WO2013105524A1 - シーラント用樹脂組成物、積層フィルムおよび包装袋 - Google Patents
シーラント用樹脂組成物、積層フィルムおよび包装袋 Download PDFInfo
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- WO2013105524A1 WO2013105524A1 PCT/JP2013/050019 JP2013050019W WO2013105524A1 WO 2013105524 A1 WO2013105524 A1 WO 2013105524A1 JP 2013050019 W JP2013050019 W JP 2013050019W WO 2013105524 A1 WO2013105524 A1 WO 2013105524A1
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- sealant
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- laminated film
- resin composition
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—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 an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal 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
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- 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
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- 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
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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- 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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- 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
- B65D31/00—Bags or like containers made of paper and having structural provision for thickness of contents
- B65D31/02—Bags or like containers made of paper and having structural provision for thickness of contents with laminated walls
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- 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
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- 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
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
- C08L23/0823—Copolymers of ethene with aliphatic cyclic olefins
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L45/00—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J145/00—Adhesives based on homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic system; Adhesives based on derivatives of such polymers
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- 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
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/31—Heat sealable
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- 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
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/514—Oriented
- B32B2307/518—Oriented bi-axially
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- 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
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- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/54—Yield strength; Tensile strength
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- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/724—Permeability to gases, adsorption
- B32B2307/7242—Non-permeable
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- 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
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- B32B2439/00—Containers; Receptacles
- B32B2439/70—Food packaging
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/40—Polymerisation processes
- C08G2261/41—Organometallic coupling reactions
- C08G2261/418—Ring opening metathesis polymerisation [ROMP]
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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- Y10T428/00—Stock material or miscellaneous articles
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- Y10T428/2852—Adhesive compositions
- Y10T428/2878—Adhesive compositions including addition polymer from unsaturated monomer
Definitions
- the present invention relates to a resin composition for a sealant, a laminated film, and a packaging bag, which are excellent in non-adsorption property and barrier property for a low molecular weight organic compound and are capable of stable heat sealing.
- Patent Document 1 describes a resin composition in which a cycloolefin copolymer (COC) is blended with a specific ethylene- ⁇ -olefin copolymer.
- Patent Document 2 discloses a cyclic olefin resin for melt extrusion in which a cyclic olefin resin (A) having a low glass transition point and a cyclic olefin resin (B) having a high glass transition point are blended in a specific blending ratio range. A composition is described.
- Patent Document 1 since the ethylene- ⁇ -olefin copolymer is a base resin (resin that is a main component), when the packaging film is used as a bag, the organic components contained in the contents are easily adsorbed to the sealant. There is a problem.
- Patent Document 2 what is used in the example is a blend of TOPAS (registered trademark) cycloolefin copolymer (COC), and the organic component contained in the contents when the packaging film is used as a bag. Has a problem that it is easily adsorbed to the sealant.
- TOPAS registered trademark
- COC cycloolefin copolymer
- the present invention has been made in view of the above circumstances, and provides a resin composition for a sealant, a laminated film, and a packaging bag capable of improving non-adsorption to an organic component contained in contents and heat sealing.
- the issue is to provide.
- a sealant resin composition comprising a cycloolefin polymer (hereinafter abbreviated as COP) and a cycloolefin copolymer (hereinafter abbreviated as COC),
- a resin composition for a sealant containing 10 to 95% by weight of an olefin polymer and 5 to 90% by weight of a cycloolefin copolymer.
- the COP is a polymer of a cyclic olefin having a norbornene skeleton or a hydrogenated product thereof.
- the COC is preferably a polymer of a cyclic olefin having a norbornene skeleton and an acyclic olefin, or a hydrogenated product thereof.
- the present invention is a laminated film having a plurality of layers including a base material and a sealant layer that is one outermost surface of the laminated film, wherein the sealant layer contains the resin composition for sealant.
- a laminated film is provided.
- this invention provides the packaging bag characterized by having the heat seal part which consists of the said laminated
- the present invention it is possible to provide a resin composition for sealant, a laminated film, and a packaging bag capable of improving the non-adsorption property with respect to the organic component contained in the contents and the heat sealing property.
- the resin composition for sealant of this embodiment is a resin composition for sealant containing a cycloolefin polymer (COP) and a cycloolefin copolymer (COC), and has a COP of 10 to 95% by weight, a COC of 5 to 90% by weight, Containing.
- COP cycloolefin polymer
- COC cycloolefin copolymer
- the laminated film of the present embodiment has a configuration in which a base material, a sealant layer, and another intermediate layer as necessary are laminated. That is, it has a plurality of layers including a sealant layer that is one of the outermost surfaces of the laminated film, a base material, and another intermediate layer, an adhesive layer, an anchor agent layer, or the like as necessary.
- the sealant layer is a layer used for heat sealing, and is disposed in the innermost layer in contact with the contents as a packaging material.
- the sealant layer is formed of the resin composition for sealant of this embodiment.
- the base material or other intermediate layer and the sealant layer may be laminated via an adhesive layer or an anchor agent layer, or may be directly laminated on the base material.
- the intermediate layer one or more layers such as a reinforcing layer, a gas barrier layer, a light-shielding layer, and a printing layer can be appropriately selected.
- the cycloolefin polymer used in the resin composition for a sealant of the present invention is, for example, a homopolymer of a cyclic olefin, a copolymer of two or more cyclic olefins, or a hydrogenated product thereof, and is usually referred to as COP (Cycloolefin polymer). It is what is done.
- the COP is preferably an amorphous polymer, more preferably a ring-opening polymer of a cyclic olefin by metathesis or the like or a hydrogenated product thereof.
- the COP is preferable because it has a higher ratio of containing an alicyclic structure than COC or the like and is excellent in non-adsorption.
- COP has a structure represented by the following chemical formula (1).
- R 1 and R 2 represent the same or different organic group having 1 to 20 carbon atoms or a hydrogen atom, and R 1 and R 2 may form a ring with each other.
- N is 1 Indicates the integer above.
- the cycloolefin copolymer used in the resin composition for sealant of the present invention is, for example, a copolymer of one or two or more cyclic olefins and one or two or more acyclic olefins or a hydrogenated product thereof, Usually, it is called COC (Cyclorefin copolymer).
- the COC is preferably an amorphous polymer, more preferably a copolymer of a cyclic olefin and ethylene or a hydrogenated product thereof.
- COC can have a structure represented by the following chemical formula (2).
- R 1 and R 2 represent the same or different organic group having 1 to 20 carbon atoms or a hydrogen atom, and R 1 and R 2 may form a ring with each other;
- R 3 represents Represents an organic group having 1 to 20 carbon atoms or a hydrogen atom, and m and p each represents an integer of 1 or more.
- examples of the organic group having 1 to 20 carbon atoms include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, i-pentyl, t-pentyl, n-hexyl, n-heptyl, n-octyl, t-octyl (1,1-dimethyl-3,3-dimethylbutyl), 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, Alkyl groups such as pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl; cycloalkyl groups such as cyclopentyl, cyclohexyl,
- Examples of the cyclic olefin used as the constituent monomer of the COP and the COC include, for example, vinylcycloalkanes having a cycloalkane having 3 to 20 carbon atoms and derivatives thereof, monocycloalkenes having 3 to 20 carbon atoms, and A derivative thereof or a cyclic olefin having a norbornene skeleton (norbornene monomer) is preferred.
- Examples of the norbornene monomer include bicyclo [2.2.1] -2-heptene (norbornene) and its derivatives, tricyclo [4.3.0.1 2,5 ] as shown in the following chemical formula (3).
- Derivatives include those having one or more organic groups (R 1 , R 2 ) having 1 to 20 carbon atoms as substituents, and those having two or more unsaturated bonds such as norbornadiene. .
- Examples of the acyclic olefin used as the constituent monomer of the COC include ethylene, ⁇ -olefins such as propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, and 3-decene. And 3-dodecene.
- the COP is preferably a polymer of a cyclic olefin having a norbornene skeleton or a hydrogenated product thereof
- the COC is a polymer of a cyclic olefin having a norbornene skeleton and an acyclic olefin or a hydrogenated product thereof.
- a commercial item can be used as COP, for example, ZEONEX and ZEONOR made by ZEON CORPORATION can be suitably used.
- Commercially available products can also be used as the COC, for example, Appel manufactured by Mitsui Chemicals, Inc., and TOPAS manufactured by Polyplastics Co., Ltd. can be preferably used.
- the sealant layer used in the laminated film of the present invention is formed using the sealant resin composition.
- An appropriate additive can be added to the resin composition as long as the object of the present invention is not impaired.
- the additive include an antioxidant, a lubricant, an anti-blocking agent, a flame retardant, an ultraviolet absorber, a light stabilizer, an antistatic agent, and a colorant.
- the glass transition temperature (Tg) of the resin composition for sealant is preferably higher than 40 ° C. When the glass transition temperature is 40 ° C. or lower, the non-adsorbability of the resulting sealant layer is lowered.
- the Tg of COP before blending is preferably 50 to 140 ° C.
- the Tg of COC is also preferably 50 to 140 ° C.
- the mixing ratio of COP and COC is 10 to 95% by weight of COP and 5 to 90% by weight of COC, where the total of both is 100% by weight.
- a stretched film excellent in mechanical properties such as heat resistance and strength and printability is preferable.
- the thickness of the substrate is usually 10 to 50 ⁇ m, preferably 10 to 30 ⁇ m.
- An anchor agent layer or an adhesive layer is preferably interposed inside the sealant layer in order to adhere the sealant layer to a substrate or other film.
- an anchor agent layer in contact with the inside of the sealant layer is formed.
- O-PET is used as the substrate, the anchor agent layer need not be used.
- an adhesive layer in contact with the inside of the sealant layer is formed.
- an adhesive resin such as acid-modified polyolefin may be used.
- an anchoring agent generally used for extrusion laminating methods such as polyurethane, polyether, alkyl titanate (organic titanium compound), etc. can be used. They can be selected together.
- an adhesive which comprises the said adhesive bond layer the adhesive agent generally used for dry lamination methods, such as a polyurethane type and a polyether type
- a gas barrier layer, a reinforcing layer, or the like may exist as an intermediate layer.
- the reinforcing layer serves to supplement the strength characteristics of the laminated film.
- the resin constituting the reinforcing layer is a polyolefin resin such as polypropylene (PP) or polyethylene (PE), biaxially oriented polyethylene terephthalate (O-PET). Biaxially stretched nylon (O—Ny), biaxially stretched polypropylene (OPP) and the like can be mentioned.
- the thickness of the reinforcing layer is usually 5 to 50 ⁇ m, preferably 10 to 30 ⁇ m.
- the gas barrier layer has a function of imparting gas barrier properties to block gas such as oxygen and water vapor from passing through the laminated film.
- gas barrier layer examples include metal foil, a vapor deposition layer of aluminum or an inorganic oxide, a gas barrier resin layer such as ethylene-vinyl alcohol copolymer (EVOH), vinylidene chloride.
- EVOH ethylene-vinyl alcohol copolymer
- These gas barrier layers can be provided on one side of the film constituting the base material or the reinforcing layer, and are generally provided as an intermediate layer between the base material and the sealant layer.
- an inorganic oxide vapor deposition layer it can also be used as the outermost layer outside the substrate (the outermost layer on the opposite side of the sealant layer in the laminated film).
- the thickness of the gas barrier layer is usually 5 to 50 ⁇ m, preferably 10 to 30 ⁇ m, when using a metal foil or a gas barrier resin layer.
- a metal vapor deposition layer or an inorganic oxide vapor deposition layer as a gas barrier layer, it can be made thinner than this.
- the method for producing the laminated film of the present invention is not particularly limited, and each layer constituting the laminated film may be appropriately laminated by an extrusion lamination method, a dry lamination method, a co-extrusion method, or a combination thereof.
- the thickness of the sealant layer depends on the use of the packaging material and is not particularly limited, but is usually about 5 to 150 ⁇ m, preferably 15 to 80 ⁇ m.
- the packaging bag of this embodiment is obtained by heat-sealing the sealant layer of the above laminated film. Since the packaging bag of this embodiment is excellent in the non-adsorption property and the barrier property of low molecular weight components, it can be suitably used as a packaging bag for foods, drinks, cosmetics, drugs, and the like.
- the form of the packaging bag can be three-sided bags, four-sided bags, joint-attached bags, gusset bags, self-standing bags, etc. It is applicable without particular limitation.
- any spout can be suitably used as long as the sealing film can be secured by joining with the sealant layer of the laminated film constituting the packaging bag.
- the spout is formed of a heat-sealable resin, and the spout and the laminated film are joined by heat sealing.
- the spout may be inserted and heat-sealed while the laminated film is overlapped with the sealant layer on the inside.
- a fusion base portion may be provided, and the flange portion or the fusion base portion may be heat sealed to the peripheral edge of the hole provided in the laminated film or the inner surface of the opening of the packaging bag.
- a resin composition for a sealant material was produced with a composition in which COP was blended in a range of 100 to 0% by weight and COC in a range of 0 to 100% by weight.
- a sealant material was produced by extrusion molding into a film having a predetermined thickness.
- the COP and COC used are as follows.
- COP cycloolefin polymer (manufactured by ZEON CORPORATION, trade name ZEONOR (registered trademark) 1020R)
- COC1 a cycloolefin copolymer (trade name TOPAS (registered trademark) 8007F-04, manufactured by Polyplastics Co., Ltd.) "COC2” ... cycloolefin copolymer (Mitsui Chemicals, trade name: Apel (registered trademark) APL8008T)
- Heat seal strength According to JIS Z 0238, the seal strength (N / 15 mm) of the heat seal part of the pouch was measured at a tensile speed of 300 mm / min and a width of 15 mm.
- the heat sealing condition is to heat and pressurize at a pressure of 0.2 MPa for 1 second at any temperature among 140 ° C., 160 ° C., 180 ° C., 200 ° C., and 220 ° C.
- the compounding ratio of COP and COC (the whole resin composition, that is, the total amount of COP and COC is 100 wt%) is COP 10 to 95 wt% and COC 5 to 90 wt%.
- the seal strength and non-adsorption were excellent.
- the tensile elongation was significantly improved as compared with COP alone (Example 1) and COC alone (Examples 11 and 23).
- COP alone Example 1
- the temperature at which a sufficient heat seal temperature was obtained was as high as 200 ° C. or higher, and a stable region of seal strength was not observed.
- the present invention can be suitably used particularly for packaging of contents containing fragrances and active ingredients such as foods and drinks, cosmetics, and drugs.
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Abstract
Description
本願は、2012年1月11日に、日本に出願された特願2012-003221号に基づき優先権を主張し、その内容をここに援用する。
特許文献2には、ガラス転移点の低い環状オレフィン系樹脂(A)と、ガラス転移点の高い環状オレフィン系樹脂(B)とを、特定の配合割合範囲でブレンドした溶融押出用環状オレフィン系樹脂組成物が記載されている。
特許文献2の場合、実施例で用いられるものはTOPAS(登録商標)社のシクロオレフィンコポリマー(COC)同士をブレンドするものであり、包装フィルムを袋としたときに内容物に含まれる上記有機成分がシーラントに吸着しやすいという問題がある。
前記COPは、ノルボルネン骨格を有する環状オレフィンの重合体またはその水素添加物である。前記COCは、ノルボルネン骨格を有する環状オレフィンと非環状オレフィンとの重合体またはその水素添加物であることが好ましい。
また、本発明は、基材と、積層フィルムの一方の最表面となるシーラント層とを含む複数の層を有する積層フィルムにおいて、前記シーラント層が、前記シーラント用樹脂組成物を含有することを特徴とする積層フィルムを提供する。
また、本発明は、前記積層フィルムからなり、前記シーラント層をヒートシールしてなるヒートシール部を有することを特徴とする包装袋を提供する。
本形態例のシーラント用樹脂組成物は、シクロオレフィンポリマー(COP)とシクロオレフィンコポリマー(COC)とを含有するシーラント用樹脂組成物であって、COP10~95重量%と、COC5~90重量%とを含有する。
ここで、シーラント層とは、ヒートシールに用いられる層であり、包装材料としては内容品に接する最内層に配置されるものである。該シーラント層が、本形態例のシーラント用樹脂組成物で形成されている。
基材または他の中間層と、シーラント層との積層は、接着剤層又はアンカー剤層を介しても良いし、基材に直接積層されていても良い。前記中間層としては、補強層、ガスバリア層、遮光層、印刷層など、適宜、一層または複数層を選択することができる。
例えば、COPは以下の化学式(1)で表される構造を有する。
例えば、COCは下記化学式(2)で表される構造を有することができる。
ノルボルネン系モノマーとしては、例えば、下記化学式(3)に示すように、ビシクロ[2.2.1]-2-ヘプテン(ノルボルネン)およびその誘導体、トリシクロ[4.3.0.12,5]-3-デセンおよびその誘導体、テトラシクロ[4.4.0.12,5.17,10]-3-ドデセンおよびその誘導体、ペンタシクロ[6.5.1.13,6.02,7.09,13]-4-ペンタデセンおよびその誘導体、ペンタシクロ[7.4.0.12,5.19,12.08,13]-3-ペンタデセンおよびその誘導体、ペンタシクロ[8.4.0.12,5.19,12.08,13]-3-ヘキサデセンおよびその誘導体、ペンタシクロ[6.6.1.13,6.02,7.09,14]-4-ヘキサデセンおよびその誘導体、ヘキサシクロ[6.6.1.13,6.110,13.02,7.09,14]-4-ヘプタデセンおよびその誘導体、ヘプタシクロ[8.7.0.12,9.14,7.111,17.03,8.012,16]-5-エイコセンおよびその誘導体、ヘプタシクロ[8.7.0.13,6.110,17.112,15.02,7.011,16]-4-エイコセンおよびその誘導体、ヘプタシクロ[8.8.0.12,9.14,7.111,18.03,8.012,17]-5-ヘンエイコセンおよびその誘導体、オクタシクロ[8.8.0.12,9.14,7.111,18.113,16.03,8.012,17]-5-ドコセンおよびその誘導体、ノナシクロ[10.9.1.14,7.113,20.115,18.02,10.03,8.012,21.014,19]-5-ペンタコセンおよびその誘導体等が挙げられる。誘導体としては、置換基として上記炭素数1~20の有機基(R1、R2)を1つまたは2つ以上有するものや、ノルボルナジエンのように不飽和結合を2以上有するもの等が挙げられる。
COPとしては市販品を用いることができ、例えば日本ゼオン株式会社製のゼオネックス、ゼオノアを好適に用いることができる。COCとしても市販品を用いることができ、例えば三井化学株式会社製のアペル、ポリプラスチックス株式会社製のTOPASを好適に用いることができる。
前記シーラント用樹脂組成物のガラス転移温度(Tg)は、40℃より高いことが好ましい。ガラス転移温度が40℃以下の場合、得られるシーラント層の非吸着性が低下する。また、ブレンド前のCOPのTgが50~140℃であることが好ましく、COCのTgも50~140℃であることが好ましい。
前記アンカー剤層を構成するアンカー剤としては、ポリウレタン系、ポリエーテル系、アルキルチタネート(有機チタン化合物)系等、一般的に押出ラミネート法に使用されるアンカー剤が使用でき、積層フィルムの用途に合わせて選択可能である。
前記接着剤層を構成する接着剤としては、ポリウレタン系、ポリエーテル系等、一般的にドライラミネート法に使用される接着剤を使用でき、積層フィルムの用途に合わせて選択可能である。
補強層は積層フィルムの強度特性を補完する役割であって、補強層を構成する樹脂としては、ポリプロピレン(PP)、ポリエチレン(PE)等のポリオレフィン系樹脂、2軸延伸ポリエチレンテレフタレート(O-PET)、2軸延伸ナイロン(O-Ny)、2軸延伸ポリプロピレン(OPP)等を挙げることができる。補強層の厚みは、通常5~50μmであり、好ましくは10~30μmである。
ガスバリア層の厚みは、金属箔またはガスバリア性樹脂層による場合は通常5~50μmであり、好ましくは10~30μmである。ガスバリア層として金属蒸着層または無機酸化物蒸着層を用いる場合には、これより薄くすることができる。
本形態例の積層フィルムにおいて、シーラント層の厚さは、包装材料の用途にも依存し、特に限定されるものではないが、通常は5~150μm程度であり、好ましくは15~80μmである。
本形態例の包装袋は、上述の積層フィルムの前記シーラント層をヒートシールして得られる。本形態例の包装袋は、低分子量成分の非吸着性およびバリア性にも優れているから、飲食物や化粧品、薬剤等の包装袋として好適に利用できる。包装袋の形態は、三方袋、四方袋、合掌貼り袋、ガゼット袋、自立袋等の包装袋(パウチ)のほか、例えばバッグインボックス用の内袋やドラム缶内装袋などの大型の袋等、特に限定なく適用可能である。
表1および表2に示すように、COPを100~0重量%、COCを0~100重量%の範囲で配合した組成により、シーラント材用樹脂組成物を製造した。次いで、得られたシーラント材用樹脂組成物を溶融混練後、押出成形により、所定の厚さのフィルム状に成形する方法によりシーラント材を製造した。
なお、用いたCOPおよびCOCは、次のとおりである。
「COP」・・・シクロオレフィンポリマー(日本ゼオン株式会社製、商品名ZEONOR(登録商標)1020R)
「COC1」・・・シクロオレフィンコポリマー(ポリプラスチックス株式会社製、商品名TOPAS(登録商標)8007F-04)
「COC2」・・・シクロオレフィンコポリマー(三井化学株式会社製、商品名アペル(登録商標)APL8008T)
厚み30μmのシーラント材とPETフィルムおよびAl箔とをドライラミネートにより貼り合わせ、PET12μm/Al箔9μm/シーラント材30μmの層構成を有する積層フィルムを得た。
上記積層フィルムを用いてパウチを作製し、下記に説明する評価を行った。ただし(4)の引張特性は、シーラント材から作製した試験片を評価した。
JIS Z 0238に準じて、パウチのヒートシール部のシール強度(N/15mm)を引張速度300mm/min、幅15mmにて測定した。ヒートシール条件は、140℃、160℃、180℃、200℃、220℃のうちのいずれかの温度において、圧力0.2MPaで1秒間加熱および加圧するものである。
(1)で測定したヒートシール強度が13N/mm以上であり、かつ、各溶着温度の前後20℃のいずれかのシール強度が±1N/15mm以内の範囲に収まる温度範囲を、安定領域と定義した。
有効成分として酢酸α-トコフェロール(ビタミンEアセテート)を含む市販の化粧水2.5mlをパウチに入れ、パウチの開口部を圧力0.2MPa、時間1秒、温度180℃でヒートシールして密封した。密封したパウチを40℃で1ヶ月ないし3ヶ月保管した後に開封し、化粧水中の酢酸α-トコフェロールの残存量を高速液体クロマトグラフィ法で定量し、前記残存量をもとに有効成分の残存率を算出した。
シーラント材の引張強度(N/15mm)及び引張伸度(%)は、JIS K 7127「プラスチック-引張特性の試験方法」に規定された測定方法に準じて測定した。試験片の幅は15mm、引張速度は300mm/minとした。引張伸度の掴み具間は50mmとした。
COC1が80重量%以上(例9~11)では、引張伸度が低く、COC1単独(例11)と同程度であった。さらに、COC1単独(例11)では、180℃程度の低温ではヒートシール強度が良いが、それ以上の温度ではヒートシール強度が下降した。
COC2が95重量%以上(例22)では、ヒートシール強度および引張伸度が低く、COC2単独(例23)と同程度かそれよりも低下した。
Claims (4)
- シクロオレフィンポリマーとシクロオレフィンコポリマーとを含有するシーラント用樹脂組成物であって、シクロオレフィンポリマー10~95重量%と、シクロオレフィンコポリマー5~90重量%とを含有することを特徴とするシーラント用樹脂組成物。
- 前記シクロオレフィンポリマーは、ノルボルネン骨格を有する環状オレフィンの重合体またはその水素添加物であり、
前記シクロオレフィンコポリマーは、ノルボルネン骨格を有する環状オレフィンと非環状オレフィンとの重合体またはその水素添加物であることを特徴とする請求項1に記載のシーラント用樹脂組成物。 - 基材と、積層フィルムの一方の最表面となるシーラント層とを含む複数の層を有する積層フィルムにおいて、
前記シーラント層が、請求項1または2に記載のシーラント用樹脂組成物を含有することを特徴とする積層フィルム。 - 請求項3に記載の積層フィルムで形成され、前記シーラント層をヒートシールしてなるヒートシール部を有することを特徴とする包装袋。
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- 2013-01-07 CA CA2857460A patent/CA2857460C/en active Active
- 2013-01-07 CN CN201380004076.5A patent/CN103958639A/zh active Pending
- 2013-01-07 KR KR20147012643A patent/KR20140121813A/ko active Search and Examination
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Cited By (15)
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US9962913B2 (en) | 2012-12-07 | 2018-05-08 | Bemis Company, Inc. | Multilayer film |
US10934070B2 (en) | 2014-02-11 | 2021-03-02 | Bemis Company, Inc. | Anti-scalping pharmaceutical packaging film |
US12065296B2 (en) | 2014-02-11 | 2024-08-20 | Amcor Flexibles North America, Inc. | Anti-scalping pharmaceutical packaging film |
US9468584B2 (en) | 2014-04-02 | 2016-10-18 | Bemis Company, Inc. | Child-resistant packaging |
JP2016172376A (ja) * | 2015-03-17 | 2016-09-29 | Dic株式会社 | バリア性積層体及びこれを用いた包装材 |
JP2017193342A (ja) * | 2016-04-18 | 2017-10-26 | キョーラク株式会社 | 積層剥離容器 |
JP6993554B2 (ja) | 2016-04-18 | 2022-01-13 | キョーラク株式会社 | 積層剥離容器 |
WO2017183502A1 (ja) * | 2016-04-18 | 2017-10-26 | キョーラク株式会社 | 積層剥離容器 |
JPWO2019069514A1 (ja) * | 2017-10-03 | 2020-09-17 | 凸版印刷株式会社 | 積層体、包装体及び包装物品 |
WO2019069514A1 (ja) * | 2017-10-03 | 2019-04-11 | 凸版印刷株式会社 | 積層体、包装体及び包装物品 |
US11607865B2 (en) | 2017-10-03 | 2023-03-21 | Toppan Printing Co., Ltd. | Laminate, package, and packaged article |
JP7298477B2 (ja) | 2017-10-03 | 2023-06-27 | 凸版印刷株式会社 | 積層体、包装体及び包装物品 |
JP2019155868A (ja) * | 2018-03-16 | 2019-09-19 | 藤森工業株式会社 | 積層フィルム及び包装袋 |
JP2020001309A (ja) * | 2018-06-29 | 2020-01-09 | 凸版印刷株式会社 | 積層体、包装体及び包装物品 |
JP7107028B2 (ja) | 2018-06-29 | 2022-07-27 | 凸版印刷株式会社 | 積層体、包装体及び包装物品 |
Also Published As
Publication number | Publication date |
---|---|
KR20140121813A (ko) | 2014-10-16 |
CA2857460C (en) | 2019-08-20 |
JPWO2013105524A1 (ja) | 2015-05-11 |
EP2803713A1 (en) | 2014-11-19 |
CA2857460A1 (en) | 2013-07-18 |
JP6093716B2 (ja) | 2017-03-08 |
EP2803713A4 (en) | 2015-07-08 |
US20150125098A1 (en) | 2015-05-07 |
CN103958639A (zh) | 2014-07-30 |
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