WO2021125100A1 - Stratifié et son procédé de recyclage et composition et article de résine recyclés le contenant - Google Patents

Stratifié et son procédé de recyclage et composition et article de résine recyclés le contenant Download PDF

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Publication number
WO2021125100A1
WO2021125100A1 PCT/JP2020/046379 JP2020046379W WO2021125100A1 WO 2021125100 A1 WO2021125100 A1 WO 2021125100A1 JP 2020046379 W JP2020046379 W JP 2020046379W WO 2021125100 A1 WO2021125100 A1 WO 2021125100A1
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Prior art keywords
layer
resin
laminate
gas barrier
resin composition
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PCT/JP2020/046379
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English (en)
Japanese (ja)
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寛之 若林
亮 田中
瞳 福武
暁 永井
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凸版印刷株式会社
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
    • B29B17/04—Disintegrating plastics, e.g. by milling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • 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
    • Y02W30/52—Mechanical processing of waste for the recovery of materials, e.g. crushing, shredding, separation or disassembly
    • 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
    • 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
    • Y02W30/80—Packaging reuse or recycling, e.g. of multilayer packaging

Definitions

  • the present disclosure relates to a laminate, a recycling method thereof, a recycled resin composition, and an article containing the same.
  • Patent Documents 1 and 2 disclose a packaging material in which a base material layer, an anchor coating agent layer, a delamination layer, and a seal layer are laminated in this order.
  • the present disclosure is useful for producing an article having excellent recyclability and maintaining sufficient strength and physical properties as compared with an article in which the virgin resin is used alone even when used in combination with the virgin resin as a recycled material. Provide the body.
  • the present disclosure also provides a recycled resin composition obtained from this laminate, an article containing the same, and a method for recycling the laminate.
  • the laminate according to one aspect of the present disclosure has a laminated structure including a first layer made of polyethylene resin and a second layer made of polypropylene resin, and at least one of the first layer and the second layer.
  • a polyethylene-polypropylene block copolymer hereinafter, sometimes referred to as “PE-PP block copolymer”
  • the PE-PP block copolymer previously contained in this laminate functions as a compatibilizer.
  • the content of the PE-PP block copolymer in the above-mentioned laminate is preferably 1 to 40 parts by mass.
  • the content of the PE-PP block copolymer is 1 part by mass or more, the dispersion effect of PE and PP can be sufficiently exhibited and sufficient physical characteristics can be ensured.
  • the content of the PE-PP block copolymer is 40 parts by mass or less, the original characteristics of PE and PP are maintained.
  • the laminate may have gas barrier properties. That is, the laminate further includes a vapor-deposited layer having a gas barrier property and a gas barrier coating layer, and even if the gas barrier coating layer contains a water-soluble polymer and a metal alkoxide or a hydrolyzate thereof. Good. Since the laminate has a gas barrier property, when it is used as a packaging material, deterioration of the contents due to moisture and oxygen can be prevented. In this case, an adhesion layer may be provided between the laminated body and the thin-film deposition layer.
  • the adhesion layer By providing the adhesion layer, the adhesion between the surface of the laminated body and the vapor deposition layer can be improved, and the surface on which the vapor deposition layer is formed can be smoothed to form a vapor deposition layer having excellent gas barrier properties. It will be possible.
  • the vapor deposition layer contains, for example, at least one element of Al and Si.
  • One aspect of the present disclosure relates to a recycled resin composition obtained by melt-kneading the above laminate.
  • One aspect of the present disclosure relates to an article containing this recycled resin composition. This article maintains sufficient strength and physical characteristics as compared with an article in which virgin resin is used alone.
  • Specific examples of articles include packaging materials, electrical / electronic parts, housings, and the like.
  • This recycling method includes a step of producing a crushed product of the above-mentioned laminate, a step of producing a melt-kneaded product of the crushed product, a step of producing a recycled resin composition (for example, pellet form) from the melt-kneaded product, and polyethylene. It includes a step of mixing at least one virgin resin of a resin and a polypropylene resin and a recycled resin composition to obtain a resin composition. According to this recycling method, it is possible to produce an article in which sufficient strength and physical characteristics are maintained as compared with an article in which the virgin resin is used alone. From the viewpoint of the strength and physical properties of the article containing the recycled resin composition, the content of the recycled resin composition in the resin composition is preferably 70 parts by mass or less based on the mass of the resin composition.
  • Laminates are provided. Further, the present disclosure provides a recycled resin composition obtained from this laminate, an article containing the same, and a method for recycling the laminate.
  • FIG. 1 is a cross-sectional view schematically showing an embodiment of the laminated body according to the present disclosure.
  • FIG. 2 is a cross-sectional view schematically showing another embodiment of the laminated body according to the present disclosure.
  • FIG. 3 is a cross-sectional view schematically showing another embodiment of the laminated body according to the present disclosure.
  • 4 (a) and 4 (b) are cross-sectional views schematically showing another embodiment of the laminated body according to the present disclosure.
  • FIG. 5 is a chart showing the process of Experiment 1.
  • FIG. 6 is a chart showing the process of Experiment 2.
  • FIG. 1 is a cross-sectional view schematically showing a laminated body according to the present embodiment.
  • the laminated body 10 shown in FIG. 1 has a two-layer structure composed of a first layer 1 and a second layer 2.
  • the first layer 1 contains a polyethylene resin 1a (PE resin) and a PE-PP block copolymer 1b dispersed therein.
  • the second layer 2 is made of polypropylene resin (PP resin).
  • the PE-PP block copolymer 1b contained in the first layer 1 functions as a compatibilizer when the laminate 10 is recycled.
  • the PE-PP block copolymer may be blended in the second layer 2. , May be blended in both the first layer 1 and the second layer 2.
  • the thicknesses of the first layer 1 and the second layer 2 may be appropriately set according to the use of the laminated body 10.
  • the thickness of the first layer 1 and the second layer 2 is preferably, for example, 0.1 to 300 ⁇ m, and is preferably 1 to 200 ⁇ m. Is more preferable, 5 to 150 ⁇ m is further preferable, and 10 to 100 ⁇ m is particularly preferable.
  • the content of the PE-PP block copolymer in the laminate 10 is preferably 1 to 40 parts by mass.
  • the content of the PE-PP block copolymer is 1 part by mass or more, the dispersion effect of PE and PP can be sufficiently exhibited and sufficient physical characteristics can be ensured.
  • the lower limit of the content of the PE-PP block copolymer may be 3 parts by mass or 8 parts by mass.
  • the content of the PE-PP block copolymer is 40 parts by mass or less, the original characteristics of PE and PP are maintained.
  • the upper limit of the content of the PE-PP block copolymer may be 38 parts by mass or 35 parts by mass.
  • the PE-PP block copolymer is composed of, for example, a polyethylene unit composed of polyethylene or an ethylene / ⁇ -olefin copolymer and a polypropylene unit composed of polypropylene or a propylene / ⁇ -olefin copolymer. It is possible to use a block copolymer. Such a block copolymer may have any structure of a diblock copolymer, a triblock copolymer, and a multi-block copolymer.
  • the polyethylene unit of the PE-PP block copolymer is compatible with the polyethylene resin constituting the first layer 1, and the polypropylene unit of the PE-PP block copolymer is compatible with the polypropylene resin constituting the second layer 2. To do.
  • FIG. 2 is a cross-sectional view schematically showing an example of a laminated body including the laminated body 10 having a gas barrier property.
  • the gas barrier laminate 30 shown in FIG. 2 is composed of a laminate 10, a gas barrier functional layer 20, and an adhesive layer 15 for adhering them.
  • the gas barrier functional layer 20 has a laminated structure including a base material 21, an adhesion layer 22, a vapor deposition layer 23, and a gas barrier coating layer 25.
  • the laminate 10 serves as a sealant layer.
  • FIG. 2 shows a case where the first layer 1 and the gas barrier coating layer 25 face each other via the adhesive layer 15, the second layer 2 and the gas barrier coating layer 25 are the adhesive layer 15.
  • the laminated body 10 and the gas barrier functional layer 20 may be bonded so as to face each other.
  • each layer of the gas barrier functional layer 20 and the adhesive layer 15 will be described.
  • the base material 21 is not particularly limited, and may be appropriately selected depending on the use of the gas barrier laminate 30.
  • Specific examples of the base material 21 include polyolefin film (PE, PP, etc.), polyester film (polyethylene terephthalate, polyethylene naphthalate, etc.), polyamide film (nylon-6, nylon-66, etc.), polystyrene film, poly. Examples thereof include vinyl chloride film, polyimide film, polycarbonate film, polyether sulfone film, acrylic film, and cellulose film (triacetyl cellulose, diacetyl cellulose, etc.).
  • polyethylene terephthalate or polyamide is preferably used for packaging of medical supplies, chemicals, foods and the like.
  • a polyolefin-based film as the base material 21.
  • the thickness of these resin films may be, for example, in the range of about 6 to 200 ⁇ m.
  • the resin film is not limited to those derived from petroleum, and may contain a resin material derived from a living organism (for example, PLA, PBS, bio-PE or bio-PET bio).
  • the base material 21 may contain additives such as an antistatic agent, an ultraviolet absorber, a plasticizer, a lubricant, and a colorant.
  • the base material 21 does not necessarily have to be a resin film, and may be, for example, paper.
  • the paper include high-quality paper, special high-quality paper, coated paper, art paper, cast-coated paper, imitation paper and kraft paper.
  • the thickness of these papers may be, for example, in the range of 100 to 800 ⁇ m.
  • the base material 21 may have various pretreatments such as corona treatment, plasma treatment, and frame treatment on the laminated surface, and a coat layer (for example, an easily adhesive layer) is provided on the laminated surface. It may be a thing.
  • the adhesion layer 22 is provided on the surface of the base material 21 for the purpose of improving the adhesion performance between the base material 21 and the vapor deposition layer 23.
  • the adhesion layer 22 is intended to uniformly form the vapor deposition layer 23 without defects by smoothing the surface on which the vapor deposition layer 23 is formed.
  • the adhesion layer 22 serves as a seal.
  • the adhesion layer 22 does not necessarily have to be provided when sufficient adhesion to the vapor deposition layer 23 can be obtained by applying the above-mentioned various pretreatments to the laminated surface of the base material 21.
  • a non-aqueous resin is preferable as the material constituting the adhesion layer 22, and specific examples thereof include a silane coupling agent, an organic titanate, a polyacrylic, a polyester, a polyurethane, a polycarbonate, a polyurea, a polyamide, a polyolefin-based emulsion, a polyimide, a melamine, and a phenol. Can be mentioned.
  • the adhesive layer 22 is imparted with heat-resistant water, it is more preferable that the adhesive layer 22 contains an organic polymer having one or more urethane bonds and urea bonds.
  • an isocyanate compound having an isocyanate group and a polyol such as acrylic or methacrylic polyol, or an amine resin having an amino group and an epoxy group and a glycidyl group
  • a urethane bond is formed by reacting an epoxy compound with, or a urea bond is formed by reacting an isocyanate compound with a solvent such as water or ethyl acetate, or an amine resin having an amino group. May be good.
  • a composite of an acrylic polyol, a polyester polyol, an isocyanate compound, a silane coupling agent, or the like is more preferable.
  • Acrylic polyol is a polymer compound obtained by polymerizing an acrylic acid derivative monomer, or a polymer compound obtained by copolymerizing an acrylic acid derivative monomer and another monomer, which has a hydroxyl group at the terminal. Is.
  • the acrylic polyol reacts with the isocyanate group of the isocyanate compound added later.
  • the polyester polyol is a polyester resin obtained from an acid raw material and an alcohol raw material by a well-known production method, and has two or more hydroxyl groups at the ends. The polyester polyol reacts with the isocyanate group of the isocyanate compound added later.
  • terephthalic acid isophthalic acid, phthalic acid, methylphthalic acid, trimellitic acid, pyromellitic acid, adipic acid, sebacic acid, succinic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexahydro
  • succinic acid maleic acid, fumaric acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexahydro
  • phthalic acid and reactive derivatives thereof include phthalic acid and reactive derivatives thereof.
  • alcohol raw materials ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-hexanediol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanedimethanol, neopentyl glycol, bishydroxyethyl terephthalate, trimethylolmethane , Trimethylolpropane, glycerin, pentaerythritol and the like.
  • the isocyanate compound is added in order to improve the adhesion to the base material and the inorganic oxide by the urethane bond formed by reacting with the acrylic polyol and the polyester polyol.
  • the isocyanate compound mainly acts as a cross-linking agent or a curing agent.
  • the isocyanate compounds include aromatic-based toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), aliphatic-based xylene diisocyanate (XDI), hexaranged isocyanate (HMDI) and other monomers. These polymers and derivatives are used, and these are used alone or as a mixture or the like.
  • silane coupling agent a silane coupling agent containing any organic functional group can be used, for example, ethyltrimethoxysilane, vinyltrimethoxysilane, ⁇ -chloropropylmethyldimethoxysilane, ⁇ -chloropropyltrimethoxysilane. , Glycydooxypropyltrimethoxysilane, ⁇ -methacryloxypropyltrimethoxysilane, ⁇ -methacryloxypropylmethyldimethoxysilane, or other silane coupling agents or hydrolyzates thereof, or two or more thereof can be used.
  • the adhesion layer 22 is formed through a step of applying a coating liquid on the surface of the base material 21.
  • a coating liquid As the coating method, the cast method, dipping method, roll coating method, gravure coating method, screen printing method, reverse coating method, spray coating method, kit coating method, die coating method, metering bar coating method, and chamber doctor are used together. Conventionally known methods such as a coating method and a curtain coating method can be used.
  • the adhesion layer 22 is formed by heating and drying the coating film formed by applying the coating liquid.
  • the thickness of the adhesion layer 22 is, for example, about 0.01 ⁇ m to 2 ⁇ m.
  • the vapor deposition layer 23 uses aluminum oxide (AlOx), silicon oxide (SiOx), magnesium fluoride (MgF 2 ), magnesium oxide (MgO), indium-tin oxide (ITO), or the like as a material having a high oxygen gas barrier property. be able to. From the viewpoint of material cost, barrier performance and transparency, the material constituting the vapor deposition layer 23 is preferably aluminum oxide or silicon oxide.
  • the vapor deposition layer 23 may be formed by vapor deposition of aluminum.
  • the thickness of the thin-film deposition layer 23 may be appropriately set depending on the intended use, but is preferably 10 to 300 nm, and more preferably 20 to 200 nm. By setting the thickness of the thin-film deposition layer 23 to 10 nm or more, it is easy to make the continuity of the thin-film deposition layer 23 sufficient, while by setting it to 300 nm or less, the occurrence of curls and cracks can be sufficiently suppressed, and sufficient barrier performance and sufficient barrier performance can be achieved. Easy to achieve flexibility.
  • the vapor deposition layer 23 can be deposited by a vacuum film forming means.
  • the vacuum deposition means there are known methods such as a vacuum deposition method, a sputtering method, and a chemical vapor deposition method (CVD method), but the vacuum deposition method is preferable because the film deposition rate is high and the productivity is high.
  • the film formation means by electron beam heating is particularly effective because the film formation rate can be easily controlled by the irradiation area and the electron beam current, and the temperature of the vapor deposition material can be raised and lowered in a short time. is there.
  • the gas barrier coating layer 25 protects the vapor-deposited layer 23 and contributes to the improvement of the water vapor barrier property, thereby exhibiting a high gas barrier property due to a synergistic effect with the vapor-deposited layer 23.
  • the gas barrier coating layer 25 is formed through a step of forming a coating film containing the following components on the surface of the vapor deposition layer 23. -At least one of a water-soluble polymer / metal alkoxide having a hydroxy group and its hydrolyzate
  • water-soluble polymer examples include polyvinyl alcohol, polyvinylpyrrolidone, starch, methyl cellulose, carboxymethyl cellulose, sodium alginate and the like.
  • polyvinyl alcohol hereinafter abbreviated as PVA
  • PVA polyvinyl alcohol
  • the PVA referred to here is generally obtained by saponifying polyvinyl acetate.
  • PVA partially saponified PVA in which several tens of percent of acetic acid groups remain, complete with only a few percent of acetic acid groups remaining. PVA or the like can be used.
  • the water-soluble polymer, together with the metal alkoxide and / its hydrolyzate forms an organic-inorganic composite by hydrolysis and dehydration condensation (eg, sol-gel method).
  • the metal alkoxide is a compound represented by the following general formula.
  • M represents a metal atom such as Si, Ti, Al, Zr, R represents an alkyl group such as -CH 3 , -C 2 H 5 , and n represents an integer corresponding to the valence of M.
  • Specific examples thereof include tetraethoxysilane [Si (OC 2 H 5 ) 4 ] and triisopropoxyaluminum [Al (O-iso-C 3 H 7 ) 3 ].
  • Tetraethoxysilane and triisopropoxyaluminum are preferable because they are relatively stable in an aqueous solvent after hydrolysis.
  • hydrolyzate and polymer of the metal alkoxide examples include the following compounds. ⁇ Hydrolysates and polymers of tetraethoxysilane: silicic acid (Si (OH) 4 ), etc. ⁇ Hydrolysates and polymers of tripropoxyaluminum: aluminum hydroxide (Al (OH) 3 ), etc.
  • the gas barrier coating layer 25 may further contain a silane coupling agent.
  • silane coupling agent examples include compounds represented by the following general formulas.
  • R 1 Si (OR 2 ) n R 1 indicates an organic functional group, and R 2 indicates an alkyl group such as CH 3 , C 2 H 5 or the like.
  • silane coupling agents such as methacryloxypropylmethyldimethoxysilane.
  • an isocyanate compound or a known additive such as a dispersant, a stabilizer, a viscosity regulator, or a colorant is added to the gas barrier coating layer 25 as necessary, as long as the gas barrier property is not impaired. Is also possible.
  • the thickness (film thickness) of the gas barrier coating layer 25 is preferably in the range of 50 to 1000 nm, and more preferably in the range of 100 to 500 nm. When the film thickness is 50 nm or more, a more sufficient gas barrier property tends to be obtained, and when the film thickness is 1000 nm or less, the thin film tends to maintain sufficient flexibility.
  • Examples of the solvent used for forming the coating film include water, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-propyl alcohol, n-butyl alcohol, n-pentyl alcohol, dimethylsulfoxide, dimethylformamide, and dimethylacetamide. , Toluene, hexane, heptane, cyclohexane, acetone, methyl ethyl ketone, diethyl ether, dioxane, tetrahydrofuran, ethyl acetate, butyl acetate. One of these solvents may be used alone, or two or more of these solvents may be used in combination.
  • methyl alcohol, ethyl alcohol, isopropyl alcohol, toluene, ethyl acetate, methyl ethyl ketone and water are preferable from the viewpoint of coatability.
  • methyl alcohol, ethyl alcohol, isopropyl alcohol and water are preferable.
  • Additives such as isocyanate compounds, silane coupling agents, dispersants, stabilizers, viscosity regulators and colorants may be added to the coating liquid as necessary, as long as the gas barrier properties are not impaired.
  • a silane compound (silane coupling agent) represented by the formula (R 1 Si (OR 2 ) 3) n may be added to the coating liquid.
  • the organic functional group (R 1 ) is preferably a non-aqueous functional group such as vinyl, epoxy, methacryloxy, ureido and isocyanate.
  • silane coupling agent examples include 1,3,5-tris (3-trialkoxysilylalkyl) isocyanurate, 3-glycidoxypropyltrimethoxysilane, and 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane. Can be mentioned.
  • the gas barrier coating layer 25 is formed through a step of applying a coating liquid on the surface of the vapor deposition layer 23.
  • a coating method the cast method, dipping method, roll coating method, gravure coating method, screen printing method, reverse coating method, spray coating method, kit coating method, die coating method, metering bar coating method, and chamber doctor are used together. Conventionally known methods such as a coating method and a curtain coating method can be used.
  • the gas barrier coating layer 25 is formed by heating and drying the coating film formed by applying the coating liquid.
  • the adhesive layer 15 adheres the laminated body 10 and the gas barrier functional layer 20.
  • the adhesive constituting the adhesive layer 15 include a polyurethane resin obtained by reacting a main agent such as a polyester polyol, a polyether polyol, an acrylic polyol, and a carbonate polyol with a bifunctional or higher functional isocyanate compound.
  • a main agent such as a polyester polyol, a polyether polyol, an acrylic polyol, and a carbonate polyol with a bifunctional or higher functional isocyanate compound.
  • a main agent such as a polyester polyol, a polyether polyol, an acrylic polyol, and a carbonate polyol with a bifunctional or higher functional isocyanate compound.
  • the various polyols one type may be used alone or two or more types may be used in combination.
  • the adhesive layer 15 may be obtained by blending the above-mentioned polyurethane resin with a carbodiimide compound, an oxazoline compound, an epoxy compound, a phosphorus compound, a silane coupling agent, or the like for the purpose of promoting adhesion.
  • the thickness of the adhesive layer 15 is, for example, 1 to 10 ⁇ m and may be 3 to 7 ⁇ m from the viewpoint of obtaining desired adhesive strength, followability, processability, and the like.
  • the laminated body 10 may be laminated on the gas barrier functional layer 20 by heat treatment.
  • the gas barrier laminate 40 shown in FIG. 3 has a laminate structure including a laminate 10 (base material), an adhesion layer 22, a vapor deposition layer 23 having a gas barrier property, and a gas barrier coating layer 25.
  • FIG. 3 shows a case where the second layer 2 and the adhesion layer 22 face each other, the first layer 1 and the adhesion layer 22 are in close contact with each other on the surface of the laminated body 10.
  • the layer 22, the thin-film deposition layer 23, and the gas barrier coating layer 25 may be formed in that order.
  • FIG. 2 a gas barrier laminate having a vapor-deposited layer 23 between the base material 21 and the gas barrier coating layer 25 is illustrated, but a packaging material that does not require a high degree of gas barrier property is not required.
  • the gas barrier laminate is applied to the above, the vapor deposition layer 23 and the adhesion layer 22 may not be provided as shown in FIG. 4A.
  • FIG. 3 shows a gas barrier laminate having a vapor-deposited layer 23 between the laminate 10 and the gas barrier coating layer 25, but the gas barrier laminate is applied to a packaging material that does not require a high degree of gas barrier property.
  • the vapor deposition layer 23 and the adhesion layer 22 may not be provided as shown in FIG. 4 (b).
  • the recycling method according to the present embodiment uses the laminated body 10 or a laminated body containing the same (for example, gas barrier laminated bodies 30, 40) as a recycled resin. That is, this recycling method includes the following steps. (A) Step of producing crushed product of laminate 10 or a laminate containing the same (b) Step of producing melt-kneaded product of crushed product (c) Recycled resin composition (for example, pellet form) from melt-kneaded product Step of Producing (d) Step of Mixing At least One Virgin Resin of Polyethylene Resin and Polypropylene Resin with a Recycled Resin Composition to Obtain a Resin Composition
  • the content of the recycled resin composition in the resin composition is preferably 70% by mass or less, preferably 40% by mass or less, based on the mass of the resin composition. Is more preferable. From the viewpoint of effective utilization of the recycled resin composition, the content of the recycled resin composition in the resin composition is preferably 1% by mass or more, and more preferably 10% by mass or more.
  • this laminate is designated as a monomaterial (all polyolefin). Can be reused.
  • Experiment 1 (Examples 1 to 12 and Comparative Examples 1 to 6) Purpose: To confirm how much the strength physical properties of the mixed resin of the recycled resin and the virgin resin are maintained compared to the strength physical properties of the virgin PE resin by compatibilizing the polyethylene resin contained in the recycled resin with the polyethylene resin. To do.
  • PE resin pellets Suntech F1810 (Asahi Kasei, film grade)
  • PP resin pellets Polypropylene resin pellets
  • Novatec FB3B manufactured by Japan Polypropylene, film grade
  • -Polyethylene-polypropylene block copolymer PE-PP block copolymer
  • -Virgin polyethylene vangin PE
  • Suntech M7620 Alignment M7620
  • -Virgin polypropylene (virgin PP): Novatec MA3 (manufactured by Japan Polypropylene, injection molding grade)
  • PE / PP Laminate A PE / PP laminate as a material for recycled resin was formed by coextrusion. Coextrusion was carried out by a small extruder, and PE resin pellets and PP resin pellets were supplied to the small extruder, respectively.
  • Tables 1 and 2 based on 100 parts by mass of the mass of the PE / PP laminate
  • PE-PP block copolymers in some cases, "PE-PP block copolymers (A)" in the drawings.
  • test piece The strength and physical properties of the test piece were evaluated by measuring tensile stress and tensile nominal strain at break. The results are shown in Tables 1 and 2.
  • Tensile stress and tensile breaking nominal strain were measured based on the method described in JIS K7161. An autograph tester AGS-X (manufactured by Shimadzu Corporation) was used as an apparatus, and the tensile test speed was 50 mm / min.
  • Test pieces made of virgin resin virgin resin (virgin PE or virgin PP) were separately prepared, and the tensile stress and tensile breaking nominal strain of these test pieces were measured, respectively.
  • Tensile stress and tensile breaking nominal strain were evaluated based on the following criteria. A: 80% or more of the measured value of virgin resin B: 60% or more and less than 80% of the measured value of virgin resin C: less than 60% of the measured value of virgin resin
  • Experiment 2 (Examples 13 to 26 and Comparative Examples 7-14) Purpose: By compatibilizing the polyethylene resin contained in the recycled resin for packaging materials, which requires gas barrier properties, the strength of the mixed resin of the recycled resin and the virgin resin is improved compared to the strength of the virgin resin. Check how long it will be retained.
  • PE resin pellets Suntech F1810 (Asahi Kasei, film grade)
  • OPP film Pipe wrench film P2161 (manufactured by Toyobo, thickness 25 ⁇ m)
  • PE-PP block copolymer Pipe wrench film P2161 (manufactured by Toyobo, thickness 25 ⁇ m)
  • PE-PP block copolymer Pipe wrench film P2161 (manufactured by Toyobo, thickness 25 ⁇ m)
  • PE-PP block copolymer Pipe wrench film P2161 (manufactured by Toyobo, thickness 25 ⁇ m)
  • PE-PP block copolymer Pipe wrench film P2161 (manufactured by Toyobo, thickness 25 ⁇ m)
  • PE-PP block copolymer Pipe wrench film P2161 (manufactured by Toyobo, thickness 25 ⁇ m)
  • PE-PP block copolymer Pipe wrench film P2161 (manufactured by Toyob
  • the test piece was evaluated through the following steps (see FIG. 6).
  • (1) Preparation of Gas Barrier Laminated Form For Examples, a PE-PP block copolymer was blended with PE resin pellets and extruded with a small extruder to obtain a PE single-layer film having a thickness of 25 ⁇ m. As for the comparative example, a PE-PP block copolymer was not blended with the PE resin pellets, and a PE single-layer film having a thickness of 25 ⁇ m was obtained by extrusion using a small extruder. On the other hand, the adhesion layer was cured on the corona-treated surface side of the OPP film (base material) by a gravure coat roll method at a coating amount of 0.1 g / m 2.
  • AlOx vapor deposition layer thickness 10 nm
  • a gas barrier coating layer was formed on the surface of the AlOx thin-film deposition layer at a coating amount of 0.3 g / m 2.
  • the above-mentioned single-layer film was attached on the surface of the gas barrier coating layer by a dry laminating method using a two-component adhesive.
  • OPP (25 ⁇ m) / adhesion layer / AlOx vapor deposition layer (thickness 10 nm) / gas barrier coating layer / adhesive layer (5 ⁇ m) / PE-PP block copolymer-containing PE single layer film (25 ⁇ m). ) was obtained.
  • a gas barrier laminate having a composition of OPP (25 ⁇ m) / adhesion layer / AlOx vapor deposition layer (thickness 10 nm) / gas barrier coating layer / adhesive layer (5 ⁇ m) / PE single layer film (25 ⁇ m) was obtained. ..
  • the amount of the PE-PP block copolymer shown in Tables 3 and 4 is based on 100 parts by mass of the total mass of the PE / PP gas barrier laminate.
  • Example 14 and 21 and Comparative Examples 7 and 11 In order to evaluate the influence of the layers for imparting gas barrier properties (adhesive layer / AlOx vapor deposition layer / gas barrier coating layer) on the recyclability, a laminate having no of these layers was prepared. That is, for Examples, an OPP (25 ⁇ m) / adhesive layer (5 ⁇ m) / PE-PP block copolymer-containing PE single-layer film was prepared. For the comparative example, OPP (25 ⁇ m) / adhesive layer (5 ⁇ m) / PE single layer film was prepared.
  • the oxygen permeability of the gas barrier laminates of Example 19 and Comparative Example 10 was about 3 cc / m 2 , day, and atm. Any water vapor permeability of the gas barrier laminates of Examples 19 and Comparative Example 10 was about 0.6g / m 2 ⁇ day. From these results, it was confirmed that the PE-PP block copolymer in the gas barrier laminate does not affect the gas barrier property.
  • Laminates are provided. Further, the present disclosure provides a recycled resin composition obtained from this laminate, an article containing the same, and a method for recycling the laminate.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Environmental & Geological Engineering (AREA)
  • Laminated Bodies (AREA)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
  • Wrappers (AREA)

Abstract

La présente invention concerne un stratifié qui présente une structure stratifiée pourvue d'une première couche (1) comprenant une résine de polyéthylène (1a) et une seconde couche (2) comprenant une résine de polypropylène, la première couche et/ou la seconde couche contenant un copolymère séquencé de polyéthylène-polypropylène (1b) qui est compatible avec la résine de polyéthylène ou la résine de polypropylène. Un procédé de recyclage selon la présente invention comprend : une étape de production d'un produit broyé du stratifié ; une étape de production d'un mélange fondu du produit broyé ; une étape de production d'une composition de résine recyclée à partir du mélange fondu ; et une étape de mélange de la composition de résine recyclée avec une résine de polyéthylène vierge et/ou une résine de polypropylène vierge pour obtenir une composition de résine.
PCT/JP2020/046379 2019-12-16 2020-12-11 Stratifié et son procédé de recyclage et composition et article de résine recyclés le contenant WO2021125100A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023074683A1 (fr) * 2021-10-28 2023-05-04 凸版印刷株式会社 Film barrière aux gaz et matériau d'emballage
WO2023153327A1 (fr) * 2022-02-14 2023-08-17 東レ株式会社 Film de polypropylène, stratifié, matériau d'emballage, corps emballé et procédé de fabrication associé
WO2024014451A1 (fr) * 2022-07-12 2024-01-18 Ｔｏｐｐａｎホールディングス株式会社 Film barrière aux gaz et stratifié barrière

Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01294748A (ja) * 1987-11-12 1989-11-28 Mitsui Petrochem Ind Ltd 樹脂組成物の製造方法
JPH0740517A (ja) * 1993-05-24 1995-02-10 Mitsubishi Chem Corp 多層中空成形体
JPH09227734A (ja) * 1996-02-26 1997-09-02 Sumika Color Kk 成形プロピレン−α−オレフィンブロック共重合体樹脂用着色マスターバッチ組成物およびコンパウンド
JP2000177043A (ja) * 1998-12-14 2000-06-27 Mitsubishi Polyester Film Copp 二軸配向積層フィルム
JP2002524302A (ja) * 1998-09-02 2002-08-06 コンヴィニエンス・フード・システムズ・べスローテン・フェンノートシャップ ポリオレフィン発泡体層を有する包装材料
JP2003253111A (ja) * 2002-03-06 2003-09-10 Teijin Chem Ltd 樹脂組成物、積層成形品、およびリサイクル方法
JP2004169005A (ja) * 2002-11-05 2004-06-17 Toray Ind Inc 積層フィルムのリサイクル方法およびリサイクル製品
JP2006008160A (ja) * 2004-06-24 2006-01-12 Nissan Motor Co Ltd 多層容器
JP2007508972A (ja) * 2003-10-27 2007-04-12 シーエフエス・ケンプテン・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング 発泡ポリオレフィン層を備えた包装材料
JP2009132028A (ja) * 2007-11-30 2009-06-18 Kyoraku Co Ltd 表皮付きプラスチック成形体並びにその製造方法及びその回収方法
JP2009184294A (ja) * 2008-02-08 2009-08-20 Mitsui Chemicals Inc マット調延伸積層フィルム
JP2013006313A (ja) * 2011-06-23 2013-01-10 Teijin Dupont Films Japan Ltd 配向積層ポリエステルフィルムおよびその製造方法
JP2013129756A (ja) * 2011-12-21 2013-07-04 Sekisui Techno Seikei Kk 改質ポリプロピレン系樹脂組成物の製造方法、並びにポリプロピレン系樹脂成形体の製造方法及びこれにより得られるポリプロピレン系樹脂成形体
JP2016221864A (ja) * 2015-06-01 2016-12-28 凸版印刷株式会社 ガスバリア積層体
JP2018127637A (ja) * 2012-10-05 2018-08-16 東洋紡株式会社 自己粘着性表面保護フィルム

Patent Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01294748A (ja) * 1987-11-12 1989-11-28 Mitsui Petrochem Ind Ltd 樹脂組成物の製造方法
JPH0740517A (ja) * 1993-05-24 1995-02-10 Mitsubishi Chem Corp 多層中空成形体
JPH09227734A (ja) * 1996-02-26 1997-09-02 Sumika Color Kk 成形プロピレン−α−オレフィンブロック共重合体樹脂用着色マスターバッチ組成物およびコンパウンド
JP2002524302A (ja) * 1998-09-02 2002-08-06 コンヴィニエンス・フード・システムズ・べスローテン・フェンノートシャップ ポリオレフィン発泡体層を有する包装材料
JP2000177043A (ja) * 1998-12-14 2000-06-27 Mitsubishi Polyester Film Copp 二軸配向積層フィルム
JP2003253111A (ja) * 2002-03-06 2003-09-10 Teijin Chem Ltd 樹脂組成物、積層成形品、およびリサイクル方法
JP2004169005A (ja) * 2002-11-05 2004-06-17 Toray Ind Inc 積層フィルムのリサイクル方法およびリサイクル製品
JP2007508972A (ja) * 2003-10-27 2007-04-12 シーエフエス・ケンプテン・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング 発泡ポリオレフィン層を備えた包装材料
JP2006008160A (ja) * 2004-06-24 2006-01-12 Nissan Motor Co Ltd 多層容器
JP2009132028A (ja) * 2007-11-30 2009-06-18 Kyoraku Co Ltd 表皮付きプラスチック成形体並びにその製造方法及びその回収方法
JP2009184294A (ja) * 2008-02-08 2009-08-20 Mitsui Chemicals Inc マット調延伸積層フィルム
JP2013006313A (ja) * 2011-06-23 2013-01-10 Teijin Dupont Films Japan Ltd 配向積層ポリエステルフィルムおよびその製造方法
JP2013129756A (ja) * 2011-12-21 2013-07-04 Sekisui Techno Seikei Kk 改質ポリプロピレン系樹脂組成物の製造方法、並びにポリプロピレン系樹脂成形体の製造方法及びこれにより得られるポリプロピレン系樹脂成形体
JP2018127637A (ja) * 2012-10-05 2018-08-16 東洋紡株式会社 自己粘着性表面保護フィルム
JP2016221864A (ja) * 2015-06-01 2016-12-28 凸版印刷株式会社 ガスバリア積層体

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023074683A1 (fr) * 2021-10-28 2023-05-04 凸版印刷株式会社 Film barrière aux gaz et matériau d'emballage
WO2023153327A1 (fr) * 2022-02-14 2023-08-17 東レ株式会社 Film de polypropylène, stratifié, matériau d'emballage, corps emballé et procédé de fabrication associé
JP7355268B1 (ja) 2022-02-14 2023-10-03 東レ株式会社 ポリプロピレンフィルム、積層体、包装材、梱包体、およびその製造方法
WO2024014451A1 (fr) * 2022-07-12 2024-01-18 Ｔｏｐｐａｎホールディングス株式会社 Film barrière aux gaz et stratifié barrière

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