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WO2018198794A1 - Film de scellement et matériau d'emballage - Google Patents

Film de scellement et matériau d'emballage Download PDF

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Publication number
WO2018198794A1
WO2018198794A1 PCT/JP2018/015358 JP2018015358W WO2018198794A1 WO 2018198794 A1 WO2018198794 A1 WO 2018198794A1 JP 2018015358 W JP2018015358 W JP 2018015358W WO 2018198794 A1 WO2018198794 A1 WO 2018198794A1
Authority
WO
WIPO (PCT)
Prior art keywords
resin
sealant film
layer
intermediate layer
film
Prior art date
Application number
PCT/JP2018/015358
Other languages
English (en)
Japanese (ja)
Inventor
桂輔 浜崎
達彦 薄井
Original Assignee
Dic株式会社
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 Dic株式会社 filed Critical Dic株式会社
Priority to JP2018545398A priority Critical patent/JP6424997B1/ja
Priority to KR1020197022725A priority patent/KR102654522B1/ko
Publication of WO2018198794A1 publication Critical patent/WO2018198794A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
    • B29C48/10—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels flexible, e.g. blown foils
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/30—Extrusion nozzles or dies
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/30—Extrusion nozzles or dies
    • B29C48/32—Extrusion nozzles or dies with annular openings, e.g. for forming tubular articles
    • B29C48/335—Multiple annular extrusion nozzles in coaxial arrangement, e.g. for making multi-layered tubular articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/49—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using two or more extruders to feed one die or nozzle
    • B29C48/495—Feedblocks
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/28—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of blown tubular films, e.g. by inflation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B32B27/325—Layered products comprising a layer of synthetic resin comprising polyolefins comprising polycycloolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/15—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
    • B32B37/153—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state at least one layer is extruded and immediately laminated while in semi-molten state
    • 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
    • B65D65/38—Packaging materials of special type or form
    • B65D65/40—Applications of laminates for particular packaging purposes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K3/1006—Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/72—Density
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2323/00—Polyalkenes
    • B32B2323/04—Polyethylene
    • B32B2323/046—LDPE, i.e. low density polyethylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B32B2439/70—Food packaging
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2581/00—Seals; Sealing equipment; Gaskets
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2003/1084—Laminates

Definitions

  • the present invention relates to a sealant film used for retort packaging that can be sterilized and cooked by heating or pressurization in a state where food or the like is packaged, and a packaging material using the sealant film.
  • Retort food can be distributed at room temperature, and is easy to handle and easy to handle in distribution, and is expected to expand into areas where cold chain development is insufficient.
  • a film for retort having easy tearability for example, a propylene film in which a resin in which a low crystalline ethylene elastomer is blended with a propylene-ethylene block copolymer is used and the birefringence is controlled within a specific range is disclosed. (See Patent Document 1).
  • a packaging material having easy cutability a cyclic olefin-based resin and a linear low-density polyethylene resin are contained as a packaging material used for a soft bag filled with a chemical solution such as physiological saline or an electrolytic solution.
  • a packaging material having an intermediate layer and an inner layer and an outer layer of a linear low-density polyethylene resin is disclosed (see Patent Document 2).
  • the propylene-based film that promotes the above birefringence has a reduction in tear strength due to the improved rigidity of the film, but the direction of tearing is not sufficiently controlled, and the straight cut ability to tear straight There was a need for improvement.
  • packaging materials using an ethylene-propylene copolymer as a sealant for heavy loads for business use or distribution in cold regions, etc. are not sufficient in impact resistance and may cause bag breakage accidents.
  • the packaging material used for the above-mentioned soft bag has easy-cutting properties and straight-cutting properties, it has been desired to further improve the cutting properties when applied to retort applications.
  • the problem to be solved by the present invention is to provide a sealant film and a packaging material having suitable bag breaking resistance and excellent in easy tearability and straight cut ability.
  • this invention makes it a subject to provide the sealant film which has suitable sealing performance. Furthermore, in the present invention, in addition to the above-described problems, it is an object to provide a sealant film that does not cause inner surface fusion or appearance unevenness of a packaging material during high-temperature processing.
  • the present invention comprises a laminated film in which an outer layer (A), an intermediate layer (B) and an inner layer (C) are laminated, the outer layer (A) and the inner layer (C) contain a polyethylene resin, and the intermediate layer (B) Contains linear low density polyethylene (b1) and cyclic olefin resin (b2), and the content of the cyclic olefin resin (b2) in the resin component contained in the intermediate layer (B) is 20
  • a sealant film having a normalized molecular orientation MORc value of 1.025 or more when the reference thickness measured by a microwave molecular orientation meter is 60 ⁇ m and is 40 mass%. is there.
  • the present invention is a method for producing a sealant film comprising a laminated film in which an outer layer (A), an intermediate layer (B) and an inner layer (C) are laminated by a coextrusion inflation method, wherein the outer layer (A)
  • the outer layer resin to be formed and the inner layer resin to form the inner layer (C) contain a polyethylene resin
  • the intermediate layer resin to form the intermediate layer (B) is linear low density polyethylene (b1) and cyclic
  • the olefin resin (b2) is contained, and the content of the cyclic olefin resin (b2) in the resin component contained in the intermediate layer resin is 20 to 40% by mass, and 1.0 to 2.3.
  • the above-described problems are solved by a method for producing a sealant film which is co-extrusion blow molded at a blow ratio of 20 to 60 and a drawdown ratio of 20 to 60.
  • the packaging bag using the sealant film of the present invention is spilled from the contents at the time of opening or after opening has started to occur. And scattering is difficult to occur.
  • it is possible to cut with simple and suitable straightness.
  • it can implement
  • the sealant film of the present invention easily realizes a packaging material that does not cause inner surface fusion or appearance irregularity during high-temperature treatment such as retort sterilization treatment while achieving suitable tearability.
  • the sealant film of the present invention can be suitably applied to high-temperature processing packaging materials such as retort food packaging materials that require high-temperature sterilization.
  • the sealant film of the present invention is suitable for these packaging materials because it can easily achieve suitable sealing properties.
  • the sealant film of the present invention comprises a laminated film in which an outer layer (A), an intermediate layer (B) and an inner layer (C) are laminated in order, and the outer layer (A) and the inner layer (C) contain a polyethylene resin,
  • the intermediate layer (B) between the outer layer (A) and the inner layer (C) contains the linear low density polyethylene (b1) and the cyclic olefin resin (b2), and the resin component contained in the intermediate layer (B)
  • the content of the cyclic olefin resin (b2) in the sealant film is 20 to 40% by mass.
  • the normalized molecular orientation MORc value is 1.025 or more when the reference thickness measured by the microwave molecular orientation meter is 60 ⁇ m.
  • the outer layer (A) of the sealant film of the present invention contains a polyethylene resin.
  • the polyethylene resin include very low density polyethylene (VLDPE), linear low density polyethylene (LLDPE), low density polyethylene (LDPE), linear medium density polyethylene (LMDPE), and medium density polyethylene (MDPE).
  • Polyethylene resin ethylene-vinyl acetate copolymer (EVA), ethylene-methyl methacrylate copolymer (EMMA), ethylene-ethyl acrylate copolymer (EEA), ethylene-methyl acrylate (EMA) copolymer, ethylene Ethylene copolymers such as ethyl acrylate-maleic anhydride copolymer (E-EA-MAH), ethylene-acrylic acid copolymer (EAA), ethylene-methacrylic acid copolymer (EMAA); -Acrylic acid copolymer ionomer, ethylene Ionomers of acrylic acid copolymer can be exemplified.
  • EVA ethylene-vinyl acetate copolymer
  • EMMA ethylene-methyl methacrylate copolymer
  • EAA ethylene-ethyl acrylate copolymer
  • EMA ethylene-methyl acrylate copolymer
  • E-EA-MAH eth
  • polyethylene resins may be used alone or in combination of two or more.
  • ultra-low density polyethylene, linear low density polyethylene, low density polyethylene, linear medium density polyethylene can be preferably used, and linear low density polyethylene is particularly preferable.
  • HDPE high density polyethylene
  • linear low density polyethylene an ethylene monomer is a main component by a low-pressure radical polymerization method using a single site catalyst, and butene-1, hexene-1, octene-1, 4-methylpentene, etc. are used as comonomers.
  • the ⁇ -olefin was copolymerized.
  • the comonomer content in LLDPE is preferably in the range of 0.5 to 20 mol%, more preferably in the range of 1 to 18 mol%.
  • the single site catalyst examples include various single site catalysts such as a metallocene catalyst system such as a combination of a metallocene compound of Group IV or V transition metal of the periodic table and an organoaluminum compound and / or an ionic compound.
  • the single-site catalyst has a uniform active site, so the molecular weight distribution of the resulting resin is sharper than a multi-site catalyst with a non-uniform active site. This is preferable because a resin having physical properties excellent in stability of seal strength and impact resistance can be obtained.
  • the polyethylene resin is preferably contained in an amount of 60% by mass or more with respect to the total amount of the resin components forming the layer, and 80% by mass or more. It is more preferable to contain, and it is further more preferable to contain 90 mass% or more. Among them, it contains only a polyethylene resin as a resin component, and preferably 60% by mass or more in the resin component is a linear low density polyethylene, more preferably 80% by mass or more, and 90% by mass or more. More preferably.
  • other resins of the above polyethylene resin may be used in combination as long as the effects of the present invention are not impaired.
  • examples of other resin types that can be used in combination include polyolefin resins other than the above polyethylene resins, and include propylene homopolymers, propylene-ethylene copolymers, propylene-butene-1 copolymers, propylene-ethylene- Examples include polypropylene resins such as butene-1 copolymer and metallocene catalyst polypropylene.
  • the lower limit is not particularly limited, but may be appropriately used at a content of 1% by mass or more according to desired properties.
  • the average density of the resin component used in the layer is preferably 0.940 g / cm 3 or more, more preferably 0.940 to 0.945 g / cm 3 layer.
  • the density of each resin used in the outer layer (A) is not particularly limited as long as the average density of the resin components used is within the above range, but in the polyethylene resin, it is preferably 0.880 g / cm 3 or more, It is more preferably 0.920 g / cm 3 or more, particularly preferably 0.940 to 0.950 g / cm 3 . In addition, it is preferable to use other resins having 0.920 g / cm 3 or more.
  • the MFR of the resin component used for the outer layer (A) is 0.1 to 20 g / 10 minutes (190 ° C., 21.18 N), preferably 0.3 to 10 g / 10 minutes (190 ° C., 21.18 N), 0.5 to 5 g / 10 min (190 ° C., 21.18 N) is preferable. MFR within this range is preferable in that good film formability can be obtained in various multilayer film forming methods.
  • the intermediate layer (B) of the sealant film of the present invention contains linear low density polyethylene (b1).
  • the density of the linear low density polyethylene (b1) is preferably 0.937 g / cm 3 or more, more preferably 0.940 g / cm 3 or more, and even more preferably 0, because it is particularly preferable to suppress unevenness in appearance. 940 to 0.945 g / cm 3 . It is preferable that the average density of the resin component in the layer of the intermediate layer (B) is 0.940 g / cm 3 or more, and more preferably a layer of 0.940 ⁇ 0.945g / cm 3.
  • the MFR of the linear low density polyethylene (b1) is 0.1 to 20 g / 10 min (190 ° C., 21.18 N), preferably 0.3 to 10 g / 10 min (190 ° C., 21.18 N), and more 0.5 to 5 g / 10 min (190 ° C., 21.18 N) is preferable.
  • the compatibility with the cyclic olefin-based resin (b2) is excellent, and preferable film forming properties can be obtained in various multilayer film forming methods.
  • the content of the linear low density polyethylene (b1) in the intermediate layer (B) is easy to obtain suitable impact resistance and heat resistance during high-temperature treatment. It is preferably 60 to 80% by mass, and more preferably 65 to 75% by mass.
  • the intermediate layer (B) of the sealant film of the present invention contains the cyclic olefin resin (b2), so that excellent easy tearability and straight cut ability can be realized.
  • the cyclic olefin-based resin (b2) include norbornene-based polymers, vinyl alicyclic hydrocarbon polymers, and cyclic conjugated diene polymers. Among these, norbornene-based polymers are preferable.
  • the norbornene-based polymer includes a ring-opening polymer of a norbornene-based monomer (hereinafter referred to as “COP”), a norbornene-based copolymer obtained by copolymerizing a norbornene-based monomer and an olefin such as ethylene (hereinafter, referred to as “COP”). , “COC”). Also particularly preferred are hydrogenated products of COP and COC.
  • the weight average molecular weight of the cyclic olefin resin is preferably 5,000 to 500,000, more preferably 7,000 to 300,000.
  • the norbornene polymer and the norbornene monomer used as a raw material are alicyclic monomers having a norbornene ring.
  • Examples of such norbornene-based monomers include norbornene, tetracyclododecene, ethylidene norbornene, vinyl norbornene, ethylidetetracyclododecene, dicyclopentadiene, dimethanotetrahydrofluorene, phenyl norbornene, methoxycarbonyl norbornene, methoxy And carbonyltetracyclododecene.
  • These norbornene monomers may be used alone or in combination of two or more.
  • the norbornene-based copolymer is a copolymer of the norbornene-based monomer and an olefin copolymerizable with the norbornene-based monomer.
  • olefin include the number of carbon atoms such as ethylene, propylene, and 1-butene.
  • examples thereof include olefins having 2 to 20; cycloolefins such as cyclobutene, cyclopentene, and cyclohexene; and non-conjugated dienes such as 1,4-hexadiene.
  • the content of the cyclic olefin-based resin (b2) contained in the intermediate layer (B) is preferably 20 to 40% by mass, and 25 to 35% by mass in the resin component contained in the intermediate layer (B). More preferably.
  • the cyclic olefin resin (b2) used in the intermediate layer (B) preferably has a glass transition temperature of 140 ° C. or lower, more preferably 50 to 140 ° C., and 70 to 120 ° C. More preferably it is.
  • the glass transition temperature (Tg) is a value obtained by measurement by DSC.
  • the MFR of the cyclic olefin resin (b2) is 0.2 to 17 g / 10 min (230 ° C., 21.18 N), preferably 3 to 15 g / 10 min (230 ° C., 21.18 N), more preferably 5 to 13 g / 10 min (230 ° C., 21.18 N).
  • An MFR within this range is preferable in terms of excellent compatibility with the linear low-density polyethylene (b1) and good film formability in various multilayer film formation methods.
  • a ring-opening polymer (COP) of a norbornene monomer for example, “ZEONOR” manufactured by Nippon Zeon Co., Ltd.
  • COP ring-opening polymer
  • Examples of the copolymer (COC) include “Appel” manufactured by Mitsui Chemicals, Inc. and “TOPAS” manufactured by Polyplastics.
  • the resin component in the intermediate layer (B) it is preferable to contain only the linear low-density polyethylene (b1) and the cyclic olefin-based resin (b2), but within the range not impairing the effects of the present invention.
  • Other resins other than the resin component may be used in combination.
  • Other resin types that can be used in combination include, for example, the polyethylene-based resin and the polypropylene-based resin exemplified in the outer layer (A).
  • the content is preferably 20% by mass or less, more preferably 10% by mass or less, in the resin component contained in the intermediate layer (B).
  • the lower limit is not particularly limited, but may be appropriately used at a content of 1% by mass or more according to desired properties.
  • the inner layer (C) in the sealant film of the present invention is a layer containing a polyethylene resin, preferably a layer having an average density of resin components in the layer of 0.940 g / cm 3 or more.
  • the said inner layer (C) is a layer used as the heat seal layer of a sealant film.
  • Examples of the polyethylene resin used for the inner layer (C) and the resin that can be used in combination with the polyethylene resin can be the same as those of the outer layer (A), and preferable ones are also the same.
  • the range similar to the said outer layer (A) can be illustrated as a preferable range.
  • high density polyethylene is used in combination with medium / low density polyethylene such as ultra low density polyethylene, linear low density polyethylene, low density polyethylene, linear medium density polyethylene, etc. It is also preferable to do.
  • medium / low density polyethylene and high density polyethylene are used in combination, the content of medium / low density polyethylene in the resin component used in the inner layer (C) is 40 to 80% by mass, and the content of high density polyethylene. Is preferably 20 to 60% by mass, more preferably 45 to 75% by mass of medium / low density polyethylene and 25 to 55% by mass of high density polyethylene.
  • the sealant film of the present invention is a laminated film in which the outer layer (A), the intermediate layer (B), and the inner layer (C) are laminated in order.
  • the sealant film of the present invention can realize a packaging material that does not cause inner surface fusion or appearance irregularity during high-temperature processing such as retort sterilization processing, while having suitable easy tearability and straight cut ability.
  • achieve suitable sealing performance and bag breaking resistance it is suitable for a retort packaging material use.
  • the sealant film of the present invention has a normalized molecular orientation MORc value of 1.025 or more, preferably 1.030 or more, more preferably when the reference thickness measured with a microwave molecular orientation meter is 60 ⁇ m. Is 1.035 or more.
  • the upper limit is not particularly limited, but is preferably 1.20 or less, more preferably 1.080 or less. In the present invention, by setting the MORc value of the sealant film within the above range, it is possible to realize excellent easy tearability and straight cut ability along with suitable bag breaking resistance.
  • the MORc value is a value indicating the degree of molecular orientation, and is measured by the following measurement method. It arrange
  • the degree of molecular orientation MOR is determined by measuring the strength.
  • MORc (tc / t) ⁇ (MOR-1) +1
  • Tc reference thickness to be corrected
  • t sample thickness
  • the normalized molecular orientation MORc can be measured with a known molecular orientation meter, for example, a microwave molecular orientation meter MOA-2000A or MOA-2012A manufactured by Oji Scientific Instruments Co., Ltd. at a resonance frequency near 4 GHz.
  • the thickness of the sealant film of the present invention may be appropriately adjusted according to the application and mode to be used, but the total thickness is 20 from the viewpoint of heat resistance in packaging applications, resistance to bag breakage during distribution, heat sealability and the like. It is preferably ⁇ 150 ⁇ m, more preferably 40 to 100 ⁇ m.
  • the thickness ratio of the outer layer (A) is preferably in the range of 10 to 40% of the total thickness of the sealant film, from the viewpoints of sealing properties, easy tearing properties, and laminating properties. % Is more preferable.
  • the thickness ratio of the inner layer (C) is preferably in the range of 10 to 40%, more preferably in the range of 15 to 30%.
  • the thickness ratio of the intermediate layer (B) is preferably 10 to 80%, more preferably 15 to 60%, and particularly preferably 20 to 50%.
  • the sealant film of the present invention since it is possible to realize suitable cut properties even when the thickness ratio of the intermediate layer (B) is low (for example, 40% or less, more preferably 30% or less), it is preferable. A cut sealant film can be obtained at low cost.
  • the thickness of the outer layer (A) is preferably 2 to 60 ⁇ m, more preferably 3 to 45 ⁇ m.
  • the thickness of the intermediate layer (B1) is preferably 4 to 120 ⁇ m, and more preferably 8 to 100 ⁇ m.
  • the thickness of the inner layer (C) is preferably 2 to 60 ⁇ m, and more preferably 3 to 45 ⁇ m.
  • the sealant film of the present invention is a laminated film in which the outer layer (A), the intermediate layer (B), and the inner layer (C) are laminated in this order, but the gas barrier layer is within the range that does not impair the effects of the present invention.
  • any other layer such as an easy adhesion layer may be provided.
  • the sealant film of the present invention preferably has an average density of the resin component in the layer of all layers is 0.940 g / cm 3 or more, more be a layer of 0.940 ⁇ 0.945g / cm 3 preferable. For this reason, when providing another layer, it is preferable that the average density of the resin component in the layer of the said other layer is also the said range.
  • additives may be blended in each layer of the sealant film of the present invention as long as the effects of the present invention are not impaired.
  • the additive include an antioxidant, a weather resistance stabilizer, an antistatic agent, an antifogging agent, an antiblocking agent, a lubricant, a nucleating agent, and a pigment.
  • a resin including a resin mixture containing two or more kinds of resins and additives used for each layer of a multilayer film is heated and melted with a separate extruder.
  • a coextrusion method in which a film is laminated in a molten state by a method such as an extrusion multilayer die method or a feed block method and then formed into a film shape by an inflation method.
  • This coextrusion method is preferable because the thickness ratio of each layer can be adjusted relatively freely, and a film having excellent hygiene and cost effectiveness can be obtained.
  • an air-cooled inflation method is preferable, and an upward air-cooled inflation method can be particularly preferably used.
  • the cylindrical molten resin can be set as a multilayer film by using several extruders and a multilayer circular die. After extruding the cylindrical molten resin upward using these, the cylindrical molten resin is expanded and taken out as necessary, and after cooling and solidifying the molten resin by air cooling, it is appropriately cut and cut as desired. A film can be obtained.
  • the blow ratio during the coextrusion inflation molding is 1.0 to 2.3 and the drawdown ratio to 20 to 60. Easy to cut.
  • the drawdown ratio in the inflation method corresponds to the ratio between the line speed V L (m / min) and the die outlet speed V 0 (m / min), and is calculated as V L / V 0 .
  • the blow ratio corresponds to the ratio between the diameter D0 of the die and the final diameter D L of the bubble, and is calculated from D L / D 0 .
  • the drawdown ratio is 20 to 60, preferably 25 to 50, and more preferably 30 to 40.
  • the blow ratio is preferably 1.0 to 2.3, more preferably 1.1 to 2.0, and still more preferably 1.2 to 1.5.
  • the temperature of the extruder and the die is preferably 180 to 220 ° C.
  • the diameter of the die is preferably 100 to 1200 mm, more preferably 100 to 800 mm, and even more preferably 150 to 500 mm.
  • the lip opening of the die is preferably 0.5 to 5 mm, more preferably 1.5 to 4.5 mm, and further preferably 2.0 to 4.0 mm.
  • the discharge amount is preferably 10 to 400 Kg / h, more preferably 20 to 300 Kg / h, and still more preferably 50 to 250 Kg / h.
  • the line speed varies depending on the diameter of the die, the blow ratio, and the discharge amount, but is preferably 10 to 150 m / min, and more preferably 20 to 100 m / min.
  • the sealant film of the present invention When the sealant film of the present invention is used as a packaging material for retort, it can be used by bonding another base film to the outer layer (A) side surface of the sealant film. Although it does not specifically limit as another base film, From a viewpoint of making the effect of this invention express easily, it is preferable to use the plastic base material, especially the resin film stretched biaxially. For applications that do not require transparency, aluminum foil can be used in combination.
  • stretched resin film examples include coextrusion using, as a central layer, biaxially stretched polyester (PET), biaxially stretched polypropylene (OPP), biaxially stretched polyamide (PA), and ethylene vinyl alcohol copolymer (EVOH).
  • PET biaxially stretched polyester
  • OPP biaxially stretched polypropylene
  • PA biaxially stretched polyamide
  • EVOH ethylene vinyl alcohol copolymer
  • Biaxially stretched polypropylene, biaxially stretched ethylene vinyl alcohol copolymer (EVOH) alumina-deposited PET, silica-deposited PET, alumina-silica binary-deposited PET, silica-deposited PA, alumina-deposited PA and the like can be mentioned. These may be used alone or in combination.
  • two processing methods are mainly used.
  • One is to apply an anchor coating agent on the laminate surface of the sealant film of the present invention or the base film, if necessary, and to heat and melt the polymer film (polyethylene, polypropylene, etc.) with the sealant film of the present invention.
  • This is an extrusion laminating method in which a thin film is extruded between the laminate surfaces of the material film, and is pressed and laminated.
  • the other is a dry laminating method in which an adhesive is applied to the laminating surface of the base film, and then the sealant film of the present invention and the base film are pressure-bonded and laminated. preferable.
  • the adhesive for laminating is generally cured by polyol / isocyanate, and is widely used for high-functional applications such as retort applications.
  • the combination of the aluminum foil and the sealant film was generally used for pasting, but various transparent vapor deposition films have come to be marketed. From the demand for improving the visibility of the contents, the transparent vapor deposition film and Bonding of sealant film is also increasing.
  • a polyol used for the adhesive for laminating for example, a polyol itself described later, or a polyester polyol obtained by reacting a polyol with a polycarboxylic acid described later, or ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, Ethylene oxide, propylene oxide, butylene starting from compounds having two active hydrogen atoms such as trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, etc.
  • polyethers obtained by addition polymerization of monomers such as oxide, styrene oxide, epichlorohydrin, tetrahydrofuran and cyclohexylene.
  • polyol examples include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, and 1,6-hexane.
  • polycarboxylic acids examples include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic anhydride, fumaric acid, 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, terephthalic acid.
  • Acid isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane-p , P'-dicarboxylic acids and anhydrides or ester-forming derivatives of these dicarboxylic acids; p-hydroxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid, ester-forming derivatives of these dihydroxycarboxylic acids, dimer acids, etc. Of the polybasic acids.
  • polyisocyanate examples include organic compounds having at least two isocyanate groups in the molecule.
  • organic polyisocyanate examples include tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, 1,6-hexamethylene diisocyanate, isophorone diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), lysine diisocyanate, trimethylhexamethylene diisocyanate, 1 , 3- (isocyanatomethyl) cyclohexane, 1,5-naphthalene diisocyanate, polyisocyanate such as triphenylmethane triisocyanate; adducts of these polyisocyanates, burettes of these polyisocyanates, or of these polyisocyanates Derivatives (modified products) of polyisocyanates such as isocyanurates are exemplified.
  • a product obtained by reacting the isocyanate and the polyol with a mixing ratio in which an isocyanate group becomes excessive may be used.
  • the equivalent ratio polyol / isocyanate of the hydroxyl group equivalent of the polyol and the isocyanate equivalent of the polyisocyanate is preferably 0.5 to 5.0.
  • the packaging material of the present invention uses the above-mentioned sealant film as a sealant, and laminates a base film on the outer layer (A) side of the sealant film, thereby realizing good sealing properties and good tearability due to suitable tearing properties. it can.
  • suitable heat resistance and resistance to bag breakage can be realized, it is possible to suppress fusion between the inner layers (C) serving as a heat seal layer and uneven appearance even during high-temperature sterilization treatment.
  • the packaging material formed by laminating the sealant film of the present invention with various base materials can be suitably applied as a packaging material for retort food.
  • the packaging material of the present invention can be suitably used as a packaging bag by making bags into various shapes such as a flat bag type, a self-supporting packaging bag (standing pouch) type, and a tube type.
  • a flat bag type a self-supporting packaging bag (standing pouch) type
  • a tube type a tube type.
  • one film-like packaging material is folded so that the sealant layers face each other, or two film-like packaging materials of the present invention are piled so that the sealant layers face each other,
  • the peripheral edge part can be heat-sealed to form a bag for a retort food or the like (retort pouch).
  • the packaging material of the present invention and the packaging bag for retort foods using the packaging material can be suitably used for packaging foods that require treatment under high-temperature hot water conditions such as boiling and retort sterilization, such as curry, It can be suitably applied to various retort food packaging applications such as stew, soup, and cooking sauces.
  • Example 1 The resin mixture which forms each layer was prepared using the following resin as a resin component which forms each layer of an outer layer, an intermediate
  • LLC (1) linear low density polyethylene having an MFR of 0.5 g / 10 min (190 ° C., 21.18 N) and a density of 0.944 g / cm 3 .
  • LLDPE LidPE (1) 70% by mass, glass transition temperature (Tg) 78 ° C., MFR 10 g / 10 min (230 ° C., 21.18 N) norbornene copolymer (hereinafter referred to as “COC”) 30 Mass% resin mixture
  • Inner layer LLDPE (1) 50 mass%, MFR 1 g / 10 min (190 ° C., 21.18 N), density 0.960 g / cm 3 high density polyethylene (hereinafter referred to as “HDPE”) 50 mass % Mixed resin.
  • HDPE high density polyethylene
  • Example 2 A laminated film was obtained in the same manner as in Example 1 except that the blow ratio was 1.5 and the drawdown ratio was 27.
  • Example 3 A laminated film was obtained in the same manner as in Example 1 except that the blow ratio was 1.8 and the drawdown ratio was 23.
  • Example 4 A laminated film was obtained in the same manner as in Example 1 except that the outer layer / intermediate layer / inner layer thickness ratio (%) was 40/25/35, the blow ratio was 1.2, and the drawdown ratio was 35.
  • Example 5 A laminated film was obtained in the same manner as in Example 1 except that the thickness ratio (%) of the outer layer / intermediate layer / inner layer was 35/30/35.
  • Example 6 A laminated film was obtained in the same manner as in Example 2 except that the resin components used for the outer layer and inner layer were as follows. Outer layer: MFR 0.9 g / 10 min (190 ° C., 21.18 N), linear low density polyethylene (hereinafter referred to as “LLDPE (2)”) having a density of 0.929 g / cm 3 , 60% by mass, HDPE 40 Mixed resin material of mass% Inner layer: Mixed resin material of 50% by mass of LLDPE (2) and 50% by mass of HDPE.
  • Example 7 A precision layer film was obtained in the same manner as in Example 2 except that the resin component used in the outer layer and the inner layer was LLDPE (2).
  • Example 8 A laminated film was obtained in the same manner as in Example 2 except that the resin component used in the intermediate layer was LLDPE (2) 70 mass% and COC 30 mass%.
  • Example 1 A laminated film was obtained in the same manner as in Example 1 except that the blow ratio was 2.5 and the drawdown ratio was 15.
  • Comparative Example 2 A laminated film was obtained in the same manner as in Example 2 except that the resin component used for the intermediate layer was LLDPE (1).
  • Example 3 The resin components forming the outer layer, the intermediate layer, and the inner layer were the same as in Example 1, and these resin mixtures were respectively supplied to three extruders and melted at 250 ° C.
  • the melted resin is supplied to a co-extruded multilayer film production apparatus (feed block and T-die temperature: 250 ° C.) using a T-die / chill roll method having a feed block, and co-melt extrusion is performed.
  • a sealant film having a total thickness of 50 ⁇ m was obtained with a three-layer structure of / intermediate layer / inner layer and a thickness ratio of each layer of 25/50/25%.
  • the attached polyester sheet is folded back in the direction of 180 °, the test piece excluding the notch on the side opposite to the tip is attached to a tensile tester, and it is torn 100 mm at a speed of 300 mm / min, and the width of the end point (W 1 ) Is actually measured.
  • Appearance unevenness A laminate film was obtained in the same manner as in (3). Using the obtained film, the bag was processed so that the inner size was 100 mm ⁇ 150 mm (heat seal width 10 mm), and 200 ml of water was sealed. After the bag-making product enclosing water was retorted at 121 ° C. for 30 minutes, the appearance unevenness was visually evaluated.
  • the sealant films of the present invention of Examples 1 to 8 had tear strength that was easy to tear and good straight-cut properties.
  • the sealant films of Examples 1 to 6 and 8 all had a peel strength of 1 N / 15 mm or less in the evaluation of inner surface fusion. Further, the sealant films of Examples 1 to 6 were not visually recognized even in appearance evaluation.
  • the sealant film of the comparative example did not have easy tearability and good straight cut property, and did not have suitable tear property.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Wrappers (AREA)
  • Laminated Bodies (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)

Abstract

L'invention concerne un film de scellement, caractérisé en ce que : le film de scellement comprend un film stratifié dans lequel une couche externe, une couche intermédiaire et une couche interne sont stratifiées; la couche externe et la couche interne contiennent une résine à base de polyéthylène; la couche intermédiaire contient un polyéthylène basse densité à chaîne droite et une résine à base d'oléfine cyclique; la teneur en résine à base d'oléfine cyclique dans les constituants de résine contenus dans la couche intermédiaire est de 20 à 40 % en masse; et la valeur de Morc d'orientation moléculaire normalisée, lorsque l'épaisseur de référence mesurée à l'aide d'un dispositif de mesure d'orientation de molécule à micro-ondes est de 60 µm, est d'au moins 1,025. Grâce à l'utilisation du film de scellement, une facilité remarquable de déchirement et des propriétés de coupe droite peuvent être obtenues, et pendant un traitement à haute température, une fusion de surface interne d'un matériau d'emballage et un aspect extérieur irrégulier de ce dernier peuvent être supprimés.
PCT/JP2018/015358 2017-04-26 2018-04-12 Film de scellement et matériau d'emballage WO2018198794A1 (fr)

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JP2021102300A (ja) * 2019-12-25 2021-07-15 Dic株式会社 積層フィルム及び包装材

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JP2015199797A (ja) * 2014-04-04 2015-11-12 積水フィルム株式会社 熱収縮フィルム
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JP2017024181A (ja) * 2015-07-15 2017-02-02 積水フィルム株式会社 特定方向に易カット性を有する積層シート及びそれを用いた包装体

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JP5510710B2 (ja) 2010-02-10 2014-06-04 東レフィルム加工株式会社 易引裂き性ポリプロピレン系未延伸フィルムおよびその積層体
JP6241112B2 (ja) 2013-07-31 2017-12-06 大日本印刷株式会社 シーラントフィルム

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JPH06220220A (ja) * 1992-11-06 1994-08-09 Daicel Chem Ind Ltd 易引裂き性フィルムおよびその製造方法
JP2000199939A (ja) * 1999-01-04 2000-07-18 Fuji Photo Film Co Ltd 写真感光材料用包装材料及びこれを用いた写真感光材料包装体
WO2004063273A1 (fr) * 2003-01-10 2004-07-29 Amcor Flexibles Winterbourne Ltd Films polymeres et emballages produits a partir de ces derniers
JP2004284351A (ja) * 2003-03-06 2004-10-14 Toyobo Co Ltd 透明性に優れた積層ポリオレフィンフィルム及び積層包装材料
JP2009172902A (ja) * 2008-01-25 2009-08-06 Toppan Printing Co Ltd 直線カット性を有するバリア性包装材料及び包装袋
US20090285511A1 (en) * 2008-03-07 2009-11-19 Pliant Corporation Cross Direction Tear Film and Package
JP2012030555A (ja) * 2010-08-02 2012-02-16 Mitsubishi Plastics Inc 多層フィルム
JP2014529520A (ja) * 2011-08-23 2014-11-13 フータマキ フィルムズ ジャーマニー ゲゼルシャフト ミット ベシュレンクテル ハフツング ウント コンパニー コマンディートゲゼルシャフト 線状引き裂き伝播を有する多層フィルム
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2021102300A (ja) * 2019-12-25 2021-07-15 Dic株式会社 積層フィルム及び包装材
JP7342694B2 (ja) 2019-12-25 2023-09-12 Dic株式会社 積層フィルム及び包装材

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