcohol. Among these films, polyester films are preferable because they are excellent in heat resistance.

  Furthermore, these films may be those further subjected to aluminum vapor deposition, alumina vapor deposition, silicon dioxide vapor deposition, acrylic treatment, and are preferably films having vapor deposited thin films of metals such as aluminum, alumina and silica or metal oxides. .

  In addition, among these, a biaxially stretched polyester film or a polyamide film (C) layer having a layer selected from the group consisting of an aluminum deposition layer, an alumina deposition layer, a silicon dioxide deposition layer, and an acrylic treatment layer is for laminating Since it is excellent in adhesiveness with a resin composition (A), light shielding property, and barrier property, it is preferable.

  Moreover, metal foils, such as aluminum, copper, iron, etc. are mentioned as a base material which comprises (C) layer of this invention, Aluminum foil is preferable at the point of stability with respect to cost or oxidation.

  Furthermore, in order to improve the adhesion with the (B) layer, the (C) layer is known to the surface in contact with the (B) layer of the (C) layer, such as corona treatment, flame treatment, or plasma treatment. It is preferable to apply a surface treatment of

  The easily openable packaging material of the present invention can be produced by a known laminating method. The laminating method includes extrusion lamination, sandwich lamination, dry lamination, nonsolvent dry lamination, wet lamination, thermal lamination and the like, and extrusion lamination is preferable from the viewpoint of cost and thin film formability.

  In order to obtain good adhesion when subjected to extrusion lamination, it is preferable that at least the surface of the molten film extruded from the die and made of polyolefin and in contact with the adhesive (B) be oxidized by air or ozone gas. When the oxidation reaction by air is allowed to proceed, the temperature of the resin composition for lamination (A) of the present invention extruded from the die is preferably 290 ° C. or higher. When the oxidation reaction is caused to proceed by the ozone gas, it is extruded from the die The temperature of the laminated resin composition (A) of the present invention is preferably 200 ° C. or higher. The amount of ozone gas to be treated is preferably 0.5 mg or more per 1 m 2 of the film of the polyolefin of the present invention extruded from a die.

  The film thickness of the resin composition for lamination (A) is 5 to 25 μm, preferably 10 to 25 μm, and more preferably 13 to 22 μm. If the film thickness of the layer comprising the resin composition for lamination (A) is less than 5 μm, it is not preferable because the substrate adhesion to the layer (C) and the oil resistance are inferior, and if it exceeds 25 μm, the economic efficiency is only deteriorated. It is not preferable because the opening strength is high and the peeling appearance is deteriorated.

The layers (A) of the easily openable packaging material constituting the present invention were heat sealed by heat sealer at 125 ° C. to 140 ° C., seal pressure 0.2 MPa, seal time 1 second, seal width 10 mm by vertical heating. The opening strength of the 100 cm ² pillow bag is preferably 5 to 25 N, more preferably 8 to 20 N. When the opening strength of the easy-open packaging material is 5N or more, the protection of the contents is sufficient as the packaging material, and when the opening strength is 25N or less, the opening strength is not too strong and the easy-openability is excellent.

  The easy-open packaging material of the present invention is excellent in easy-openability and oil resistance, and has high substrate adhesion to the (C) layer, so it is a pillow package of a content containing oil and fat components such as snacks and instant noodles. It can be suitably used as a wide variety of easily openable packaging materials such as lids of polyethylene and polypropylene containers as well as packaging materials such as bags and three-way sealed bags.

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.
(1) Melt mass flow rate (MFR)
It measured based on JISK6922-1 (1997).
(2) Density Measured according to JIS K6922-1 (1997).
(3) Glass transition point The glass transition point was performed under nitrogen stream using DSC200 manufactured by Seiko Instruments Inc. That is, DSC measurement was performed from -100 ° C. to 100 ° C. at a temperature rising rate of 10 ° C./min using 10 mg of a cured product of a two-component curing polyurethane adhesive to determine a glass transition point.
(4) Storage Modulus The storage modulus was measured in tensile mode using Rheogel E4000 manufactured by UBM.
The frequency was set to 10 Hz, and the storage elastic modulus was determined in the range of -100 to 200 ° C.
(5) Opening strength Using a hot tack tester manufactured by Tester Sangyo Co., Ltd., the laminated body formed in the order of 3 layers of (A) layer / (B) layer / (C) layer obtained from the example, sealing temperature Heat sealed at 140 ° C, sealing pressure 0.2MPa, sealing time 1 second by vertical heating to make a 100cm ² pillow bag, and then using a tensile tester (TENSILON RTE-1210 made by ORIENTEC), pull 300mm / min At speed, the pillow bag was opened and the opening strength was measured. Moreover, the peeling appearance confirmed the presence or absence of a tear in a laminated body.
(6) Oil resistance About 20 g of pellets were press molded using a 50 t automatic press manufactured by Shinto Kogyo Co., Ltd. The size of the molded article was 150 mm × 150 mm × 1 mm. The obtained molded product was immersed in a salad oil (trade name: Nisshin salad oil) at 60 ° C. for 24 hours, and the weight change rate before and after immersion was examined.
(7) Moldability During extrusion lamination, it was confirmed whether molding defects such as film breakage and large width fluctuation did not occur, and a stable laminate film was obtained.

  Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

Production Example of Resin Composition (A-1) for Lamination of Layer (A) As a resin composition (A-1) for lamination of layer, an ethylene having a melt mass flow rate of 20 g / 10 min and a density of 964 kg / m ³・ Α-olefin copolymer (made by Tosoh Corp., trade name: Nipolone Hard 1000), high pressure method low density polyethylene having a melt mass flow rate of 3 g / 10 min, density 924 kg / m ³ (made by Tosoh Corp., trade name: Petrocene 205) ) And polybutene with a density of 911 kg / m ³ (Lyoundell Bassel, trade name Polybutene-1 PB 8340M) at a weight ratio of 25/65/10, and a 50 mmφ screw and strand Set temperature 1 using a single-screw extruder with die (manufactured by Plaka Co., Ltd.) The mixture was extruded in the form of a strand at a temperature of 80 ° C. and a discharge rate of 25 kg / hour, and pelletized using a strand cutter (manufactured by Seiwa Iron Works, Ltd.). The MFR, density and oil resistance of this resin composition for lamination (A-1) were evaluated. The results are shown in Table 1.

Production Example of Resin Composition for Lamination of Layer (A-2) As a Resin Composition (A-2) for Lamination of Layer: Ethylene having a melt mass flow rate of 20 g / 10 min and a density of 964 kg / m ³・ Α-olefin copolymer (made by Tosoh Corp., trade name: Nipolone Hard 1000), high pressure method low density polyethylene having a melt mass flow rate of 3 g / 10 min, density 924 kg / m ³ (made by Tosoh Corp., trade name: Petrocene 205) And (A-1) except that a ratio of 27/58/15 by weight of polybutene with a melt mass flow rate of 4 g / 10 min and a density of 911 kg / m ³ (manufactured by Lyoundell Bassel, trade name Polybutene-1 PB 8340 M) was dry blended. It manufactured by the method similar to the manufacture example of. The MFR, density, and oil resistance of the resin composition for lamination (A-2) were evaluated. The results are shown in Table 1.

Production Example of Polyolefin (A-3) of Layer (A) As a resin composition (A-3) for lamination of layer (A), an ethylene · α-olefin having a melt mass flow rate of 20 g / 10 min and a density of 964 kg / m ³ Copolymer (Tosoh Co., Ltd., trade name Nipolone Hard 1000) and melt mass flow rate 13 g / 10 min, high-pressure low density polyethylene with density 919 kg / m ³ (Tosoh Co., trade name Petrocene 212) and melt mass flow Example of (A-1) except that dry blending of polybutene with a rate of 4 g / 10 min and density of 911 kg / m ³ (Lyoundell Bassel, trade name Polybutene-1 PB 8340 M) at a weight ratio of 33/57/10 It manufactured by the same method. The MFR, density, and oil resistance of the resin composition for lamination (A-3) were evaluated. The results are shown in Table 1.

Production Example of Polyolefin (A-4) of Layer (A) As a resin composition (A-4) for lamination of layer (A), an ethylene · α-olefin having a melt mass flow rate of 20 g / 10 min and a density of 964 kg / m ³ Copolymer (Tosoh Co., Ltd., trade name Nipolone Hard 1000) and melt mass flow rate 13 g / 10 min, high-pressure low density polyethylene with density 919 kg / m ³ (Tosoh Co., trade name Petrocene 212) and melt mass flow Example of (A-1) except that dry blending of polybutene with a rate of 4 g / 10 min and density of 915 kg / m ³ (Lyoundell Bassel, trade name Polybutene-1 PB 0300 M) at a weight ratio of 33/57/10 It manufactured by the same method. The MFR, density, and oil resistance of the resin composition for laminate (A-4) were evaluated. The results are shown in Table 1.

Production Example of Resin Composition for Lamination of Layer (A-5) As a resin composition for lamination of layer (A-5) for layer (A-5), high pressure with a melt mass flow rate of 8 g / 10 min and density of 919 kg / m ³ Low density polyethylene (made by Tosoh Corp., trade name Petrocene 203) and melt mass flow rate 4 g / 10 min, poly butene of density 911 kg / m ³ (Lyoundell Bassel, trade name Polybutene-1 PB 8340 M) in weight ratio 90 / It manufactured by the method similar to the manufacture example of (A-1) except having carried out dry blending of the ratio of ten. The MFR, density, and oil resistance of the resin composition for lamination (A-5) were evaluated. The results are shown in Table 1.

Production Example of Resin Composition for Lamination of Layer (A-6) As a Resin Composition (A-6) for Lamination of Layer: Ethylene having a melt mass flow rate of 20 g / 10 min and a density of 964 kg / m ³・ Α-olefin copolymer (made by Tosoh Corp., trade name: Nipolone Hard 1000), high pressure method low density polyethylene having a melt mass flow rate of 3 g / 10 min, density 924 kg / m ³ (made by Tosoh Corp., trade name: Petrocene 205) Were prepared by the same method as the production example of (A-1) except that dry blending was performed at a weight ratio of 23/77. The MFR, density, and oil resistance of the resin composition for lamination (A-6) were evaluated. The results are shown in Table 1.

Production Example of Resin Composition for Lamination of Layer (A-7) As a Resin Composition (A-7) for Lamination of Layer: Ethylene having a melt mass flow rate of 20 g / 10 min and a density of 964 kg / m ³・ Α-olefin copolymer (made by Tosoh Corp., trade name: Nipolone Hard 1000), high pressure method low density polyethylene having a melt mass flow rate of 3 g / 10 min, density 924 kg / m ³ (made by Tosoh Corp., trade name: Petrocene 205) And (A-1) except that a weight ratio of 70/20/10 of polybutene (Lyoundell Bassel, trade name: Polybutene-1 PB 8340M) having a melt mass flow rate of 4 g / 10 min and a density of 911 kg / m ³ was used. It manufactured by the method similar to the manufacture example of. The MFR, density, and oil resistance of this resin composition for laminate (A-7) were evaluated. The results are shown in Table 1.

Production Example of Resin Composition for Lamination of Layer (A-8) As a resin composition for lamination of layer (A-8) for layer (A-8), ethylene having a melt mass flow rate of 20 g / 10 min and a density of 964 kg / m ³ · Α-olefin copolymer (manufactured by Tosoh Corp., trade name: Nipolone Hard 1000), high pressure method low density polyethylene having a melt mass flow rate of 70 g / 10 min, density 916 kg / m ³ (trade name: Petrocen 249, manufactured by Tosoh Corp.) (A-1) except that the polymer blend was melt-blended with a melt mass flow rate of 4 g / 10 min and a density of 911 kg / m ³ of polybutene (Lyoundell Bassel, trade name Polybutene-1 PB 8340M) in a weight ratio of 37/53/10. It manufactured by the method similar to the manufacture example of. The MFR, density, and oil resistance of the resin composition for laminate (A-8) were evaluated. The results are shown in Table 1.

実施例１
（Ａ）層としてラミネート用樹脂組成物（Ａ−１）を用い、９０ｍｍφのスクリューを有する押出ラミネーター（（株）ムサシノキカイ製）へ供給し、基材の引取速度を１００ｍ／分として、開口幅を６００ｍｍとしたＴダイより３２０℃の温度で押出し、（Ｃ）層として第一給紙部から繰り出した二軸延伸ポリエステルフィルム（東洋紡績（株）製 商品名東洋紡エステルフィルムＥ−５１００、厚み２５μｍ、以下、ＰＥＴと記す場合がある）のコロナ処理面に、（Ｂ）層の接着剤として以下に示す比率で配合した接着剤（Ｂ）を塗布し溶剤を乾燥した上にラミネート用樹脂組成物（Ａ−１）が２０μｍの厚さになるように押出ラミネートしたラミネートフィルムを得た。このラミネートフィルムを使って開封強度、剥離外観を評価した。結果を表２に示す。
接着剤（Ｂ）：
ポリエステル系ポリウレタン樹脂（東ソー（株）製、商品名ニッポラン３２２８）とポリイソシアネート（東ソー（株）製、商品名コロネートＨＬ）を重量比１００／１０で混合し、酢酸エチルを用いて固形分濃度を７％となるように希釈した。

Example 1
(A) Using a resin composition for lamination (A-1) as a layer, it is supplied to an extrusion laminator (made by Musa Shinokai Co., Ltd.) having a screw of 90 mmφ, and the opening width is 100 m / min. A biaxially stretched polyester film (made by Toyobo Co., Ltd., trade name Toyobo Ester Film E-5100, 25 μm thick, extruded as a (C) layer from a first sheet feeding section, extruded at a temperature of 320 ° C. from a T-die of 600 mm. An adhesive (B) blended in the following ratio as an adhesive for the layer (B) is coated on the corona-treated side of the PET (hereinafter sometimes referred to as PET), the solvent is dried, and a resin composition for laminating ( A laminate film was obtained by extrusion lamination such that A-1) had a thickness of 20 μm. The opening strength and peel appearance were evaluated using this laminated film. The results are shown in Table 2.
Adhesive (B):
Polyester-based polyurethane resin (Tosoh Corp., trade name: Nipporan 3228) and polyisocyanate (Tosoh Corp., trade name: Coronate HL) are mixed at a weight ratio of 100/10, and the solid content concentration is adjusted using ethyl acetate It was diluted to 7%.

Example 2
A laminate film was produced in the same manner as in Example 1 except that an adhesive compounded at the ratio shown below was used as an adhesive agent, and the physical properties of the obtained laminate film were evaluated. The results are shown in Table 1.
Adhesive (B):
Polyester-based polyurethane resin (Tosoh Corp., trade name: Nipporan 3228) and polyisocyanate (Tosoh Corp., trade name: Coronate HL) are mixed at a weight ratio of 100/5, and the solid content concentration is adjusted using ethyl acetate It was diluted to 7%.

Example 3
A laminate film was produced in the same manner as in Example 2 except that the resin composition for lamination (A-2) was used as the layer (A), and the physical properties of the obtained laminate film were evaluated. The results are shown in Table 2.

Example 4
A laminate film was produced in the same manner as in Example 2 except that the resin composition for lamination (A-3) was used as the layer (A), and the physical properties of the obtained laminate film were evaluated. The results are shown in Table 2.

Example 5
A laminate film was produced in the same manner as in Example 2 except that the resin composition for lamination (A-4) was used as the layer (A), and the physical properties of the obtained laminate film were evaluated. The results are shown in Table 2.

Example 6
A laminate film was produced in the same manner as in Example 2 except that the resin composition for lamination (A-5) was used as the layer (A), and the physical properties of the obtained laminate film were evaluated. The results are shown in Table 2.

Example 7
A laminate film was produced in the same manner as in Example 4 except that an adhesive compounded at a ratio shown below was used as an adhesive agent, and the physical properties of the obtained laminate film were evaluated. The results are shown in Table 1.
Adhesive (B):
Polyester-based polyurethane resin (Tosoh Corp., trade name: Nipporan 3228) and polyisocyanate (Tosoh Corp., trade name: Coronate HL) are mixed at a weight ratio of 100/5, and the solid content concentration is adjusted using ethyl acetate It was diluted to 12%.

Example 8
A laminate film was produced in the same manner as in Example 4 except that an adhesive compounded at a ratio shown below was used as an adhesive agent, and the physical properties of the obtained laminate film were evaluated. The results are shown in Table 1.
Adhesive (B):
Polyester-based polyurethane resin (Tosoh Corp., trade name: Nipporan 3228) and polyisocyanate (Tosoh Corp., trade name: Coronate HL) are mixed at a weight ratio of 100/10, and the solid content concentration is adjusted using ethyl acetate It was diluted to 7%.

Example 9
(C) An aluminum-deposited polyester film (made by Reiko Co., Ltd., trade name Diaraster ST, thickness 12 μm, hereinafter sometimes referred to as VM-PET) used as the layer from the first sheet feeding section A laminate film was produced in the same manner as in Example 4, and the physical properties of the obtained laminate film were evaluated. The results are shown in Table 2.

Example 10
(C) Example except using nylon film (made by Toyobo Co., Ltd. trade name Toyobo Harden film N-1100, thickness 25 μm, hereinafter sometimes referred to as Amide) fed as a layer from the first paper feeding unit A laminate film was prepared by the same method as 4 and the physical properties of the obtained laminate film were evaluated. The results are shown in Table 2.

比較例１
（Ａ）層の厚みを３０μｍとした以外は実施例２と同様の方法でラミネートフィルムを作成しようと試みたが、開封強度が高く、剥離外観に劣った。結果を表３に示す。

Comparative Example 1
An attempt was made to make a laminate film in the same manner as in Example 2 except that the thickness of the layer (A) was set to 30 μm, but the opening strength was high and the peel appearance was inferior. The results are shown in Table 3.

Comparative example 2
A laminate film was prepared in the same manner as in Example 4 except that the adhesive compounded in the ratio shown below was used as an adhesive agent, and the physical properties of the obtained laminate film were evaluated. It was inferior to. The results are shown in Table 3.
Adhesive (B):
Polyester-based polyurethane resin (Tosoh Corp., trade name: Nipporan 3228) and polyisocyanate (Tosoh Corp., trade name: Coronate L) are mixed at a weight ratio of 100/5, and the solid content concentration is adjusted using ethyl acetate It was diluted to 12%.

Comparative example 3
A laminate film was prepared in the same manner as in Example 4 except that the adhesive compounded in the ratio shown below was used as an adhesive agent, and the physical properties of the obtained laminate film were evaluated. It was inferior to. The results are shown in Table 3.
Adhesive (B):
Polyester-based polyurethane resin (Tosoh Corp., trade name: Nipporan 3228) and polyisocyanate (Tosoh Corp., trade name: Coronate L) are mixed at a weight ratio of 100/10, and the solid content concentration is adjusted using ethyl acetate It was diluted to 7%.

Comparative example 4
A laminate film was prepared in the same manner as in Example 4 except that the adhesive compounded in the ratio shown below was used as an adhesive agent, and the physical properties of the obtained laminate film were evaluated. It was inferior to. The results are shown in Table 3.
Adhesive (B):
A polyurethane adhesive (Mitsui Chemical Co., Ltd., trade name: Takelac A3210) and an isocyanate curing agent (Mitsui Chemical Co., Ltd., trade name: Takenate A3072) are mixed at a weight ratio of 3/1, and ethyl acetate is used. The solid concentration was diluted to 7%.

Comparative example 5
A laminate film was prepared in the same manner as in Example 1 except that the resin composition for lamination (A-6) was used as the layer (A), and the physical properties of the obtained laminate film were evaluated. High and inferior to peel appearance. The results are shown in Table 3.

Comparative example 6
A laminate film was prepared in the same manner as in Example 2 except that the resin composition for lamination (A-7) was used as the layer (A), and the physical properties of the obtained laminate film were evaluated. , Inferior to peeling appearance. The results are shown in Table 3.

Comparative example 7
An attempt was made to make a laminate film in the same manner as in Example 2 except that the resin composition for lamination (A-8) was used as the layer (A), but no stable laminate film was obtained. The results are shown in Table 3.

Claims (12)

A resin composition for lamination comprising at least (A) layer, (B) layer, and (C) layer in order of 3 layers, and (A) layer satisfying the following requirements (a) to (d), (B) layer An adhesive that satisfies the following requirements (e) to (g), and an easily openable packaging material wherein the (C) layer is composed of at least one or more base materials.
(A) Composition containing polyethylene and polybutene homopolymer (b) The density measured based on JIS K 6922-1 is 910 to 947 kg / m ³
(C) Melt mass flow rate measured according to JIS K6922-1: 2 to 30 g / 10 min (d) Film thickness: 5 to 25 μm
(E) The film thickness is 0.01 to 1.0 μm
(F) Glass transition point measured based on JIS K7121 is -30 to + 10 ° C
(G) Storage modulus E 'at 20 ° C. is 1.0 × 10 ^{6 to} 2.5 × 10 ⁷ Pa The easily openable packaging material according to claim 1, wherein the (A) layer is formed on the (C) layer by extrusion lamination through the (B) layer. The compounding ratio of the resin composition for laminating the layer (A) is a composition comprising 80 to 98% by weight of polyethylene and 2 to 20% by weight of polybutene homopolymer (the total of polyethylene and polybutene homopolymer is 100% by weight). The easily openable packaging material according to claim 1 or 2, characterized in that The easy-openability according to any one of claims 1 to 3, wherein the layer (B) is a two-component curable polyurethane adhesive comprising a main component polyol component and a curing agent isocyanate component. Packaging material. The easily openable packaging material according to claim 4, wherein the isocyanate component comprises an aliphatic isocyanate modified product. The easily openable material according to claim 4 or 5, wherein a ratio of the number of hydroxyl groups (OH) of the polyol component to the number of isocyanate groups of the isocyanate component (NCO / OH) is 0.5 to 2.5. . (A) the layer of polyethylene high-pressure process low-density polyethylene constituting the laminating resin composition, the ethylene-alpha-olefin copolymer, high density polyethylene, ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer, ethylene-et chill acrylate copolymer, ethylene-butyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-acrylic acid copolymer, contains at least one selected from the group consisting of maleic anhydride modified polyethylene The easily openable packaging material according to any one of claims 1 to 6, characterized in that The base material of the (C) layer is at least one film selected from the group consisting of polyester, polyamide, polypropylene, ethylene-vinyl acetate copolymer saponified product and polyvinyl alcohol. 7. The easily openable packaging material according to any one of the above. The base material of said (C) layer is at least 1 sort (s) of vapor deposition film which has a vapor deposition thin film which consists of a metal or metal oxide of aluminum, an alumina, a silica, It is characterized by the above-mentioned. Easy-to-open packaging material as described. The base material of the said (C) layer is aluminum foil, The easily openable packaging material as described in any one of the Claims 1 to 7 and 9 characterized by the above-mentioned. Easy-open packaging material according to any one of claims 1 to 1 0, characterized in that a packaging fat component-containing contents. The opening strength of the pillow bag obtained by heat-sealing layer (A) with each other at 125 ° C. to 140 ° C. in a heat sealer, claims 1 to 1 1 any one characterized in that it is a 2~25N The packaging bag which consists of an easily openable packaging material as described in a term.