WO2019181942A1 - スキンパック用組成物、スキンパック用シーラント、及びスキンパック用包装体 - Google Patents
スキンパック用組成物、スキンパック用シーラント、及びスキンパック用包装体 Download PDFInfo
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- WO2019181942A1 WO2019181942A1 PCT/JP2019/011443 JP2019011443W WO2019181942A1 WO 2019181942 A1 WO2019181942 A1 WO 2019181942A1 JP 2019011443 W JP2019011443 W JP 2019011443W WO 2019181942 A1 WO2019181942 A1 WO 2019181942A1
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Definitions
- the present invention relates to a composition for skin pack, a sealant for skin pack, and a package for skin pack.
- Skin pack packaging is a differential pressure in which the bottom material tray with the contents (that is, the item to be packaged) enters the vacuum chamber, the vacuum chamber is evacuated, the heated lid film is heated, and the upper chamber is released. In this case, the contents of the contents are vacuum-packed by tightly adhering and pseudo-adhering the contents to the contents.
- a film for skin pack packaging of sliced ham, bacon, processed fishery products, etc. generally a laminated structure of polyvinyl chloride (PVC) / polyvinylidene chloride (PVDC) / ethylene-vinyl acetate copolymer (EVA)
- PVC polyvinyl chloride
- PVDC polyvinylidene chloride
- EVA ethylene-vinyl acetate copolymer
- the outer layer is an ionomer resin (IO) layer
- the intermediate layer is an ethylene-vinyl acetate copolymer saponified product (EVOH) layer
- the innermost layer An ethylene-vinyl acetate copolymer resin (EVA) or hot melt resin (HM) layer having a vinyl acetate content of 8 mol% or more and 20 mol% or less is disposed on the ionomer resin (IO) layer thickness ratio to the total film thickness.
- IO ionomer resin
- IO ethylene-vinyl acetate copolymer saponified product
- An object of the present invention is to provide a skin pack composition capable of obtaining a film for skin pack in which the occurrence of yarn string phenomenon is suppressed while maintaining good easy peelability as compared with a conventional film for skin pack. It is another object of the present invention to provide a skin pack sealant and a skin pack package using the same.
- the present invention includes the following aspects. ⁇ 1> An ionomer (A) of an ethylene / unsaturated carboxylic acid copolymer having a melt flow rate (JIS K7210-1999, 190 ° C., load 2160 g) of 6 g / 10 min or more, and a melt flow rate (JIS K7210-1999, 190 ° C.). And a polyolefin (B) having a load of 2160 g) of 6 g / 10 min or less.
- the composition of the polyolefin (B) is 100% by mass of the resin component in the skin pack composition.
- the composition for skin packs whose content is 20 mass% or more and 50 mass% or less.
- composition for skin pack according to ⁇ 1> wherein the unsaturated carboxylic acid content of the ethylene / unsaturated carboxylic acid copolymer is 10% by mass or more and 20% by mass or less.
- polyolefin (B) contains at least one selected from the group consisting of a structural unit derived from propylene and a structural unit derived from 1-butene.
- the ionomer (A) is at least one selected from the group consisting of a zinc ionomer of an ethylene / unsaturated carboxylic acid copolymer and a sodium ionomer of an ethylene / unsaturated carboxylic acid copolymer, ⁇ 1> to ⁇ 3 >
- the tackifier resin (C) is included, and the content of the tackifier resin (C) is 5% by mass or more and 25% by mass or less with respect to 100% by mass of the resin component in the skin pack composition.
- ⁇ 7> ⁇ 1>- ⁇ 6> A skin pack sealant comprising the skin pack composition according to any one of ⁇ 1> to ⁇ 6>.
- a skin pack packaging body for skin-packing contents by providing a first film and a second film, and bringing the first film and the second film into close contact with each other, At least one of the first film and the second film is a skin pack package having the skin pack sealant according to ⁇ 7>.
- a composition for skin pack that can obtain a sealant for skin pack in which the occurrence of yarn string phenomenon is suppressed while maintaining good easy peelability as compared with a conventional sealant for skin pack,
- a sealant for skin pack and a package for skinpack using the same are provided.
- ⁇ in a numerical range means including the numerical values before and after “ ⁇ ”.
- the upper limit value or the lower limit value described in a numerical range may be replaced with the upper limit value or the lower limit value of another numerical range described.
- the upper limit value or the lower limit value described in a certain numerical range may be replaced with the values shown in the examples.
- the amount of each component in the composition is the total amount of the plurality of substances present in the composition unless there is a specific indication when there are a plurality of substances corresponding to each component in the composition. means.
- “(meth) acrylic acid” represents at least one of acrylic acid and methacrylic acid.
- the composition for skin pack in the present specification comprises an ionomer (A) of an ethylene / unsaturated carboxylic acid copolymer having a melt flow rate (JIS K7210-1999, 190 ° C., load 2160 g) of 6 g / 10 min or more, And a polyolefin (B) having a melt flow rate (JIS K7210-1999, 190 ° C., load 2160 g) of 6 g / 10 min or less.
- A ionomer
- B polyolefin having a melt flow rate (JIS K7210-1999, 190 ° C., load 2160 g) of 6 g / 10 min or less.
- the composition for skin pack has the above-described configuration, thereby obtaining a sealant for skin pack in which the occurrence of yarn wrinkle phenomenon is suppressed while maintaining good easy peelability as compared with the conventional sealant for skin pack. It is considered possible.
- melt flow rate is a value [g / 10 minutes] measured at 190 ° C. under a load of 2160 g in accordance with JIS K7210-1999.
- the ionomer (A) of an ethylene / unsaturated carboxylic acid copolymer means that at least a part of the acidic groups of the ethylene / unsaturated carboxylic acid copolymer (that is, the base polymer) is a metal ion.
- the ethylene / unsaturated carboxylic acid copolymer (that is, the base polymer) that forms the ionomer is a copolymer obtained by copolymerizing at least ethylene and an unsaturated carboxylic acid, and is derived from ethylene. And a structural unit derived from an unsaturated carboxylic acid.
- the ethylene / unsaturated carboxylic acid copolymer may be a block copolymer, a random copolymer, or a graft copolymer. From the viewpoint of being industrially available, the ethylene / unsaturated carboxylic acid copolymer is preferably a random copolymer.
- the structural unit derived from the unsaturated carboxylic acid examples include structural units derived from acrylic acid, methacrylic acid, fumaric acid, maleic acid, and the like.
- the structural unit derived from unsaturated carboxylic acid is preferably a structural unit derived from acrylic acid or a structural unit derived from methacrylic acid, and most preferably a structural unit derived from methacrylic acid. .
- the unsaturated carboxylic acid content of the ionomer (A) of the ethylene / unsaturated carboxylic acid copolymer in the present specification is 10% by mass or more and 20% by mass relative to the total constitutional unit of the ethylene / unsaturated carboxylic acid copolymer. It is preferably from 10% by mass to 17% by mass, more preferably from 10% by mass to 18% by mass, from the viewpoint of suppressing the occurrence of the yarn warp phenomenon.
- the unsaturated carboxylic acid content of the ethylene / unsaturated carboxylic acid copolymer means the content of the structural unit derived from the unsaturated carboxylic acid relative to all the structural units of the ethylene / unsaturated carboxylic acid copolymer.
- the content of the structural unit derived from ethylene is preferably 80% by mass or more and 90% by mass or less, and 82% by mass or more and 90% by mass with respect to all the structural units of the ethylene / unsaturated carboxylic acid copolymer. More preferably, it is 83 mass% or more and 90 mass% or less.
- the ethylene / unsaturated carboxylic acid copolymer is a structural unit derived from a monomer other than ethylene and the unsaturated carboxylic acid (hereinafter, It may also be referred to as “other structural unit”.
- Examples of other structural units include unsaturated carboxylic acid esters, unsaturated hydrocarbons other than ethylene (eg, propylene, butene, 1,3-butadiene, pentene, 1,3-pentadiene, 1-hexene, etc.), vinyl Esters (eg, vinyl acetate, vinyl propionate, etc.), oxides such as vinyl sulfuric acid, vinyl nitric acid, halogen compounds (eg, vinyl chloride, vinyl fluoride, etc.), primary and secondary amine compounds containing vinyl groups, one Examples include structural units derived from carbon oxide, sulfur dioxide and the like. Among these, the other structural unit is preferably a structural unit derived from an unsaturated carboxylic acid ester.
- the unsaturated carboxylic acid ester is not particularly limited as long as it can be copolymerized with ethylene and an unsaturated carboxylic acid, and examples thereof include unsaturated carboxylic acid alkyl esters.
- the unsaturated carboxylic acid alkyl ester include methyl acrylate, ethyl acrylate, isopropyl acrylate, isobutyl acrylate, n-butyl acrylate, isooctyl acrylate and the like, alkyl methacrylate, methyl methacrylate, ethyl methacrylate
- the alkyl group has 1 to 12 carbon atoms in the alkyl ester such as alkyl ester such as methacrylic acid alkyl ester such as isobutyl methacrylate, n-butyl methacrylate, isooctyl methacrylate, and maleic acid alkyl ester such as dimethyl maleate and diethyl maleate.
- unsaturated carboxylic acid alkyl esters include methyl acrylate, ethyl acrylate, isopropyl acrylate, isobutyl acrylate, n-butyl acrylate, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, and n methacrylate.
- -Acrylic acid such as butyl and isooctyl methacrylate or alkyl ester of methacrylic acid is preferable, and lower alkyl ester of acrylic acid or methacrylic acid (for example, alkyl ester having 2 to 5 carbon atoms in the alkyl group) is more preferable.
- the ethylene / unsaturated carboxylic acid copolymer includes a structural unit derived from an unsaturated carboxylic acid ester
- preferred specific examples of the ethylene / unsaturated carboxylic acid copolymer include ethylene / (meth) acrylic acid. ⁇ (Meth) acrylic acid alkyl ester copolymer (for example, ethylene / (meth) acrylic acid / methyl acrylate copolymer, ethylene / (meth) acrylic acid / ethyl acrylate copolymer, ethylene / (meth) acrylic) Acid / butyl acrylate copolymer).
- the content of the other structural units is preferably 0.1% by mass to 10% by mass with respect to all the structural units of the ethylene / unsaturated carboxylic acid copolymer, from the viewpoint of ensuring flexibility, and preferably 1% by mass to 5% The mass% is more preferable.
- the metal ion used for neutralization of the acidic group which an ethylene and unsaturated carboxylic acid type copolymer has.
- the metal ion include alkali metal ions such as lithium, sodium, potassium, rubidium and cesium, alkaline earth metal ions such as magnesium and calcium, transition metal ions such as zinc, and various metal ions such as aluminum.
- the metal ion is preferably at least one selected from the group consisting of zinc ions, magnesium ions and sodium ions, and at least selected from the group consisting of zinc ions and sodium ions.
- One type is more preferable, and zinc ion is still more preferable.
- a metal ion may be used individually by 1 type, or may use 2 or more types together.
- the degree of neutralization of the ionomer (A) of the ethylene / unsaturated carboxylic acid copolymer is preferably 90 mol% or less, more preferably 5 mol% to 80 mol%, and more preferably 10 mol% to 70 mol. % Is more preferable.
- the degree of neutralization is 90 mol% or less, ion aggregation can be moderately suppressed, fluidity reduction can be further suppressed, and moldability can be more suitably maintained.
- the degree of neutralization is 5 mol% or more, the performance as an ionomer resin can be more effectively exhibited.
- the “neutralization degree” means the blending ratio of metal ions (moles) relative to the number of moles of acidic groups, particularly carboxy groups, in the ethylene / unsaturated carboxylic acid copolymer (that is, the base polymer). %).
- ionomer (A) of the ethylene / unsaturated carboxylic acid copolymer a commercially available product may be used.
- examples of commercially available products include Mitsui DuPont Polychemical Co., Ltd., Hi Milan (registered trademark) series, and the like.
- the melt flow rate (MFR) of the ionomer (A) of the ethylene / unsaturated carboxylic acid copolymer is 6 g / 10 min or more and preferably 8 g / 10 min or more from the viewpoint of suppressing the occurrence of the yarn warp phenomenon. 10 g / 10 min or more is more preferable, and 12 g / 10 min or more is further preferable.
- the upper limit of the melt flow rate (MFR) is not particularly limited, but is preferably 400 g / 10 min or less, more preferably 30 g / 10 min or less, further preferably 25 g / 10 min or less, and most preferably 20 g / 10 min or less from the viewpoint of workability. .
- the composition for skin pack in the present specification contains a polyolefin (B) having a melt flow rate (JIS K7210-1999, 190 ° C., load 2160 g) of 6 g / 10 min or less.
- the melt flow rate (MFR) of the polyolefin (B) in the present invention is 6 g / 10 min or less.
- the melt flow rate (MFR) of the polyolefin (B) is preferably 5 g / 10 min or less, and more preferably 4 g / 10 min or less. Good easy peelability can be obtained when the melt flow rate (MFR) of the polyolefin (B) is 6 g / 10 min or less.
- the lower limit of the melt flow rate (MFR) is not particularly limited, but is preferably 1 g / 10 min or more and more preferably 2 g / 10 min or more from the viewpoint of workability.
- the polyolefin (B) preferably contains at least one selected from the group consisting of a structural unit derived from propylene and a structural unit derived from 1-butene from the viewpoint of releasability, and includes a structural unit derived from propylene. Is more preferable.
- the polyolefin (B) preferably contains as a main component at least one selected from the group consisting of a structural unit derived from propylene and a structural unit derived from 1-butene.
- Polyolefin (B) includes propylene homopolymer, co-polymer of propylene mainly composed of propylene and other ⁇ -olefins (for example, ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, etc.) Examples thereof include 1-butene homopolymer, copolymers of 1-butene and other ⁇ -olefins, and the like.
- the “main component” means that the content of the structural unit is 50% by mass or more based on the total structural unit of the polyolefin (B).
- Polyolefin (B) contains as a main component at least one selected from the group consisting of structural units derived from propylene and structural units derived from 1-butene” means that polyolefin (B) is derived from propylene. When the unit and the structural unit derived from 1-butene are included, it means that the total content of the structural unit derived from propylene and the structural unit derived from 1-butene is 50% by mass or more. More specifically, examples of the polyolefin (B) include polypropylene, propylene / ethylene random copolymer, propylene / ethylene / 1-butene random copolymer, poly-1-butene, 1-butene / propylene random copolymer, and the like. Can be illustrated as a representative example.
- the composition for skin packs in the present specification is characterized in that the content of the ionomer (A) of the ethylene / unsaturated carboxylic acid copolymer is a skin from the viewpoint of maintaining good easy peelability and suppressing the occurrence of stringiness.
- the resin component in the pack composition is 100% by mass, preferably 40% by mass to 80% by mass, more preferably 50% by mass to 75% by mass, and more preferably 50% by mass to 70% by mass. More preferably.
- the content of the polyolefin (B) is 20% by mass or more and 50% by mass or less, and 20% by mass or more and 45% by mass or less, based on 100% by mass of the resin component in the skin pack composition.
- the “resin component” means an ionomer (A), a polyolefin (B) and a tackifying resin (C) contained in the composition for skin pack.
- composition for skin packs in this specification may further contain tackifying resin (C).
- tackifying resin (C) examples include aliphatic hydrocarbon resins, alicyclic hydrocarbon resins, aromatic hydrocarbon resins, styrene resins, terpene resins, rosins and the like.
- aliphatic hydrocarbon resins include polymers based on C 4 to C 5 mono- or diolefins such as 1-butene, isobutylene, butadiene, 1,3-pentadiene, isoprene and piperylene.
- alicyclic hydrocarbon resins include resins obtained by polymerizing a diene component in the spent C 4 to C 5 fraction after cyclization and dimerization, resins obtained by polymerizing cyclic monomers such as cyclopentadiene, aromatic Examples include resins obtained by intranuclear hydrogenation of an aromatic hydrocarbon resin.
- aromatic hydrocarbon resins include resins based on C 9 to C 10 vinyl aromatic hydrocarbons such as vinyl toluene, indene and ⁇ -methylstyrene.
- the “main component” means that the content of the constituent unit is 50% by mass or more based on the total constituent units of the hydrocarbon resin.
- styrene-based hydrocarbon resins include polymers such as styrene, vinyl toluene, ⁇ -methyl styrene, and isopropenyl toluene.
- terpene resins include ⁇ -pinene polymers, ⁇ -pinene polymers, dipentene polymers, terpene-phenol copolymers, ⁇ -pinene-phenol copolymers, hydrogenated terpene resins, and the like.
- rosins examples include rosin, polymerized rosin, hydrogenated rosin, rosin ester, rosin phenol resin and esters thereof.
- hydrogenated resins such as hydrogenated aromatic hydrocarbon resins and hydrogenated terpene resins is particularly preferred.
- the content of the tackifier resin (C) is preferably 0% by mass or more and 25% by mass or less, based on 100% by mass of the resin component of the skin pack composition, from the viewpoint of maintaining good easy peelability. More preferably, the content is from 5% by weight to 25% by weight, more preferably from 5% by weight to 25% by weight, and particularly preferably from 5% by weight to 20% by weight. % Or less is most preferable
- any additive can be blended in the skin pack composition in the present specification.
- additives include antioxidants, heat stabilizers, light stabilizers, antistatic agents, lubricants, and colorants.
- lubricants include fatty acid amides, high molecular weight polyethylene glycols, hydrogenated castor oil, and silica.
- Such a lubricant is about 100 ppm to 10000 ppm in the case of an organic compound lubricant and 0.1% by mass to 3% in the case of an inorganic compound lubricant such as silica with respect to 100 parts by mass of the total amount of the composition for skin pack. It is effective to add about mass%.
- a lubricant when used, when the composition for skin pack in this specification is subjected to extrusion coating processing on a base material, blocking of films and sticking to a metal roll are prevented, and work in subsequent steps such as rewinding is performed. There is an advantage of enhancing the sex.
- the skin pack composition in the present specification preferably has a melt flow rate of 1 g / 10 min to 400 g / 10 min, more preferably 1 g / 10 min to 150 g / 10 min in view of moldability and sealing properties. .
- the sealant for skin packs according to the present disclosure includes the composition for skin packs described above.
- the composition for skin pack can be used as a single layer, but it can also be used by laminating the sealant as a heat seal layer on a substrate.
- Such a substrate examples include a stretched or unstretched film, for example, polyester such as polyethylene terephthalate, polyamide, polypropylene, polyethylene, ethylene / vinyl acetate copolymer, ethylene / unsaturated carboxylate copolymer Polymer, ethylene / unsaturated carboxylic acid copolymer or its ionomer, ethylene / vinyl alcohol copolymer film, paper, aluminum foil, aluminum, silica, alumina, magnesia deposited film, polyvinylidene chloride and polyvinyl alcohol Examples thereof include a film coated with a gas barrier material such as. These base materials may be a single layer or a laminate of two or more layers.
- polyester such as polyethylene terephthalate, polyamide, polypropylene, polyethylene, ethylene / vinyl acetate copolymer, ethylene / unsaturated carboxylate copolymer Polymer, ethylene / unsaturated carboxylic acid copolymer or its ionomer
- the method for laminating the skin pack composition on the base material in the present specification includes the method of directly laminating the skin pack composition onto the base material, the composition for skin pack made into a film by inflation or T-die casting.
- There are general methods such as so-called thermal laminating method, dry laminating method, sand laminating method, coextrusion inflation method, coextrusion T-die method, etc., in which an object is laminated with a base material, and any method can be applied.
- the thickness of the sealant for skin pack is preferably 1 ⁇ m to 200 ⁇ m, more preferably 2 ⁇ m to 100 ⁇ m, and most preferably 5 ⁇ m to 50 ⁇ m.
- the thickness of the substrate is preferably about 30 ⁇ m to 500 ⁇ m from the viewpoint of operability when peeling off.
- the thickness of the substrate is not particularly limited.
- the package for a skin pack according to the present disclosure includes a first film and a second film, and skin-packs the contents by bringing the first film and the second film into close contact with each other.
- the package for skin packs wherein at least one of the first film and the second film has the sealant for skin packs.
- the sealant for skin packs is disposed on at least a part of the surfaces of the first film and the second film that are in contact with the contents.
- the sealant for skin pack is preferably disposed on at least a part of the surface in contact with the contents of at least one of the first film and the second film.
- the sealant for skin pack is disposed on at least a part of the surface of the first film and the second film on the side where the first film and the second film face each other. It is preferable.
- the contents include various items such as various foods and beverages and pharmaceuticals, and are not particularly limited as long as they can be skin-packed.
- the package for skin packs in this specification includes at least a first film and a second film. And the aspect provided with the sealant for skin packs containing the composition for skin packs in this specification in both the 1st film and the 2nd film may be sufficient, and only for 1st films for the said skin packs The aspect provided with a sealant may be sufficient, and the aspect provided with the said sealant for skin packs only in a 2nd film may be sufficient.
- first film and the second film may be a single layer or a laminate of two or more layers.
- first film and the second film may have the same layer configuration or different layer configurations, and are not particularly limited.
- the first film and the second film contains an ionomer (D).
- the first film may have at least one layer containing an ionomer (D), and the second film may have a skin pack sealant.
- the first film may have a skin pack sealant.
- the second film may have at least one layer containing the ionomer (D).
- the first film may be an aspect having at least one layer containing an ionomer (D) and a sealant for skin pack, and the second film has at least a layer containing an ionomer (D).
- the aspect which has 1 layer and the sealant for skin packs may be sufficient.
- the specific layer configuration of the first film and the second film and the combination of the first film and the second film can be appropriately combined depending on the use and purpose of the skin pack packaging body. Is.
- the ionomer (D) in the layer containing the ionomer (D) is not particularly limited as long as it is a synthetic resin utilizing the cohesive force of metal ions.
- the metal ion include alkali metal ions such as lithium, sodium, potassium, rubidium and cesium, alkaline earth metal ions such as magnesium and calcium, transition metal ions such as zinc, and various metal ions such as aluminum. Is more preferably at least one selected from the group consisting of zinc ions and sodium ions, and more preferably zinc ions.
- the base polymer that forms the ionomer (D) is not particularly limited, but is preferably an ethylene / unsaturated carboxylic acid copolymer, and examples thereof include the ionomer (A).
- the ionomer (D) is preferably a zinc ionomer.
- the layer containing zinc ionomer is preferably disposed on at least a part of the surface in contact with the contents.
- the zinc ionomer preferably uses an ethylene / unsaturated carboxylic acid copolymer as a base polymer.
- the case where the first film is applied to the lid material side and the second film is applied to the tray (bottom material) side is taken as an example, and for the skin pack in this specification A package is demonstrated.
- a layer containing PP PP
- a layer containing nylon Ny
- a glycol-modified polyethylene terephthalate resin layer PET-G
- a foamed base material a sealant for skin packs (EZP) in this specification
- a layer structure can be formed.
- the ionomer (D) may be the same as or different from the ionomer (A) contained in the sealant for skin pack (EZP) in the present specification.
- the description of the adhesive layer is omitted, it can be used as appropriate between the respective layers as necessary.
- the laminated structure of the lid material is the layer (IO) containing the ionomer (D), the EVOH layer (B), the ethylene-vinyl acetate copolymer resin layer.
- the layers are laminated in the order of (EVA), and in these layers, the ethylene-vinyl acetate copolymer resin layer (EVA) is on the side closest to the contents.
- the ethylene-vinyl acetate copolymer resin layer (EVA) may be in direct contact with the contents, or a separate layer may be provided between the ethylene-vinyl acetate copolymer resin layer (EVA) and the contents. It may be through a layer.
- a preferred combination is [(1-1) or (1-2) or (1-6) or (1-7)] and [(2-1) or ( 2-3)], (1-5) and [((2-1) or (2-2)], and a more preferable combination is [(1-1) or (1-2)] and [( 2-1) or (2-3)], and a more preferred combination is (1-2) and (2-1).
- the lid material has at least one layer containing ionomer (D), while the tray (bottom material) is the skin according to the present disclosure.
- this is an embodiment having a sealant for pack (EZP).
- This embodiment can be suitably used for the purpose of skin-packing foods, drugs and the like.
- At least a part of the surface where the lid material contacts the food (content) is a layer containing zinc ionomer, and at least the surface where the tray (bottom material) contacts the food (content)
- a part is the sealant for skin packs according to the present disclosure containing zinc ionomer, it can be said to be the most desirable embodiment because of the effect of extending the shelf life of the food (content).
- melt flow rate was measured according to JIS K7210-1999.
- PP-1 Polypropylene (Random type, MFR (190 ° C., 2160 g load) 3.1 g / 10 min, MFR (230 ° C., 2160 g load) 6 g / 10 min Prime Polymer F317DV)
- PP-2 Polypropylene (homotype, MFR (190 ° C., 2160 g load) 3.2 g / 10 minutes, MFR (230 ° C., 2160 g load) 7 g / 10 minutes Prime Polymer F107BV)
- PP-3 Polypropylene (Random type, MFR (190 ° C., 2160 g load) 6.5 g / 10 min, MFR (230 ° C., 2160 g load) 25 g / 10 min Prime Polymer F329RA)
- PB-1 Polybutene-1 (Homotype, MFR (190 ° C., 2160 g load) 3.7 g / 10 min, BL
- Zn ionomer peel strength The obtained laminate is placed on a Zn ionomer film (base material) having a thickness of 0.1 mm so that the sealant layer side of the laminate faces the Zn ionomer film, a pressing force of 0.2 MPa, a heating temperature of 160 ° C., It heat-sealed on the conditions of the heating time 1.0 second, and was left to stand at room temperature for 24 hours. Thereafter, both surfaces of a 15 mm wide test piece cut out in the MD direction and the TD direction from the laminate were pulled in the opposite direction (in the peeling direction at 180 ° C.) to obtain the maximum stress.
- This maximum stress (N / 15 mm) was defined as the peel strength (N / 15 mm) in the MD direction and TD direction of the Zn ionomer of the resin composition.
- the measurement results are shown in Table 1.
- the peel strength is preferably greater than 1.0 N / 15 mm and not greater than 10 N / 15 mm.
- the Zn ionomer film was made of a Zn neutralized ethylene / methacrylic acid copolymer (ethylene unit content 85 mass%, methacrylic acid unit content 15 mass%, Zn neutralization degree 59%, MFR (190 ° C., 2160 g). (Load) 0.9 g / 10 min), and was produced at 230 ° C. with a 40 mm ⁇ single-layer cast molding machine.
- Example 2 The laminated body obtained in Example 1 was heated on a Na ionomer film (base material) having a thickness of 0.1 mm so that the sealant layer side of the laminated body faces the Na ionomer film, with a pressing force of 0.2 MPa. Heat sealing was performed under conditions of a temperature of 140 ° C. and a heating time of 1.0 second, and left at room temperature for 24 hours. Thereafter, both sides of a 15 mm-wide test piece cut out from the laminate were pulled in the opposite direction (with a peeling direction of 180 ° C.) to obtain the maximum stress.
- This maximum stress (N / 15 mm) was defined as the resin composition's Na ionomer peel strength (N / 15 mm). Measurement was performed in the same manner as the above conditions except that the heat seal temperature was changed, and the peel strength against Na ionomer of the resin composition at a heat seal temperature of 160 ° C. was also obtained. Moreover, the presence or absence of the yarn wrinkle phenomenon was observed in the same manner as described above. The results are shown in Table 2.
- the peel strength is preferably more than 1.0 N / 15 mm and not more than 10 N / 15 mm.
- the Na ionomer film is an ethylene / methacrylic acid copolymer neutralized Na (ethylene unit content 85 mass%, methacrylic acid unit content 15 mass%, Na neutralization degree 54%, MFR (190 ° C., 2160 g). It was produced at 230 ° C. using a 40 mm ⁇ single layer cast molding machine using a load of 0.9 g / 10 min.
- Example 2 The laminate obtained in Example 1 was placed on a 0.1 mm thick EVA (ethylene / vinyl acetate copolymer) film (base material) so that the sealant layer side of the laminate was opposed to the EVA film. Heat sealing was performed under the conditions of a pressing force of 0.2 MPa, a heating temperature of 140 ° C., and a heating time of 1.0 second, and left at room temperature for 24 hours. Thereafter, both sides of a 15 mm-wide test piece cut out from the laminate were pulled in the opposite direction (with a peeling direction of 180 ° C.) to obtain the maximum stress. This maximum stress (N / 15 mm) was defined as the EVA peel strength (N / 15 mm) of the resin composition.
- EVA ethylene / vinyl acetate copolymer
- the EVA film is an ethylene / vinyl acetate copolymer (ethylene unit content 90% by mass, vinyl acetate unit content 10% by mass, MFR (190 ° C., 2160 g load) 9 g / 10 min. It produced at 200 degreeC with the cast molding machine.
- Example 2 The laminated body obtained in Example 1 was pressed on an LDPE (low density polyethylene) film (base material) having a thickness of 0.1 mm so that the sealant layer side of the laminated body faces the LDPE film. It heat-sealed on the conditions of 2 MPa, the heating temperature of 140 degreeC, and the heating time of 1.0 second, and was left to stand at room temperature for 24 hours. Thereafter, both sides of a 15 mm-wide test piece cut out from the laminate were pulled in the opposite direction (with a peeling direction of 180 ° C.) to obtain the maximum stress. This maximum stress (N / 15 mm) was taken as the LDPE peel strength (N / 15 mm) of the resin composition.
- LDPE low density polyethylene
- the peel strength is preferably greater than 1.0 N / 15 mm and not greater than 10 N / 15 mm.
- the LDPE film was produced at 200 ° C. with a 40 mm ⁇ single-layer cast molding machine using high-pressure low-density polyethylene (917 kg / m 3, MFR (190 ° C., 2160 g load) 7 g / 10 min).
- the sealant for skin packs obtained from the composition for skin packs of this example the occurrence of the yarn wrinkle phenomenon was suppressed while maintaining good peelability.
- the sealant for skin packs obtained from the composition for skin packs of Comparative Examples had poor peelability, or even if the peelability was good, the yarn wrinkle phenomenon occurred. The thing of was also inferior compared with the Example.
- the sealant for skin pack obtained from the composition for skin pack of Example 1 has good easy peelability for various substrates including Zn ionomer film. While maintaining this, the occurrence of stringiness was not observed.
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Abstract
Description
従来、スライスハム、ベーコン、水産加工品等をスキンパック包装するためのフィルムとして、一般に、ポリ塩化ビニル(PVC)/ポリ塩化ビニリデン(PVDC)/エチレン-酢酸ビニル共重合体(EVA)の積層構造を有するフィルムが使用されている。
しかしながら、鋭利な骨等が含まれる水産加工品を収容する場合や低温下で保存する場合には、フィルムの穴開き(ピンホール発生)に対する抵抗力(以下、「突き刺し強度」ともいう。)に劣る場合がある。また、底材(例えばトレー)がポリプロピレン(PP)樹脂の場合には、フィルムとトレーとの接着性に劣る問題があった。さらに、環境問題から包材の脱塩素化も求められている。
また、突き刺し強度及び内容物密着性に優れるスキンパック蓋材用共押出多層フィルムとして、外層にアイオノマー樹脂(IO)層、中間層にエチレン-酢酸ビニル共重合体けん化物(EVOH)層、最内層に酢酸ビニル含有率が8モル%以上20モル%以下のエチレン-酢酸ビニル共重合体樹脂(EVA)又はホットメルト樹脂(HM)層を配し、フィルム総厚に対するアイオノマー樹脂(IO)層厚比が40%以上70%以下であり、エチレン-酢酸ビニル共重合体けん化物(EVOH)層厚比が10%以下であるスキンパック蓋材用共押出多層フィルムが開示されている(例えば、特許第5034237号公報参照)。
本発明の課題は、従来のスキンパック用フィルムと比較し、良好な易剥離性を維持しつつ、糸曳現象の発生が抑制されたスキンパック用フィルムを得ることができるスキンパック用組成物、並びにこれを用いたスキンパック用シーラント及びスキンパック用包装体を提供することである。
<1>
メルトフローレート(JIS K7210-1999、190℃、荷重2160g)が6g/10min以上である、エチレン・不飽和カルボン酸共重合体のアイオノマー(A)と、メルトフローレート(JIS K7210-1999、190℃、荷重2160g)が6g/10min以下であるポリオレフィン(B)と、を含むスキンパック用組成物であり、上記スキンパック用組成物中の樹脂成分100質量%に対して、上記ポリオレフィン(B)の含有量が20質量%以上50質量%以下であるスキンパック用組成物。
<2>
上記エチレン・不飽和カルボン酸共重合体の不飽和カルボン酸含有量が10質量%以上20質量%以下である、<1>に記載のスキンパック用組成物。
<3>
上記ポリオレフィン(B)がプロピレンに由来する構成単位及び1-ブテンに由来する構成単位からなる群から選ばれる少なくとも1種を含む、<1>又は<2>に記載のスキンパック用組成物。
<4>
上記アイオノマー(A)は、エチレン・不飽和カルボン酸共重合体の亜鉛アイオノマー及びエチレン・不飽和カルボン酸共重合体のナトリウムアイオノマーからなる群から選ばれる少なくとも1種である、<1>~<3>のいずれかに1つに記載のスキンパック用組成物。
<5> 上記スキンパック用組成物中の樹脂成分100質量%に対して、上記アイオノマー(A)の含有量が40質量%以上80質量%以下である、<1>~<4>のいずれかに1つに記載のスキンパック用組成物。
<6>
更に、粘着付与樹脂(C)を含み、上記スキンパック用組成物中の樹脂成分100質量%に対して、上記粘着付与樹脂(C)の含有量が5質量%以上25質量%以下である、<1>~<5>のいずれか1つに記載のスキンパック用組成物。
<7>
<1>~<6>のいずれか1つに記載のスキンパック用組成物を含むスキンパック用シーラント。
<8>
第1のフィルムと、第2のフィルムとを備え、上記第1のフィルムと上記第2のフィルムとを互いに密着させることにより内容物をスキンパックするためのスキンパック用包装体であって、上記第1のフィルム及び上記第2のフィルムの少なくとも一方は、<7>に記載のスキンパック用シーラントを有するスキンパック用包装体。
<9>
上記スキンパック用シーラントは、上記第1のフィルム及び上記第2のフィルムの少なくとも一方の、上記内容物と接触する面の少なくとも一部に配置される、<8>に記載のスキンパック用包装体。
<10>
上記第1のフィルムは、アイオノマー(D)を含む層を少なくとも1層有し、上記第2のフィルムは、上記スキンパック用シーラントを有する、<8>又は<9>に記載のスキンパック用包装体。
<11>
上記アイオノマー(D)は、亜鉛アイオノマーを含み、上記アイオノマー(D)を含む層は、上記第1のフィルムの、上記内容物と接触する面の少なくとも一部に配置される、<10>に記載のスキンパック用包装体。
本明細書において、組成物中の各成分の量は、組成物中に各成分に該当する物質が複数存在する場合は、特に断らない限り、組成物中に存在する該複数の物質の総量を意味する。
本明細書において、「(メタ)アクリル酸」とは、アクリル酸及びメタクリル酸の少なくとも一方を表す。
本明細書におけるスキンパック用組成物は、メルトフローレート(JIS K7210-1999、190℃、荷重2160g)が6g/10min以上である、エチレン・不飽和カルボン酸共重合体のアイオノマー(A)と、メルトフローレート(JIS K7210-1999、190℃、荷重2160g)が6g/10min以下であるポリオレフィン(B)と、を含む。
なお、特に記載しない限り、メルトフローレート(MFR)は、JIS K7210-1999に準拠して、190℃、2160g荷重で測定される値〔g/10分〕である。
本明細書において、エチレン・不飽和カルボン酸共重合体のアイオノマー(A)とは、エチレン・不飽和カルボン酸系共重合体(つまり、ベースポリマー)が有する酸性基の少なくとも一部が、金属イオンで中和された化合物を意味する。
工業的に入手可能な観点から、エチレン・不飽和カルボン酸系共重合体としては、ランダム共重合体であることが好ましい。
これらの中でも、不飽和カルボン酸に由来する構成単位としては、アクリル酸に由来する構成単位又はメタクリル酸に由来する構成単位であることが好ましく、メタクリル酸に由来する構成単位であることが最も好ましい。
他の構成単位としては、例えば、不飽和カルボン酸エステル、エチレン以外の不飽和炭化水素(例えば、プロピレン、ブテン、1,3-ブタジエン、ペンテン、1,3-ペンタジエン、1-ヘキセン等)、ビニルエステル(例えば、酢酸ビニル、プロピオン酸ビニル等)、ビニル硫酸、ビニル硝酸等の酸化物、ハロゲン化合物(例えば、塩化ビニル、フッ化ビニル等)、ビニル基含有の1級及び2級アミン化合物、一酸化炭素、二酸化硫黄等に由来する構成単位が挙げられる。
これらの中でも、他の構成単位としては、不飽和カルボン酸エステルに由来する構成単位であることが好ましい。
不飽和カルボン酸アルキルエステルとしては、例えば、アクリル酸メチル、アクリル酸エチル、アクリル酸イソプロピル、アクリル酸イソブチル、アクリル酸n-ブチル、アクリル酸イソオクチル等のアクリル酸アルキルエステル、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸イソブチル、メタクリル酸n-ブチル、メタクリル酸イソオクチル等のメタクリル酸アルキルエステル、マレイン酸ジメチル、マレイン酸ジエチル等のマレイン酸アルキルエステル等のアルキルエステル中のアルキル基の炭素数が1~12である不飽和カルボン酸アルキルエステルが挙げられる。
金属イオンとしては、例えば、リチウム、ナトリウム、カリウム、ルビジウム、セシウム等のアルカリ金属イオン、マグネシウム、カルシウム等のアルカリ土類金属イオン、亜鉛等の遷移金属イオン、アルミニウム等の各種金属イオンなどが挙げられる。
工業化製品を容易に入手可能な点から、金属イオンは、亜鉛イオン、マグネシウムイオン及びナトリウムイオンからなる群から選ばれる少なくとも1種であることが好ましく、亜鉛イオン及びナトリウムイオンからなる群から選ばれる少なくとも一種であることがより好ましく、亜鉛イオンであることが更に好ましい。
金属イオンは、1種を単独で用いてもよく、又は、2種以上を併用してもよい。
中和度が90モル%以下であると、イオン凝集を適度に抑制でき、かつ、流動性の低下をより抑制でき、成形加工性をより好適に維持できる。
中和度が5モル%以上であると、アイオノマー樹脂としての性能をより効果的に発揮することが可能である。
なお、本明細書において「中和度」とは、エチレン・不飽和カルボン酸系共重合体(つまり、ベースポリマー)が有する酸性基、特にカルボキシ基のモル数に対する、金属イオンの配合比率(モル%)を示す。
メルトフローレート(MFR)の上限は特に制限はないが、加工性の観点から400g/10min以下が好ましく、30g/10min以下がより好ましく、25g/10min以下が更に好ましく、20g/10min以下が最も好ましい。
本明細書におけるスキンパック用組成物は、メルトフローレート(JIS K7210-1999、190℃、荷重2160g)が6g/10min以下であるポリオレフィン(B)を含有する。
本発明におけるポリオレフィン(B)のメルトフローレート(MFR)は、6g/10min以下である。ポリオレフィン(B)のメルトフローレート(MFR)は、5g/10min以下が好ましく、4g/10min以下がより好ましい。
ポリオレフィン(B)のメルトフローレート(MFR)が、6g/10min以下であることにより、良好な易剥離性を得ることができる。メルトフローレート(MFR)の下限は特に限定はないが加工性の観点から1g/10min以上が好ましく、2g/10min以上がより好ましい。
ここで、「主成分」とは、その構成単位の含有量がポリオレフィン(B)の全構成単位に対して50質量%以上であることを意味する。「ポリオレフィン(B)は、プロピレンに由来する構成単位及び1-ブテンに由来する構成単位からなる群から選ばれる少なくとも1種を主成分として含む」とは、ポリオレフィン(B)がプロピレンに由来する構成単位及び1-ブテンに由来する構成単位を含む場合には、プロピレンに由来する構成単位及び1-ブテンに由来する構成単位の総含有量が50質量%以上であることを意味する。
より具体的には、ポリオレフィン(B)としては、ポリプロピレン、プロピレン・エチレンランダム共重合体、プロピレン・エチレン・1-ブテンランダム共重合体、ポリ1-ブテン、1-ブテン・プロピレンランダム共重合体などを代表例として例示することができる。
また、同様の観点から、ポリオレフィン(B)の含有量はスキンパック用組成物中の樹脂成分を100質量%として20質量%以上50質量%以下であり、20質量%以上45質量%以下であることが好ましく、25質量%以上45質量%以下であることがより好ましい。
本明細書において「樹脂成分」とは、スキンパック用組成物に含まれるアイオノマー(A)、ポリオレフィン(B)及び粘着付与樹脂(C)を意味する。
また、本明細書におけるスキンパック用組成物は、更に粘着付与樹脂(C)を含んでいてもよい。
粘着付与樹脂(C)の例としては、脂肪族系炭化水素樹脂、脂環族系炭化水素樹脂、芳香族系炭化水素樹脂、スチレン系樹脂、テルペン樹脂、ロジン類などが挙げられる。
脂環族系炭化水素樹脂の例としては、スペントC4~C5留分中のジエン成分を環化二量体化後重合させた樹脂、シクロペンタジエンなどの環状モノマーを重合させた樹脂、芳香族系炭化水素樹脂を核内水添した樹脂などが挙げられる。芳香族系炭化水素樹脂の例としては、ビニルトルエン、インデン、α-メチルスチレンなどのC9~C10のビニル芳香族炭化水素を主成分とした樹脂などが挙げられる。
ここで、「主成分」とは、当該構成単位の含有量が、炭化水素樹脂の全構成単位に対して50質量%以上であることを意味する。
滑剤を使用した場合、本明細書におけるスキンパック用組成物を、基材に押出コーティング加工する際に、フィルム同士のブロッキングや金属ロールへのスティックを防止するとともに、巻き戻し等の後工程の作業性を高めるという利点がある。
本開示に係るスキンパック用シーラントは、上記のスキンパック用組成物を含む。
シーラントにおいて、スキンパック用組成物は、単層で使用することができるが、基材にシーラントをヒートシール層として積層して使用することもできる。このような基材としては、延伸又は無延伸のフィルムであって、例えば、ポリエチレンテレフタレートのようなポリエステル、ポリアミド、ポリプロピレン、ポリエチレン、エチレン・酢酸ビニル共重合体、エチレン・不飽和カルボン酸エステル共重合体、エチレン・不飽和カルボン酸共重合体又はそのアイオノマー、エチレン・ビニルアルコール共重合体等のフィルム、紙、アルミ箔、アルミニウム、シリカ、アルミナ、マグネシアなどを蒸着したフィルム、ポリ塩化ビニリデンやポリビニルアルコールなどのガスバリアー材をコーティングしたフィルムなどを例示することができる。これら基材は単層であってもよく、2層以上の積層品であってもよい。
本明細書におけるスキンパック用シーラントの厚みは1μm~200μmが好ましく、2μm~100μmがより好ましく、5μm~50μmが最も好ましい。
また、スキンパック用シーラントを剥離フィルムとして使用する場合は基材の厚みは剥がすときの操作性の観点から30μm~500μm程度が好ましい。スキンパック用シーラントを底材として使用する場合は基材の厚みに特に制限はない。
本開示に係るスキンパック用包装体は、第1のフィルムと、第2のフィルムとを備え、上記第1のフィルムと上記第2のフィルムとを互いに密着させることにより内容物をスキンパックするためのスキンパック用包装体であって、上記第1のフィルムと上記第2のフィルムの少なくとも一方は、上記のスキンパック用シーラントを有するものである。
また、スキンパック用シーラントは、第1のフィルム及び第2のフィルムの、内容物と接触する面の少なくとも一部に配置されることが好ましい。別の実施形態によれば、スキンパック用シーラントは、第1のフィルム及び第2のフィルムの少なくとも一方の、内容物と接触する面の少なくとも一部に配置されることが好ましい。
別の実施形態によれば、スキンパック用シーラントは、第1のフィルム及び第2のフィルムの少なくとも一方の、第1のフィルムと第2のフィルムが対向する側の面の少なくとも一部に配置されることが好ましい。
ここで、内容物とは、各種飲食品や医薬品等の様々なものを含んでおり、スキンパックできるものであれば特に限定されるものでない。
そして、第1のフィルムと第2のフィルムの両方に、本明細書におけるスキンパック用組成物を含むスキンパック用シーラントを備える態様であってもよいし、第1のフィルムのみに上記スキンパック用シーラントを備える態様であってもよいし、第2のフィルムのみに上記スキンパック用シーラントを備える態様であってもよい。
また、第1のフィルムが、アイオノマー(D)を含む層を少なくとも1層とスキンパック用シーラントとを有する態様であってもよいし、第2のフィルムが、アイオノマー(D)を含む層を少なくとも1層とスキンパック用シーラントとを有する態様であってもよい。
なお、第1のフィルムと第2のフィルムの具体的な層構成や、第1のフィルムと第2のフィルムとの組み合わせは、スキンパック用包装体の用途や目的に応じて適宜組み合わせることができるものである。
金属イオンとしては、例えば、リチウム、ナトリウム、カリウム、ルビジウム、セシウム等のアルカリ金属イオン、マグネシウム、カルシウム等のアルカリ土類金属イオン、亜鉛等の遷移金属イオン、アルミニウム等の各種金属イオンなどが挙げられるが、亜鉛イオン及びナトリウムイオンからなる群から選ばれる少なくとも一種であることがより好ましく、亜鉛イオンであることが更に好ましい。
また、アイオノマー(D)を形成するベースポリマーは特に限定されるものではないが、エチレン・不飽和カルボン酸系共重合体であることが好ましく、上記のアイオノマー(A)が例示できる。
ここで、亜鉛アイオノマーとは、ベースポリマーとしてエチレン・不飽和カルボン酸系共重合体を使用していることが好ましい。
ここで、アイオノマー(D)を含む層(IO)、EVOH層(B)、エチレン-酢酸ビニル共重合体樹脂層(EVA)、ホットメルト樹脂層(HM)、ポリエチレンを含む層(PE)、ポリプロピレンを含む層(PP)、ナイロンを含む層(Ny)、グリコール変性ポリエチレンテレフタレート樹脂層(PET-G)、発泡基材、本明細書におけるスキンパック用シーラント(EZP)で表した場合、例えば以下の層構成を形成することができる。
上記アイオノマー(D)とは、本明細書におけるスキンパック用シーラント(EZP)に含まれるアイオノマー(A)と同一のものであってもよいし、異なるものであってもよい。
なお、接着剤層の表記については省略しているが、必要に応じて各層間に適宜使用することができる。
(1-1)IO/B/EVA(内容物側)
(1-2)PE/IO/B/EVA/IO(内容物側)
(1-3)IO/B/HM(内容物側)
(1-4)IO/B/IO/EVA(内容物側)
(1-5)IO/EVA/IO/EZP(内容物側)
(1-6)Ny/IO/B/EVA/IO(内容物側)
(1-7)PE/IO/Ny/B/EVA/IO(内容物側)
(1-8)Ny/IO/Ny/B/Ny/EVA/IO(内容物側)
(1-9)PET-G/B/IO/EZP(内容物側)
<トレー(底材)>
(2-1)発泡基材/PP/B/EZP(内容物側)
(2-2)PP/B/PP/IO(内容物側)
(2-3)PP/B/PP/EZP(内容物側)
この実施形態は、食品や薬剤等をスキンパックする用途に好適に使用することができる。
また、メルトフローレート(MFR)は、JISK7210-1999に準拠して測定した。
-樹脂組成物の調製-
以下の樹脂を表1に示す配合割合で仕込み量が10kgとなるように混合した。この混合物を、押出機(65mmφ、L/D=28、先端ダルメージフライトスクリュー)に投入し、加工温度160℃にて溶融混練することで樹脂組成物を作製し、本発明における樹脂組成物(実施例)と、比較用の樹脂組成物(比較例)を得た。
・アイオノマー1:エチレン・メタクリル酸共重合体のZn中和物(エチレン単位含有量85質量%、メタクリル酸単位含有量15質量%、Zn中和度21%、MFR(190℃ ,2160g荷重)16g/10分)
・アイオノマー2:エチレン・メタクリル酸共重合体のZn中和物(エチレン単位含有量89質量%、メタクリル酸単位含有量11質量%、Na中和度37%、MFR(190℃ ,2160g荷重)11g/10分)
・アイオノマー3:エチレン・メタクリル酸共重合体のZn中和物(エチレン単位含有量85質量%、メタクリル酸単位含有量15質量%、Zn中和度23%、MFR(190℃ ,2160g荷重)5g/10分)
・アイオノマー4:エチレン・メタクリル酸共重合体のZn中和物(エチレン単位含有量88質量%、メタクリル酸単位含有量12質量%、Zn中和度36%、MFR(190℃ ,2160g荷重)1.5g/10分)
・アイオノマー5:エチレン・メタクリル酸共重合体のNa中和物(エチレン単位含有量85質量%、メタクリル酸単位含有量15質量%、Na中和度30%、MFR(190℃ ,2160g荷重)2.8g/10分)
・PP-1:ポリプロピレン (ランダムタイプ、MFR(190℃ ,2160g荷重)3.1g/10分、MFR(230℃ ,2160g荷重)6g/10分 プライムポリマー社製F317DV)
・PP-2:ポリプロピレン (ホモタイプ、MFR(190℃ ,2160g荷重)3.2g/10分、MFR(230℃ ,2160g荷重)7g/10分 プライムポリマー社製F107BV)
・PP-3:ポリプロピレン (ランダムタイプ、MFR(190℃ ,2160g荷重)6.5g/10分、MFR(230℃ ,2160g荷重)25g/10分 プライムポリマー社製F329RA)
・PB-1:ポリブテン-1 (ホモタイプ、MFR(190℃ ,2160g荷重)3.7g/10分 三井化学社製BL4000)
・粘着付与樹脂:荒川化学工業(株)社製“アルコン AM-1” (環球法軟化点115℃の脂環族炭化水素樹脂)
ただし、比較例2、3に示す樹脂組成物は造粒性が悪く、積層体を作製することができなかった。
なお、表1中の「-」との標記は、該当成分を含まないことを示す。
得られた樹脂組成物を用いて積層体を作製した。詳細には、40mmφ3種3層のキャスト成形機を用いて、加工温度200℃、共押出する樹脂としてエチレン・メタクリル酸共重合体(酸含量9質量%、MFR8g/10分)を選択し230℃で、加工速度25m/分の押出ラミネート法により、予め作成したPET(12μm)/PE(15μm)の基材上にエチレン・メタクリル酸共重合体40μm厚、上記で得られた樹脂組成物20μm厚、で積層し、PET(12μm)/PE(15μm)/エチレン・メタクリル酸共重合体(40μm)/樹脂組成物(シーラント層)(20μm)の積層体を作製した。
得られた積層体を、厚さ0.1mmのZnアイオノマーのフィルム(基材)上に、積層体のシーラント層側がZnアイオノマーフィルムと対向するように、押圧力0.2MPa、加熱温度160℃、加熱時間1.0秒の条件でヒートシールし、室温で24時間放置した。その後、積層体からMD方向およびTD方向に切り出した15mm幅の試験片の両面を反対方向に(180℃の剥離方向で)引張り、最大応力を求めた。この最大応力(N/15mm)を、樹脂組成物の対ZnアイオノマーのMD方向およびTD方向の剥離強度(N/15mm)とした。測定結果を表1に示す。
ここで、1.0N/15mmを超え10N/15mm以下が好ましい剥離強度である。
尚、Znアイオノマーフィルムは、エチレン・メタクリル酸共重合体のZn中和物(エチレン単位含有量85質量%、メタクリル酸単位含有量15質量%、Zn中和度59%、MFR(190℃ ,2160g荷重)0.9g/10分)を用いて、40mmφ単層キャスト成形機にて230℃で作製した。
上記の剥離強度の評価において、剥離部を目視観察した。剥離部分に細い糸状の樹脂が形成される場合がある。これは通称、糸曳き現象と呼ばれる。この現象は外見だけでなく、食品である内容物を取り出す際に、糸片が万が一食品に着いてしまうなどの異物混入の観点から嫌われる特性である。目視にて糸曳き現象の有無を記録した。測定結果を表1に示す。
実施例1で得られた積層体を、厚さ0.1mmのNaアイオノマーのフィルム(基材)上に、積層体のシーラント層側がNaアイオノマーフィルムと対向するように、押圧力0.2MPa、加熱温度140℃、加熱時間1.0秒の条件でヒートシールし、室温で24時間放置した。その後、積層体から切り出した15mm幅の試験片の両面を反対方向に(180℃の剥離方向で)引張り、最大応力を求めた。この最大応力(N/15mm)を、樹脂組成物の対Naアイオノマー剥離強度(N/15mm)とした。ヒートシール温度を変えた他は上記条件と同じように測定して、ヒートシール温度160℃における樹脂組成物の対Naアイオノマー剥離強度も求めた。また、上記と同様に糸曳現象の有無を観察した。
結果を表2に示す。
ここで、1.0N/15mmを超え、10N/15mm以下が好ましい剥離強度である。
尚、Naアイオノマーフィルムは、エチレン・メタクリル酸共重合体のNa中和物(エチレン単位含有量85質量%、メタクリル酸単位含有量15質量%、Na中和度54%、MFR(190℃ ,2160g荷重)0.9g/10分を用いて、40mmφ単層キャスト成形機にて230℃で作製した。
実施例1で得られた積層体を、厚さ0.1mmのEVA(エチレン・酢酸ビニル共重合体)のフィルム(基材)上に、積層体のシーラント層側がEVAフィルムと対向するように、押圧力0.2MPa、加熱温度140℃、加熱時間1.0秒の条件でヒートシールし、室温で24時間放置した。その後、積層体から切り出した15mm幅の試験片の両面を反対方向に(180℃の剥離方向で)引張り、最大応力を求めた。この最大応力(N/15mm)を、樹脂組成物の対EVA剥離強度(N/15mm)とした。ヒートシール温度を変えた他は上記条件と同じように測定して、ヒートシール温度160℃における樹脂組成物の対EVA剥離強度も求めた。また、上記と同様に糸曳現象の有無を観察した。
結果を表2に示す。
ここで、1.0N/15mmを超え10N/15mm以下が好ましい剥離強度である。
尚、EVAフィルムは、エチレン・酢酸ビニル共重合体(エチレン単位含有量90質量%、酢酸ビニル単位含有量10質量%、MFR(190℃ ,2160g荷重)9g/10分を用いて、40mmφ単層キャスト成形機にて200℃で作製した。
実施例1で得られた積層体を、厚さ0.1mmのLDPE(低密度ポリエチレン)のフィルム(基材)上に、積層体のシーラント層側がLDPEフィルムと対向するように、押圧力0.2MPa、加熱温度140℃、加熱時間1.0秒の条件でヒートシールし、室温で24時間放置した。その後、積層体から切り出した15mm幅の試験片の両面を反対方向に(180℃の剥離方向で)引張り、最大応力を求めた。この最大応力(N/15mm)を、樹脂組成物の対LDPE剥離強度(N/15mm)とした。ヒートシール温度を変えた他は上記条件と同じように測定して、ヒートシール温度160℃における樹脂組成物の対LDPE剥離強度も求めた。また、上記と同様に糸曳現象の有無を観察した。
結果を表2に示す。
ここで、1.0N/15mmを超え10N/15mm以下が好ましい剥離強度である。
尚、LDPEフィルムは、高圧法低密度ポリエチレン(917kg/m3、MFR(190℃ ,2160g荷重)7g/10分を用いて、40mmφ単層キャスト成形機にて200℃で作製した。
また、表2から分かるように、実施例1のスキンパック用組成物から得られたスキンパック用シーラントは、Znアイオノマーのフィルムをはじめとする様々な基材に対して、良好な易剥離性を維持しつつ、糸曳現象の発生はみられなかった。
本明細書に記載された全ての文献、特許出願、および技術規格は、個々の文献、特許出願、および技術規格が参照により取り込まれることが具体的かつ個々に記された場合と同程度に、本明細書中に参照により取り込まれる。
Claims (11)
- メルトフローレート(JIS K7210-1999、190℃、荷重2160g)が6g/10min以上である、エチレン・不飽和カルボン酸共重合体のアイオノマー(A)と、
メルトフローレート(JIS K7210-1999、190℃、荷重2160g)が6g/10min以下であるポリオレフィン(B)と、
を含むスキンパック用組成物であり、
前記スキンパック用組成物中の樹脂成分100質量%に対して、前記ポリオレフィン(B)の含有量が20質量%以上50質量%以下であるスキンパック用組成物。 - 前記エチレン・不飽和カルボン酸共重合体の不飽和カルボン酸含有量が10質量%以上20質量%以下である、請求項1に記載のスキンパック用組成物。
- 前記ポリオレフィン(B)がプロピレンに由来する構成単位及び1-ブテンに由来する構成単位からなる群から選ばれる少なくとも1種を含む、請求項1又は請求項2に記載のスキンパック用組成物。
- 前記アイオノマー(A)は、エチレン・不飽和カルボン酸共重合体の亜鉛アイオノマー及びエチレン・不飽和カルボン酸共重合体のナトリウムアイオノマーからなる群から選ばれる少なくとも1種である、請求項1~請求項3のいずれか一項に記載のスキンパック用組成物。
- 前記スキンパック用組成物中の樹脂成分100質量%に対して、前記アイオノマー(A)の含有量が40質量%以上80質量%以下である、請求項1~請求項4のいずれか一項に記載のスキンパック用組成物。
- 更に、粘着付与樹脂(C)を含み、
前記スキンパック用組成物中の樹脂成分100質量%に対して、前記粘着付与樹脂(C)の含有量が5質量%以上25質量%以下である、請求項1~請求項5のいずれか1項に記載のスキンパック用組成物。 - 請求項1~請求項6のいずれか1項に記載のスキンパック用組成物を含むスキンパック用シーラント。
- 第1のフィルムと、第2のフィルムとを備え、前記第1のフィルムと前記第2のフィルムとを互いに密着させることにより内容物をスキンパックするためのスキンパック用包装体であって、
前記第1のフィルム及び前記第2のフィルムの少なくとも一方は、請求項7に記載のスキンパック用シーラントを有するスキンパック用包装体。 - 前記スキンパック用シーラントは、前記第1のフィルム及び前記第2のフィルムの少なくとも一方の、前記内容物と接触する面の少なくとも一部に配置される、請求項8に記載のスキンパック用包装体。
- 前記第1のフィルムは、アイオノマー(D)を含む層を少なくとも1層有し、
前記第2のフィルムは、前記スキンパック用シーラントを有する、請求項8又は請求項9に記載のスキンパック用包装体。 - 前記アイオノマー(D)は、亜鉛アイオノマーを含み、前記アイオノマー(D)を含む層は、前記第1のフィルムの、前記内容物と接触する面の少なくとも一部に配置される、請求項10に記載のスキンパック用包装体。
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