WO2023013690A1 - 熱収縮性フィルム及びその製造方法 - Google Patents
熱収縮性フィルム及びその製造方法 Download PDFInfo
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- WO2023013690A1 WO2023013690A1 PCT/JP2022/029832 JP2022029832W WO2023013690A1 WO 2023013690 A1 WO2023013690 A1 WO 2023013690A1 JP 2022029832 W JP2022029832 W JP 2022029832W WO 2023013690 A1 WO2023013690 A1 WO 2023013690A1
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- Prior art keywords
- raw material
- heat
- resin
- shrinkable film
- virgin
- Prior art date
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Images
Classifications
-
- 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
- B32B7/02—Physical, chemical or physicochemical properties
- B32B7/027—Thermal properties
- B32B7/028—Heat-shrinkability
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Definitions
- the present invention relates to a heat-shrinkable film and its manufacturing method.
- Patent Document 1 discloses a method for manufacturing a heat-shrinkable film using recycled raw materials.
- the heat-shrinkable film produced by this production method contains virgin raw materials and recycled raw materials.
- the same raw material for example, a raw material containing polyester resin as a main component, is used as the virgin raw material and the recycled raw material in order to suppress deterioration of various physical properties such as optical properties.
- the purpose of the present invention is to provide a high-quality heat-shrinkable film using recycled raw materials, and to provide a manufacturing method thereof.
- a method for producing a heat-shrinkable film according to the first aspect of the present invention includes the following. ⁇ Preparing a packaging material containing a plurality of film labels having a resin layer mainly composed of a thermoplastic resin and a printed layer ⁇ The first virgin raw material of the thermoplastic resin and the thermoplastic resin different from the first virgin raw material preparing a second virgin raw material of resin; recovering one or more recycled raw materials of thermoplastic resin from the resin layer; forming a resin film having a surface layer that Collecting the recycled raw material of the one or more thermoplastic resins includes dividing at least one of the packaging material and the resin layer from which the printed layer has been removed into pieces; separating the printed layer from at least one of the individual pieces to obtain at least one of the resin layer from which the printed layer has been removed and the individual pieces of the resin layer from which the printed layer has been removed.
- Forming the resin film includes forming the core layer containing at least the recycled raw material and the first virgin raw material, and the surface layer mainly composed of the second virgin raw material, and forming the first At least one of molding the core layer containing at least a virgin raw material, the second virgin raw material, and the surface layer containing 25% by weight or less of the recycled raw material.
- a method for producing a heat-shrinkable film according to a second aspect of the present invention is the method for producing a heat-shrinkable film according to the first aspect, wherein molding the resin film comprises: molding the core layer containing at least a virgin raw material and the surface layer mainly composed of the second virgin raw material, wherein the recycled raw material is a first recycled raw material of a first thermoplastic resin; and a second recycled raw material of a second thermoplastic resin different from the first thermoplastic resin.
- a method for producing a heat-shrinkable film according to a third aspect of the present invention is the method for producing a heat-shrinkable film according to the first aspect or the second aspect, wherein the first virgin raw material is the first thermoplastic resin virgin raw materials.
- a heat-shrinkable film according to a fourth aspect of the present invention is a method for producing a heat-shrinkable film according to any one of the first aspect to the third aspect, wherein molding the resin film includes: forming the core layer so that the ratio of the second recycled raw material in the recycled raw material of is 25% by weight or less.
- a heat-shrinkable film according to a fifth aspect of the present invention is a method for producing a heat-shrinkable film according to any one of the first aspect to the fourth aspect, wherein molding the resin film includes: molding the core layer so that the ratio of the recycled raw material in is 2.5% by weight or more and 80% by weight or less.
- a heat-shrinkable film according to a sixth aspect of the present invention is a method for producing a heat-shrinkable film according to any one of the first to fifth aspects, wherein the first thermoplastic resin is a polystyrene resin. , the second thermoplastic resin is a polyester-based resin.
- a heat-shrinkable film according to a seventh aspect of the present invention is a method for producing a heat-shrinkable film according to any one of the first to sixth aspects, wherein the first thermoplastic resin is a polypropylene-based resin and petroleum and the second thermoplastic resin is a polyethylene-based resin and a cyclic olefin-based resin.
- a heat-shrinkable film according to an eighth aspect of the present invention is a method for producing a heat-shrinkable film according to any one of the first to seventh aspects, wherein molding the resin film comprises: molding the core layer containing at least a raw material, the surface layer containing the second virgin raw material, and 25% by weight or less of the recycled raw material, wherein the recycled raw material is a third thermoplastic resin. A recycled raw material and a fourth recycled raw material of a fourth thermoplastic resin different from the third thermoplastic resin.
- a heat-shrinkable film according to a ninth aspect of the present invention is a method for producing a heat-shrinkable film according to any one of the first to eighth aspects, wherein the second virgin raw material is the third thermoplastic resin virgin raw materials.
- a heat-shrinkable film according to a tenth aspect of the present invention is a method for producing a heat-shrinkable film according to any one of the first to ninth aspects, wherein molding the resin film includes: Forming the surface layer so that the ratio of the fourth recycled raw material in the recycled raw material is 15% by weight or less.
- the heat-shrinkable film according to the eleventh aspect of the present invention is laminated on at least one surface of a core layer containing a virgin raw material and a recycled raw material, and the virgin raw material of the core layer is substantially and a surface layer composed only of different virgin raw materials.
- the surface of the core layer containing the recycled raw material is covered with the surface layer composed essentially of only the virgin raw material, the optical properties and the like are less likely to deteriorate. Therefore, even when the recycled raw material is used, the quality of the heat-shrinkable film is high.
- a heat-shrinkable film according to a twelfth aspect of the present invention is the heat-shrinkable film according to the eleventh aspect, wherein the recycled raw material of the core layer is a first recycled raw material and is different from the first recycled raw material. Contains the second recycled raw material.
- the laminated film containing the layer made of the first recycled raw material and the layer made of the second recycled raw material is recycled as the core layer. It can be used as a raw material.
- the heat-shrinkable film according to the thirteenth aspect of the present invention is the heat-shrinkable film according to the twelfth aspect, wherein the first recycled raw material is the same raw material as the virgin raw material of the core layer.
- the quality is further improved.
- the heat-shrinkable film according to the fourteenth aspect of the present invention is the heat-shrinkable film according to the thirteenth aspect, wherein the ratio of the second recycled raw material in the recycled raw material of the core layer is 25% by weight or less.
- the quality is further improved.
- a heat-shrinkable film according to a fifteenth aspect of the present invention is the heat-shrinkable film according to any one of the eleventh to fourteenth aspects, wherein the ratio of the recycled raw material in the core layer is 2.5. % by weight or more and 80% by weight or less.
- the impact strength is high.
- a heat-shrinkable film according to a sixteenth aspect of the present invention includes a core layer containing a virgin raw material, and a virgin raw material different from the virgin raw material of the core layer, which is laminated on at least one surface of the core layer, and a recycled raw material. and a surface layer containing, the ratio of the recycled raw material in the surface layer is 25% by weight or less.
- the surface of the core layer is covered with a surface layer containing a low percentage of recycled raw materials, optical properties and the like are less likely to deteriorate. Therefore, even when the recycled raw material is used, the quality of the heat-shrinkable film is high.
- a heat-shrinkable film according to a seventeenth aspect of the present invention is the heat-shrinkable film according to the sixteenth aspect, wherein the recycled raw material for the surface layer is a third recycled raw material and a third recycled raw material different from the third recycled raw material. 4 Includes recycled materials.
- the laminated film including the layer composed of the third recycled raw material and the layer composed of the fourth recycled raw material in other words, the laminated film containing different raw materials is combined with the recycled raw material on the surface layer.
- the heat-shrinkable film according to the eighteenth aspect of the present invention is the heat-shrinkable film according to the seventeenth aspect, wherein the third recycled raw material is the same raw material as the virgin raw material of the surface layer.
- the quality is further improved.
- the heat-shrinkable film according to the nineteenth aspect of the present invention is the heat-shrinkable film according to the eighteenth aspect, wherein the ratio of the fourth recycled raw material in the recycled raw material of the surface layer is 15% by weight or less.
- the quality is further improved.
- FIG. 1 is a cross-sectional view showing an example of the layer structure of the heat-shrinkable film 10 of the first embodiment.
- the heat-shrinkable film 10 of this embodiment is used, for example, as a base film for a heat-shrinkable film label attached to a container such as a PET bottle or a metal can.
- the heat-shrinkable film 10 includes a core layer 20 and a surface layer 30 laminated on the core layer 20 .
- the core layer 20 of the heat-shrinkable film 10 of the present embodiment is composed of a recycled raw material different from the virgin raw material.
- the heat-shrinkable film 10 of the present embodiment is configured so that the film surface is less likely to be roughened and the quality is high even when the core layer 20 is composed of a recycled raw material that is different from the virgin raw material. be done.
- the total thickness of the heat-shrinkable film 10 is, for example, preferably 10 ⁇ m or more, more preferably 12 ⁇ m or more, even more preferably 15 ⁇ m or more, preferably 70 ⁇ m or less, and 65 ⁇ m or less. and more preferably 60 ⁇ m or less. That is, the total thickness of the heat-shrinkable film 10 is preferably 10 ⁇ m or more and 70 ⁇ m or less, more preferably 12 ⁇ m or more and 65 ⁇ m or less, and even more preferably 15 ⁇ m or more and 60 ⁇ m or less. When the thickness of the entire heat-shrinkable film is within the above range, excellent heat-shrinkability, excellent converting properties such as printing and center sealing, or excellent wearability can be obtained.
- the core layer 20 contains a virgin raw material (first virgin raw material) and a recycled raw material.
- a virgin raw material of the core layer 20 a known thermoplastic resin can be appropriately selected and used.
- Virgin raw materials for the core layer 20 include, for example, polyamide-based resins, polyester-based resins, polyethylene-based resins, polyvinyl alcohol-based resins, polypropylene-based resins, polystyrene-based resins, cyclic olefin-based resins, and petroleum-based resins.
- the virgin raw material of the core layer 20 is preferably polystyrene-based resin, polyester-based resin, petroleum-based resin, or polypropylene-based resin from the viewpoint of heat shrinkability. Alone is more preferred.
- Polystyrene resin and polyester resin As the polystyrene resin, from the viewpoint of exhibiting heat shrinkability, for example, a styrene-butadiene copolymer, a styrene-isoprene copolymer, a styrene-isoprene-butadiene copolymer, or a styrene-acrylic copolymer. can be used.
- the polyester-based resin for example, a resin obtained by condensation polymerization of a dicarboxylic acid component and a diol component can be used.
- Polypropylene resin for example, a binary or ternary random copolymer containing propylene as a main component and an ⁇ -olefin as a copolymer component is preferable from the viewpoint of exhibiting heat shrinkability.
- the ratio of ⁇ -olefin as a copolymer component is preferably 1 to 10 mol %.
- the propylene-based resin may be a mixture of different propylene- ⁇ -olefin random copolymers.
- the ⁇ -olefin is not particularly limited, but includes ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene and the like, and includes two or more ⁇ -olefins.
- the polypropylene-based resin may contain long-chain branched polypropylene, propylene-based elastomer, and the like.
- Petroleum-based resins are C4-C5 fractions (mainly C5 fractions), C5-C9 fractions (mainly C9 fractions), or mixtures thereof after removing ethylene, propylene, butadiene, etc. by thermal decomposition of naphtha. It is a resin obtained by polymerization, and examples thereof include alicyclic petroleum resins from cyclopentadiene or its dimers and aromatic petroleum resins from C9 components. From the viewpoint of suppressing softening of the heat-shrinkable film 10 at 100° C. or less and ensuring transparency and rigidity, a hydrogenated alicyclic petroleum resin having a partially or completely hydrogenated alicyclic structure is used. preferable.
- Terpene resins include terpene resins from ⁇ -pinene or ⁇ -pinene, copolymers of ⁇ -pinene and ⁇ -pinene, aromatic modified terpene resins, terpene-phenol resins, and hydrogenated terpene resins.
- rosin resins include gum rosin, wood rosin, tall oil rosin, esterified rosin modified with glycerin, pentaerythritol, etc., and hydrogenated rosin resins.
- the recycled raw material of the core layer 20 is, for example, a deinked packaging material including a film label including a printed layer collected from the market, or a deinked packaging material that has been downgraded in the printing process.
- a deinked packaging material including a film label including a printed layer collected from the market
- a deinked packaging material that has been downgraded in the printing process.
- one or more thermoplastic resins recovered from the resin composition that is not formed into a film such as resin composition lumps and strand waste generated in the molding apparatus during the film manufacturing process, may be included.
- the deinked material, offcuts and resin composition generated in the manufacturing process of the film label are collectively referred to as "manufacturing intermediate material".
- the recycled raw material of the core layer 20 of the present embodiment includes a first recycled raw material of a first thermoplastic resin and a second recycled raw material of a second thermoplastic resin different from the first thermoplastic resin.
- different thermoplastic resins are not limited to different types of thermoplastic resins, and even if the same type of thermoplastic resin, the Vicat softening temperature, glass transition point, copolymerization A case where the composition, weight average molecular weight, etc. are different is also included.
- the first recycled raw material is preferably a recycled raw material of the same thermoplastic resin as the virgin thermoplastic resin of the core layer 20 .
- the first recycled raw material a combination of a petroleum-based resin and a polypropylene-based resin, or a single polystyrene-based resin is particularly preferable.
- the first thermoplastic resin may be a single thermoplastic resin, or two or more different thermoplastic resins. It may be a combination of plastic resins.
- the ratio RX of the recycled raw material in the entire thermoplastic resin of the core layer 20 can be arbitrarily selected. From the viewpoint of increasing the impact strength, the ratio RX is preferably in the range of 2.5 wt % or more and 80 wt % or less, and more preferably in the range of 3 wt % or more and 25 wt % or less.
- the ratio RA of the second recycled raw material in the recycled raw material (the first recycled raw material + the second recycled raw material) in the entire thermoplastic resin of the core layer 20 can be arbitrarily selected.
- the ratio RA is preferably 25% by weight or less, and 15% by weight or less, from the viewpoint of improving the quality of the heat-shrinkable film 10. is more preferably 10% by weight or less.
- the thickness of the core layer 20 is, for example, preferably 5 ⁇ m or more and 50 ⁇ m or less, more preferably 7 ⁇ m or more and 40 ⁇ m or less.
- the surface layer 30 is laminated on at least one surface of the core layer 20 via an adhesive layer, for example. In this embodiment, the surface layers 30 are laminated on both surfaces of the core layer 20 . The surface layer 30 may be laminated on only one surface of the core layer 20 .
- the surface layer 30 is substantially composed only of a virgin raw material (second virgin raw material) of a thermoplastic resin different from the virgin raw material (first virgin raw material) of the core layer 20 .
- the virgin raw material for the surface layer 30 can be arbitrarily selected from, for example, the thermoplastic resins exemplified as the virgin raw materials for the core layer 20.
- the thermoplastic resins exemplified as the virgin raw materials for the core layer 20.
- polyethylene resins, cyclic olefin resins and polyester resins described above are preferable.
- a combination of olefin-based resins or a single polyester-based resin is more preferable.
- substantially composed only of a virgin raw material different from the virgin raw material of the core layer 20 means that the surface layer 30 is composed of the virgin raw material and the recycled material to such an extent that the surface is not substantially roughened. It includes cases where raw materials are included. In other words, the surface layer 30 is mainly composed of a virgin raw material different from the virgin raw material of the core layer 20 . When the surface layer 30 contains a recycled raw material, the recycled raw material of the surface layer 30 is preferably the same raw material as the virgin raw material of the surface layer 30 . There may be two or more types of recycled raw materials contained in the surface layer 30 and two or more types of virgin raw materials that substantially constitute the surface layer 30 .
- Polyethylene-based resins include linear low-density polyethylene, branched low-density polyethylene, ethylene-vinyl acetate copolymer, ionomer resin, or mixtures thereof. Furthermore, copolymers of ethylene and ⁇ -olefins are also mentioned as ethylene-based resins.
- ⁇ -olefins examples include ⁇ -olefins having 3 to 20 carbon atoms, and specific examples include propylene, 1-butene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like.
- the ratio of ⁇ -olefin as a copolymer component is preferably 1 to 25 mol %.
- the ethylene-based resin may be a mixture of different ethylene- ⁇ -olefin random copolymers.
- the copolymer containing ethylene as a main component may be a random copolymer or a block copolymer.
- Cyclic olefin resin The cyclic olefin-based resin can reduce the crystallinity of the heat-shrinkable film, increase the heat-shrinkage rate, and improve the stretchability during production.
- Cyclic olefin-based resins include, for example, (a) random copolymers of ethylene or propylene and cyclic olefins, (b) ring-opening polymers of the cyclic olefins or copolymers with ⁇ -olefins, and (c) the above ( b) hydrogenated products of polymers; and (d) graft-modified products of (a) to (c) with unsaturated carboxylic acids and derivatives thereof.
- Cyclic olefins are not particularly limited, and examples include norbornene, 6-methylnorbornene, 6-ethylnorbornene, 5-propylnorbornene, 6-n-butylnorbornene, 1-methylnorbornene, 7-methylnorbornene, 5,6-dimethyl norbornene and derivatives thereof such as norbornene, 5-phenylnorbornene, 5-benzylnorbornene and the like.
- Further examples include tetracyclododecene, 8-methyltetracyclo-3-dodecene, 8-ethyltetracyclo-3-dodecene, 5,10-dimethyltetracyclo-3-dodecene, tetracyclododecene and derivatives thereof.
- the ⁇ -olefin is as described above.
- the thickness of the surface layer 30 is, for example, preferably 1 ⁇ m or more and 30 ⁇ m or less, more preferably 2 ⁇ m or more and 20 ⁇ m or less, and even more preferably 3 ⁇ m or more and 10 ⁇ m or less.
- the surface layer 30 may contain an antiblocking agent for exhibiting antiblocking performance.
- an antiblocking agent antiblocking fine particles
- organic fine particles organic fine particles such as acrylic resin fine particles, styrene resin fine particles, styrene-acrylic resin fine particles, urethane resin fine particles, and silicone resin fine particles can be used. These may or may not be crosslinked, but are preferably crosslinked in order to increase the heat resistance of the fine particles. Among them, from the viewpoint of compatibility with the styrene resin, acrylic resin fine particles are preferable, and polymethyl methacrylate crosslinked fine particles are more preferable.
- the surface of the core layer 20 containing the recycled raw material is covered with the surface layer 30 substantially composed of only the virgin raw material (in other words, the main component is the second virgin raw material). Therefore, the optical characteristics and the like are less likely to deteriorate. Therefore, even if the core layer 20 is made of a recycled raw material different from the virgin raw material, the quality of the heat-shrinkable film 10 is high.
- the recycled raw material of the core layer 20 contains the first recycled raw material and the second recycled raw material different from the first recycled raw material, the layer composed of the first recycled raw material and the second recycled raw material are formed.
- a laminated film containing a layer to be formed, in other words, a laminated film containing different raw materials can be used as the recycled raw material for the core layer 20 .
- first recycled raw material and the first virgin raw material are a combination of a petroleum-based resin and a polypropylene-based resin
- second recycled raw material and the second virgin raw material are a combination of a polyethylene-based resin and a cyclic olefin-based resin
- heat shrinkage The natural shrinkage of the heat-shrinkable film 10 can be suppressed while maintaining quality such as modulus and surface properties.
- the core layer 20 contains a recycled material, the compressive strength can be improved.
- the heat-shrinkable film 10X of the second embodiment is different from the first embodiment in that it includes a core layer 20X and a surface layer 30X, and other configurations are the same as those of the first embodiment.
- the heat-shrinkable film 10X of the second embodiment will be described, focusing on the parts that differ from the first embodiment.
- FIG. 2 is a cross-sectional view showing an example of the layer structure of the heat-shrinkable film 10X of the second embodiment.
- the heat-shrinkable film 10X includes a core layer 20X and a surface layer 30X laminated on at least one surface of the core layer 20X.
- the surface layer of the heat-shrinkable film contains recycled raw materials, the surface of the film may be roughened and the glossiness, printing properties, etc. may be lowered.
- the heat-shrinkable film 10X of the present embodiment is configured so that the film surface is less likely to be roughened and the quality is high even when the surface layer 30X is composed of a recycled raw material.
- the core layer 20X is substantially composed of only the virgin raw material (first virgin raw material) (in other words, the first virgin raw material is the main component). Any thermoplastic resin exemplified for the core layer 20 of the heat-shrinkable film 10 of the first embodiment can be used as the virgin raw material of the core layer 20X, for example.
- the surface layer 30X contains a virgin raw material (second virgin raw material) and a recycled raw material.
- the virgin raw material for the surface layer 30X is different from the virgin raw material for the core layer 20X.
- Any thermoplastic resin exemplified for the surface layer 30 of the heat-shrinkable film 10 of the first embodiment can be used as the virgin raw material for the surface layer 30X.
- the virgin raw material of the surface layer 30X is a polyester-based resin.
- the recycled raw material of the surface layer 30X of the second embodiment includes a third recycled raw material of a third thermoplastic resin and a fourth recycled raw material of a fourth thermoplastic resin different from the third thermoplastic resin.
- different thermoplastic resins are the same as defined in the first embodiment.
- the third recycled raw material is preferably the same raw material as the virgin raw material of the surface layer 30X.
- the third recycled raw material is a polyester-based resin
- the fourth recycled raw material is a polystyrene-based resin.
- the ratio RY of the recycled raw material in the entire thermoplastic resin of the surface layer 30X is 25% by weight or less from the viewpoint of suppressing the occurrence of roughness on the surface of the surface layer 30X.
- the ratio RB of the fourth recycled raw material in the recycled raw material (the third recycled raw material + the fourth recycled raw material) in the entire thermoplastic resin of the surface layer 30X can be arbitrarily selected.
- the ratio RB is preferably 15% by weight or less from the viewpoint of improving the quality of the heat-shrinkable film 10X.
- the recycled raw material of the surface layer 30X contains the third recycled raw material and the fourth recycled raw material different from the third recycled raw material
- the layer composed of the third recycled raw material and the fourth recycled raw material In other words, a laminated film containing different raw materials can be used as the recycled raw material for the surface layer 30X.
- FIG. 3 is a flow chart showing the flow of the method for manufacturing the heat-shrinkable film 10 using the packaging material as the starting material.
- a method for manufacturing the heat-shrinkable film 10 will be described with reference to FIG.
- packaging materials are prepared as starting materials for manufacturing the heat-shrinkable film 10 .
- the packaging material includes a plurality of film labels that are primarily salvaged from the market. These film labels have a resin layer containing a thermoplastic resin as a main component, and a printed layer composed of ink laminated on the resin layer.
- the resin layer of the film label of this embodiment contains at least a first thermoplastic resin and a second thermoplastic resin.
- the film label may contain a mixture of the first thermoplastic resin and the second thermoplastic resin in one resin layer.
- at least some film labels may have an overcoat layer comprised of an overcoat agent.
- the film label may or may not be heat-shrinkable.
- packaging materials include other packaging materials that do not have a printed layer, such as films mainly composed of a first thermoplastic resin, a second thermoplastic resin, and mixed resins thereof.
- the first thermoplastic resin is a combination of polypropylene-based resin and petroleum-based resin
- the second thermoplastic resin is a combination of cyclic olefin-based resin and polyethylene-based resin.
- the first thermoplastic resin is a polystyrene-based resin
- the second thermoplastic resin is a polyester-based resin.
- a virgin raw material of the first thermoplastic resin (first virgin raw material) and a virgin raw material of the second thermoplastic resin (second virgin raw material) are separately prepared.
- each of the packaging materials is separated into chips (step S1).
- a method for singulating the packaging material is not particularly limited, and a known slitter, shredder, pulverizer, cutting machine, or the like can be used.
- the individual pieces of packaging material thus obtained are also referred to as fluff.
- the size of the fluff is not particularly limited, it is preferably a size that can be supplied to an extruder.
- the printed layer is separated from the resin layer of the fluff, and a deinking process is performed to obtain individual pieces of the resin layer from which the printed layer has been removed (hereinafter also referred to as "deinked fluff") (step S2).
- a method of deinking treatment is not particularly limited, and a known method can be adopted. More specifically, as disclosed in Japanese Patent Application Laid-Open No. 11-333952, etc., a method of removing the printed layer by immersing the fluff in an alkaline aqueous solution can be used.
- the overcoat layer is also separated from the resin layer to some extent and removed from the resin layer.
- the deinking fluff obtained in step S2 contains the first thermoplastic resin and the second thermoplastic resin. Further, a small amount of acrylic acid (methacrylic acid) ester-based resin derived from the overcoat agent may remain in the deinking fluff.
- step S3 the deinked fluff obtained in step S2 is immersed in an acidic aqueous solution to neutralize the alkalinity.
- the acidic aqueous solution is not particularly limited, for example, an acetic acid aqueous solution can be used.
- an alkaline aqueous solution is used in step S2
- provision of step S3 can save the amount of water used in the cleaning process described later.
- the deinking fluff is washed with water to wash off at least one of the alkaline aqueous solution and the acidic aqueous solution adhering to the deinking fluff (step S4).
- the washed deinking fluff is dried to remove remaining moisture (step S5).
- the drying method is not particularly limited, and drying can be performed using a hot air dryer, a vacuum dryer, an air blower, or the like.
- the drying temperature is preferably below the temperature at which the thermoplastic resin contained in the deinking fluff does not adhere.
- step S5 that is, the first recycled raw material of the first thermoplastic resin and the second recycled raw material of the second thermoplastic resin
- the first virgin raw material are added to the core layer 20.
- a resin film including the core layer 20 and the surface layer 30 is molded (step S6). More specifically, the deinked fluff obtained in step S5 and other raw materials are supplied to an extruder and melt-kneaded to extrude a resin film in which at least the core layer 20 and the surface layer 30 are laminated. to mold.
- the extrusion molding may be co-extrusion of the core layer 20 and the surface layer 30, and in this embodiment, the co-extrusion is performed so that the surface layers 30 are laminated on both sides of the core layer 20, respectively. Additionally, co-extrusion may be performed such that an adhesive layer is laminated between the core layer 20 and the surface layer 30 .
- the core layer 20 is formed by including the above-described first virgin raw material, the first recycled raw material of the first thermoplastic resin, and the second thermoplastic resin as the second recycled raw material in the raw materials.
- the core layer 20 may be formed by including raw materials other than the packaging material used as the starting raw material, for example, the above-described production intermediate materials in the recycled raw materials.
- step S6 may include molding the core layer 20 further including a recycled raw material of the first thermoplastic resin or the second thermoplastic resin derived from a raw material other than the starting raw material.
- Step S6 further includes forming the surface layer 30 whose main component is the above-described second virgin raw material.
- the surface layer 30 is formed so that 100% of the thermoplastic resin forming the surface layer 30 is the virgin raw material of the second thermoplastic resin.
- step S6 the resin film formed in step S6 is cooled and solidified while being taken up by a take-up roll, and then uniaxially or biaxially stretched. Thereby, the heat-shrinkable film 10 is obtained (step S7).
- Examples 1 to 7 are examples relating to the heat-shrinkable film 10 of the first embodiment.
- Examples 8 and 9 are examples relating to the heat-shrinkable film 10X of the second embodiment.
- surface layers are laminated on both sides of the core layer.
- These heat-shrinkable films are mainly composed of at least one of polystyrene-based resin and polyester-based resin.
- Table 2 shows the specifications of the heat-shrinkable films of Examples 10 to 12 and the heat-shrinkable film of Reference Example 2.
- These heat-shrinkable films have surface layers laminated on both sides of a core layer. Moreover, it has an olefin resin (polyolefin resin, cyclic olefin resin and petroleum resin) as a main component and has a specific gravity of less than 1.
- polyester resin The virgin raw material of the polyester resin contains 100 mol% of a component derived from terephthalic acid as a dicarboxylic acid component, 65 mol% of a component derived from ethylene glycol as a diol component, 20 mol% of a component derived from diethylene glycol, and 1 , 4-cyclohexanedimethanol.
- the glass transition temperature is 70°C.
- Polystyrene resin> A virgin raw material for polystyrene resin is a styrene-butadiene copolymer.
- the styrene-butadiene copolymer has a styrene content of 81.3% by weight and a butadiene content of 18.7% by weight.
- the Vicat softening temperature is 80°C.
- a virgin raw material for polypropylene resin is a random copolymer containing propylene as a main component and an ⁇ -olefin as a copolymer component. It has a density of 0.9 kg/m 3 , a melt flow rate (MFR) at 230°C of 5.5 g/10 min, a Vicat softening temperature of 111°C and a melting point of 132°C.
- Polyethylene resin Virgin raw materials for polyethylene resins are metallocene low-density polyethylenes containing ethylene as a main component and an ⁇ -olefin as a copolymer component. The density is 0.915 kg/m 3 , the MFR based on JIS K7210 is 1.0 g/10 min, the Vicat softening temperature is 98°C, and the melting point is 118°C.
- Petroleum resin The virgin raw material of petroleum-based resin is a hydrogenated alicyclic petroleum resin having a completely hydrogenated alicyclic structure, which is used for adhesives and plastic modifiers.
- the density is 0.98 kg/m 3 and the Vicat softening temperature is 125°C.
- Cyclic olefin resin Virgin raw materials for cyclic olefin resins are high-purity cyclic olefin copolymers. It has a density of 1.01 kg/m 3 , a melt volume rate (MVR) according to ISO 1133 of 12 cm 3 /10 min (230°C, 2.16 kg) and a glass transition temperature of 78°C.
- MVR melt volume rate
- the method for producing the heat-shrinkable film of Reference Example 1 is as follows. First, using the raw materials shown in Table 1 as the raw materials constituting the core layer and the surface layer, they were put into an extruder with a barrel temperature of 160 to 250 ° C., extruded from a multi-layer die at 210 ° C. into a sheet with a three-layer structure, and 30 It was solidified by cooling with a take-up roll at °C. Next, after stretching in a tenter stretching machine with a preheating zone of 105° C., a stretching zone of 89 to 91° C., and a heat setting zone of 85° C. at a stretching ratio of 6 times, it is wound up by a winder to obtain a direction perpendicular to the main shrinking direction. was MD (Machine Direction) and the main shrinking direction was TD (Transverse Direction).
- MD Machine Direction
- TD Transverse Direction
- the method for producing the heat-shrinkable film of Reference Example 2 is as follows. First, using the raw materials shown in Table 2 as the raw materials constituting the core layer and the surface layer, they were put into an extruder with a barrel temperature of 190 to 210 ° C., extruded from a multi-layer die at 180 ° C. into a three-layer structure sheet, and 30 It was solidified by cooling with a take-up roll at °C. Next, after stretching in a tenter stretching machine with a preheating zone of 110° C., a stretching zone of 82 to 87° C., and a heat setting zone of 82° C.
- the film is wound up by a winder to obtain a direction perpendicular to the main shrinking direction.
- a heat-shrinkable film was obtained in which the direction of shrinkage was MD and the main shrinkage direction was TD.
- the production method of the recycled raw materials of Examples and Comparative Examples is as follows.
- a printed layer was laminated on one side of the heat-shrinkable films of Reference Examples 1 and 2 using a gravure printing machine.
- an overcoat layer was laminated on the other surface.
- the overcoat layer is a layer containing an acrylic acid (methacrylic acid) ester-based resin as a main component.
- the heat-shrinkable film having the printed layer was processed into chips by a pulverizer, deinked, and dried with hot air to prepare recycled raw materials of Examples and Comparative Examples.
- the methods for producing heat-shrinkable films of Examples 1 to 9 and Comparative Examples are as follows.
- the raw materials shown in Table 1 are used as raw materials for forming the core layer and the surface layer, and the raw materials are mixed at the ratios shown in Table 1 to form the core layer and the surface layer according to Examples 1 to 9 and Comparative Examples.
- a raw material composition was obtained. Using this raw material composition, heat-shrinkable films of Examples 1 to 9 and Comparative Example were produced in the same manner as the heat-shrinkable film of Reference Example 1.
- the ratio RA in the table indicates the ratio of the polyester-based resin derived from the surface layer of the reference example to the total thermoplastic resin constituting the core layer
- the ratio RB shows the ratio of the total thermoplastic resin constituting the surface layer to the reference 4 shows the percentage of polystyrene resin derived from the core layer of the example.
- the method for producing the heat-shrinkable films of Examples 10 to 12 is as follows.
- the raw materials shown in Table 2 were used as raw materials for forming the core layer and the surface layer, and the raw materials for forming the core layer and the surface layer according to Examples 10 to 12 were obtained by mixing the raw materials at the ratios shown in Table 2.
- the acrylic resin content in Table 2 is the content of the acrylic acid (methacrylic acid) ester resin derived from the overcoat layer of Reference Example 2 with respect to 100% by weight of the total thermoplastic resin constituting each heat-shrinkable film. be.
- the acrylic resin content was calculated based on the area of the signal derived from the side chain of polymethyl methacrylate in the 1 H-NMR spectrum obtained by NMR measurement of each heat-shrinkable film.
- thermoplastic resin constituting the core layer Using this raw material composition, heat-shrinkable films of Examples 10 to 12 were produced in the same manner as the heat-shrinkable film of Reference Example 2.
- the ratio RA in the table indicates the ratio of the polyethylene-based resin and the cyclic olefin-based resin derived from the surface layer of the reference example to the total thermoplastic resin constituting the core layer.
- L MD in the following formula (1) is the length of the test piece in the MD direction after heat shrinking
- L TD in the following formula (2) is the length of the test piece in the MD direction after heat shrinking. It is.
- the heat shrinkage ratio was measured using two test pieces for the heat shrinkable film of each example, comparative example, and reference example, and the average value was used.
- Thermal shrinkage rate (%) ⁇ (100-L MD )/100 ⁇ x 100
- Thermal shrinkage rate (%) ⁇ (100-L TD )/100 ⁇ x 100 (2)
- NDH5000 manufactured by Nippon Denshoku Industries Co., Ltd.
- the heat-shrinkable films of Examples 1-12, Comparative Examples, and Reference Examples 1-2 were cut into samples having a size of MD 100 mm ⁇ TD 100 mm to obtain test pieces.
- the obtained test piece was measured by a method according to JIS P8134 using a film impact tester manufactured by Toyo Seiki Seisakusho. Specifically, a test piece is fixed on a table. Next, by removing the hook that fixes the arm of the film impact tester, the fan-shaped arm rotates around its axis, and the impact head attached to the tip of the arm breaks through the test piece.
- the impact strength is quantified as the energy required when the impact head breaks through the test piece.
- the impact strength is measured 5 times and the average value is obtained.
- Young's modulus> The heat-shrinkable films of Examples 1-12, Comparative Examples, and Reference Examples 1-2 were cut into samples having a size of MD 250 mm ⁇ TD 5 mm to obtain test pieces. The obtained test piece was measured by a method based on ASTM D882 using Strograph VE-1D manufactured by Toyo Seiki Seisakusho. The Young's modulus was measured using four test pieces for each example, comparative example, and reference example, and the average value was calculated.
- Table 3 is a table showing test results of Examples 1 to 9, Comparative Example and Reference Example 1.
- the heat-shrinkable films of Examples 1 to 8 gave substantially the same results as the heat-shrinkable film of Reference Example 1 for each measurement item.
- the heat-shrinkable film of Example 9 has a slightly higher haze than the heat-shrinkable film of Reference Example 1 and a slightly lower glossiness than the heat-shrinkable film of Reference Example 1, but other measurement items As for the heat-shrinkable film of Reference Example 1, substantially the same results were obtained.
- the surface of the core layer containing the recycled raw material is covered with a surface layer composed substantially only of virgin raw material
- the heat-shrinkable films of Examples 8 and 9 are , the surface of the core layer is covered with a surface layer having a low ratio RY, so that the heat-shrinkable film of Reference Example 1 has physical properties similar to those of the heat-shrinkable film.
- the heat-shrinkable film of Comparative Example had a higher haze than the heat-shrinkable film of Reference Example and a lower glossiness than the heat-shrinkable film of Reference Example 1 among the measurement items. This is probably because the heat-shrinkable film of the comparative example had a lower glossiness because the core layer contained a recycled raw material different from the virgin raw material.
- Table 4 is a table showing test results of Examples 10 to 12 and Reference Example 2. It was confirmed that the heat-shrinkable films of the examples had a wet heat shrinkage rate at a level that caused no problem in use. In addition, the heat-shrinkable films of Examples were all improved in natural shrinkage rate as compared with the heat-shrinkable film of Reference Example 2. This is presumably because the core layer contains a recycled raw material, especially a cyclic olefin resin. Compressive strength was also improved. The haze and glossiness of the heat-shrinkable films of each example were slightly inferior to those of Reference Example 2, but it was confirmed that the levels were satisfactory in use.
- each of the above embodiments is an illustration of the form that the heat-shrinkable film of the present invention can take, and is not intended to limit the form.
- the heat-shrinkable film relating to the present invention can take forms different from those exemplified in each embodiment.
- One example is a form in which a part of the configuration of each embodiment is replaced, changed, or omitted, or a form in which a new configuration is added to each embodiment.
- the first recycled raw material for the core layer 20 was the same raw material as the virgin raw material for the core layer 20, but the first recycled raw material may be a raw material different from the virgin raw material for the core layer 20. good. That is, in this modification, the virgin raw material of the core layer 20, the first recycled raw material, and the second recycled raw material are different raw materials.
- the recycled raw material of the core layer 20 contains the first recycled raw material and the second recycled raw material, but the recycled raw material of the core layer 20 may be only the first recycled raw material.
- the first recycled raw material may be the same raw material as the virgin raw material of the core layer 20 or may be a raw material different from the virgin raw material of the core layer 20 .
- the core layer 20X substantially contains only virgin raw materials, but the core layer 20X may contain recycled raw materials as in the first embodiment.
- the third recycled raw material for the surface layer 30X is the same raw material as the virgin raw material for the surface layer 30X, but the third recycled raw material may be a raw material different from the virgin raw material for the surface layer 30X. That is, in this modification, the virgin raw material of the surface layer 30X, the third recycled raw material, and the fourth recycled raw material are different raw materials.
- the recycled raw material for the surface layer 30X includes the third recycled raw material and the fourth recycled raw material, but the recycled raw material for the surface layer 30X may be only the third recycled raw material.
- the third recycled raw material may be the same raw material as the virgin raw material of the surface layer 30X, or may be a raw material different from the virgin raw material of the surface layer 30X.
- steps S1 to S5 in the above embodiment may be changed. For example, after deinking to separate the printed layer from the packaging material, neutralization, washing, drying, etc. are performed as necessary, and then the resin layer of the packaging material from which the printed layer has been removed is separated into pieces and removed. You may gain Ink Fluff. In addition, at least one of singulation, neutralization, washing and drying may be omitted as appropriate, and may be performed twice or more as necessary. Also, the reclaimed raw material may be used in step S6 after going through a step of being pelletized instead of being in the form of fluff.
- the heat-shrinkable film 10X includes a surface layer 30X containing the deinked fluff (recycled raw material) obtained in step S5 and the second virgin raw material, and a core layer containing at least the first virgin raw material. It can be manufactured by molding a resin film having 20X. In this case, the surface layer 30X is molded so as to contain 20% by weight or less of recycled raw material with respect to the entire thermoplastic resin contained in the surface layer 30X.
- the deinking fluff may include a third recycled raw material of a third thermoplastic resin and a fourth recycled raw material of a fourth thermoplastic resin different from the third thermoplastic resin, and the second virgin raw material is It may be a virgin raw material of the third thermoplastic resin.
- step S6 may include forming the surface layer 30X so that the proportion of the fourth recycled raw material in the entire thermoplastic resin contained in the surface layer 30X is 15% by weight or less.
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Abstract
Description
・熱可塑性樹脂を主成分とする樹脂層と、印刷層とを有するフィルムラベルを複数含む包装資材を準備すること
・熱可塑性樹脂の第1バージン原料と、前記第1バージン原料とは異なる熱可塑性樹脂の第2バージン原料とを準備すること
・前記樹脂層から、1または複数の熱可塑性樹脂の再生原料を回収すること
・前記再生原料を原料に含め、コア層と、前記コア層に積層される表層とを備える樹脂フィルムを成形すること。
前記1または複数の熱可塑性樹脂の再生原料を回収することは、前記包装資材および前記印刷層が除去された前記樹脂層の少なくとも一方を個片化することと、前記包装資材および前記包装資材の個片の少なくとも一方から前記印刷層を分離して、前記印刷層が除去された前記樹脂層および前記印刷層が除去された前記樹脂層の個片の少なくとも一方を得ることとを含む。
前記樹脂フィルムを成形することは、前記再生原料と、前記第1バージン原料とを少なくとも含む前記コア層と、前記第2バージン原料を主成分とする前記表層とを成形すること、および前記第1バージン原料を少なくとも含む前記コア層と、前記第2バージン原料と、25重量%以下の前記再生原料とを含む前記表層とを成形することの少なくとも一方を含む。
<1―1.熱収縮性フィルムの構成>
図1は、第1実施形態の熱収縮性フィルム10の層構成の一例を示す断面図である。本実施形態の熱収縮性フィルム10は、例えば、ペットボトル、または、金属罐等の容器に装着される熱収縮性のフィルムラベルのベースフィルムとして用いられる。熱収縮性フィルム10は、コア層20と、コア層20に積層される表層30と、を含む。本実施形態の熱収縮性フィルム10のコア層20は、バージン原料とは異なる原料の再生原料を含んで構成される。一般的に、熱収縮性フィルムにバージン原料の原料とは異なる再生原料を用いる場合、フィルム表面が荒れ、光沢度および印刷特性等が低下する傾向にある。本実施形態の熱収縮性フィルム10は、コア層20がバージン原料とは異なる原料の再生原料を含んで構成される場合であっても、フィルム表面に荒れが生じにくく、品質が高いように構成される。
コア層20は、バージン原料(第1バージン原料)および再生原料を含む。コア層20のバージン原料は、公知の熱可塑性樹脂を適宜選択して用いることができる。コア層20のバージン原料は、例えば、ポリアミド系樹脂、ポリエステル系樹脂、ポリエチレン系樹脂、ポリビニルアルコール系樹脂、ポリプロピレン系樹脂、ポリスチレン系樹脂、環状オレフィン系樹脂、石油系樹脂等を挙げることができる。コア層20のバージン原料は、熱収縮性の観点から、ポリスチレン系樹脂、ポリエステル系樹脂、石油系樹脂、または、ポリプロピレン系樹脂が好ましく、中でも石油系樹脂およびポリプロピレン系樹脂の組み合わせ、またはポリスチレン系樹脂単独がより好ましい。
ポリスチレン系樹脂としては、熱収縮性を発現する観点から、例えば、スチレンブタジエン共重合体、スチレン-イソプレン共重合体、スチレン-イソプレン-ブタジエン共重合体、または、スチレン-アクリル系共重合体等を用いることができる。ポリエステル系樹脂としては、例えば、ジカルボン酸成分とジオール成分とを縮重合させることによって得られる樹脂を用いることができる。
ポリプロピレン系樹脂としては、熱収縮性を発現する観点から、例えば、プロピレンを主成分として、α-オレフィンを共重合成分とする二元、または、三元ランダム共重合体が好ましい。共重合成分であるα-オレフィンの比率は1~10モル%であるのが好ましい。また、プロピレン系樹脂は、異なるプロピレン-α-オレフィンランダム共重合体の混合物であってもよい。α-オレフィンとしては特に限定されないが、エチレン、1-ブテン、1-ペンテン、1-ヘキセン、4-メチル-1-ペンテン、1-オクテン等が挙げられ、2種類以上のα-オレフィンが含まれても良い。ポリプロピレン系樹脂には、長鎖分岐ポリプロピレン、プロピレン系エラストマー等が含まれていてもよい。
石油系樹脂は、ナフサの熱分解によってエチレン、プロピレン、ブタジエン等を取り去った残りのC4~C5留分(主としてC5留分)やC5~C9留分(主としてC9留分)、あるいはこれらの混合物を重合して得られる樹脂であり、例えばシクロペンタジエンまたはその二量体からの脂環式石油樹脂やC9成分からの芳香族石油樹脂が挙げられる。熱収縮性フィルム10の100℃以下における軟化を抑制したり、透明性や剛性を確保する観点からは、一部または完全に水素化された脂環構造を有する、水添脂環式石油樹脂が好ましい。また、C5留分やC9留分中の単一、または複数の成分を精製し重合したものであっても同じく使用することができる。また、石油系樹脂の少なくとも一部は、テルペン樹脂やロジン樹脂等で代用されてもよい。テルペン樹脂としては、αピネンまたはβピネンからのテルペン樹脂、αピネンおよびβピネン等の共重合物、芳香族変性テルペン樹脂、テルペン-フェノール樹脂、および水添テルペン樹脂等が挙げられる。ロジン樹脂としては、ガムロジン、ウッドロジン、トール油ロジン、グリセリンやペンタエリスリトール等で変性したエステル化ロジン、および水添ロジン系樹脂等が挙げられる。
表層30は、例えば、接着層を介してコア層20の表面の少なくとも一方に積層される。本実施形態では、表層30は、コア層20の表面の両面に積層される。表層30は、コア層20の表面の一方のみに積層されてもよい。
ポリエチレン系樹脂としては、直鎖状低密度ポリエチレン、分岐状低密度ポリエチレン、エチレン-酢酸ビニル共重合体、アイオノマー樹脂、またはこれらの混合物が挙げられる。さらに、エチレンとα-オレフィンとの共重合体もエチレン系樹脂として挙げられる。α-オレフィンとしては、炭素数3~20のα-オレフィンを挙げることができ、具体的には、例えば、プロピレン、1-ブテン、3-メチル-1-ブテン、3-メチル-1-ペンテン、4-メチル-1-ペンテン、1-ペンテン、1-ヘキセン、1-ヘプテン、1-オクテン、1-デセン、1-テトラデセン、1-ヘキサデセン、1-オクタデセン、1-エイコセン等が挙げられる。共重合成分であるα-オレフィンの比率は1~25モル%であるのが好ましい。また、エチレン系樹脂は、異なるエチレン-α-オレフィンランダム共重合体の混合物であってもよい。エチレンを主成分とする共重合体は、ランダム共重合体であってもよく、ブロック共重合体であってもよい。
環状オレフィン系樹脂は、熱収縮性フィルムの結晶性を低下させ、熱収縮率を高めるとともに、製造時の延伸性も高めることができる。環状オレフィン系樹脂とは、例えば(a)エチレンまたはプロピレンと環状オレフィンとのランダム共重合体、(b)該環状オレフィンの開環重合体またはα-オレフィンとの共重合体、(c)上記(b)の重合体の水素添加物、(d)不飽和カルボン酸およびその誘導体等による(a)~(c)のグラフト変性物等である。
熱収縮性フィルム10によれば、実質的にバージン原料のみによって構成される(言い換えると、第2バージン原料を主成分とする)表層30によって、再生原料を含むコア層20の表面が覆われているため、光学特性等が低下しにくい。このため、コア層20にバージン原料とは異なる原料の再生原料を用いた場合であっても、熱収縮性フィルム10の品質が高い。
第2実施形態の熱収縮性フィルム10Xは、コア層20Xおよび表層30Xを備える点において、第1実施形態と異なり、その他の構成は、第1実施形態と同様である。以下では、第2実施形態の熱収縮性フィルム10Xについて、第1実施形態と異なる部分を中心に説明する。
図2は、第2実施形態の熱収縮性フィルム10Xの層構成の一例を示す断面図である。熱収縮性フィルム10Xは、コア層20X、および、コア層20Xの少なくとも一方の表面に積層される表層30Xを含む。熱収縮性フィルムの表層に再生原料が含まれる場合、フィルム表面が荒れ、光沢度および印刷特性等が低下するおそれがある。本実施形態の熱収縮性フィルム10Xは、表層30Xが再生原料を含んで構成される場合であっても、フィルム表面に荒れが生じにくく、品質が高いように構成される。
本実施形態では、コア層20Xは、実質的にバージン原料(第1バージン原料)のみによって構成される(言い換えると、第1バージン原料を主成分とする)。コア層20Xのバージン原料は、例えば、第1実施形態の熱収縮性フィルム10のコア層20で例示した、任意の熱可塑性樹脂を用いることができる。
表層30Xは、バージン原料(第2バージン原料)および再生原料を含む。表層30Xのバージン原料は、コア層20Xのバージン原料とは異なる。表層30Xのバージン原料は、第1実施形態の熱収縮性フィルム10の表層30で例示した、任意の熱可塑性樹脂を用いることができる。本実施形態では、表層30Xのバージン原料は、ポリエステル系樹脂である。
熱収縮性フィルム10Xによれば、割合RYが低い表層30Xによって、コア層20Xの表面が覆われているため、光学特性等が低下しにくい。このため、再生原料を用いた場合であっても、熱収縮性フィルム10Xの品質が高い。
図3は、包装資材を出発原料として熱収縮性フィルム10を製造する方法の流れを示すフローチャートである。以下、図3を参照しながら、熱収縮性フィルム10の製造方法について説明する。
<4-1.全体概要>
本願発明者(ら)は、実施例の熱収縮性フィルム、比較例の熱収縮性フィルム、および、参考例1の熱収縮性フィルムを製造し、熱収縮性フィルムの物性を測定する試験を実施した。表1は、実施例1~9の熱収縮性フィルム、比較例の熱収縮性フィルム、および、参考例1の熱収縮性フィルムに関する諸元を示す表である。比較例の熱収縮性フィルムは、表層を有していない。参考例1の熱収縮性フィルムは、表層およびコア層がバージン原料のみによって構成される。実施例1~7は、第1実施形態の熱収縮性フィルム10に関する実施例である。実施例8、9は、第2実施形態の熱収縮性フィルム10Xに関する実施例である。実施例1~9の熱収縮性フィルムは、コア層の両面に表層が積層されている。これらの熱収縮性フィルムは、ポリスチレン系樹脂およびポリエステル系樹脂の少なくとも一方を主成分とする。また、表2は、実施例10~12の熱収縮性フィルム、および、参考例2の熱収縮性フィルムに関する諸元を示す表である。これらの熱収縮性フィルムは、コア層の両面に表層が積層されている。また、オレフィン系樹脂(ポリオレフィン系樹脂、環状オレフィン系樹脂および石油系樹脂)を主成分とし、比重が1未満である。
実施例、比較例、および、参考例の熱収縮性フィルムに用いられるバージン原料の諸元は、次のとおりである。
ポリエステル系樹脂のバージン原料は、ジカルボン酸成分としてテレフタル酸に由来する成分を100モル%、ジオール成分としてエチレングリコールに由来する成分を65モル%、ジエチレングリコールに由来する成分を20モル%、および、1、4-シクロヘキサンジメタノールに由来する成分を15モル%含有する。ガラス転移温度は、70℃である。
ポリスチレン系樹脂のバージン原料は、スチレン-ブタジエン共重合体である。スチレン-ブタジエン共重合体は、スチレン含有量が81.3重量%、ブタジエン含有量が18.7重量%である。ビカット軟化温度は、80℃である。
ポリプロピレン系樹脂のバージン原料は、プロピレンを主成分、α-オレフィンを共重合成分とするランダム共重合体である。密度は0.9kg/m3、230℃におけるメルトフローレート(MFR)は5.5g/10min、ビカット軟化温度は111℃、融点は132℃である。
ポリエチレン系樹脂のバージン原料は、エチレンを主成分、α-オレフィンを共重合成分とするメタロセン系低密度ポリエチレンである。密度は0.915kg/m3、JIS K7210に基づくMFRは1.0g/10min、ビカット軟化温度は98℃、融点は118℃である。
石油系樹脂のバージン原料は、粘着剤やプラスチック改質剤の用途品であり、完全に水素化された脂環構造を有する、水添脂環式石油樹脂である。密度は0.98kg/m3、ビカット軟化温度は125℃である。
環状オレフィン系樹脂のバージン原料は、高純度環状オレフィンコポリマーである。密度は1.01kg/m3、ISO 1133に基づくメルトボリュームレート(MVR)は12cm3/10分(230℃、2.16kg)、ガラス転移温度は78℃である。
参考例1の熱収縮性フィルムの製造方法は、次のとおりである。まず、コア層および表層を構成する原料として表1に示される原料を用い、バレル温度が160~250℃の押出機に投入し、210℃の多層ダイスから3層構造のシート状に押出し、30℃の引き取りロールにて冷却固化した。次いで、予熱ゾーン105℃、延伸ゾーン89~91℃、熱固定ゾーン85℃のテンター延伸機内で延伸倍率6倍にて延伸した後、巻き取り機で巻き取ることによって、主収縮方向と直交する方向がMD(Machine Direction)、主収縮方向がTD(Transverse Direction)となる熱収縮性フィルムを得た。
実施例および比較例の再生原料の製造方法は、次のとおりである。参考例1および2の熱収縮性フィルムの一方の面に、グラビア印刷機を用いて印刷層を積層した。更に、参考例2については、もう一方の面にオーバーコート層を積層した。オーバーコート層は、アクリル酸(メタクリル酸)エステル系樹脂を主成分とする層である。次に、印刷層を有する熱収縮性フィルムを粉砕機でチップ状に加工し、脱墨処理を施し、熱風で乾燥処理を行うことによって、実施例および比較例の再生原料を作製した。
実施例1~9、および、比較例の熱収縮性フィルムの製造方法は次のとおりである。コア層および表層を構成する原料として表1に示される原料を用い、これらを表1に示す割合で混合することで、実施例1~9、および、比較例に係るコア層および表層を構成する原料組成物を得た。この原料組成物を用いて、参考例1の熱収縮性フィルムと同様の方法によって、実施例1~9、および、比較例の熱収縮性フィルムを作製した。表中の割合RAは、コア層を構成する熱可塑性樹脂全体のうち、参考例の表層に由来するポリエステル系樹脂の割合を示し、割合RBは、表層を構成する熱可塑性樹脂全体のうち、参考例のコア層に由来するポリスチレン系樹脂の割合を示す。
本願発明者(ら)は、実施例1~12、比較例、および、参考例1~2の熱収縮性フィルムについて、以下の項目を測定する試験を実施した。
実施例1~12、比較例、および、参考例1~2で得られた熱収縮性フィルムを、MD100mm×TD100mmの大きさのサンプルにカットし、試験片を得た。得られた試験片を、70℃、80℃、90℃の温水、および、沸騰水(100℃)に10秒間浸漬させた後、試験片を取り出し、15℃の水に5秒間浸漬し、次式(1)に従いMD方向の熱収縮率を求め、次式(2)に従いTD方向の熱収縮率を求めた。なお、次式(1)中のLMDは、熱収縮後の試験片のMD方向の長さであり、次式(2)中のLTDは、熱収縮後の試験片のMD方向の長さである。なお、収熱縮率は、各実施例、比較例、および、各参考例の熱収縮性フィルムにつき、2つの試験片を用いて測定し、その平均値を用いた。
熱収縮率(%)={(100-LMD)/100}×100・・・(1)
熱収縮率(%)={(100-LTD)/100}×100・・・(2)
JIS Z7136に準ずる方法により、ヘイズメーター(日本電色工業社製、NDH5000)を用いて、実施例1~12、比較例、および、参考例1~2の熱収縮性フィルムに対しヘイズを測定した。なお、ヘイズについては、各実施例、比較例、および、各参考例につき、4つの試験片を用いて測定し、その平均値を算出した。
JIS Z8741に準ずる方法により、日本電色工業社製のVG-2000型を用いて、各実施例、比較例、および、各参考例の熱収縮性フィルムに対し、入射角45°における光沢度を測定した。
実施例1~12、比較例、および、参考例1~2の熱収縮性フィルムを、MD100mm×TD100mmの大きさのサンプルにカットし、試験片を得た。得られた試験片を、(株)東洋精機製作所製のフィルムインパクトテスターを用いてJIS P8134に準ずる方法により、測定した。具体的には、台の上に、試験片を固定する。次に、フィルムインパクトテスターのアームを固定しているフックを取り外すことで、軸を中心に扇形のアームが回転し、アームの先端に取り付けられた衝撃ヘッドが試験片を突き破る。衝撃強度は、衝撃ヘッドが試験片を突き破る時に必要なエネルギーを衝撃強度として数値化する。衝撃強度は、5回測定を行い、平均値を求める。
実施例1~12、比較例、および、参考例1~2の熱収縮性フィルムについて、JIS P8126に準拠した方法で圧縮強度を測定した。具体的には以下の方法を用いた。得られた熱収縮性フィルムを長さ152.4mm、幅12.7mmの短冊状にカットし、予め作製した支持具に円筒状にセットした後、支持具をリングクラッシュテスタ(東洋精機製作所社製、型式D)の架台に乗せ、測定を行った。測定は縦方向(フィルムの流れ方向)の圧縮強度のみで行い、n=8としその平均値を値とした。
実施例1~12、比較例、および、参考例1~2の熱収縮性フィルムを、MD250mm×TD5mmの大きさのサンプルにカットし、試験片を得た。得られた試験片を、東洋精機製作所社製ストログラフVE-1Dを用いてASTM D882に準拠した方法で測定した。なお、ヤング率は、各実施例、比較例、および、各参考例につき、4つの試験片を用いて測定し、その平均値を算出した。
実施例1~12、比較例、および、参考例1~2の熱収縮性フィルムを、東京精密株式会社製サーフコム570Aにセットし、ISO13565-1規格に準拠して、Ra(算術平均粗さ),Ramax(最大高さ粗さ),Rz(十点平均粗さ)を測定した。測定条件は次のとおりである。
・カットオフ:0.8mm
・測定端子の駆動速度:0.3mm/秒
・測定長さ:20.0mm
・測定倍率:縦倍率×10,000、横倍率×5
実施例10~12および参考例2の熱収縮性フィルムの任意の箇所から、MD100mm×TD100mmのサンプルをそれぞれ3枚ずつ切り出した。各サンプルを一定温度に調整した低温恒温器(IL-82 ヤマト科学社製)に7日間静置した後、各サンプルのMD方向の長さLMD(mm)およびTD方向の長さLTD(mm)をそれぞれ計測した。温度条件は、30℃および40℃とした。各サンプルについて、上記の式(1)および(2)に従い、MD方向およびTD方向の自然収縮率(%)の平均値を算出した。
表3は、実施例1~9、比較例および参考例1の試験結果を示す表である。実施例1~8の熱収縮性フィルムは、各測定項目について、参考例1の熱収縮性フィルムと概ね同様の結果が得られた。また、実施例9の熱収縮性フィルムは、ヘイズが参考例1の熱収縮性フィルムよりも若干高く、かつ、光沢度が参考例1の熱収縮性フィルムよりも若干低いものの、他の測定項目については、参考例1の熱収縮性フィルムと概ね同様の結果が得られた。実施例1~7の熱収縮性フィルムは、実質的にバージン原料のみによって構成される表層によって、再生原料を含むコア層の表面が覆われており、実施例8、9の熱収縮性フィルムは、割合RYが低い表層によって、コア層の表面が覆われているため、参考例1の熱収縮性フィルムの物性に近い物性を有しているためと考えられる。一方、比較例の熱収縮性フィルムは、各測定項目のうちのヘイズが参考例の熱収縮性フィルムよりも高く、光沢度が参考例1の熱収縮性フィルムよりも低かった。比較例の熱収縮性フィルムは、コア層がバージン原料とは異なる原料の再生原料を含むため、光沢度が低下したためであると考えられる。
上記各実施形態は本発明に関する熱収縮性フィルムが取り得る形態の例示であり、その形態を制限することを意図していない。本発明に関する熱収縮性フィルムは、各実施形態に例示された形態とは異なる形態を取り得る。その一例は、各実施形態の構成の一部を置換、変更、もしくは、省略した形態、または、各実施形態に新たな構成を付加した形態である。以下に各実施形態の変形例の幾つかの例を示す。
第1実施形態では、コア層20の第1再生原料は、コア層20のバージン原料と同じ原料であったが、第1再生原料は、コア層20のバージン原料とは異なる原料であってもよい。すなわち、この変形例では、コア層20のバージン原料と、第1再生原料と、第2再生原料とは、異なる原料である。
第1実施形態では、コア層20の再生原料は、第1再生原料および第2再生原料を含んでいたが、コア層20の再生原料は、第1再生原料のみであってもよい。この変形例では、第1再生原料は、コア層20のバージン原料と同じ原料であってもよく、コア層20のバージン原料とは異なる原料であってもよい。
第2実施形態では、コア層20Xは、実質的にバージン原料のみを含んでいたが、コア層20Xは、第1実施形態と同様に、再生原料を含んでいてもよい。
第2実施形態では、表層30Xの第3再生原料は、表層30Xのバージン原料と同じ原料であったが、第3再生原料は、表層30Xのバージン原料とは異なる原料であってもよい。すなわち、この変形例では、表層30Xのバージン原料と、第3再生原料と、第4再生原料とは、異なる原料である。
第2実施形態では、表層30Xの再生原料は、第3再生原料および第4再生原料を含んでいたが、表層30Xの再生原料は、第3再生原料のみであってもよい。この変形例では、第3再生原料は、表層30Xのバージン原料と同じ原料であってもよく、表層30Xのバージン原料とは異なる原料であってもよい。
上記実施形態のステップS1~ステップS5の順序は、変更されてもよい。例えば、包装資材から印刷層を分離する脱墨処理を行った後、必要に応じて中和、洗浄および乾燥等を行い、その後印刷層が除去された包装資材の樹脂層を個片化し、脱墨フラフを得てもよい。また、個片化、中和、洗浄および乾燥のうち少なくとも1つは適宜省略されてもよいし、必要に応じて2回以上行われてもよい。また、再生原料は、フラフの形態ではなく、ペレット化される工程を経た後に、ステップS6で用いられてもよい。
熱収縮性フィルム10Xは、上記実施形態のステップS6において、ステップS5で得られた脱墨フラフ(再生原料)と、第2バージン原料とを含む表層30Xと、第1バージン原料を少なくとも含むコア層20Xとを備える樹脂フィルムの成形を行うことにより製造することができる。この場合、表層30Xは、表層30Xに含まれる熱可塑性樹脂全体に対し、20重量%以下の再生原料を含むように成形される。この場合、脱墨フラフは、第3熱可塑性樹脂の第3再生原料と、第3熱可塑性樹脂とは異なる第4熱可塑性樹脂の第4再生原料とを含んでもよく、第2バージン原料は、第3熱可塑性樹脂のバージン原料であってもよい。さらに、ステップS6は、表層30Xに含まれる熱可塑性樹脂全体中の再生原料における第4再生原料の割合が15重量%以下となるように表層30Xを成形することを含んでもよい。
20、20X:コア層
30、30X:表層
Claims (12)
- 熱可塑性樹脂を主成分とする樹脂層と、印刷層とを有するフィルムラベルを複数含む包装資材を準備することと、
熱可塑性樹脂の第1バージン原料と、前記第1バージン原料とは異なる熱可塑性樹脂の第2バージン原料とを準備することと、
前記樹脂層から、1または複数の熱可塑性樹脂の再生原料を回収することと、
前記再生原料を原料に含め、コア層と、前記コア層に積層される表層とを備える樹脂フィルムを成形することと
を含み、
前記1または複数の熱可塑性樹脂の再生原料を回収することは、
前記包装資材および前記印刷層が除去された前記樹脂層の少なくとも一方を個片化することと、
前記包装資材および前記包装資材の個片の少なくとも一方から前記印刷層を分離して、前記印刷層が除去された前記樹脂層および前記印刷層が除去された前記樹脂層の個片の少なくとも一方を得ることと、
を含み、
前記樹脂フィルムを成形することは、
前記再生原料と、前記第1バージン原料とを少なくとも含む前記コア層と、前記第2バージン原料を主成分とする前記表層とを成形すること、および
前記第1バージン原料を少なくとも含む前記コア層と、前記第2バージン原料と、25重量%以下の前記再生原料とを含む前記表層とを成形することの少なくとも一方を含む、
熱収縮性フィルムの製造方法。 - 前記樹脂フィルムを成形することは、前記再生原料と、前記第1バージン原料とを少なくとも含む前記コア層と、前記第2バージン原料を主成分とする前記表層とを成形することを含み、
前記再生原料は、第1熱可塑性樹脂の第1再生原料と、前記第1熱可塑性樹脂とは異なる第2熱可塑性樹脂の第2再生原料とを含む、
請求項1に記載の熱収縮性フィルムの製造方法。 - 前記第1バージン原料は、前記第1熱可塑性樹脂のバージン原料である、
請求項2に記載の熱収縮性フィルムの製造方法。 - 前記樹脂フィルムを成形することは、前記コア層中の前記再生原料における前記第2再生原料の割合が25重量%以下となるように前記コア層を成形することを含む、
請求項3に記載の熱収縮性フィルムの製造方法。 - 前記樹脂フィルムを成形することは、前記コア層中の前記再生原料の割合が2.5重量%以上80重量%以下となるように前記コア層を成形することを含む、
請求項1に記載の熱収縮性フィルムの製造方法。 - 前記第1熱可塑性樹脂は、ポリスチレン系樹脂であり、前記第2熱可塑性樹脂は、ポリエステル系樹脂である、
請求項2に記載の熱収縮性フィルムの製造方法。 - 前記第1熱可塑性樹脂は、ポリプロピレン系樹脂および石油系樹脂であり、前記第2熱可塑性樹脂は、ポリエチレン系樹脂および環状オレフィン系樹脂である、
請求項2に記載の熱収縮性フィルムの製造方法。 - 前記樹脂フィルムを成形することは、前記第1バージン原料を少なくとも含む前記コア層と、前記第2バージン原料と、25重量%以下の前記再生原料とを含む前記表層とを成形することを含み、
前記再生原料は、第3熱可塑性樹脂の第3再生原料と、前記第3熱可塑性樹脂とは異なる第4熱可塑性樹脂の第4再生原料とを含む、
請求項1に記載の熱収縮性フィルムの製造方法。 - 前記第2バージン原料は、前記第3熱可塑性樹脂のバージン原料である、
請求項8に記載の熱収縮性フィルムの製造方法。 - 前記樹脂フィルムを成形することは、前記表層中の再生原料における前記第4再生原料の割合が、15重量%以下となるように前記表層を成形することを含む、
請求項9に記載の熱収縮性フィルムの製造方法。 - バージン原料および再生原料を含むコア層と、
前記コア層の少なくとも一方の表面に積層され、実質的には、前記コア層のバージン原料とは異なるバージン原料のみによって構成される表層と、を備える
熱収縮性フィルム。 - バージン原料を含むコア層と、
前記コア層の少なくとも一方の表面に積層され、前記コア層のバージン原料とは異なるバージン原料、および、再生原料を含む表層と、を備え、
前記表層における前記再生原料の割合は、25重量%以下である
熱収縮性フィルム。
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Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001350411A (ja) * | 2000-06-05 | 2001-12-21 | Fuji Seal Inc | 熱収縮性ラベルからのインキ層の除去方法 |
JP2002060518A (ja) * | 2000-08-18 | 2002-02-26 | Mitsubishi Plastics Ind Ltd | ポリエステル系フィルム及び印刷インキの剥離方法 |
JP2006123482A (ja) * | 2004-09-29 | 2006-05-18 | Mitsubishi Plastics Ind Ltd | 熱収縮性積層フィルムおよび該フィルムを用いた成形品、容器 |
JP2006159901A (ja) * | 2004-11-10 | 2006-06-22 | Mitsubishi Plastics Ind Ltd | 熱収縮性積層フィルム、並びに該フィルムを用いた成形品、熱収縮性ラベル及び容器 |
JP2006289727A (ja) * | 2005-04-08 | 2006-10-26 | Toyobo Co Ltd | 熱収縮性ポリエステル系フィルムおよび熱収縮性ラベル |
JP2008000908A (ja) * | 2006-06-20 | 2008-01-10 | Npo Hiroshima Junkangata Shakai Suishin Kiko | 廃プラスチックの薄物製品へのリサイクル方法 |
JP2012006236A (ja) * | 2010-06-24 | 2012-01-12 | Teijin Dupont Films Japan Ltd | 熱可塑性樹脂フィルムの製造装置及び製造方法 |
WO2020066652A1 (ja) * | 2018-09-25 | 2020-04-02 | Dic株式会社 | 積層フィルムの分離回収方法 |
JP6849141B1 (ja) * | 2020-05-27 | 2021-03-24 | 三菱ケミカル株式会社 | 熱収縮性フィルムの製造方法 |
-
2022
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- 2022-08-03 TW TW111129220A patent/TW202313805A/zh unknown
- 2022-08-03 JP JP2023540389A patent/JPWO2023013690A1/ja active Pending
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001350411A (ja) * | 2000-06-05 | 2001-12-21 | Fuji Seal Inc | 熱収縮性ラベルからのインキ層の除去方法 |
JP2002060518A (ja) * | 2000-08-18 | 2002-02-26 | Mitsubishi Plastics Ind Ltd | ポリエステル系フィルム及び印刷インキの剥離方法 |
JP2006123482A (ja) * | 2004-09-29 | 2006-05-18 | Mitsubishi Plastics Ind Ltd | 熱収縮性積層フィルムおよび該フィルムを用いた成形品、容器 |
JP2006159901A (ja) * | 2004-11-10 | 2006-06-22 | Mitsubishi Plastics Ind Ltd | 熱収縮性積層フィルム、並びに該フィルムを用いた成形品、熱収縮性ラベル及び容器 |
JP2006289727A (ja) * | 2005-04-08 | 2006-10-26 | Toyobo Co Ltd | 熱収縮性ポリエステル系フィルムおよび熱収縮性ラベル |
JP2008000908A (ja) * | 2006-06-20 | 2008-01-10 | Npo Hiroshima Junkangata Shakai Suishin Kiko | 廃プラスチックの薄物製品へのリサイクル方法 |
JP2012006236A (ja) * | 2010-06-24 | 2012-01-12 | Teijin Dupont Films Japan Ltd | 熱可塑性樹脂フィルムの製造装置及び製造方法 |
WO2020066652A1 (ja) * | 2018-09-25 | 2020-04-02 | Dic株式会社 | 積層フィルムの分離回収方法 |
JP6849141B1 (ja) * | 2020-05-27 | 2021-03-24 | 三菱ケミカル株式会社 | 熱収縮性フィルムの製造方法 |
JP6904495B1 (ja) * | 2020-05-27 | 2021-07-14 | 三菱ケミカル株式会社 | 熱収縮性フィルム、包装資材、成形品または容器 |
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