WO2023080499A1 - Film barrière multicouche, son procédé de fabrication et matériau d'emballage le comprenant - Google Patents

Film barrière multicouche, son procédé de fabrication et matériau d'emballage le comprenant Download PDF

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Publication number
WO2023080499A1
WO2023080499A1 PCT/KR2022/016081 KR2022016081W WO2023080499A1 WO 2023080499 A1 WO2023080499 A1 WO 2023080499A1 KR 2022016081 W KR2022016081 W KR 2022016081W WO 2023080499 A1 WO2023080499 A1 WO 2023080499A1
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Prior art keywords
barrier film
resin
layer
resin layer
multilayer barrier
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PCT/KR2022/016081
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English (en)
Korean (ko)
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한권형
이석인
Original Assignee
에스케이마이크로웍스 주식회사
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Publication of WO2023080499A1 publication Critical patent/WO2023080499A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/0036—Heat treatment
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/18—Handling of layers or the laminate
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/18—Handling of layers or the laminate
    • B32B38/1808—Handling of layers or the laminate characterised by the laying up of the layers
    • B32B38/1816—Cross feeding of one or more of the layers
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B2038/0052—Other operations not otherwise provided for
    • B32B2038/0068—Changing crystal orientation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/514—Oriented
    • B32B2307/518—Oriented bi-axially
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/716—Degradable
    • B32B2307/7163—Biodegradable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B32B2307/7244—Oxygen barrier
    • 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
    • Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
    • Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics

Definitions

  • the present invention relates to a multilayer barrier film, a manufacturing method thereof, and a packaging material including the same.
  • Plastic films often used for packaging include cellophane, polyvinyl chloride (PVC), polyethylene (PE), polypropylene (PP), nylon, and polyethylene terephthalate (PET). .
  • polyvinyl chloride films generate harmful substances such as dioxins when incinerated, so their use is subject to many regulations.
  • polyethylene film lacks heat resistance and mechanical properties, so its use is limited except for low-grade packaging applications.
  • Polypropylene, nylon, and polyethylene terephthalate have relatively stable molecular structures and have good mechanical properties.
  • they when landfilled without special treatment after being used for packaging, they are hardly decomposed due to chemical and biological stability and accumulate in the ground. It shortens the life of the landfill and causes problems of soil pollution.
  • polylactic acid films which are aliphatic polyesters with high biodegradability of the resin itself, have recently been used in various ways, but these films have good mechanical properties, but have a unique crystal structure. Due to the lack of flexibility, its use is limited.
  • Japanese Patent Publication No. 2006-272712 discloses a method for producing a film using only a biodegradable aliphatic polyester other than polylactic acid, but in this case, the glass transition temperature is too low and biaxial stretching Not only is it not easy to manufacture the film by this method, but the final film has low mechanical strength and high thermal shrinkage, causing many problems during processing.
  • Japanese Patent Publication No. 2003-160202 discloses a method of imparting flexibility and heat sealing to a film by blending polylactic acid with aliphatic-aromatic co-polyester, but according to this method, polylactic acid Due to the low compatibility with and aliphatic-aromatic co-polyester and the use of a plasticizer, the transparency of the final film is significantly lowered and the water permeability is high, making it difficult to use it for packaging applications requiring transparency and low water permeability.
  • Patent Document 1 Japanese Unexamined Patent Publication No. 2006-272712
  • Patent Document 2 Japanese Unexamined Patent Publication No. 2003-160202
  • An object of the present invention is conceived to solve the problems of the prior art described above.
  • Another object of the present invention is a first resin layer comprising an aliphatic polyester-based polymer; And a second resin layer containing ethylene vinyl alcohol (Ethylene Vinyl Alcohol, EVOH); a multilayer barrier film in which two or more different resin layers are alternately laminated and have a moisture permeability of 100 g/m2.day or less, and It is intended to provide a manufacturing method thereof.
  • ethylene vinyl alcohol Ethylene Vinyl Alcohol, EVOH
  • a multilayer barrier film in which two or more different resin layers are alternately laminated and have a moisture permeability of 100 g/m2.day or less, and It is intended to provide a manufacturing method thereof.
  • Another object of the present invention is to provide a high-quality, eco-friendly packaging material that is biodegradable to a certain level, environmentally friendly, and has improved transparency and moisture permeability by using the multilayer barrier film.
  • the present invention is a first resin layer comprising an aliphatic polyester-based polymer; And a second resin layer containing ethylene vinyl alcohol (Ethylene Vinyl Alcohol, EVOH); wherein two or more different resin layers are alternately laminated and have a moisture permeability of 100 g/m 2 .day or less, a multilayer barrier film provides
  • the present invention comprises the steps of preparing a first resin containing an aliphatic polyester polymer and a second resin containing ethylene vinyl alcohol, respectively (step 1); melt-extruding the first resin and the second resin to obtain a sheet in which two or more different resin layers are alternately laminated by alternately laminating first and second resin layers (step 2); and biaxially stretching and heat-setting the laminated sheets to obtain a multilayer barrier film (step 3), wherein the multilayer barrier film has a moisture permeability of 100 g/m 2 .day or less, a method for manufacturing a multilayer barrier film. to provide.
  • the present invention includes a multilayer barrier film, the multilayer barrier film comprising a first resin layer containing an aliphatic polyester-based polymer; and a second resin layer containing ethylene vinyl alcohol; wherein two or more different resin layers are alternately laminated, and the water permeability of the multilayer barrier film is 100 g/m 2 .day or less, providing a packaging material.
  • a multilayer barrier film includes a first resin layer including an aliphatic polyester-based polymer; And a second resin layer containing ethylene vinyl alcohol (Ethylene Vinyl Alcohol, EVOH); has a structure in which two or more different resin layers are alternately laminated, and has a water permeability of 100 g/m 2 .day or less. It is characterized in that excellent transparency and moisture barrier properties can be implemented at the same time.
  • a first resin layer including an aliphatic polyester-based polymer and a second resin layer containing ethylene vinyl alcohol (Ethylene Vinyl Alcohol, EVOH); has a structure in which two or more different resin layers are alternately laminated, and has a water permeability of 100 g/m 2 .day or less. It is characterized in that excellent transparency and moisture barrier properties can be implemented at the same time.
  • EVOH ethylene vinyl alcohol
  • the manufacturing method of the multilayer barrier film according to the embodiment is an economical and efficient method, and can further improve moldability, processability, and productivity.
  • the multilayer barrier film according to the embodiment not only does not cause delamination along with the above characteristics, but also has environmentally friendly characteristics because it is biodegradable at a certain level or higher in nature by including a material having biodegradability, It is possible to provide high-quality packaging materials that can be used for
  • Embodiments are not limited to the contents disclosed below, and may be modified in various forms unless the gist of the invention is changed.
  • one component is described as being formed on “one side”/"the other side” or “upper”/”bottom” of another component, when one component is described as being formed on “one side”/"the other side” of another component.
  • “ or “upper” / “lower” includes all those formed directly or indirectly through other components.
  • a multilayer barrier film includes a first resin layer including an aliphatic polyester-based polymer; And a second resin layer containing ethylene vinyl alcohol (Ethylene Vinyl Alcohol, EVOH); two or more different resin layers including are alternately laminated, and the water permeability is 100 g/m 2 .day or less by satisfying the point , excellent transparency and moisture barrier properties can be improved at the same time.
  • a first resin layer including an aliphatic polyester-based polymer and a second resin layer containing ethylene vinyl alcohol (Ethylene Vinyl Alcohol, EVOH); two or more different resin layers including are alternately laminated, and the water permeability is 100 g/m 2 .day or less by satisfying the point , excellent transparency and moisture barrier properties can be improved at the same time.
  • EVOH ethylene vinyl alcohol
  • the first resin layer may include an aliphatic polyester-based polymer as a main component.
  • the term 'main component' means that the ratio of a specific component to the total components is 50% by weight or more, 70% by weight or more, 80% by weight or more, 90% by weight or more, 95% by weight or more, or 98% by weight or more. It means, 100% by weight or less, 98% by weight or less, 95% by weight or less, or 90% by weight or less.
  • the first resin layer may include 95% to 100% by weight of the aliphatic polyester-based polymer.
  • the aliphatic polyester-based polymer is at least one selected from the group consisting of polylactic acid, polycaprolactone, polyhydroxyalkanoate, polyglycolic acid, polybutylene succinate, polybutylene adipate, and copolymers thereof. includes
  • the first resin layer may include a polylactic acid-based polymer as a main component.
  • the first resin layer contains a polylactic acid polymer in an amount of 50% by weight or more, 70% by weight or more, 80% by weight or more, 90% by weight or more, 95% by weight or more based on the total weight of the first resin layer, or It may contain 98% by weight or more, but is not limited thereto.
  • the polylactic acid-based polymer is based on biomass, unlike petroleum-based resins, it is possible to utilize renewable resources and emits less carbon dioxide, which is the main culprit of global warming, compared to conventional resins during production, It is eco-friendly as it is biodegraded by moisture and microorganisms when landfilled.
  • the polylactic acid-based polymer may have a weight average molecular weight (Mw) of 100,000 to 1,000,000 g/mol, 100,000 to 800,000 g/mol, 100,000 to 500,000 g/mol, or 100,000 to 300,000 g/mol.
  • the weight average molecular weight (Mw) may be measured by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • the polylactic acid-based polymer may include L-lactic acid, D-lactic acid, D, L-lactic acid, or a combination thereof. Specifically, the polylactic acid-based polymer may be a random copolymer of L-lactic acid and D-lactic acid.
  • the content of the D-lactic acid is 1% to 5% by weight, 1% to 4% by weight, 2% to 4% by weight, 1% to 3% by weight based on the total weight of the polylactic acid-based polymer. %, 2% to 3% by weight, or 1% to 2% by weight.
  • the content of D-lactic acid satisfies the above range, processability during stretching of the film may be improved.
  • the content of the L-lactic acid is 80% to 99% by weight, 83% to 99% by weight, 85% to 99% by weight, or 90% to 99% by weight based on the total weight of the polylactic acid-based polymer. weight percent.
  • heat resistance of the film may be improved.
  • the melting temperature (Tm) of the polylactic acid-based resin may be 50 °C to 300 °C, 100 °C to 250 °C, 110 °C to 220 °C, or 120 °C to 200 °C.
  • the polylactic acid-based resin may have a glass transition temperature (Tg) of 30 °C to 100 °C, 30 °C to 80 °C, 40 °C to 80 °C, 40 °C to 70 °C, or 45 °C to 65 °C.
  • Tg glass transition temperature
  • melting viscosity (V Pla ) is 5,000 poise to 15,000 poise, 5,000 poise to 12,000 poise, 7,000 poise to 12,000 poise, 7,500 poise to 11,000 poise, or 8,000 poise to 10,000 pois It can be e.
  • the melt viscosity is measured at 210 °C and a shear rate of 100 s -1 using a rheometer.
  • melt viscosity of the first resin layer may be 5,000 poise to 15,000 poise, 5,000 poise to 12,000 poise, 7,000 poise to 12,000 poise, 7,500 poise to 11,000 poise, or 8,000 poise to 10,000 poise at 210 °C.
  • the first resin layer includes the aliphatic polyester-based polymer alone, or copolymerizes the aliphatic polyester-based polymer with a small amount of other hydroxy carboxylic acid units and includes it as a resin of the first resin layer,
  • the aliphatic polyester-based polymer is mixed with a small amount of vinyl acetate and vinyl laurate copolymer and included as a resin of the first resin layer, or the aliphatic polyester-based polymer is mixed with a core-shell structured butyl acrylate-based rubber It may be included as the resin of the first resin layer.
  • the first resin layer may further include one or more additives selected from the group consisting of a conventional electrostatic agent, an antistatic agent, an antioxidant, a heat stabilizer, a sunscreen, an antiblocking agent, and other inorganic lubricants.
  • the additive may be appropriately added within a range that does not impair the effect of the invention according to the embodiment.
  • the second resin layer may include ethylene vinyl alcohol as a main component.
  • the second resin layer may include 95 wt % to 100 wt % of ethylene vinyl alcohol.
  • the ethylene vinyl alcohol is a polymer resin formed by copolymerization of ethylene and vinyl alcohol, and has excellent moisture barrier properties.
  • the ratio of ethylene in the monomer composition before copolymerization is equal to or greater than a specific content.
  • the ethylene content of the ethylene vinyl alcohol may be 25 mol% or more.
  • the ethylene content of the ethylene vinyl alcohol is 30 mol% or more, 35 mol% or more, 40 mol% or more, 42 mol% or more, 44 mol% or more, 45 mol% or more, 50 mol% or more, 55 mol% or more , or 50 mol% or more, and may be 90 mol% or less, 85 mol% or less, 80 mol% or less, 75 mol% or less, or 70 mol% or less.
  • the ethylene content of the ethylene vinyl alcohol may be 25 mol% to 90 mol%, 35 mol% to 90 mol%, 40 mol% to 90 mol%, or 50 mol% to 90 mol%, but is limited thereto it is not going to be
  • the ethylene content of the ethylene vinyl alcohol is within the above-described range, a film having excellent barrier properties for blocking moisture and satisfying transparency may be implemented.
  • the ethylene content of the ethylene vinyl alcohol is within the above range, it can be widely used not only as a non-food packaging material but also as a food packaging material.
  • the ethylene content can be measured by Proton (H) NMR.
  • the multilayer barrier film according to the embodiment includes the ethylene vinyl alcohol as the second resin layer, compatibility with the aliphatic polyester-based resin included in the first resin layer is excellent, so that desired effects can be easily achieved.
  • the second resin layer is made of an aliphatic polyester-based resin or an aliphatic-aromatic copolymerized polyester-based resin (eg, polybutylene adipate terephthalate (PBAT) resin) other than the butenediol vinyl alcohol copolymer.
  • PBAT polybutylene adipate terephthalate
  • optical properties such as haze may be relatively high, and moisture permeability is very high, so that the effect as a moisture barrier film cannot be realized. That is, there may be limitations in using it for packaging purposes of packaging materials that are vulnerable to moisture.
  • the degree of polymerization of the ethylene vinyl alcohol may be 1,000 to 6,000, 1,000 to 5,000, or 1,300 to 5,000.
  • the degree of polymerization can be measured by gel permeation chromatography (GPC).
  • the weight average molecular weight (Mw) of the ethylene vinyl alcohol may be 50,000 to 600,000 g/mol, 50,000 to 500,000 g/mol, 100,000 to 500,000 g/mol, or 100,000 to 400,000 g/mol.
  • the weight average molecular weight (Mw) may be measured by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • the melting temperature (Tm) of the ethylene vinyl alcohol may be 130°C to 210°C, 150°C to 210°C, 150°C to 200°C, or 150°C to 190°C.
  • the glass transition temperature (Tg) of the ethylene vinyl alcohol may be 40 °C to 90 °C, 50 °C to 90 °C, 50 °C to 80 °C, or 50 °C to 70 °C.
  • the melt viscosity (V EVOH ) at 210° C. of the ethylene vinyl alcohol may be 3,000 poise to 15,000 poise, 3,000 poise to 12,000 poise, 3,000 poise to 10,000 poise, or 4,000 poise to 9,000 poise. At this time, the melt viscosity is measured at 210 °C and a shear rate of 100 s -1 using a rheometer.
  • melt viscosity of the second resin layer at 210 °C 2,000 poise to 20,000 poise, 2,000 poise to 15,000 poise, 3,000 poise to 10,000 poise, 4,000 poise to 15,000 poise, 4,000 poise to 12,000 poise, or 4,000 poise to 10,000 poise can be
  • the ethylene vinyl alcohol may have a density of 1.1 to 1.3 g/cm 3 , 1.1 to 1.25 g/cm 3 , 1.14 to 1.25 g/cm 3 , or 1.14 to 1.21 g/cm 3 as measured by ASTM D792.
  • MI Melt index
  • the second resin layer may further include one or more additives selected from the group consisting of a conventional electrostatic agent, an antistatic agent, an antioxidant, a heat stabilizer, a sunscreen, an antiblocking agent, and other inorganic lubricants.
  • the additive may be appropriately added within a range that does not impair the effect of the invention according to the embodiment.
  • a third resin layer containing a different resin as a main component from that used in the first resin layer and the second resin layer is used as the first resin layer and the second resin layer within a range that does not impair the effects of the present invention. It can also be used by stacking alternately.
  • a resin usable for the third resin layer may be an aliphatic polyester-based resin, an aliphatic-aromatic copolymerized polyester-based resin, or a gas impermeable resin.
  • the aliphatic polyester-based resin or aliphatic-aromatic copolymerized polyester-based resin is polybutylene adipate terephthalate (PBAT) resin, polybutylene succinate (PBS) resin, polybutylene adipate (PBA) resins, polybutylenesuccinate-adipate (PBSA) resins, polybutylenesuccinate-terephthalate (PBST) resins, polyhydroxybutylate-valerate (PHBV) resins, polycaprolactone (PCL) resins, and It may include at least one selected from the group consisting of polybutylene succinate adipate terephthalate (PBSAT) resins.
  • PBAT polybutylene succinate
  • PBA polybutylene adipate
  • PBSA polybutylenesuccinate-adipate
  • PBST polybutylenesuccinate-terephthalate
  • PHBV polyhydroxybutylate-valerate
  • PCL polycaprolactone
  • the gas impermeable resin is from the group consisting of polyvinyl alcohol (PVOH), polychlorotrifluoroethylene (PCTFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE) and polyvinylidene fluoride (PVDF)
  • PVOH polyvinyl alcohol
  • PCTFE polychlorotrifluoroethylene
  • ECTFE ethylene-chlorotrifluoroethylene copolymer
  • PVDF polyvinylidene fluoride
  • the third resin layer may further include one or more additives selected from the group consisting of a conventional electrostatic agent, an antistatic agent, an antioxidant, a heat stabilizer, a sunscreen, an antiblocking agent, and other inorganic lubricants.
  • the additive may be appropriately added within a range that does not impair the effect of the invention according to the embodiment.
  • At least one side of the surface of the film is corona treated to increase the processability of the film, or inorganic particle coating for antistatic or anti-blocking Alternatively, a coating treatment may be performed to improve printability with the printed layer.
  • the multilayer barrier film according to one embodiment may further include a corona layer disposed on one side or the other side of the first resin layer.
  • the corona layer may be directly formed on one surface or the other surface of the first resin layer.
  • a corona layer in the multi-layer barrier film By further including a corona layer in the multi-layer barrier film, contamination such as oil on the surface of the multi-layer barrier film can be removed, and adhesive strength can be increased by making a surface compatible with the bonding site, and the surface can be chemically and physically modified to provide hydrophilic properties. , adhesion, printability, coating properties, deposition properties, etc. can be further improved.
  • the corona layer is formed by corona treatment of the first resin layer, and may include a polar functional group selected from the group consisting of -CO, -COOH, and -OH.
  • the surface tension of the first resin layer with respect to the corona-treated surface may be 38 dyn/cm or more, such as 38 to 70 dyn/cm, such as 38 to 68 dyn/cm, or, for example, 38 to 66 dyn/cm. there is.
  • the surface tension of the corona-treated surface of the first resin layer satisfies the above range, adhesion, printability, coating characteristics, deposition characteristics, etc. of the multilayer barrier film may be further improved.
  • the multilayer barrier film according to another embodiment may further include a coating layer disposed on one side or the other side of the first resin layer.
  • the coating layer may include a primer coating layer, and in this case, performance such as antistatic property, printability, and deposition strength may be improved.
  • the primer coating layer includes a corona layer on one side or the other side of the first resin layer, or when the multilayer barrier film includes the corona layer, and includes a corona layer on one side or the other side of the first resin layer, and one side or the other side of the corona layer.
  • the primer coating layer may be included on the other surface.
  • a primer coating layer may be formed by performing a primer treatment on one surface or the other surface of the first resin layer.
  • a primer coating layer may be formed by priming one surface or the other surface of the corona layer disposed on one surface or the other surface of the first resin layer.
  • the primer coating layer may include at least one selected from the group consisting of ammonium-based compounds having antistatic properties, phosphoric acid-based compounds, and polymers such as acrylic resins and urethane-based resins.
  • the surface resistance of the primer coating layer may be 0.1 to 30 ⁇ / ⁇ , 0.2 to 28 ⁇ / ⁇ , 0.3 to 26 ⁇ / ⁇ , 0.4 to 24 ⁇ / ⁇ or 1 to 20 ⁇ / ⁇ .
  • the surface resistance is, for example, evaluated for antistatic performance by a surface resistance meter under a relative humidity (60% ⁇ 10%) at room temperature (22° C. ⁇ 2° C.).
  • the thickness of the coating layer may be appropriately adjusted depending on the use and purpose of the multilayer film, and specifically may be 15 nm to 50 nm, 20 nm to 45 nm, 25 nm to 40 nm, or 30 nm to 35 nm, but is limited thereto. It doesn't work.
  • a multilayer barrier film includes a first resin layer including an aliphatic polyester-based polymer; And a second resin layer containing ethylene vinyl alcohol; two or more types of different resin layers including are laminated alternately.
  • the multilayer barrier film according to the embodiment includes a first resin layer containing an aliphatic polyester-based polymer as a main component; and a second resin layer containing ethylene vinyl alcohol as a main component; two or more different resin layers including may be alternately laminated.
  • the total number of layers of the multilayer barrier film may be adjusted in consideration of the thickness of individual layers of the film, but may be 5 or more layers. For example, it may be 5 or more, 7 or more, 10 or more, 11 or more, 15 or more, 20 or more, 25 or more, or 29 or more, 1,000 or less, 800 or less, 500 or less. , 300 layers or less, 200 layers or less, 100 layers or less, or 70 layers or less.
  • the multilayer barrier film according to the embodiment may have a stacked structure of 5 or more layers.
  • the multilayer barrier film according to the embodiment may have a laminated structure of 10 or more layers, 15 layers or more, 20 layers or more, or 25 or more layers, 500 layers or less, 400 layers or less, 300 layers or less, 250 layers or less, 200 layers or less, It may be a laminated structure of 150 layers or less, or 100 layers or less.
  • the multilayer barrier film according to the embodiment may have a laminated structure of 5 to 500 layers, 5 to 300 layers, 10 to 200 layers, or 15 to 100 layers, but is not limited thereto.
  • the adhesive property between each layer is excellent and interfacial peeling does not occur between each layer, so it is excellent in terms of processability, moldability, and productivity.
  • the water permeability is increased, which may be inappropriate for use as a packaging material, and in particular, interfacial peeling may occur between each layer.
  • the defect rate of the packaging material may significantly increase.
  • the multilayer barrier film has a laminated structure in which the total number of layers exceeds the above-mentioned range, the thickness of each layer becomes relatively thin, and interfacial tension acts between different thin layers. As the force accumulates, the intermolecular attraction becomes very strong.
  • the barrier film according to the embodiment realizes excellent moisture barrier performance through a structure in which thin films are laminated, thereby increasing the recent It can also conform to the thinning trend.
  • the multilayer barrier film according to the embodiment may be a multilayer coextruded film or a multilayer bonding film.
  • the multilayer barrier film may be a multilayer coextruded film.
  • the multilayer barrier film according to the embodiment uses only the first resin layer rather than the structure in which the second resin layers are alternately laminated, the water permeability is significantly increased, making it difficult to expect a role as a waterproof packaging material requiring low water permeability, When the first resin layer and the second resin layer are blended and used, the water permeability is high and the haze is also very high, making it difficult to function as a packaging material requiring transparency.
  • the multilayer barrier film may include a first resin layer as an outermost layer on both sides. Specifically, the outermost layer on both sides of the multilayer barrier film is the first resin layer.
  • the outermost layer of the multilayer barrier film is a first resin layer containing an aliphatic polyester-based polymer, specifically, a polylactic acid-based polymer as a main component, it is more advantageous in stretching, and is more advantageous in terms of moldability, processability, and productivity. can be advantageous If the outermost layer of the multilayer barrier film is a second resin layer containing ethylene vinyl alcohol as a main component, it is not easy to stretch or cast, and adhesion easily occurs, resulting in reduced formability, processability and productivity. there is.
  • the sum of the thicknesses of the outermost layers on both sides may be 5% or more, 10% or more, 15% or more, 20% or more, 25% or more, or 30% or more, and 70% or less of the total thickness of the film. , 60% or less, 50% or less, 45% or less, or 40% or less, but is not limited thereto.
  • the sum of the thicknesses of the outermost layers on both sides may be 5 to 50%, 10 to 50%, 20 to 50%, 20 to 40%, or 30% to 40% of the total thickness of the film. It is not limited.
  • each of the resin layers in contact with the outermost layer on both sides may be a second resin layer.
  • the average thickness ratio of individual layers of the first resin layer and the second resin layer excluding the outermost layer on both sides may be 1:0.5 to 2.
  • the average thickness ratio of individual layers of the first resin layer and the second resin layer excluding the outermost layer on both sides may be, for example, 1:0.5 to 1.5, for example, 1:0.5 to 1.3, but is not limited thereto.
  • physical properties such as haze and moisture permeability of the multilayer barrier film may be uniformly improved.
  • the average thickness of each layer of the first resin layer may be 10 nm or more, 50 nm or more, 100 nm or more, 150 nm or more, or 200 nm or more, and 1,000 nm or less. , 800 nm or less, 700 nm or less, or 500 nm or less. For example, it may be 50 nm to 500 nm, or 150 nm to 500 nm, but is not limited thereto.
  • the total thickness of the first resin layer excluding the outermost layer on both sides may be 1 ⁇ m or more, 3 ⁇ m or more, 5 ⁇ m or more, 6 ⁇ m or more, or 7 ⁇ m or more, and may be 50 ⁇ m or less, 30 ⁇ m or less It may be less than 10 ⁇ m, less than 20 ⁇ m, or less than 10 ⁇ m. For example, it may be 1 ⁇ m to 20 ⁇ m, 5 ⁇ m to 15 ⁇ m, or 5 ⁇ m to 10 ⁇ m, but is not limited thereto.
  • the average thickness of each layer of the second resin layer may be 10 nm or more, 50 nm or more, 100 nm or more, 150 nm or more, or 200 nm or more, and 1,000 nm or less. , 800 nm or less, 700 nm or less, or 500 nm or less. For example, it may be 50 nm to 500 nm, or 150 nm to 500 nm, but is not limited thereto.
  • the total thickness of the second resin layer excluding the outermost layer on both sides may be 1 ⁇ m or more, 3 ⁇ m or more, 5 ⁇ m or more, 6 ⁇ m or more, or 7 ⁇ m or more, 50 ⁇ m or less, 30 ⁇ m or less It may be less than 10 ⁇ m, less than 20 ⁇ m, or less than 10 ⁇ m. For example, it may be 1 ⁇ m to 20 ⁇ m, 5 ⁇ m to 15 ⁇ m, or 5 ⁇ m to 10 ⁇ m, but is not limited thereto.
  • the total thickness of the multilayer barrier film may be 5 ⁇ m or more, 7 ⁇ m or more, 10 ⁇ m or more, 15 ⁇ m or more, or 20 ⁇ m or more, and 100 ⁇ m or less, 80 ⁇ m or less, or 70 ⁇ m or less , or 50 ⁇ m or less, but is not limited thereto.
  • it may be 10 ⁇ m to 50 ⁇ m, or 15 ⁇ m to 30 ⁇ m, but is not limited thereto.
  • the range related to the layer/film thickness satisfies the above range, it is more advantageous to achieve the desired effect in the embodiment, and in particular, the appearance and mechanical properties of the film can also be improved. In addition, it may be easy to make a desired shape by folding or crumpling the film for food packaging to wrap food.
  • the multilayer barrier film according to the embodiment is characterized by simultaneously having a high level of waterproof performance and transparency.
  • Water permeability of the multilayer barrier film according to the embodiment is 100 g/m 2 .day or less, 80 g/m 2 .day or less, 70 g/m 2 .day or less, 60 g/m 2 .day or less, 50 g/m 2 .day or less m 2 .day or less, 40 g/m 2 .day or less, 30 g/m 2 .day or less, 25 g/m 2 .day or less, or 20 g/m 2 .day or less.
  • the moisture permeability was measured according to the ASTM F1249 standard at a temperature of 37.6 ° C and a permeable area of 50 cm 2 using a moisture permeability measuring device of MOCON PERMATRAN_W 3/33 MA.
  • the haze of the multilayer barrier film may be 10% or less, 8% or less, 5% or less, 4% or less, or 3% or less.
  • the haze was measured using a Hazemeter (model name: SEP-H) of Nihon Semitsu Kogaku.
  • the light transmittance of the multilayer barrier film may be 85% to 95%, or 90% to 93% based on a wavelength of 550 nm.
  • the multilayer barrier film may have a tensile strength of 5 to 30 Kg/mm 2 , 10 to 30 Kg/mm 2 , or 10 to 25 Kg/mm 2 based on ASTM D882.
  • the elongation of the upper multilayer barrier film may be 30% to 300%, 50% to 300%, 50% to 250%, or 50% to 200% based on ASTM D882.
  • the multilayer barrier film may have a Young's modulus of 100 to 500 Kg/mm 2 , 100 to 400 Kg/mm 2 , or 200 to 400 Kg/mm 2 based on ASTM D882.
  • the heat shrinkage rate of the multilayer barrier film is 0% to 10%, 1% to 10%, 1% to 8%, or 1% to 5% when the change before and after being placed in a convection oven at 100 ° C. for 5 minutes is observed.
  • the multi-layer barrier film may have a biodegradation rate of at least 30% or more, preferably 40% or more, and more preferably 50% or more, in view of the characteristics of products intended to reduce environmental load.
  • the multilayer barrier film according to the embodiment satisfies high levels of moisture barrier properties, transparency, and biodegradability at the same time, it can be used as a packaging material in various fields to provide a high-quality, eco-friendly packaging material.
  • the manufacturing method of the multilayer barrier film according to the embodiment is an economical and efficient method, and can further improve formability, processability and productivity.
  • a method for manufacturing a multilayer barrier film includes preparing a first resin containing an aliphatic polyester polymer and a second resin containing ethylene vinyl alcohol (step 1); melt-extruding the first resin and the second resin to obtain a sheet in which two or more different resin layers are alternately laminated by alternately laminating first and second resin layers (step 2); and biaxially stretching and heat-setting the laminated sheets to obtain a multilayer barrier film (step 3), wherein the multilayer barrier film has a moisture permeability of 100 g/m 2 .day or less.
  • Step 1 a step (Step 1) of preparing a first resin containing an aliphatic polyester-based polymer and a second resin containing ethylene vinyl alcohol, respectively, is performed.
  • the melt viscosity of the first resin layer is 5,000 to 15,000 poise at 210 ° C
  • the melt viscosity of the second resin layer is 3,000 to 10,000 poise at 210 ° C.
  • the melt viscosity of the second resin may be the same as or different from that of the first resin. Specifically, it is preferable that the difference between the melt viscosity of the first resin and the melt viscosity of the second resin is small.
  • the difference between the melt viscosity of the first resin and the melt viscosity of the second resin may be 1,000 poise or less, 500 poise or less, 300 poise or less, or 100 poise or less, but is not limited thereto.
  • the method of manufacturing the multi-layer barrier film is a sheet in which two or more different resin layers are alternately laminated by melting and extruding the first resin and the second resin, respectively, and alternately laminating the first resin layer and the second resin layer. It may include a step (step 2) of obtaining
  • the melt extrusion temperature of the first resin layer is 160 ° C to 230 ° C, or 180 ° C to 220 ° C
  • the melt extrusion temperature of the second resin layer is 180 ° C to 230 ° C, or 190 ° C to 210 ° C.
  • the melt-extrusion temperature of the first resin and the melt-extrusion temperature of the second resin may be the same or different, and the difference between the melt-extrusion temperature of the first resin and the melt-extrusion temperature of the second resin is, for example, 30 ° C. It may be below 30°C, below 20°C, below 15°C, below 10°C, or below 5°C, but is not limited thereto.
  • melt-extrusion temperatures of the first resin and the second resin satisfy the aforementioned ranges, processability, productivity, and moldability may be improved.
  • the first resin layer and the second resin layer may be obtained by appropriately controlling the melt extrusion temperature of the first resin and the second resin, and by alternately stacking them, two or more different thermoplastic resin layers are alternately formed.
  • a desired level of moisture barrier property and transparency can be realized without causing delamination in the final film.
  • the first resin and the second resin prepared in step 1 may be melt-extruded using two extruders and a multilayer feed block in which two layers are alternately laminated, respectively, with an extruder.
  • the branched first resin layer and the second resin layer are alternately laminated and passed through a die, and the temperature is 10 ° C. to 40°C, or 15°C to 25°C to obtain an unstretched multilayer sheet by adhering to a cooling roll.
  • it may be laminated so that the first resin layer is located on the outermost layer on both sides.
  • the description related to the outermost layer is as described above.
  • drying the first resin and the second resin may be further included before the melt extrusion.
  • the drying step may be performed for 2 hours to 24 hours, or 4 hours to 24 hours under conditions of, for example, 60°C to 120°C, 70°C to 100°C, or 80°C to 90°C.
  • the drying conditions of each of the first resin and the second resin may be the same or different.
  • the method of manufacturing the multilayer barrier film may include a step (step 3) of obtaining a multilayer barrier film by biaxially stretching and heat-setting the laminated sheets.
  • the laminated sheet may be biaxially stretched, and the biaxially stretched step is, for example, preheating at 50° C. to 80° C., followed by longitudinal stretching 2 to 4 times in the machine direction (MD) at 40° C. to 100° C. and transverse stretching 3 to 6 times in a transverse direction (TD) at 50° C. to 150° C.
  • MD machine direction
  • TD transverse direction
  • the physical properties and moldability of the multilayer barrier film can be further improved, so that a high-quality packaging material can be realized.
  • the thickness variation of the multilayer film is severe, and the mechanical properties and thermal properties of the non-stretching side may be deteriorated.
  • the heat setting step may be performed at 50 °C to 150 °C, 70 °C to 150 °C, 100 °C to 150 °C, or 110 °C to 140 °C.
  • a corona layer, a coating layer, or both may be further formed on one or the other surface of the first resin layer.
  • a corona layer may be formed by corona treatment of the first resin layer.
  • corona discharge occurs when a high frequency-high voltage output is applied between the discharge electrode and the treatment roll.
  • the corona treatment can be performed by passing through a desired surface.
  • the corona discharge intensity may be, for example, 3 to 20 kW.
  • the corona discharge treatment effect may be insignificant, and conversely, when the corona discharge intensity exceeds the above range, excessive surface modification may cause surface damage.
  • composition and physical properties of the corona layer are as described above.
  • a coating layer may be formed on one surface or the other surface of the first resin layer.
  • the coating layer may include a primer coating layer, and the primer coating layer is at least one selected from the group consisting of polymers such as ammonium-based compounds, phosphoric acid-based compounds, and acrylic resins and urethane-based resins on one side or the other side of the first resin layer. It is possible to further improve adhesive properties by forming surface roughness by priming with a primer composition containing.
  • the primer coating layer forms a corona layer on one surface or the other surface of the first resin layer, or, when the multilayer film includes the corona layer, forms a corona layer on one surface or the other surface of the first resin layer, and on one surface or the other surface of the corona layer.
  • the primer coating layer may be formed on the top.
  • the primer composition may contain a curing agent component, and more specific examples include 4,4'-diaminodiphenylmethane (DDM), aromatic diamine, and mixtures thereof.
  • DDM 4,4'-diaminodiphenylmethane
  • the amount of the curing agent component may be added in an amount of 0.1 to 50% by weight based on the total weight of the primer composition.
  • the primer treatment method conventional methods used in the art may be used, and for example, spray spraying, brushing, rolling, and the like may be used.
  • the primer composition is applied to the surface of the first resin layer using an airless spray under the conditions of an induction time of 1 to 30 minutes, a spray pressure of 5 to 500 Mpa, a nozzle diameter of 0.46 to 0.58 mm, and a spray angle of 40 to 80 °. can spray.
  • surface treatment such as plasma treatment, ultraviolet irradiation treatment, flame treatment, or saponification treatment may be appropriately performed in order to increase the adhesiveness of the multilayer barrier film.
  • the multilayer barrier film When the multilayer barrier film is manufactured according to the manufacturing method of the embodiment, it is economical and efficient, and it may be more effective to manufacture a multilayer barrier film having desired configuration and physical properties.
  • the multilayer barrier film is manufactured according to the above-described manufacturing method, it is economical and efficient, and it may be more effective to manufacture a multilayer barrier film having desired configuration and physical properties.
  • the packaging material according to the embodiment has the characteristics of the multilayer barrier film and is biodegradable to a certain level or more, so it has environmentally friendly properties, and thus can function as a high-quality packaging material in various fields.
  • the packaging material includes a multilayer barrier film
  • the multilayer barrier film includes a first resin layer including an aliphatic polyester-based polymer; and a second resin layer containing ethylene vinyl alcohol; two or more different resin layers are alternately laminated, and the water permeability of the multilayer barrier film is 100 g/m 2 .day or less.
  • the packaging material may be, for example, in the form of a film that can be used as a general disposable packaging material and food packaging material, and may be in the form of a fiber that can be used as a fabric, knitted fabric, non-woven fabric, rope, etc., and food such as lunch boxes. It may be in the form of a container that can be used as a packaging container.
  • the packaging material can provide excellent physical properties and quality by including a multilayer film that simultaneously has high levels of moisture barrier properties and transparency and does not cause interfacial peeling between layers.
  • a packaging material having environmentally friendly characteristics by being biodegradable above a certain level, it can be used in various fields as a packaging material and exhibit excellent characteristics.
  • the packaging material When using the packaging material, it is possible to preserve the good appearance of the packaging material without deterioration as much as possible over a long period of time, so it can be advantageous in extending the shelf life of food, especially when the packaging material is used for food packaging.
  • a polylactic acid resin (Nature Works LLC, 4032D) having a D-lactic acid content of about 1.4% by weight and a melt viscosity of about 8,770 poise at 210 ° C. as a resin of the first resin layer and a resin of the second resin layer at 210 ° C.
  • Ethylene vinyl alcohol having a melt viscosity of about 6,800 poise, an ethylene content of 38 mol%, and a density of 1.17 g/cm 3 was used.
  • the resin of the first resin layer is dried at about 80 ° C. for 6 hours with a dehumidifying dryer, and the resin of the second resin layer is dried at about 80 ° C. for 2 hours with a dehumidifying dryer to remove moisture, and then the two extruders and the two layers are alternately
  • Each of the resin of the first resin layer and the resin of the second resin layer was melt-extruded with an extruder having a temperature of 210° C. using the stacked multi-layer feed block.
  • the first resin layer is branched into 15 layers and the second resin layer is branched into 14 layers, and then the branched first resin layer and the second resin layer are alternately stacked on a 780 mm die. It was passed through and brought into close contact with a cooling roll cooled to about 21 DEG C to obtain an unstretched multilayer sheet of 29 layers. At this time, the first resin layer was placed on the outermost layer on both sides, and the sum of the thicknesses of the outermost layers on both sides was 30% of the total thickness.
  • the multilayer sheet thus obtained was stretched 3.0 times in the machine direction at about 65° C. and 3.9 times in the transverse direction at about 120° C., heat-set at 120° C., and a relaxation rate of 1% was applied, so that the overall thickness of the multilayer film was 20 ⁇ m, 29 ⁇ m.
  • a layered multilayer barrier film was prepared.
  • multi-layered multi-layers were performed in the same manner as in Experimental Example 1, except that the number of layers of each of the first and second resin layers, the sum of the thicknesses of the outermost layers on both sides, and the ethylene content of EVOH were different.
  • a barrier film was prepared.
  • the number of layers of each of the first resin layer and the second resin layer, the thickness ratio of the PLA layer: EVOH layer: PLA layer were set to about 1: 1: 1, and stretched 3.8 times in the transverse direction.
  • a multilayer barrier film was prepared in the same manner as in Experimental Example 1 except for the points and the like.
  • a single layer film was prepared using the resin of the first resin layer used in Experimental Example 1. Specifically, a single-layer film was prepared in the same manner as in Experimental Example 1, except that the resin of the first resin layer was dried at about 60 ° C. for 8 hours in a dehumidifying dryer and stretched 3.8 times in the transverse direction. .
  • the resin of the first resin layer and the resin of the second resin layer used in Experimental Example 1 were hand mixed at a weight ratio of 70:30, respectively, and then blended in a 45 pie twin screw extruder at 200 ° C.
  • a single-layer film was prepared in the same manner as in Experimental Example 1, except that it was dried for 8 hours at about 60 ° C. in a dehumidifying dryer and that it was stretched 3.8 times in the transverse direction.
  • polybutylene which is an aliphatic-aromatic copolymerized polyester-based resin having a melt viscosity of about 6,300 poise at 210 ° C. and an aliphatic component content of about 50 mol% among acid components, as the resin of the second resin layer.
  • a multilayer barrier film was prepared in the same manner as in Experimental Example 1, except that adipate terephthalate (PBAT) resin was used.
  • PBAT adipate terephthalate
  • the haze was measured by Nihon Semitsu Kogaku's Hazemeter (model name: SEP-H) in accordance with the ASTM D1003 standard.
  • the moisture permeability was measured according to the ASTM F1249 standard at a temperature of 37.6 ° C and a permeable area of 50 cm 2 using a moisture permeability measuring device of MOCON PERMATRAN_W 3/33 MA.
  • the multilayer films according to Experimental Examples 1 to 5 can be used in an eco-friendly manner for various purposes including packaging applications requiring transparency and waterproof performance.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
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  • Laminated Bodies (AREA)

Abstract

Un mode de réalisation concerne un film barrière multicouche, son procédé de fabrication, et un matériau d'emballage le comprenant. Dans le film barrière multicouche, au moins deux types de différentes couches de résine sont stratifiés en alternance, les couches de résine comprenant : une première couche de résine contenant un polymère à base de polyester aliphatique; et une seconde couche de résine contenant de l'éthylène alcool de vinyle (EVOH), et la perméabilité à l'eau du film barrière multicouche est inférieure ou égale à 100 g/m 2.jour.
PCT/KR2022/016081 2021-11-05 2022-10-20 Film barrière multicouche, son procédé de fabrication et matériau d'emballage le comprenant WO2023080499A1 (fr)

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Citations (5)

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Publication number Priority date Publication date Assignee Title
JP2008155432A (ja) * 2006-12-22 2008-07-10 Dainippon Printing Co Ltd バリア性を有するヒ−トシ−ル性フィルム
US20180304573A1 (en) * 2015-10-19 2018-10-25 Denka Company Limited Laminated sheet and formed container
KR20200046620A (ko) * 2018-10-25 2020-05-07 (주) 세림비앤지 생분해성 라미네이팅이 다층 코팅된 커피 및 음료용 생분해성 종이컵
KR102158171B1 (ko) * 2020-01-10 2020-09-23 주식회사 알커미스 재활용이 가능한 다층필름 및 이를 이용한 식품용 용기
JP2021024591A (ja) * 2019-07-31 2021-02-22 東ソー株式会社 衛生薄葉紙用包装フィルム及び包装体

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Publication number Priority date Publication date Assignee Title
JP4005339B2 (ja) 2001-11-22 2007-11-07 ユニチカ株式会社 生分解性ごみ袋
JP2006272712A (ja) 2005-03-29 2006-10-12 Ajinomoto Co Inc ポリブチレンサクシネート積層フィルムの製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008155432A (ja) * 2006-12-22 2008-07-10 Dainippon Printing Co Ltd バリア性を有するヒ−トシ−ル性フィルム
US20180304573A1 (en) * 2015-10-19 2018-10-25 Denka Company Limited Laminated sheet and formed container
KR20200046620A (ko) * 2018-10-25 2020-05-07 (주) 세림비앤지 생분해성 라미네이팅이 다층 코팅된 커피 및 음료용 생분해성 종이컵
JP2021024591A (ja) * 2019-07-31 2021-02-22 東ソー株式会社 衛生薄葉紙用包装フィルム及び包装体
KR102158171B1 (ko) * 2020-01-10 2020-09-23 주식회사 알커미스 재활용이 가능한 다층필름 및 이를 이용한 식품용 용기

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