WO2022209039A1 - Vinylidene chloride-based resin film, and filled/packaged product using same - Google Patents

Vinylidene chloride-based resin film, and filled/packaged product using same Download PDF

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Publication number
WO2022209039A1
WO2022209039A1 PCT/JP2021/045866 JP2021045866W WO2022209039A1 WO 2022209039 A1 WO2022209039 A1 WO 2022209039A1 JP 2021045866 W JP2021045866 W JP 2021045866W WO 2022209039 A1 WO2022209039 A1 WO 2022209039A1
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WO
WIPO (PCT)
Prior art keywords
vinylidene chloride
resin film
chloride resin
mass
film
Prior art date
Application number
PCT/JP2021/045866
Other languages
French (fr)
Japanese (ja)
Inventor
健一 増田
Original Assignee
株式会社クレハ
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 株式会社クレハ filed Critical 株式会社クレハ
Priority to KR1020237032414A priority Critical patent/KR20230147707A/en
Priority to CN202180095661.5A priority patent/CN116981629A/en
Priority to JP2023510232A priority patent/JP7496030B2/en
Publication of WO2022209039A1 publication Critical patent/WO2022209039A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/02—Wrappers or flexible covers
    • B65D65/04—Wrappers or flexible covers non-rectangular
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D75/00—Packages comprising articles or materials partially or wholly enclosed in strips, sheets, blanks, tubes, or webs of flexible sheet material, e.g. in folded wrappers
    • B65D75/04—Articles or materials wholly enclosed in single sheets or wrapper blanks
    • B65D75/06—Articles or materials wholly enclosed in single sheets or wrapper blanks in sheets or blanks initially folded to form tubes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/08—Homopolymers or copolymers of vinylidene chloride

Definitions

  • the present invention relates to a vinylidene chloride resin film and a filling package using the same.
  • a package manufactured by filling a tubular film with a content such as livestock meat or fish meat and tying both ends of the tubular film is formed by stacking the strip-shaped film into a tubular shape and stacking the side edges and longitudinally sealing to form a tubular film.
  • a mechanism, a mechanism for filling a tubular film with a content, and a mechanism for ligating both ends of the tubular film filled with the content, and after producing the package, the content is It is known that retort processing is performed for the purpose of sterilization and cooking. Since it is necessary to retain the taste and color of the contents after retort processing, the film used for the package is made of a material with excellent oxygen gas barrier properties, such as a vinylidene chloride resin (see, for example, Patent Documents 1).
  • the present invention has been made in view of the above problems, and an object of the present invention is to provide a vinylidene chloride resin film that eliminates the insufficient retention period of the color of the contents before and after retort processing when the contents are filled and packaged. , and to provide a filling package using the same.
  • the present inventors have found that the above problems can be solved by controlling the rate of change in the oxygen gas permeability of a vinylidene chloride resin film before and after a specific retort treatment within a specific range, and have completed the present invention. Completed.
  • the vinylidene chloride-based resin film according to the present invention contains a vinylidene chloride-based resin, and the cylindrical vinylidene chloride-based resin film having both ends in the longitudinal direction is filled with a content containing 20% by mass of lipid.
  • the filled package body is subjected to pressure heat sterilization in hot water of 120 ° C. at 0.2 MPa for 10 minutes, and the thickness of the vinylidene chloride resin film before the pressure heat sterilization is converted to 40 ⁇ m.
  • a (cm 3 /m 2 ⁇ day ⁇ atm) be the oxygen gas permeability of
  • B (cm 3 /m 2 ⁇ day ⁇ atm) the rate of change in oxygen gas permeability obtained by (B ⁇ A)/A ⁇ 100 is 35.0% or less.
  • the vinylidene chloride resin film preferably has a rate of change of oxygen gas permeability of 1.5% or less.
  • the vinylidene chloride resin film preferably has a rate of change of oxygen gas permeability of -10.0% or more.
  • the vinylidene chloride resin film preferably has a rate of change of oxygen gas permeability of -8.0% or more.
  • the vinylidene chloride resin film preferably further contains a resin other than the vinylidene chloride resin.
  • the resin other than the vinylidene chloride-based resin preferably contains at least one resin selected from the group consisting of ultra-low density polyethylene and ionomer resins.
  • the resin content excluding the vinylidene chloride-based resin is 0.5% by mass or more and less than 3% by mass.
  • the vinylidene chloride resin is preferably a copolymer of 60% by mass or more and 95% by mass or less of vinylidene chloride and 5% by mass or more and 40% by mass or less of vinyl chloride.
  • a filling package according to the present invention comprises the vinylidene chloride resin film and contents.
  • ADVANTAGE OF THE INVENTION it is possible to provide a vinylidene chloride-based resin film and a filling package using the same, which eliminates the insufficient retention period of the color of the contents before and after the retort treatment when the contents are filled and packaged. can.
  • the vinylidene chloride-based resin film according to the present invention is a vinylidene chloride-based resin film containing a vinylidene chloride-based resin, wherein 20% by mass of The filled package, which is filled and enclosed with the content containing the lipid, is subjected to pressure and heat sterilization in hot water of 120 ° C. at 0.2 MPa for 10 minutes, and the vinylidene chloride before the pressure and heat sterilization.
  • a (cm 3 /m 2 ⁇ day ⁇ atm) be the oxygen gas permeability in terms of the thickness of 40 ⁇ m of the resin film, and the oxygen gas permeability in terms of the thickness of 40 ⁇ m of the vinylidene chloride resin film after the pressure and heat sterilization.
  • the rate of change in oxygen gas permeability obtained by (B - A) / A x 100 is 35.0% or less, preferably 30 0% or less, more preferably 20.0% or less, even more preferably 2.0% or less, and particularly preferably 1.5% or less.
  • the rate of change in the oxygen gas permeability is 35.0% or less, it is easy to eliminate the insufficient retention period of the color of the contents.
  • the lower limit of the rate of change in oxygen gas permeability is not particularly limited, and may be ⁇ 10.0% or more, or ⁇ 8.0% or more.
  • the lipid used for measuring the rate of change in oxygen gas permeability is not particularly limited, and pork fat is used, for example.
  • the vinylidene chloride resin film may further contain a resin other than the vinylidene chloride resin.
  • the resin other than the vinylidene chloride resin can contain at least one resin selected from the group consisting of ultra-low density polyethylene and ionomer resin.
  • Polyvinylidene chloride resin Polyvinylidene chloride-based resin (hereinafter sometimes referred to as "PVDC”) may be a homopolymer of vinylidene chloride, and contains 60 to 98% by mass of vinylidene chloride and another monomer 2 copolymerizable with vinylidene chloride. It may be a copolymer with up to 40% by mass.
  • Other monomers copolymerizable with vinylidene chloride include, for example, vinyl chloride; alkyl acrylate esters such as methyl acrylate, ethyl acrylate, butyl acrylate, and lauryl acrylate (wherein the alkyl group has 1 to 18 carbon atoms); ); methacrylic acid alkyl esters such as methyl methacrylate, butyl methacrylate, and lauryl methacrylate (alkyl group has 1 to 18 carbon atoms); vinyl cyanide such as acrylonitrile; aromatic vinyl such as styrene; carbon number such as vinyl acetate vinyl esters of aliphatic carboxylic acids of 1 to 18; alkyl vinyl ethers of 1 to 18 carbon atoms; vinyl polymerizable unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid and fumaric acid; maleic acid, fumaric acid and itaconic acid and alkyl esters of vinyl polymerizable
  • PVDC polyvinyl styrene-maleic anhydride
  • methyl acrylate acrylate
  • lauryl acrylate polystyrene-maleic anhydride
  • Other monomers copolymerizable with vinylidene chloride may be used alone or in combination of two or more.
  • the copolymerization ratio of other monomers is more preferably 3 to 35% by mass, still more preferably 3 to 29% by mass, and particularly preferably 4 to 22% by mass.
  • the copolymerization ratio of other monomers is 3% by mass or more, the melt processability is less likely to decrease, and on the other hand, when the copolymerization ratio of other monomers is 35% by mass or less, gas barrier properties are less likely to decrease.
  • two or more kinds of PVDC may be mixed in order to improve melt processability.
  • PVDC can be synthesized by any polymerization method such as suspension polymerization method, emulsion polymerization method and solution polymerization method. PVDC may be used individually
  • PVDC contains 60% by mass or more and 95% by mass or less of vinylidene chloride and 5% by mass of vinyl chloride.
  • % or more and 40 mass% or less more preferably a copolymer of 63 mass% or more and 90 mass% or less of vinylidene chloride and 10 mass% or more and 37 mass% or less of vinyl chloride, Even more preferably, it is a copolymer of 66 to 85% by mass of vinylidene chloride and 15 to 34% by mass of vinyl chloride, and 69 to 83% by mass of vinylidene chloride and 17% by mass of vinyl chloride. It is particularly preferable to be a copolymer with more than 31% by mass or less.
  • Ultra-low density polyethylene refers to polyethylene having a density of 0.915 g/cm 3 or less, for example ethylene- ⁇ -olefin copolymers with C4-C8 ⁇ -olefin comonomers such as butene, hexene, octene, and the like. Ultra-low density polyethylene may be used singly or in combination of two or more.
  • the ionomer resin means a compound in which at least part of the acidic groups of the ethylene/unsaturated carboxylic acid copolymer (base polymer) are neutralized with metal ions.
  • An ionomer resin may be used individually by 1 type, or may be used in combination of 2 or more type.
  • Structural units derived from unsaturated carboxylic acids include, for example, structural units derived from acrylic acid, methacrylic acid, fumaric acid, or maleic acid.
  • the ethylene/unsaturated carboxylic acid-based copolymer (base polymer) forming the ionomer resin is at least a copolymer of ethylene and an unsaturated carboxylic acid. and a structural unit derived from an acid.
  • (meth)acrylic acid is preferable as the structural unit derived from unsaturated carboxylic acid.
  • the ethylene/unsaturated carboxylic acid copolymer contains structural units derived from monomers other than ethylene and unsaturated carboxylic acids, in addition to structural units derived from ethylene and structural units derived from unsaturated carboxylic acids. You can stay.
  • the metal ion used for neutralizing the acidic group of the ethylene/unsaturated carboxylic acid copolymer (base polymer) is not particularly limited, and alkali metal ions such as lithium, sodium, potassium, rubidium and cesium are preferred. , especially sodium.
  • (meth)acryl means at least one of "acryl” and “methacryl”.
  • the vinylidene chloride-based resin film according to the present invention for the purpose of improving various properties and / or molding processability, if necessary, other resins other than polyvinylidene chloride-based resin, ultra-low density polyethylene, and ionomer resin may contain.
  • resins are not particularly limited, and examples include polyethylene wax, oxidized polyethylene wax, low-density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymer (EVA), ethylene-acrylic acid copolymer (EAA), Ethylene-methacrylic acid copolymer (EMAA), ethylene-methyl acrylate copolymer (EMA), ethylene-ethyl acrylate copolymer (EEA), ethylene-butyl acrylate copolymer (EBA) and the like can be mentioned.
  • EVA ethylene-vinyl acetate copolymer
  • EAA ethylene-acrylic acid copolymer
  • EEMAA Ethylene-methacrylic acid copolymer
  • EMA ethylene-methyl acrylate copolymer
  • EAA ethylene-ethyl acrylate copolymer
  • EBA ethylene-butyl acrylate copolymer
  • Other resin may be used individually by 1 type,
  • the content of the resin other than the vinylidene chloride-based resin is preferably 0.5% by mass or more and less than 3.0% by mass, and 1.0% by mass or more and less than 3.0% by mass. is more preferable, and 1.0% by mass or more and 2.5% by mass or less is particularly preferable.
  • the content is 0.5% by mass or more, the effect of suppressing discoloration of contents after pressurized heat sterilization (retort treatment) tends to be sufficient.
  • the content is less than 3.0% by mass, the film is less likely to become cloudy.
  • the rate of change of the oxygen gas permeability can be adjusted by changing the content.
  • the content of the vinylidene chloride resin is preferably more than 97.0% by mass and 99.5% by mass or less, and more than 97.0% by mass and 99.0% by mass or less. More preferably, 97.5% by mass or more and 99.0% by mass or less is particularly preferable.
  • a heat-stabilizing agent is added for the purpose of improving various properties and molding processability of cylindrical packaging films conventionally provided in filled packaging bodies.
  • Various additives such as agents, plasticizers, processing aids, colorants, ultraviolet absorbers, pH adjusters, and dispersing aids can be incorporated.
  • heat stabilizers include epoxy compounds such as epoxidized vegetable oils, epoxidized animal oils, epoxidized fatty acid esters, and epoxy resin prepolymers; epoxy group-containing resins; and the like, preferably epoxidized vegetable oils.
  • the types and amounts of additives to be added can be selected in the same manner as in the various additives used in conventional cylindrical packaging films provided in filled packages.
  • An additive may be used individually by 1 type, or may be used in combination of 2 or more type.
  • a part or all of the additive may be contained in the monomer composition during the PVDC polymerization step, or may be blended into the PVDC after the polymerization.
  • a filling package according to the present invention comprises the vinylidene chloride resin film according to the present invention and contents. According to the filling package, it is possible to solve the problem of insufficient retention period of the color of the contents before and after the retort treatment.
  • the content is not particularly limited, and may contain lipids.
  • lipids For example, sausage, cheese, butter, hamburger, etc., solid or pasty processed foods, etc. Contents that are conventionally filled in a filling package. can be used.
  • the composition and shape of the content can be selected as appropriate. Particularly preferred contents include livestock sausages and fish sausages.
  • the method for manufacturing the filled package according to the present invention is not particularly limited as long as the content is filled and packaged with the vinylidene chloride resin film according to the present invention to obtain the filled package according to the present invention.
  • a filling package according to an embodiment of the present invention and a method for manufacturing the same will be described in detail below.
  • Cylindrical packaging film A filling package according to an embodiment of the present invention is a filling package comprising a tubular packaging film and a content, wherein the tubular packaging film has a vertical sealing portion extending in the longitudinal direction. with both longitudinal ends converging.
  • the packaging film includes the vinylidene chloride resin film according to the present invention.
  • the packaging film may be made of the vinylidene chloride resin film according to the present invention.
  • the size and thickness of the cylindrical packaging film are not particularly limited, and are determined according to the size of the contents to be filled.
  • the peripheral length of the tubular packaging film is, for example, 15 to 400 mm, often 30 to 300 mm, and widely adopted is in the range of 40 to 200 mm, and the longitudinal length of the tubular packaging film is For example, the range is 50-400 mm, often 70-300 mm, and the widely adopted range is 80-250 mm.
  • the thickness of the cylindrical packaging film is determined in consideration of the strength and barrier properties of the film according to the content to be filled. is in the range of 20-150 ⁇ m.
  • a heat-shrinkable film (uniaxially stretched film or biaxially stretched film) can also be used as the cylindrical packaging film.
  • a laminated film can be used to increase the strength of the cylindrical packaging film, improve gas barrier properties, improve heat resistance, adjust shrinkage, etc.
  • the vinylidene chloride resin according to the present invention Laminated films of films with other films such as polyethylene terephthalate film or polypropylene film can be used. Further, the cylindrical packaging film may be printed.
  • the cylindrical packaging film in the present invention can be obtained by a method conventionally adopted as a method for manufacturing a cylindrical packaging film to be provided in a filled package. Specifically, a strip-shaped packaging film is rolled into a tubular shape so that both side edges extending in the longitudinal direction are overlapped to form a tubular film, and then the both side edges of the tubular film are vertically sealed. , can form a tubular packaging film.
  • a method for producing a strip-shaped packaging film for forming a cylindrical packaging film is not particularly limited.
  • a sheet-shaped or tubular extruded film is produced by extrusion molding, and if necessary, it is stretched to give it heat shrinkability.
  • a two-ply strip-shaped packaging film can be obtained, and if necessary, by cutting in the longitudinal direction, a strip-shaped packaging film having a desired width can be produced.
  • the tubular packaging film is a laminated film
  • a strip-shaped packaging film laminated by coextrusion molding or extrusion lamination may be produced, or a plurality of films may be bonded together with an adhesive such as a urethane adhesive.
  • a laminated strip of packaging film may be produced.
  • the cylindrical packaging film is to be printed, the obtained belt-shaped packaging film may be printed.
  • a cylindrical packaging film provided in a filling package according to an embodiment of the present invention has a vertical sealing portion extending in the longitudinal direction.
  • the longitudinal seal portion is conventionally provided for the same purpose as the longitudinal seal portion extending in the longitudinal direction provided on a cylindrical packaging film provided in a filling package. That is, a band-shaped packaging film is rolled into a tubular shape so that both side edges extending in the longitudinal direction are overlapped to form a tubular film, and then the both side edges of the tubular film are subjected to high-frequency dielectric heating and ultrasonic heating.
  • Cylindrical packaging is continuously sealed (bonded) in the longitudinal direction (vertical direction) according to conventional methods such as welding by heating, laser heating, resistance heating, etc., bonding with adhesives (including heat sealing), etc.
  • a film is formed.
  • the vertical seal portion is provided over the entire length of the tubular packaging film in the longitudinal direction, so that the contents filled and enclosed in the tubular packaging film can be preserved in a sealed state.
  • the width of the vertical seal portion extending in the longitudinal direction provided on the tubular packaging film can be appropriately determined.
  • a filling package according to an embodiment of the present invention comprises a tubular packaging film having longitudinally extending longitudinal seal portions and having both ends in the longitudinal direction converged. That is, in the filling package according to one embodiment of the present invention, the cylindrical packaging film is filled with contents such as processed foods containing lipids, and then both ends in the longitudinal direction of the cylindrical packaging film are bundled. It is formed by and can store the contents in a hermetically sealed state.
  • the bundling of both ends in the longitudinal direction of the tubular packaging film is conventionally performed for the tubular packaging film provided in the filling packaging body. wire clips or transverse sealing films or other means of convergence can be employed.
  • contents filled and enclosed in the tubular packaging film provided in the filling package according to one embodiment of the present invention are particularly limited. are similar to those described above, and may include, for example, lipids.
  • the filled package according to one embodiment of the present invention is provided with a longitudinally extending longitudinally sealed portion, and a cylindrical packaging film having both ends in the longitudinal direction converged is filled with contents and sealed.
  • a filling package comprising: the packaging film comprising the resin film according to the present invention.
  • the packaging film may be made of the resin film according to the present invention.
  • the shape and size of the filled package are usually determined according to the shape and size of the tubular packaging film.
  • a method for manufacturing a filled package according to an embodiment of the present invention includes a cylindrical packaging film having a vertical seal portion extending in the longitudinal direction and having both ends in the longitudinal direction converged. It is a filled package in which an object is filled and enclosed, and the packaging film is not particularly limited as long as a filled package containing the resin film according to the present invention can be obtained.
  • the manufacturing method includes, for example, a tubular film forming step of forming a tubular film by winding a strip-shaped packaging film into a tubular shape so that both side edges extending in the longitudinal direction overlap; the both side edges of the tubular film.
  • a strip-shaped packaging film is rolled into a tubular shape so that both side edges extending in the longitudinal direction are overlapped to form a tubular film.
  • a strip-shaped packaging film can be produced according to the method described above. For example, both side edges may overlap along the outer peripheral surface perpendicular to the longitudinal direction of the strip-shaped packaging film, and if desired, both side edges may rise from the outer peripheral surface and overlap to overlap the cylindrical film. may be formed.
  • the side edges of the tubular film are longitudinally sealed to form a tubular packaging film having longitudinally extending longitudinally sealed portions. That is, the longitudinally extending longitudinally-extending sealing portions are formed by continuously longitudinally sealing both longitudinally overlapping edge portions of a tubular film formed from a belt-like packaging film with a predetermined longitudinally extending width. do.
  • the cylindrical packaging film contains polyvinylidene chloride resin, which is a polar resin, vertical sealing by high-frequency dielectric heating is preferable from the viewpoint of efficiency of vertical sealing and ease of adjustment of sealing strength.
  • the cylindrical film is passed between the seal electrode and the ground electrode of the high-frequency dielectric heating device while running along both side edges extending in the longitudinal direction. By supplying high-frequency power between these two electrodes, a continuous longitudinal seal portion is formed by high-frequency welding on both overlapping side edges of the tubular film.
  • the cylindrical packaging film obtained by the vertical sealing process is filled with contents. That is, while the tubular packaging film is running from top to bottom at a predetermined speed, the contents are continuously supplied to the opening of the tubular packaging film from a nozzle of a filling device equipped with a pump and a nozzle. to fill.
  • the filling device, the mechanism for running and guiding the cylindrical packaging film, etc. can be appropriately selected from those known per se, and the running speed of the cylindrical packaging film, the filling speed of the contents, etc. are within the usual range. can be selected as appropriate.
  • the end bundling step as a method for bundling the edges, conventionally, a method of bundling both ends in the longitudinal direction of a cylindrical packaging film provided in a filling package, for example, a metal clip such as an aluminum wire clip, is used. wire clips or transverse sealing films or other means of convergence can be employed.
  • Example 1 Manufacture of base material film
  • the obtained vinylidene chloride-based resin composition is melt-extruded using an extruder screw with a diameter of 40 mm, followed by inflation of 2.4 times in MD (longitudinal direction) and 4.0 times in TD (lateral direction). Biaxial stretching was performed, and the insides of the annular films were overlapped to obtain a strip-shaped vinylidene chloride resin film a having a thickness of 40 ⁇ m (thickness of two films having a thickness of 20 ⁇ m), which was used as a base material film.
  • the vinylidene chloride resin film a was cut to a width of 65 mm, subjected to high-frequency dielectric heating sealing and molded into a cylindrical shape, while contents containing lipids (52% by mass of pork, 21.5% by mass of ice water, 20% by mass of pork fat, An automatic filling and packaging machine (Kureha company, product name: KAP3000 automatic filling and packaging machine), while converging the ends of the film, the film is clipped with vinylidene chloride resin tape and sealed with an ultrasonic seal to form a filling package (hereinafter referred to as Also referred to as “filled package before pressure heat sterilization”).
  • the folding width half the length of the circumference
  • the cut length the content is extracted from the cylindrical package
  • the cylindrical base film is flattened
  • the conditions were adjusted so that the length when measured in the longitudinal direction was 190 mm and the mass was 35 g.
  • the filled package was subjected to pressure heat sterilization (retort treatment) in hot water of 120°C at 0.2 MPa for 10 minutes to obtain a filled package after pressure heat sterilization.
  • Example 2 In Example 1, except that an ionomer resin (manufactured by Dow, trade name: Surlyn 1707, sodium ion neutralized ethylene-methacrylic acid copolymer, density 0.95 g/cm 3 ) was used instead of ultra-low density polyethylene.
  • film b was obtained as a base material film, and further, filled packages before and after pressure and heat sterilization were obtained.
  • Example 1 film c was obtained in the same manner as in Example 1 except that ultra-low density polyethylene was not added, and used as a base material film. Obtained.
  • the blended resin refers to the ultra-low density polyethylene in Example 1 and the ionomer resin in Example 2.
  • Example 1 in which ultra-low density polyethylene is added, has a smaller rate of change in oxygen gas permeability than Comparative Example 1.
  • Example 2 in which the ionomer resin was added, the oxygen gas permeability after retort treatment (B) was lower than the oxygen gas permeability before retort treatment (A), and the barrier property was improved.
  • B oxygen gas permeability after retort treatment
  • A oxygen gas permeability before retort treatment
  • the barrier property was improved.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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Abstract

Provided are: a vinylidene chloride-based resin film which, when a content is filled and packaged in the vinylidene chloride-based resin film, makes it possible to eliminate the shortage of a color retention period for the content before and after a retorting treatment; and a filled/packaged product which is produced using the vinylidene chloride-based resin film.　The vinylidene chloride-based resin film according to the present invention comprises a vinylidene chloride-based resin, and is configured such that, when a content containing 20% by mass of a lipid is filled and packed in the vinylidene chloride-based resin film which is bundled at both length-direction ends thereof so as to form a tubular shape to thereby produce a filled/packaged product, then the filled/packaged product is subjected to sterilization by pressurization and heating at 0.2 MPa in hot water having a temperature of 120°C for 10 minutes, the oxygen transmission rate of the vinylidene chloride-based resin film before the sterilization by pressurization and heating in terms of the thickness of 40 μm is defined as A (cm3/m2･day･atm), and the oxygen transmission rate of the vinylidene chloride-based resin film after the sterilization by pressurization and heating in terms of the thickness of 40 μm is defined as B (cm3/m2･day･atm), the rate of change in the oxygen transmission rate which is determined in accordance with the formula: (B-A)/A×100 is 35.0% or less.

Description

塩化ビニリデン系樹脂フィルム、及びそれを用いた充填包装体Vinylidene chloride resin film and filling package using the same
　本発明は、塩化ビニリデン系樹脂フィルム、及びそれを用いた充填包装体に関する。 The present invention relates to a vinylidene chloride resin film and a filling package using the same.
　畜肉や魚肉等の内容物を筒状フィルムに充填し、両端を結紮して製造される包装体は、帯状のフィルムを筒状に巻き側縁部を重ね縦シールして筒状フィルムを形成する機構と、筒状フィルムに内容物を充填する機構と、内容物が充填された筒状フィルムの両端を結紮する機構とを備える包装体製造装置で製造でき、包装体を製造後、内容物の殺菌や調理を目的としたレトルト処理が行われることが知られている。レトルト処理後には、内容物の味や色の保持が求められるため、上記包装体に用いられるフィルムには、塩化ビニリデン系樹脂等の酸素ガスバリア性が優れる材料が用いられている（例えば、特許文献１参照）。 A package manufactured by filling a tubular film with a content such as livestock meat or fish meat and tying both ends of the tubular film is formed by stacking the strip-shaped film into a tubular shape and stacking the side edges and longitudinally sealing to form a tubular film. a mechanism, a mechanism for filling a tubular film with a content, and a mechanism for ligating both ends of the tubular film filled with the content, and after producing the package, the content is It is known that retort processing is performed for the purpose of sterilization and cooking. Since it is necessary to retain the taste and color of the contents after retort processing, the film used for the package is made of a material with excellent oxygen gas barrier properties, such as a vinylidene chloride resin (see, for example, Patent Documents 1).
特開２００５－２３１６３９号公報JP-A-2005-231639
　従来は、上記包装体に用いられるレトルト処理前の塩化ビニリデン系樹脂フィルムの酸素ガス透過度が小さいほど、内容物の味や色の保持期間が長くなると考えられていた。しかし、塩化ビニリデン系樹脂フィルムのレトルト処理後の酸素ガス透過度がレトルト処理前よりも大きくなる場合があり、レトルト処理前の酸素ガス透過度が小さくても、内容物の味や色の保持期間が不十分となることがあった。 Conventionally, it was thought that the lower the oxygen gas permeability of the vinylidene chloride resin film before retort treatment used in the package, the longer the taste and color of the contents would be retained. However, the oxygen gas permeability of the vinylidene chloride resin film after retort treatment may be higher than that before retort treatment. was sometimes insufficient.
　本発明は、上記の問題に鑑みてなされたものであり、その目的は、内容物を充填包装したとき、レトルト処理前後において、該内容物の色の保持期間不足を解消する塩化ビニリデン系樹脂フィルム、及びそれを用いた充填包装体を提供することである。 The present invention has been made in view of the above problems, and an object of the present invention is to provide a vinylidene chloride resin film that eliminates the insufficient retention period of the color of the contents before and after retort processing when the contents are filled and packaged. , and to provide a filling package using the same.
　本発明者らは、特定のレトルト処理前後において、塩化ビニリデン系樹脂フィルムの酸素ガス透過度の変化率を特定の範囲に制御することにより、上記課題を解決することができることを見出し、本発明を完成するに至った。 The present inventors have found that the above problems can be solved by controlling the rate of change in the oxygen gas permeability of a vinylidene chloride resin film before and after a specific retort treatment within a specific range, and have completed the present invention. Completed.
　本発明に係る塩化ビニリデン系樹脂フィルムは、塩化ビニリデン系樹脂を含有し、長手方向の両端部が集束された筒状の前記塩化ビニリデン系樹脂フィルムに、２０質量％の脂質を含む内容物が充填されて封入されてなる充填包装体を、０．２ＭＰａにおいて１２０℃の熱水中で１０分間の加圧加熱殺菌に供し、前記加圧加熱殺菌前の前記塩化ビニリデン系樹脂フィルムの厚さ４０μｍ換算の酸素ガス透過度をＡ（ｃｍ３／ｍ２・ｄａｙ・ａｔｍ）とし、前記加圧加熱殺菌後の前記塩化ビニリデン系樹脂フィルムの厚さ４０μｍ換算の酸素ガス透過度をＢ（ｃｍ３／ｍ２・ｄａｙ・ａｔｍ）としたときに、（Ｂ－Ａ）／Ａ×１００で求められる酸素ガス透過度の変化率が３５．０％以下である。 The vinylidene chloride-based resin film according to the present invention contains a vinylidene chloride-based resin, and the cylindrical vinylidene chloride-based resin film having both ends in the longitudinal direction is filled with a content containing 20% by mass of lipid. The filled package body is subjected to pressure heat sterilization in hot water of 120 ° C. at 0.2 MPa for 10 minutes, and the thickness of the vinylidene chloride resin film before the pressure heat sterilization is converted to 40 μm. Let A (cm 3 /m 2 ·day · atm) be the oxygen gas permeability of , and B (cm 3 /m 2 ·day·atm), the rate of change in oxygen gas permeability obtained by (B−A)/A×100 is 35.0% or less.
　上記塩化ビニリデン系樹脂フィルムは、前記酸素ガス透過度の変化率が１．５％以下であることが好ましい。 The vinylidene chloride resin film preferably has a rate of change of oxygen gas permeability of 1.5% or less.
　上記塩化ビニリデン系樹脂フィルムは、前記酸素ガス透過度の変化率が－１０．０％以上であることが好ましい。 The vinylidene chloride resin film preferably has a rate of change of oxygen gas permeability of -10.0% or more.
　上記塩化ビニリデン系樹脂フィルムは、前記酸素ガス透過度の変化率が－８．０％以上であることが好ましい。 The vinylidene chloride resin film preferably has a rate of change of oxygen gas permeability of -8.0% or more.
　上記塩化ビニリデン系樹脂フィルムは、更に、塩化ビニリデン系樹脂を除く樹脂を含有することが好ましい。 The vinylidene chloride resin film preferably further contains a resin other than the vinylidene chloride resin.
　上記塩化ビニリデン系樹脂フィルムにおいて、前記塩化ビニリデン系樹脂を除く樹脂が、超低密度ポリエチレン及びアイオノマー樹脂からなる群より選ばれる少なくとも１種の樹脂を含有することが好ましい。 In the vinylidene chloride-based resin film, the resin other than the vinylidene chloride-based resin preferably contains at least one resin selected from the group consisting of ultra-low density polyethylene and ionomer resins.
　前記塩化ビニリデン系樹脂フィルムにおいて、前記塩化ビニリデン系樹脂を除く樹脂の含有率が０．５質量％以上３質量％未満であることが好ましい。 In the vinylidene chloride-based resin film, it is preferable that the resin content excluding the vinylidene chloride-based resin is 0.5% by mass or more and less than 3% by mass.
　上記塩化ビニリデン系樹脂フィルムにおいて、前記塩化ビニリデン系樹脂が、塩化ビニリデン６０質量％以上９５質量％以下と塩化ビニル５質量％以上４０質量％以下との共重合体であることが好ましい。 In the vinylidene chloride resin film, the vinylidene chloride resin is preferably a copolymer of 60% by mass or more and 95% by mass or less of vinylidene chloride and 5% by mass or more and 40% by mass or less of vinyl chloride.
　本発明に係る充填包装体は、上記塩化ビニリデン系樹脂フィルムと内容物とを備える。 A filling package according to the present invention comprises the vinylidene chloride resin film and contents.
　本発明によれば、内容物を充填包装したとき、レトルト処理前後において、該内容物の色の保持期間不足を解消する塩化ビニリデン系樹脂フィルム、及びそれを用いた充填包装体を提供することができる。 ADVANTAGE OF THE INVENTION According to the present invention, it is possible to provide a vinylidene chloride-based resin film and a filling package using the same, which eliminates the insufficient retention period of the color of the contents before and after the retort treatment when the contents are filled and packaged. can.
＜塩化ビニリデン系樹脂フィルム＞
　本発明に係る塩化ビニリデン系樹脂フィルムは、塩化ビニリデン系樹脂を含有する塩化ビニリデン系樹脂フィルムであって、長手方向の両端部が集束された筒状の前記塩化ビニリデン系樹脂フィルムに、２０質量％の脂質を含む内容物が充填されて封入されてなる充填包装体を、０．２ＭＰａにおいて１２０℃の熱水中で１０分間の加圧加熱殺菌に供し、前記加圧加熱殺菌前の前記塩化ビニリデン系樹脂フィルムの厚さ４０μｍ換算の酸素ガス透過度をＡ（ｃｍ３／ｍ２・ｄａｙ・ａｔｍ）とし、前記加圧加熱殺菌後の前記塩化ビニリデン系樹脂フィルムの厚さ４０μｍ換算の酸素ガス透過度をＢ（ｃｍ３／ｍ２・ｄａｙ・ａｔｍ）としたときに、（Ｂ－Ａ）／Ａ×１００で求められる酸素ガス透過度の変化率は３５．０％以下であり、好ましくは３０．０％以下、より好ましくは２０．０％以下、更により好ましくは２．０％以下、特に好ましくは１．５％以下である。前記酸素ガス透過度の変化率が３５．０％以下であると、内容物の色の保持期間不足が解消されやすい。前記酸素ガス透過度の変化率の下限値は特に限定されず、－１０．０％以上でよく、－８．０％以上でもよい。なお、酸素ガス透過度の変化率を測定する際に用いられる脂質としては、特に限定されず、例えば、豚脂肪が用いられる。 <Vinylidene chloride resin film>
The vinylidene chloride-based resin film according to the present invention is a vinylidene chloride-based resin film containing a vinylidene chloride-based resin, wherein 20% by mass of The filled package, which is filled and enclosed with the content containing the lipid, is subjected to pressure and heat sterilization in hot water of 120 ° C. at 0.2 MPa for 10 minutes, and the vinylidene chloride before the pressure and heat sterilization. Let A (cm 3 /m 2 · day · atm) be the oxygen gas permeability in terms of the thickness of 40 μm of the resin film, and the oxygen gas permeability in terms of the thickness of 40 μm of the vinylidene chloride resin film after the pressure and heat sterilization. When the degree is B (cm 3 /m 2 · day · atm), the rate of change in oxygen gas permeability obtained by (B - A) / A x 100 is 35.0% or less, preferably 30 0% or less, more preferably 20.0% or less, even more preferably 2.0% or less, and particularly preferably 1.5% or less. When the rate of change in the oxygen gas permeability is 35.0% or less, it is easy to eliminate the insufficient retention period of the color of the contents. The lower limit of the rate of change in oxygen gas permeability is not particularly limited, and may be −10.0% or more, or −8.0% or more. The lipid used for measuring the rate of change in oxygen gas permeability is not particularly limited, and pork fat is used, for example.
　上記塩化ビニリデン系樹脂フィルムは、更に、塩化ビニリデン系樹脂を除く樹脂を含有してもよい。上記塩化ビニリデン系樹脂を除く樹脂は、超低密度ポリエチレン及びアイオノマー樹脂からなる群より選ばれる少なくとも１種の樹脂を含有することができる。 The vinylidene chloride resin film may further contain a resin other than the vinylidene chloride resin. The resin other than the vinylidene chloride resin can contain at least one resin selected from the group consisting of ultra-low density polyethylene and ionomer resin.
〔ポリ塩化ビニリデン系樹脂〕
　ポリ塩化ビニリデン系樹脂（以下、「ＰＶＤＣ」ということがある。）は、塩化ビニリデンのホモ重合体でもよく、塩化ビニリデン６０～９８質量％と、塩化ビニリデンと共重合可能な他の単量体２～４０質量％との共重合体でもよい。塩化ビニリデンと共重合可能な他の単量体としては、例えば、塩化ビニル；アクリル酸メチル、アクリル酸エチル、アクリル酸ブチル、アクリル酸ラウリル等のアクリル酸アルキルエステル（アルキル基の炭素数１～１８）；メタクリル酸メチル、メタクリル酸ブチル、メタクリル酸ラウリル等のメタクリル酸アルキルエステル（アルキル基の炭素数１～１８）；アクリロニトリル等のシアン化ビニル；スチレン等の芳香族ビニル；酢酸ビニル等の炭素数１～１８の脂肪族カルボン酸のビニルエステル；炭素数１～１８のアルキルビニルエーテル；アクリル酸、メタクリル酸、マレイン酸、フマル酸等のビニル重合性不飽和カルボン酸；マレイン酸、フマル酸、イタコン酸等のビニル重合性不飽和カルボン酸のアルキルエステル（部分エステルを含み、アルキル基の炭素数１～１８）等が挙げられる。より好ましくは塩化ビニル、アクリル酸メチル、及びアクリル酸ラウリルから選ばれる少なくとも１種である。塩化ビニリデンと共重合可能な他の単量体は、１種を単独で用いても、２種以上を組み合わせて用いてもよい。他の単量体の共重合割合は、より好ましくは３～３５質量％、更に好ましくは３～２９質量％、特に好ましくは４～２２質量％の範囲である。他の単量体の共重合割合が３質量％以上であると溶融加工性が低下しにくく、他方、他の単量体の共重合割合が３５質量％以下であるとガスバリア性が低下しにくい。また、溶融加工性を向上させるために２種以上のＰＶＤＣを混合してもよい。ＰＶＤＣは、懸濁重合法、乳化重合法、溶液重合法等の任意の重合法により合成することができる。ＰＶＤＣは、１種を単独で用いても、２種以上を組み合わせて用いてもよい。 [Polyvinylidene chloride resin]
Polyvinylidene chloride-based resin (hereinafter sometimes referred to as "PVDC") may be a homopolymer of vinylidene chloride, and contains 60 to 98% by mass of vinylidene chloride and another monomer 2 copolymerizable with vinylidene chloride. It may be a copolymer with up to 40% by mass. Other monomers copolymerizable with vinylidene chloride include, for example, vinyl chloride; alkyl acrylate esters such as methyl acrylate, ethyl acrylate, butyl acrylate, and lauryl acrylate (wherein the alkyl group has 1 to 18 carbon atoms); ); methacrylic acid alkyl esters such as methyl methacrylate, butyl methacrylate, and lauryl methacrylate (alkyl group has 1 to 18 carbon atoms); vinyl cyanide such as acrylonitrile; aromatic vinyl such as styrene; carbon number such as vinyl acetate vinyl esters of aliphatic carboxylic acids of 1 to 18; alkyl vinyl ethers of 1 to 18 carbon atoms; vinyl polymerizable unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid and fumaric acid; maleic acid, fumaric acid and itaconic acid and alkyl esters of vinyl polymerizable unsaturated carboxylic acids (including partial esters, the alkyl group having 1 to 18 carbon atoms). More preferably, it is at least one selected from vinyl chloride, methyl acrylate, and lauryl acrylate. Other monomers copolymerizable with vinylidene chloride may be used alone or in combination of two or more. The copolymerization ratio of other monomers is more preferably 3 to 35% by mass, still more preferably 3 to 29% by mass, and particularly preferably 4 to 22% by mass. When the copolymerization ratio of other monomers is 3% by mass or more, the melt processability is less likely to decrease, and on the other hand, when the copolymerization ratio of other monomers is 35% by mass or less, gas barrier properties are less likely to decrease. . Moreover, two or more kinds of PVDC may be mixed in order to improve melt processability. PVDC can be synthesized by any polymerization method such as suspension polymerization method, emulsion polymerization method and solution polymerization method. PVDC may be used individually by 1 type, or may be used in combination of 2 or more type.
　特に、塩化ビニリデンと共重合可能な他の単量体が塩化ビニルである場合、溶融加工性、ガスバリア性等の観点から、ＰＶＤＣは、塩化ビニリデン６０質量％以上９５質量％以下と塩化ビニル５質量％以上４０質量％以下との共重合体であることが好ましく、塩化ビニリデン６３質量％以上９０質量％以下と塩化ビニル１０質量％以上３７質量％以下との共重合体であることがより好ましく、塩化ビニリデン６６質量％以上８５質量％以下と塩化ビニル１５質量％以上３４質量％以下との共重合体であることが更により好ましく、塩化ビニリデン６９質量％以上８３質量％以下と塩化ビニル１７質量％以上３１質量％以下との共重合体であることが特に好ましい。 In particular, when the other monomer copolymerizable with vinylidene chloride is vinyl chloride, from the viewpoint of melt processability, gas barrier properties, etc., PVDC contains 60% by mass or more and 95% by mass or less of vinylidene chloride and 5% by mass of vinyl chloride. % or more and 40 mass% or less, more preferably a copolymer of 63 mass% or more and 90 mass% or less of vinylidene chloride and 10 mass% or more and 37 mass% or less of vinyl chloride, Even more preferably, it is a copolymer of 66 to 85% by mass of vinylidene chloride and 15 to 34% by mass of vinyl chloride, and 69 to 83% by mass of vinylidene chloride and 17% by mass of vinyl chloride. It is particularly preferable to be a copolymer with more than 31% by mass or less.
〔超低密度ポリエチレン〕
　超低密度ポリエチレンとは、密度が０．９１５ｇ／ｃｍ３以下のポリエチレンであって、例えば、ブテン、ヘキセン、オクテン等のＣ４～Ｃ８のα－オレフィンコモノマーを有するエチレン－α－オレフィンコポリマーを表す。超低密度ポリエチレンは、１種を単独で用いても、２種以上を組み合わせて用いてもよい。 [Ultra-low density polyethylene]
Ultra-low density polyethylene refers to polyethylene having a density of 0.915 g/cm 3 or less, for example ethylene-α-olefin copolymers with C4-C8 α-olefin comonomers such as butene, hexene, octene, and the like. Ultra-low density polyethylene may be used singly or in combination of two or more.
〔アイオノマー樹脂〕
　アイオノマー樹脂とは、エチレン・不飽和カルボン酸系共重合体（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。アイオノマー樹脂は、１種を単独で用いても、２種以上を組み合わせて用いてもよい。 [Ionomer resin]
The ionomer resin means a compound in which at least part of the acidic groups of the ethylene/unsaturated carboxylic acid copolymer (base polymer) are neutralized with metal ions. An ionomer resin may be used individually by 1 type, or may be used in combination of 2 or more type.
　不飽和カルボン酸に由来する構成単位としては、例えば、アクリル酸、メタクリル酸、フマル酸、又はマレイン酸等に由来する構成単位が挙げられる。 Structural units derived from unsaturated carboxylic acids include, for example, structural units derived from acrylic acid, methacrylic acid, fumaric acid, or maleic acid.
　アイオノマー樹脂を形成するエチレン・不飽和カルボン酸系共重合体（ベースポリマー）は、少なくとも、エチレンと、不飽和カルボン酸と、の共重合体であり、エチレンに由来する構成単位と、不飽和カルボン酸に由来する構成単位と、を有している。 The ethylene/unsaturated carboxylic acid-based copolymer (base polymer) forming the ionomer resin is at least a copolymer of ethylene and an unsaturated carboxylic acid. and a structural unit derived from an acid.
　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、（メタ）アクリル酸であることが好ましい。 Among these, (meth)acrylic acid is preferable as the structural unit derived from unsaturated carboxylic acid.
　エチレン・不飽和カルボン酸系共重合体は、エチレンに由来する構成単位と、不飽和カルボン酸に由来する構成単位とに加えて、エチレン及び不飽和カルボン酸以外のモノマーに由来する構成単位を含んでいてもよい。 The ethylene/unsaturated carboxylic acid copolymer contains structural units derived from monomers other than ethylene and unsaturated carboxylic acids, in addition to structural units derived from ethylene and structural units derived from unsaturated carboxylic acids. You can stay.
　エチレン・不飽和カルボン酸系共重合体（ベースポリマー）が有する酸性基の中和に用いられる金属イオンとしては、特に制限はなく、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が好ましく、特にナトリウムが好ましい。 The metal ion used for neutralizing the acidic group of the ethylene/unsaturated carboxylic acid copolymer (base polymer) is not particularly limited, and alkali metal ions such as lithium, sodium, potassium, rubidium and cesium are preferred. , especially sodium.
　なお、本明細書において、「（メタ）アクリル」とは、「アクリル」及び「メタクリル」の少なくとも一方を意味する。 In this specification, "(meth)acryl" means at least one of "acryl" and "methacryl".
〔他の樹脂〕
　本発明に係る塩化ビニリデン系樹脂フィルムは、種々の特性及び／又は成形加工性の改良を目的として、必要に応じて、ポリ塩化ビニリデン系樹脂、超低密度ポリエチレン、及びアイオノマー樹脂以外の他の樹脂を含有してもよい。他の樹脂としては、特に限定されず、例えば、ポリエチレンワックス、酸化ポリエチレンワックス、低密度ポリエチレン、高密度ポリエチレン、エチレン－酢酸ビニル共重合体（ＥＶＡ）、エチレン―アクリル酸共重合体（ＥＡＡ）、エチレン－メタクリル酸共重合体（ＥＭＡＡ）、エチレン－メチルアクリレート共重合体（ＥＭＡ）、エチレン－エチルアクリレート共重合体（ＥＥＡ）、エチレンーブチルアクリレート共重合体（ＥＢＡ）等が挙げられる。他の樹脂は、１種を単独で用いても、２種以上を組み合わせて用いてもよい。 [Other resins]
The vinylidene chloride-based resin film according to the present invention, for the purpose of improving various properties and / or molding processability, if necessary, other resins other than polyvinylidene chloride-based resin, ultra-low density polyethylene, and ionomer resin may contain. Other resins are not particularly limited, and examples include polyethylene wax, oxidized polyethylene wax, low-density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymer (EVA), ethylene-acrylic acid copolymer (EAA), Ethylene-methacrylic acid copolymer (EMAA), ethylene-methyl acrylate copolymer (EMA), ethylene-ethyl acrylate copolymer (EEA), ethylene-butyl acrylate copolymer (EBA) and the like can be mentioned. Other resin may be used individually by 1 type, or may be used in combination of 2 or more type.
〔樹脂の含有率〕
　本発明に係る塩化ビニリデン系樹脂フィルムにおいて、塩化ビニリデン系樹脂を除く樹脂の含有率は、０．５質量％以上３．０質量％未満が好ましく、１．０質量％以上３．０質量％未満がより好ましく、１．０質量％以上２．５質量％以下が特に好ましい。上記含有率が０．５質量％以上であると加圧加熱殺菌（レトルト処理）後の内容物の退色の抑制効果が十分となりやすい。上記含有率が３．０質量％未満であるとフィルムが白濁しにくい。また、上記含有率を変えることによって、酸素ガス透過度の変化率を調整することができる。一方、本発明に係る塩化ビニリデン系樹脂フィルムにおいて、塩化ビニリデン系樹脂の含有率は、９７．０質量％超９９．５質量％以下が好ましく、９７．０質量％超９９．０質量％以下がより好ましく、９７．５質量％以上９９．０質量％以下が特に好ましい。 [Resin content]
In the vinylidene chloride-based resin film according to the present invention, the content of the resin other than the vinylidene chloride-based resin is preferably 0.5% by mass or more and less than 3.0% by mass, and 1.0% by mass or more and less than 3.0% by mass. is more preferable, and 1.0% by mass or more and 2.5% by mass or less is particularly preferable. When the content is 0.5% by mass or more, the effect of suppressing discoloration of contents after pressurized heat sterilization (retort treatment) tends to be sufficient. When the content is less than 3.0% by mass, the film is less likely to become cloudy. In addition, the rate of change of the oxygen gas permeability can be adjusted by changing the content. On the other hand, in the vinylidene chloride resin film according to the present invention, the content of the vinylidene chloride resin is preferably more than 97.0% by mass and 99.5% by mass or less, and more than 97.0% by mass and 99.0% by mass or less. More preferably, 97.5% by mass or more and 99.0% by mass or less is particularly preferable.
〔添加剤〕
　本発明に係る塩化ビニリデン系樹脂フィルムには、必要に応じて、従来、充填包装体に備えられる筒状の包装フィルムに対し、種々の特性や成形加工性の改良を目的として添加される熱安定剤、可塑剤、加工助剤、着色剤、紫外線吸収剤、ｐＨ調整剤、分散助剤等の各種添加剤を含有させることができる。例えば、熱安定剤としては、エポキシ化植物油、エポキシ化動物油、エポキシ化脂肪酸エステル、エポキシ樹脂プレポリマー等のエポキシ化合物；エポキシ基含有樹脂等が挙げられ、好ましくはエポキシ化植物油である。添加剤の種類及び添加量は、従来、充填包装体に備えられる筒状の包装フィルムにおいて、使用される各種添加剤におけると同様に選択することができる。添加剤は、１種を単独で用いても、２種以上を組み合わせて用いてもよい。また、添加剤は、その使用量の一部又は全部をＰＶＤＣの重合工程で単量体組成物中に含有させてもよいし、重合後にＰＶＤＣにブレンドしてもよい。 〔Additive〕
In the vinylidene chloride resin film according to the present invention, if necessary, a heat-stabilizing agent is added for the purpose of improving various properties and molding processability of cylindrical packaging films conventionally provided in filled packaging bodies. Various additives such as agents, plasticizers, processing aids, colorants, ultraviolet absorbers, pH adjusters, and dispersing aids can be incorporated. For example, heat stabilizers include epoxy compounds such as epoxidized vegetable oils, epoxidized animal oils, epoxidized fatty acid esters, and epoxy resin prepolymers; epoxy group-containing resins; and the like, preferably epoxidized vegetable oils. The types and amounts of additives to be added can be selected in the same manner as in the various additives used in conventional cylindrical packaging films provided in filled packages. An additive may be used individually by 1 type, or may be used in combination of 2 or more type. A part or all of the additive may be contained in the monomer composition during the PVDC polymerization step, or may be blended into the PVDC after the polymerization.
＜充填包装体及びその製造方法＞
　本発明に係る充填包装体は、本発明に係る塩化ビニリデン系樹脂フィルムと内容物とを備える。上記充填包装体によれば、レトルト処理前後において、上記内容物の色の保持期間不足を解消することができる。 <Filled package and its manufacturing method>
A filling package according to the present invention comprises the vinylidene chloride resin film according to the present invention and contents. According to the filling package, it is possible to solve the problem of insufficient retention period of the color of the contents before and after the retort treatment.
　上記内容物としては、特に限定されず、脂質を含んでもよく、例えば、ソーセージ、チーズ、バター、ハンバーグ等の、固体状又はペースト状の加工食品等、従来、充填包装体に充填される内容物を用いることができる。内容物の組成や形状は適宜選択することができる。特に好ましい内容物としては、畜肉ソーセージや魚肉ソーセージ等が挙げられる。 The content is not particularly limited, and may contain lipids. For example, sausage, cheese, butter, hamburger, etc., solid or pasty processed foods, etc. Contents that are conventionally filled in a filling package. can be used. The composition and shape of the content can be selected as appropriate. Particularly preferred contents include livestock sausages and fish sausages.
　本発明に係る充填包装体の製造方法としては、本発明に係る塩化ビニリデン系樹脂フィルムにより内容物が充填包装されて、本発明に係る充填包装体が得られる限り、特に限定されない。 The method for manufacturing the filled package according to the present invention is not particularly limited as long as the content is filled and packaged with the vinylidene chloride resin film according to the present invention to obtain the filled package according to the present invention.
　以下、本発明の一実施形態に係る充填包装体及びその製造方法について詳述する。 A filling package according to an embodiment of the present invention and a method for manufacturing the same will be described in detail below.
１．筒状の包装フィルム
　本発明の一実施形態に係る充填包装体は、筒状の包装フィルム及び内容物を備える充填包装体であって、該筒状の包装フィルムは、長手方向に延びる縦シール部を備え、長手方向の両端部が集束されたものである。上記包装フィルムは、本発明に係る塩化ビニリデン系樹脂フィルムを含む。上記包装フィルムは、本発明に係る塩化ビニリデン系樹脂フィルムからなるものでもよい。 1. Cylindrical packaging film A filling package according to an embodiment of the present invention is a filling package comprising a tubular packaging film and a content, wherein the tubular packaging film has a vertical sealing portion extending in the longitudinal direction. with both longitudinal ends converging. The packaging film includes the vinylidene chloride resin film according to the present invention. The packaging film may be made of the vinylidene chloride resin film according to the present invention.
〔筒状の包装フィルムの大きさ及び厚み〕
　筒状の包装フィルムの大きさ及び厚みは、特に限定されず、充填される内容物の大きさに応じて定められる。筒状の包装フィルムの周長は、例えば、１５～４００ｍｍ、多くの場合３０～３００ｍｍ、広く採用されるのは４０～２００ｍｍの範囲であり、筒状の包装フィルムの長手方向の長さは、例えば、５０～４００ｍｍ、多くの場合７０～３００ｍｍ、広く採用されるのは８０～２５０ｍｍの範囲である。また、筒状の包装フィルムの厚みは、充填される内容物に応じたフィルムの強度やバリア性等を勘案して定められるが、例えば、１５～３００μｍ、多くの場合１８～２００μｍ、広く採用されるのは２０～１５０μｍの範囲である。 [Size and thickness of cylindrical packaging film]
The size and thickness of the cylindrical packaging film are not particularly limited, and are determined according to the size of the contents to be filled. The peripheral length of the tubular packaging film is, for example, 15 to 400 mm, often 30 to 300 mm, and widely adopted is in the range of 40 to 200 mm, and the longitudinal length of the tubular packaging film is For example, the range is 50-400 mm, often 70-300 mm, and the widely adopted range is 80-250 mm. In addition, the thickness of the cylindrical packaging film is determined in consideration of the strength and barrier properties of the film according to the content to be filled. is in the range of 20-150 μm.
　筒状の包装フィルムとしては、熱収縮性フィルム（一軸延伸フィルム又は二軸延伸フィルム）を使用することもできる。更に、筒状の包装フィルムの強度の増大、ガスバリア性の改良、耐熱性の改良、収縮性の調整等のために、積層フィルムを使用することもでき、例えば、本発明に係る塩化ビニリデン系樹脂フィルムと、ポリエチレンテレフタレートフィルム又はポリプロピレンフィルム等の他のフィルムとの積層フィルムを使用することができる。また、筒状の包装フィルムは、印刷が施されたものでもよい。 A heat-shrinkable film (uniaxially stretched film or biaxially stretched film) can also be used as the cylindrical packaging film. Furthermore, a laminated film can be used to increase the strength of the cylindrical packaging film, improve gas barrier properties, improve heat resistance, adjust shrinkage, etc. For example, the vinylidene chloride resin according to the present invention Laminated films of films with other films such as polyethylene terephthalate film or polypropylene film can be used. Further, the cylindrical packaging film may be printed.
〔筒状の包装フィルムの製造〕
　本発明における筒状の包装フィルムは、従来、充填包装体に備えられる筒状の包装フィルムを製造する方法として採用されている方法によって得ることができる。具体的には、帯状の包装フィルムを、長手方向に延びる両側縁部が重なるように筒状に巻いて筒状フィルムを形成し、次いで、筒状フィルムの前記両側縁部を縦シールすることにより、筒状の包装フィルムを形成することができる。 [Production of cylindrical packaging film]
The cylindrical packaging film in the present invention can be obtained by a method conventionally adopted as a method for manufacturing a cylindrical packaging film to be provided in a filled package. Specifically, a strip-shaped packaging film is rolled into a tubular shape so that both side edges extending in the longitudinal direction are overlapped to form a tubular film, and then the both side edges of the tubular film are vertically sealed. , can form a tubular packaging film.
〔帯状の包装フィルムの製造〕
　筒状の包装フィルムを形成するための帯状の包装フィルムの製造方法は、特に限定されない。例えば、押出成形によって、シート状又は管状の押出フィルムを製造し、必要に応じて延伸処理して熱収縮性を付与した後、管状の押出フィルムの場合は内側同士を重ねて所定の幅を有する２枚重ねの帯状の包装フィルムを得ることができ、更に必要に応じ長手方向に切断することにより、所望の幅を有する帯状の包装フィルムを製造することができる。筒状の包装フィルムが積層フィルムである場合は、共押出成形又は押出ラミネーションにより積層した帯状の包装フィルムを製造してもよいし、複数のフィルムを接着剤、例えばウレタン系接着剤により接着させて積層した帯状の包装フィルムを製造してもよい。筒状の包装フィルムを印刷が施されたものとする場合は、得られた帯状の包装フィルムに印刷を施してもよい。 [Production of strip-shaped packaging film]
A method for producing a strip-shaped packaging film for forming a cylindrical packaging film is not particularly limited. For example, a sheet-shaped or tubular extruded film is produced by extrusion molding, and if necessary, it is stretched to give it heat shrinkability. A two-ply strip-shaped packaging film can be obtained, and if necessary, by cutting in the longitudinal direction, a strip-shaped packaging film having a desired width can be produced. When the tubular packaging film is a laminated film, a strip-shaped packaging film laminated by coextrusion molding or extrusion lamination may be produced, or a plurality of films may be bonded together with an adhesive such as a urethane adhesive. A laminated strip of packaging film may be produced. When the cylindrical packaging film is to be printed, the obtained belt-shaped packaging film may be printed.
〔長手方向に延びる縦シール部〕
　本発明の一実施形態に係る充填包装体に備えられる筒状の包装フィルムは、長手方向に延びる縦シール部を備えるものである。上記縦シール部は、従来、充填包装体に備えられる筒状の包装フィルムに備えられる長手方向に延びる縦シール部と同様の趣旨で備えられるものである。即ち、帯状の包装フィルムを長手方向に延びる両側縁部が重なるように筒状に巻いて筒状フィルムを形成し、次いで、該筒状フィルムの前記の両側縁部を、高周波誘電加熱、超音波加熱、レーザー加熱、抵抗加熱等による溶着、接着剤による接着（ヒートシールを含む。）等の常法に従って、長手方向（縦方向）に連続してシール（接着）することにより、筒状の包装フィルムが形成されるものである。縦シール部は、筒状の包装フィルムの長手方向の全長に亘って備えられ、これにより、筒状の包装フィルムに充填されて封入される内容物を密封状態に保存することができる。筒状の包装フィルムに備えられる長手方向に延びる縦シール部の幅は、適宜定めることができる。 [Vertical seal portion extending in the longitudinal direction]
A cylindrical packaging film provided in a filling package according to an embodiment of the present invention has a vertical sealing portion extending in the longitudinal direction. The longitudinal seal portion is conventionally provided for the same purpose as the longitudinal seal portion extending in the longitudinal direction provided on a cylindrical packaging film provided in a filling package. That is, a band-shaped packaging film is rolled into a tubular shape so that both side edges extending in the longitudinal direction are overlapped to form a tubular film, and then the both side edges of the tubular film are subjected to high-frequency dielectric heating and ultrasonic heating. Cylindrical packaging is continuously sealed (bonded) in the longitudinal direction (vertical direction) according to conventional methods such as welding by heating, laser heating, resistance heating, etc., bonding with adhesives (including heat sealing), etc. A film is formed. The vertical seal portion is provided over the entire length of the tubular packaging film in the longitudinal direction, so that the contents filled and enclosed in the tubular packaging film can be preserved in a sealed state. The width of the vertical seal portion extending in the longitudinal direction provided on the tubular packaging film can be appropriately determined.
〔長手方向の両端部の集束〕
　本発明の一実施形態に係る充填包装体は、長手方向に延びる縦シール部を備え、長手方向の両端部が集束された筒状の包装フィルムを備える。即ち、本発明の一実施形態に係る充填包装体は、筒状の包装フィルムに脂質を含む加工食品等の内容物を充填した後に、筒状の包装フィルムの長手方向の両端部を集束することによって形成され、内容物を密封状態に保存することができる。筒状の包装フィルムの長手方向の両端部の集束は、従来、充填包装体に備えられる筒状の包装フィルムについてされていた長手方向の両端部の集束方法、例えば、アルミワイヤクリップ等の金属製のワイヤクリップ或いは横シールフィルム又はその他の手段による集束方法を採用することができる。 [Convergence of both ends in the longitudinal direction]
A filling package according to an embodiment of the present invention comprises a tubular packaging film having longitudinally extending longitudinal seal portions and having both ends in the longitudinal direction converged. That is, in the filling package according to one embodiment of the present invention, the cylindrical packaging film is filled with contents such as processed foods containing lipids, and then both ends in the longitudinal direction of the cylindrical packaging film are bundled. It is formed by and can store the contents in a hermetically sealed state. The bundling of both ends in the longitudinal direction of the tubular packaging film is conventionally performed for the tubular packaging film provided in the filling packaging body. wire clips or transverse sealing films or other means of convergence can be employed.
２．筒状の包装フィルムに充填されて封入された内容物
　本発明の一実施形態に係る充填包装体に備えられる、前記の筒状の包装フィルムに充填されて封入された内容物としては、特に限定されず、前述と同様であり、例えば、脂質を含んでもよい。 2. Contents Filled and Enclosed in Cylindrical Packaging Film The contents filled and enclosed in the tubular packaging film provided in the filling package according to one embodiment of the present invention are particularly limited. are similar to those described above, and may include, for example, lipids.
３．充填包装体
　本発明の一実施形態に係る充填包装体は、長手方向に延びる縦シール部を備え、長手方向の両端部が集束された筒状の包装フィルムに、内容物が充填されて封入されてなる充填包装体であって、上記包装フィルムは、本発明に係る樹脂フィルムを含む。上記包装フィルムは、本発明に係る樹脂フィルムからなるものであってもよい。充填包装体の形状及び大きさは、通常、筒状の包装フィルムの形状及び大きさに従って定まる。 3. Filled package The filled package according to one embodiment of the present invention is provided with a longitudinally extending longitudinally sealed portion, and a cylindrical packaging film having both ends in the longitudinal direction converged is filled with contents and sealed. A filling package comprising: the packaging film comprising the resin film according to the present invention. The packaging film may be made of the resin film according to the present invention. The shape and size of the filled package are usually determined according to the shape and size of the tubular packaging film.
４．充填包装体の製造方法
　本発明の一実施形態に係る、充填包装体の製造方法は、長手方向に延びる縦シール部を備え、長手方向の両端部が集束された筒状の包装フィルムに、内容物が充填されて封入されてなる充填包装体であって、前記包装フィルムは、本発明に係る樹脂フィルムを含む充填包装体を得ることができる限り、特に限定されない。上記製造方法としては、例えば、帯状の包装フィルムを、長手方向に延びる両側縁部が重なるように筒状に巻いて筒状フィルムを形成する筒状フィルム形成工程；前記筒状フィルムの前記両側縁部を縦シールして、長手方向に延びる縦シール部を備える筒状の包装フィルムを形成する縦シール工程；前記筒状の包装フィルムに内容物を充填する充填工程；及び前記筒状の包装フィルムの長手方向の両端部を集束する端部集束工程；を含む、充填包装体の製造方法が挙げられる。 4. Method for Manufacturing Filled Package A method for manufacturing a filled package according to an embodiment of the present invention includes a cylindrical packaging film having a vertical seal portion extending in the longitudinal direction and having both ends in the longitudinal direction converged. It is a filled package in which an object is filled and enclosed, and the packaging film is not particularly limited as long as a filled package containing the resin film according to the present invention can be obtained. The manufacturing method includes, for example, a tubular film forming step of forming a tubular film by winding a strip-shaped packaging film into a tubular shape so that both side edges extending in the longitudinal direction overlap; the both side edges of the tubular film. a vertical sealing step of vertically sealing the portion to form a tubular packaging film having a vertical sealing portion extending in the longitudinal direction; a filling step of filling the tubular packaging film with content; and the tubular packaging film a step of bundling both ends in the longitudinal direction of the filled package.
〔筒状フィルム形成工程〕
　帯状の包装フィルムを、長手方向に延びる両側縁部が重なるように筒状に巻いて筒状フィルムを形成する。帯状の包装フィルムは先に説明した方法に従って製造することができる。例えば、両側縁部が帯状の包装フィルムの長手方向に直交する外周面に沿って重なるようにすればよく、所望によっては、両側縁部が前記の外周面から立ち上がって重なるようにして筒状フィルムを形成してもよい。 [Cylindrical film forming step]
A strip-shaped packaging film is rolled into a tubular shape so that both side edges extending in the longitudinal direction are overlapped to form a tubular film. A strip-shaped packaging film can be produced according to the method described above. For example, both side edges may overlap along the outer peripheral surface perpendicular to the longitudinal direction of the strip-shaped packaging film, and if desired, both side edges may rise from the outer peripheral surface and overlap to overlap the cylindrical film. may be formed.
〔縦シール工程〕
　前記筒状フィルムの前記両側縁部を縦シールして、長手方向に延びる縦シール部を備える筒状の包装フィルムを形成する。即ち、帯状の包装フィルムから形成された筒状フィルムの長手方向に重なって延びる両側縁部を、長手方向に延びる所定の幅で連続的に縦シールすることにより長手方向に延びる縦シール部を形成する。 [Vertical sealing process]
The side edges of the tubular film are longitudinally sealed to form a tubular packaging film having longitudinally extending longitudinally sealed portions. That is, the longitudinally extending longitudinally-extending sealing portions are formed by continuously longitudinally sealing both longitudinally overlapping edge portions of a tubular film formed from a belt-like packaging film with a predetermined longitudinally extending width. do.
　縦シールする方法は、高周波誘電加熱、超音波加熱、レーザー加熱、抵抗加熱等による溶着、接着剤による接着（ヒートシールを含む。）等の常法を採用することができる。筒状の包装フィルムは、極性を有する樹脂であるポリ塩化ビニリデン系樹脂を含むことから、縦シールの効率性や、シール強度の調整の容易さ等の観点から、高周波誘電加熱による縦シールが好ましい。具体的には、筒状フィルムの長手方向に重なって延びる両側縁部を走行させながら、高周波誘電加熱装置のシール電極とアース電極との間を通過させる。この両電極の間に高周波電力を供給することにより、筒状フィルムの重なった両側縁部に高周波溶着による連続的な縦シール部が形成される。 Usual methods such as welding by high-frequency dielectric heating, ultrasonic heating, laser heating, resistance heating, etc., and bonding with adhesives (including heat sealing) can be used for vertical sealing. Since the cylindrical packaging film contains polyvinylidene chloride resin, which is a polar resin, vertical sealing by high-frequency dielectric heating is preferable from the viewpoint of efficiency of vertical sealing and ease of adjustment of sealing strength. . Specifically, the cylindrical film is passed between the seal electrode and the ground electrode of the high-frequency dielectric heating device while running along both side edges extending in the longitudinal direction. By supplying high-frequency power between these two electrodes, a continuous longitudinal seal portion is formed by high-frequency welding on both overlapping side edges of the tubular film.
〔充填工程〕
　縦シール工程によって得られた筒状の包装フィルムには、内容物を充填する。即ち、筒状の包装フィルムを、例えば、上方から下方に所定速度で走行させながら、筒状の包装フィルムの開口部に、ポンプとノズルとを備える充填装置のノズルから内容物を連続的に供給して充填を行う。充填装置や、筒状の包装フィルムを走行させ案内する機構等はそれ自体公知のものから適宜選択することができ、筒状の包装フィルムの走行及び内容物の充填速度等は、通常の範囲内において適宜選択することができる。 [Filling process]
The cylindrical packaging film obtained by the vertical sealing process is filled with contents. That is, while the tubular packaging film is running from top to bottom at a predetermined speed, the contents are continuously supplied to the opening of the tubular packaging film from a nozzle of a filling device equipped with a pump and a nozzle. to fill. The filling device, the mechanism for running and guiding the cylindrical packaging film, etc. can be appropriately selected from those known per se, and the running speed of the cylindrical packaging film, the filling speed of the contents, etc. are within the usual range. can be selected as appropriate.
〔端部集束工程〕
　内容物が充填された筒状の包装フィルムの長手方向の両端部を集束することにより、筒状の包装フィルムに、内容物が充填されて封入されてなる充填包装体を得ることができる。具体的には、内容物が充填された筒状の包装フィルムを走行させながら、例えば一対のローラからなるしごき装置を使用して、本発明の一実施形態に係る充填包装体の下端部に相当する箇所の下方及び上端部に相当する箇所の上方の筒状の包装フィルムに内容物の不存在部を形成し、該内容物の不存在部の上端部及び下端部を集束することにより、本発明の一実施形態に係る充填包装体の下端部及び上端部を形成し、所定の長さに切断して本発明の一実施形態に係る充填包装体を得る。端部集束工程において、端部を集束する方法としては、従来、充填包装体に備えられる筒状の包装フィルムについてされていた長手方向の両端部の集束方法、例えば、アルミワイヤクリップ等の金属製のワイヤクリップ或いは横シールフィルム又はその他の手段による集束方法を採用することができる。 [Edge-focusing process]
By bundling both ends in the longitudinal direction of the tubular packaging film filled with the contents, a filled package in which the tubular packaging film is filled with the contents and enclosed can be obtained. Specifically, while running the cylindrical packaging film filled with the contents, for example, using a squeezing device consisting of a pair of rollers, the lower end portion of the filled package according to one embodiment of the present invention By forming a content-free part on the tubular packaging film below the part where the contents are filled and above the part corresponding to the upper end, A filling package according to an embodiment of the present invention is obtained by forming a lower end portion and an upper end portion of the filling package and cutting it to a predetermined length. In the end bundling step, as a method for bundling the edges, conventionally, a method of bundling both ends in the longitudinal direction of a cylindrical packaging film provided in a filling package, for example, a metal clip such as an aluminum wire clip, is used. wire clips or transverse sealing films or other means of convergence can be employed.
　以下に実施例及び比較例を示して本発明を更に説明するが、本発明は、本実施例に限定されるものではない。 The present invention will be further described below with reference to examples and comparative examples, but the present invention is not limited to these examples.
〔実施例１〕
（母材フィルムの製造）
　塩化ビニリデン（ＶＤ）及び塩化ビニル（ＶＣ）の重合時におけるモノマー仕込み質量比（ＶＤ／ＶＣ）が８１／１９で重合時間が３８時間である共重合体（８５質量部）と塩化ビニリデン（ＶＤ）及び塩化ビニル（ＶＣ）の重合時におけるモノマー仕込み質量比（ＶＤ／ＶＣ）が７１／２９で重合時間が３７時間である共重合体（１５質量部）とを混ぜ合わせて得た共重合体混合物１００質量部に、ジブチルセバケート（ＤＢＳ）及びエポキシ化植物油を合計５．４質量部配合し、更にエポキシ基含有ポリマー、酸化防止剤、界面活性剤、エルカ酸アミド、炭酸カルシウム、及び色材（タンゴ）を合計１．７質量部加え、更に超低密度ポリエチレン（東ソー製、商品名：ＬＵＭＩＴＡＣ　２２－６、密度０．９００ｇ／ｃｍ３）を２．５質量部加えて、塩化ビニリデン系樹脂組成物を得た。次に、得られた塩化ビニリデン系樹脂組成物を、直径４０ｍｍの押出機スクリューを用いて溶融押出した後、ＭＤ（長手）に２．４倍、ＴＤ（短手）に４．０倍のインフレーション二軸延伸を行い、環状フィルムの内側同士を重ね合わせて、厚み４０μｍ（厚み２０μｍのフィルム２枚の厚み）の帯状の塩化ビニリデン系樹脂フィルムａを得て母材フィルムとした。 [Example 1]
(Manufacture of base material film)
A copolymer (85 parts by mass) and vinylidene chloride (VD) having a monomer charge mass ratio (VD/VC) of 81/19 and a polymerization time of 38 hours during the polymerization of vinylidene chloride (VD) and vinyl chloride (VC) and a copolymer (15 parts by mass) having a monomer charge mass ratio (VD/VC) during polymerization of vinyl chloride (VC) of 71/29 and a polymerization time of 37 hours. A total of 5.4 parts by mass of dibutyl sebacate (DBS) and epoxidized vegetable oil are added to 100 parts by mass, and further epoxy group-containing polymer, antioxidant, surfactant, erucamide, calcium carbonate, and coloring material ( Tango) was added in total of 1.7 parts by mass, and 2.5 parts by mass of ultra-low density polyethylene (manufactured by Tosoh, trade name: LUMITAC 22-6, density 0.900 g/cm 3 ) was added to obtain a vinylidene chloride resin composition. got stuff Next, the obtained vinylidene chloride-based resin composition is melt-extruded using an extruder screw with a diameter of 40 mm, followed by inflation of 2.4 times in MD (longitudinal direction) and 4.0 times in TD (lateral direction). Biaxial stretching was performed, and the insides of the annular films were overlapped to obtain a strip-shaped vinylidene chloride resin film a having a thickness of 40 μm (thickness of two films having a thickness of 20 μm), which was used as a base material film.
（充填包装体の製造）
　塩化ビニリデン系樹脂フィルムａを幅６５ｍｍに裁断し、高周波誘電加熱シールを行い筒状に成形しながら、脂質を含む内容物（豚肉５２質量％、氷水２１．５質量％、豚脂肪２０質量％、コーンスターチ５質量％、食塩１．４質量％、トリポリリン酸ナトリウム０．０５質量％、アスコルビン酸ナトリウム０．０４質量％、及び亜硝酸ナトリウム０．０１質量％を含むペースト）を自動充填包装機（クレハ社製、商品名：ＫＡＰ３０００型自動充填包装機）にて充填し、フィルムの端部を収束しつつ、塩化ビニリデン系樹脂テープでクリップしたものを超音波シールで密封して充填包装体（以下、「加圧加熱殺菌前の充填包装体」ともいう。）を得た。なお、筒状の母材フィルムにおいては、折幅（円周の半分の長さ）が２８ｍｍ、カット長（筒状包装体から内容物を抜き取り、筒状の母材フィルムを平らに押し広げて長手方向に測定した際の長さ）が１９０ｍｍ、質量が３５ｇとなるように条件を調整した。充填包装体を０．２ＭＰａにおいて１２０℃の熱水中で１０分間の加圧加熱殺菌（レトルト処理）に供し、加圧加熱殺菌後の充填包装体を得た。 (Manufacture of filled packages)
The vinylidene chloride resin film a was cut to a width of 65 mm, subjected to high-frequency dielectric heating sealing and molded into a cylindrical shape, while contents containing lipids (52% by mass of pork, 21.5% by mass of ice water, 20% by mass of pork fat, An automatic filling and packaging machine (Kureha company, product name: KAP3000 automatic filling and packaging machine), while converging the ends of the film, the film is clipped with vinylidene chloride resin tape and sealed with an ultrasonic seal to form a filling package (hereinafter referred to as Also referred to as “filled package before pressure heat sterilization”). In addition, in the cylindrical base film, the folding width (half the length of the circumference) is 28 mm, the cut length (the content is extracted from the cylindrical package, and the cylindrical base film is flattened The conditions were adjusted so that the length when measured in the longitudinal direction was 190 mm and the mass was 35 g. The filled package was subjected to pressure heat sterilization (retort treatment) in hot water of 120°C at 0.2 MPa for 10 minutes to obtain a filled package after pressure heat sterilization.
〔実施例２〕
　実施例１において、超低密度ポリエチレンの代わりにアイオノマー樹脂（Ｄｏｗ製、商品名：Ｓｕｒｌｙｎ　１７０７、エチレン－メタクリル酸共重合体のナトリウムイオン中和物、密度０．９５ｇ／ｃｍ３）を用いた以外は実施例１と同様にして、フィルムｂを得て母材フィルムとし、更に、加圧加熱殺菌前及び加圧加熱殺菌後の充填包装体を得た。 [Example 2]
In Example 1, except that an ionomer resin (manufactured by Dow, trade name: Surlyn 1707, sodium ion neutralized ethylene-methacrylic acid copolymer, density 0.95 g/cm 3 ) was used instead of ultra-low density polyethylene. In the same manner as in Example 1, film b was obtained as a base material film, and further, filled packages before and after pressure and heat sterilization were obtained.
〔比較例１〕
　実施例１において、超低密度ポリエチレンを添加しない以外は実施例１と同様にして、フィルムｃを得て母材フィルムとし、更に、加圧加熱殺菌前及び加圧加熱殺菌後の充填包装体を得た。 [Comparative Example 1]
In Example 1, film c was obtained in the same manner as in Example 1 except that ultra-low density polyethylene was not added, and used as a base material film. Obtained.
＜測定方法＞
〔酸素ガス透過度〕
・加圧加熱殺菌（レトルト処理）前
　塩化ビニリデン系樹脂フィルムにマスキング処理（面積１２．５６ｃｍ２（２ｃｍ×２ｃｍ×３．１４））して測定した。
・加圧加熱殺菌（レトルト処理）後
　充填包装体（内容物：ソーセージ）から塩化ビニリデン系樹脂フィルムを剥離し、マスキング処理（面積１２．５６ｃｍ２）して測定した。
・測定機：ＭＯＣＯＮ社製酸素透過率測定装置ＯＸＴＲＡＮ　２／２１
・測定温湿度：２３℃，ｄｒｙ <Measurement method>
[Oxygen gas permeability]
- Before pressurized heat sterilization (retort treatment) Measurement was performed after a vinylidene chloride resin film was masked (area: 12.56 cm 2 (2 cm x 2 cm x 3.14)).
- After pressurized heat sterilization (retort treatment) The vinylidene chloride resin film was peeled off from the filled package (contents: sausage), masked (area 12.56 cm 2 ), and measured.
・Measuring machine: Oxygen permeability measuring device OXTRAN 2/21 manufactured by MOCON
・Measurement temperature and humidity: 23°C, dry
〔熱収縮率〕
　塩化ビニリデン系樹脂フィルムを５ｃｍ×５ｃｍに切り出し、吊り下げ治具に固定し、１２０℃に設定したギアオーブンに入れた。その後、吊り下げ治具を回転させながら５分間加熱し、フィルムを取り出した。約２３℃の室温で自然冷却後、ＭＤ（長手）の寸法ＤｃｍとＴＤ（短手）の寸法Ｅｃｍを測定し、次式から収縮率を算出した。
　　　ＭＤの熱収縮率（％）：（１－Ｄ／５）×１００
　　　ＴＤの熱収縮率（％）：（１－Ｅ／５）×１００ [Heat shrinkage rate]
A vinylidene chloride resin film was cut into a size of 5 cm x 5 cm, fixed to a hanging jig, and placed in a gear oven set at 120°C. After that, the film was heated for 5 minutes while rotating the hanging jig, and the film was taken out. After natural cooling at room temperature of about 23° C., the MD (longitudinal) dimension Dcm and TD (lateral) dimension Ecm were measured, and the shrinkage ratio was calculated from the following equation.
Thermal shrinkage rate of MD (%): (1-D/5) x 100
Thermal shrinkage rate of TD (%): (1-E/5) x 100
〔退色変化〕
　加圧加熱殺菌（レトルト処理）直後と２３℃にて１か月保存後に充填包装体から母材フィルムを剥離してソーセージの色味を比較し、赤色から褐色への色の変化が相対的に小さかった場合を〇、当該変化が相対的に大きかった場合を×とした。 [Discoloration change]
Immediately after pressurized heat sterilization (retort treatment) and after storage at 23 ° C. for 1 month, the base material film was peeled off from the filled package and the color of the sausage was compared. A case where the change was small was indicated by ◯, and a case where the change was relatively large was indicated by ×.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
ブレンド樹脂の含有率（質量％）の計算：
２．５／（８５＋１５＋５．４＋１．７＋２．５）×１００＝２．２８≒２．３
　なお、表中、ブレンド樹脂とは、実施例１における超低密度ポリエチレン及び実施例２におけるアイオノマー樹脂をいう。 Calculation of blended resin content (% by mass):
2.5/(85+15+5.4+1.7+2.5)×100=2.28≈2.3
In the table, the blended resin refers to the ultra-low density polyethylene in Example 1 and the ionomer resin in Example 2.
　超低密度ポリエチレンを添加した実施例１は、比較例１よりも酸素ガス透過度の変化率が小さい。アイオノマー樹脂を添加した実施例２は、レトルト処理後（Ｂ）の酸素ガス透過度がレトルト処理前（Ａ）の酸素ガス透過度よりも小さく、バリア性が向上している。この理由は必ずしも明らかでないが、アイオノマー樹脂が内容物の脂質を吸収して塩化ビニリデン系樹脂への脂質の拡散を抑制すると共に塩化ビニリデン系樹脂の結晶化を促進したためと考えられる。 Example 1, in which ultra-low density polyethylene is added, has a smaller rate of change in oxygen gas permeability than Comparative Example 1. In Example 2, in which the ionomer resin was added, the oxygen gas permeability after retort treatment (B) was lower than the oxygen gas permeability before retort treatment (A), and the barrier property was improved. Although the reason for this is not entirely clear, it is believed that the ionomer resin absorbed the lipids in the contents, inhibited the diffusion of the lipids into the vinylidene chloride resin, and accelerated the crystallization of the vinylidene chloride resin.

Claims (9)

  1. 　塩化ビニリデン系樹脂を含有する塩化ビニリデン系樹脂フィルムであって、
    　長手方向の両端部が集束された筒状の前記塩化ビニリデン系樹脂フィルムに、２０質量％の脂質を含む内容物が充填されて封入されてなる充填包装体を、０．２ＭＰａにおいて１２０℃の熱水中で１０分間の加圧加熱殺菌に供し、前記加圧加熱殺菌前の前記塩化ビニリデン系樹脂フィルムの厚さ４０μｍ換算の酸素ガス透過度をＡ（ｃｍ３／ｍ２・ｄａｙ・ａｔｍ）とし、前記加圧加熱殺菌後の前記塩化ビニリデン系樹脂フィルムの厚さ４０μｍ換算の酸素ガス透過度をＢ（ｃｍ３／ｍ２・ｄａｙ・ａｔｍ）としたときに、（Ｂ－Ａ）／Ａ×１００で求められる酸素ガス透過度の変化率が３５．０％以下である塩化ビニリデン系樹脂フィルム。     A vinylidene chloride resin film containing a vinylidene chloride resin,
    A filled package obtained by filling and enclosing a content containing 20% by mass of lipid in the cylindrical vinylidene chloride resin film with both ends in the longitudinal direction is heated at 120 ° C. at 0.2 MPa. It is subjected to pressure heat sterilization in water for 10 minutes, and the oxygen gas permeability of the vinylidene chloride resin film before the pressure heat sterilization is converted to a thickness of 40 μm and is defined as A (cm 3 /m 2 day atm). , when the oxygen gas permeability of the vinylidene chloride resin film after the pressure and heat sterilization in terms of the thickness of 40 μm is B (cm 3 /m 2 · day · atm), (BA) / A × A vinylidene chloride resin film having a rate of change in oxygen gas permeability determined by 100 of 35.0% or less.
  2. 　前記酸素ガス透過度の変化率が１．５％以下である請求項１に記載の塩化ビニリデン系樹脂フィルム。 The vinylidene chloride resin film according to claim 1, wherein the rate of change in oxygen gas permeability is 1.5% or less.
  3. 　前記酸素ガス透過度の変化率が－１０．０％以上である請求項１又は２に記載の塩化ビニリデン系樹脂フィルム。 The vinylidene chloride resin film according to claim 1 or 2, wherein the rate of change in oxygen gas permeability is -10.0% or more.
  4. 　前記酸素ガス透過度の変化率が－８．０％以上である請求項１～３のいずれか１項に記載の塩化ビニリデン系樹脂フィルム。 The vinylidene chloride resin film according to any one of claims 1 to 3, wherein the rate of change in oxygen gas permeability is -8.0% or more.
  5. 　更に、塩化ビニリデン系樹脂を除く樹脂を含有する請求項１～４のいずれか１項に記載の塩化ビニリデン系樹脂フィルム。 The vinylidene chloride resin film according to any one of claims 1 to 4, which further contains a resin other than vinylidene chloride resin.
  6. 　前記塩化ビニリデン系樹脂を除く樹脂が、超低密度ポリエチレン及びアイオノマー樹脂からなる群より選ばれる少なくとも１種の樹脂を含有する請求項５に記載の塩化ビニリデン系樹脂フィルム。 The vinylidene chloride resin film according to claim 5, wherein the resin other than the vinylidene chloride resin contains at least one resin selected from the group consisting of ultra-low density polyethylene and ionomer resin.
  7. 　前記塩化ビニリデン系樹脂フィルムにおいて、前記塩化ビニリデン系樹脂を除く樹脂の含有率が０．５質量％以上３質量％未満である請求項５又は６に記載の塩化ビニリデン系樹脂フィルム。 The vinylidene chloride resin film according to claim 5 or 6, wherein the content of the resin other than the vinylidene chloride resin in the vinylidene chloride resin film is 0.5% by mass or more and less than 3% by mass.
  8. 　前記塩化ビニリデン系樹脂が、塩化ビニリデン６０質量％以上９５質量％以下と塩化ビニル５質量％以上４０質量％以下との共重合体である請求項１～７のいずれか１項に記載の塩化ビニリデン系樹脂フィルム。 The vinylidene chloride according to any one of claims 1 to 7, wherein the vinylidene chloride resin is a copolymer of 60% by mass to 95% by mass of vinylidene chloride and 5% by mass to 40% by mass of vinyl chloride. based resin film.
  9. 　請求項１～８のいずれか１項に記載の塩化ビニリデン系樹脂フィルムと内容物とを備える充填包装体。 A filling package comprising the vinylidene chloride resin film according to any one of claims 1 to 8 and a content.
PCT/JP2021/045866 2021-03-30 2021-12-13 Vinylidene chloride-based resin film, and filled/packaged product using same WO2022209039A1 (en)

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JP2015164860A (en) * 2014-03-03 2015-09-17 株式会社クレハ Easily-openable and retort-resistant filling package
WO2015141361A1 (en) * 2014-03-17 2015-09-24 株式会社クレハ Packaging film
JP2019073306A (en) * 2017-10-16 2019-05-16 旭化成株式会社 Cylindrical packaging body
JP2020070058A (en) * 2018-10-31 2020-05-07 日本水産株式会社 Package by vinylidene chloride resin film

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JP4542796B2 (en) 2004-02-17 2010-09-15 株式会社クレハ Package manufacturing apparatus, package manufacturing method, and package

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015164860A (en) * 2014-03-03 2015-09-17 株式会社クレハ Easily-openable and retort-resistant filling package
WO2015141361A1 (en) * 2014-03-17 2015-09-24 株式会社クレハ Packaging film
JP2019073306A (en) * 2017-10-16 2019-05-16 旭化成株式会社 Cylindrical packaging body
JP2020070058A (en) * 2018-10-31 2020-05-07 日本水産株式会社 Package by vinylidene chloride resin film

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