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WO2025192296A1 - Film multicouche anticondensation, stratifié, matériau d'emballage, matériau de couvercle et récipient de scellage supérieur - Google Patents

Film multicouche anticondensation, stratifié, matériau d'emballage, matériau de couvercle et récipient de scellage supérieur

Info

Publication number
WO2025192296A1
WO2025192296A1 PCT/JP2025/006755 JP2025006755W WO2025192296A1 WO 2025192296 A1 WO2025192296 A1 WO 2025192296A1 JP 2025006755 W JP2025006755 W JP 2025006755W WO 2025192296 A1 WO2025192296 A1 WO 2025192296A1
Authority
WO
WIPO (PCT)
Prior art keywords
layer
multilayer film
fog
laminate
resin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/JP2025/006755
Other languages
English (en)
Japanese (ja)
Inventor
満 武士田
カタンユー クンタラウト
悠城 鏑木
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
DIC Corp
Original Assignee
DIC Corp
Dainippon Ink and Chemicals Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by DIC Corp, Dainippon Ink and Chemicals Co Ltd filed Critical DIC Corp
Publication of WO2025192296A1 publication Critical patent/WO2025192296A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • 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

Definitions

  • the present invention relates to a multilayer film that combines anti-fogging properties and easy-open properties, and is suitable for use as a lid material for food packaging containers, as well as a laminate using the same.
  • a suitable multilayer film for lid material which comprises a laminate layer (A) primarily composed of linear polyethylene (a) and containing no anti-fogging agent, an intermediate layer (B) containing linear polyethylene (b1) and an anti-fogging agent (b2), and a heat-sealable layer (C) containing a polypropylene resin (c1) and an anti-fogging agent (c2), laminated in the order (A)/(B)/(C), where the combined mass of the anti-fogging agent (b2) and the anti-fogging agent (c2) is in the range of 0.8 to 1.6 mass% relative to the total mass of the multilayer film, the wetting tension of both outer surfaces of the multilayer film is in the range of 35 to 45 mN/
  • Patent Document 1 The anti-fog multilayer film described in Patent Document 1 was not designed to be used as a top-sealed container that would be directly heated in a microwave oven, and there is still room for improvement.
  • the present invention aims to provide an anti-fogging multilayer film suitable for use as a lid for a top-sealed container when heated directly in a microwave oven, a laminate obtained by laminating this multilayer film onto a base film, and packaging materials and top-sealed containers that use this laminate.
  • the inventors have discovered an anti-fog multilayer film suitable for use as a lid for top-sealed containers that are directly heated in a microwave oven. Before microwave heating, the film has sufficient seal strength to withstand distribution and allow opening, but during or immediately after heating, the seal strength decreases to a level that allows easy opening even when the container is hot.
  • the present invention provides an anti-fog multilayer film that has, in this order, at least a layer (A) whose main resin component is linear polyethylene, an adhesive layer (B) whose main resin components are linear polyethylene and a polypropylene-based resin and which contains an anti-fog agent, and a heat-seal layer (C) whose main resin component is a polypropylene-based resin and which contains an anti-fog agent, and that has a seal strength of 10 to 18 N/15 mm at room temperature and a seal strength of 4 to 8 N/15 mm at 100°C.
  • the present invention also provides a laminate containing the anti-fog multilayer film described above.
  • the present invention also provides a packaging material containing the anti-fog multilayer film described above.
  • the present invention also provides a covering material containing the anti-fog multilayer film described above.
  • the present invention also provides a top-sealed container containing the anti-fogging multilayer film described above.
  • the present invention provides an anti-fogging multilayer film suitable for use as a lid for top-sealed containers that are heated directly in a microwave oven, and also provides a laminate obtained by laminating this multilayer film onto a base film, as well as packaging materials and top-sealed containers that use this laminate.
  • the anti-fogging multilayer film of the present invention comprises, in this order, at least a layer (A) containing linear polyethylene as the main resin component, an adhesive layer (B) containing linear polyethylene and a polypropylene-based resin as the main resin components and containing an anti-fogging agent, and a heat-sealable layer (C) containing a polypropylene-based resin as the main resin component and containing an anti-fogging agent.
  • the heat-sealable layer (C) is the layer to be attached to the container, and the layer (A) is the outer layer of the container.
  • the layer (A) in the present invention has a linear polyethylene (a) as the main resin component (main component).
  • the layer (A) in the present invention does not have to be composed of a single layer, and may have a single layer or a laminate structure of two or more layers. Even in the case of two or more layers, the main resin component is the linear polyethylene (a).
  • main resin component means that the specific resin is contained in an amount of 65% by mass or more, and preferably 80% by mass or more, relative to the total amount of resin components that make up the layer.
  • Linear polyethylene (a) The linear polyethylene (a) is obtained by copolymerizing ethylene monomer as a main component with an ⁇ -olefin such as butene-1, hexene-1, octene-1, or 4-methylpentene as a comonomer by low-pressure radical polymerization using a single-site catalyst.
  • the comonomer content is preferably in the range of 0.5 to 20 mol%, more preferably in the range of 1 to 18 mol%.
  • the single-site catalyst may be a metallocene catalyst system that combines a metallocene compound of a transition metal from Group IV or V of the periodic table with an organoaluminum compound and/or an ionic compound. Furthermore, because single-site catalysts have uniform active sites, the molecular weight distribution of the resulting resin is sharper than with multi-site catalysts, which have non-uniform active sites. This results in less precipitation of low-molecular-weight components when formed into a film, and is therefore preferable because it results in a resin with excellent physical properties, such as stable adhesive strength between resin layers.
  • the density of the linear polyethylene (a) used in layer (A) is preferably 0.920 to 0.950 g/cm 3 , more preferably 0.925 to 0.945 g/cm 3 , and even more preferably 0.930 to 0.940 g/cm 3.
  • a density within this range provides appropriate rigidity, excellent mechanical strength such as pinhole resistance, and improved film formability, extrusion suitability, and heat resistance.
  • the melting point is preferably in the range of 60 to 130°C, more preferably 70 to 125°C. If the melting point is in this range, processing stability and processability when co-extruded with other layers are improved.
  • the MFR (190°C, 21.18N) of the linear polyethylene (a) is preferably 2 to 20 g/10 min, more preferably 3 to 10 g/10 min. If the MFR is in this range, the extrusion moldability of the film is improved.
  • layer (A) is primarily composed of the linear polyethylene (a), but other resins may be used in combination with it to improve adhesion to adhesives or inks when laminating with other substrates using an adhesive or when printing, etc.
  • ethylene-based resins are preferred as other resins that can be used in combination from the viewpoint of the transparency of the resulting multilayer film.
  • Examples include ethylene-based copolymers such as branched polyethylene, ethylene-vinyl acetate copolymer (EVA), ethylene-methyl methacrylate copolymer (EMMA), ethylene-ethyl acrylate copolymer (EEA), ethylene-methyl acrylate (EMA) copolymer, ethylene-maleic anhydride copolymer (E-MAH), ethylene-ethyl acrylate-maleic anhydride copolymer (E-EA-MAH), ethylene-acrylic acid copolymer (EAA), and ethylene-methacrylic acid copolymer (EMAA); as well as ionomers of ethylene-acrylic acid copolymer, ionomers of ethylene-methacrylic acid copolymer, and copolymers of ethylene and monomers having a cyclic olefin structure, such as norbornene-based monomers. These may be used alone or in combination of two or more.
  • EVA
  • Layer (A) may or may not contain an anti-fogging agent, which will be described later. If an anti-fogging agent is contained, the content is preferably in the range of 0.2 to 1.5 mass% relative to the total mass of layer (A), and more preferably in the range of 0.4 to 1.0 mass%. Anti-fogging agents will be described later.
  • layer (A) is the outer layer of the container, and therefore may be laminated or directly printed with ink for display purposes. In such cases, anti-fog agent that bleeds out onto the surface may cause peeling of the laminating adhesive or ink, or may result in poor printing. If such concerns exist, it is preferable to configure layer (A) to consist of two or more layers, with the outermost layer not containing an anti-fog agent.
  • a layer (A1) containing linear polyethylene as the main resin component and containing no antifogging agent preferably contains two layers: a layer (A1) containing linear polyethylene as the main resin component and containing no antifogging agent, and a layer (A2) containing linear polyethylene as the main resin component and containing an antifogging agent.
  • the layer (A1) containing no antifogging agent is the outer layer of the container, and the layer (A2) containing the antifogging agent is located between the layer (A1) and the adhesive layer (B) described below.
  • the layer (A) that does not contain an antifogging agent may be referred to as "layer (A1)”
  • the layer that contains an antifogging agent may be referred to as "layer (A2)."
  • the content of the antifogging agent in the layer (A2) containing the antifogging agent is preferably in the range of 0.5 to 4.0 mass% relative to the total mass of the layer (A2), and particularly preferably in the range of 1.0 to 3.0 mass%. Antifogging agents will be described later.
  • the thickness of the layer (A) is not particularly limited, but the total thickness of the layer (A) is generally in the range of 15 to 70 ⁇ m, and more preferably in the range of 20 to 60 ⁇ m.
  • the layer (A) is composed of two or more layers, that is, a layer (A1) of a material not containing the antifogging agent and a layer (A2) containing the antifogging agent, the thickness of the layer (A1) is preferably 5 to 40 ⁇ m, and the thickness of the layer (A2) is preferably 5 to 40 ⁇ m.
  • the adhesive layer (B) of the present invention which contains linear polyethylene and a polypropylene-based resin as main resin components and an antifogging agent, contains linear polyethylene (b1) and a polypropylene-based resin (b2) as main resin components and an antifogging agent.
  • the linear polyethylene (b1) in the present invention may be the same as the linear polyethylene (a) used in the layer (A) described above.
  • the density of the linear polyethylene (b1) used in layer (B) is preferably 0.920 to 0.950 g/cm 3 , more preferably 0.925 to 0.945 g/cm 3 , and even more preferably 0.930 to 0.940 g/cm 3.
  • a density within this range provides appropriate rigidity, excellent mechanical strength such as pinhole resistance, and improved film formability, extrusion suitability, and heat resistance.
  • the melting point is preferably in the range of 60 to 130°C, more preferably 70 to 125°C.
  • the MFR (190°C, 21.18N) of the linear polyethylene (a) is preferably 2 to 20 g/10 min, more preferably 3 to 10 g/10 min. If the MFR is in this range, the extrusion moldability of the film is improved.
  • the polypropylene resin (b2) in the present invention is not particularly limited as long as it can be laminated with the aforementioned layer (A), and examples thereof include propylene homopolymers, propylene- ⁇ -olefin random copolymers, such as propylene-ethylene copolymers, propylene-butene-1 copolymers, propylene-ethylene-butene-1 copolymers, and metallocene-catalyzed polypropylenes. These may be used alone or in combination of two or more. Propylene- ⁇ -olefin random copolymers are desirable, and as described above, propylene- ⁇ -olefin random copolymers polymerized using a metallocene catalyst are particularly preferred.
  • the polypropylene resin (b2) preferably has an MFR (230°C) of 0.5 to 30.0 g/10 min and a melting point of 110 to 165°C, and more preferably an MFR (230°C) of 2.0 to 15.0 g/10 min and a melting point of 115 to 162°C. If the MFR and melting point are within these ranges, the film shrinks less during heat sealing, and the film's film-forming properties are also improved.
  • the proportion of the linear polyethylene (b1) and polypropylene resin (b2) used in the adhesive layer (B) is preferably in the range of 90:10 to 50:50 by weight, and more preferably 80:20 to 60:40, per 100 parts by weight of the resin. A weight ratio within this range ensures good adhesive strength with both the layer (A) and the heat-seal layer (C).
  • the anti-fogging agent is not particularly limited as long as it is known to be generally added to olefin-based resins to impart anti-fogging properties.
  • anionic surfactants nonionic surfactants, cationic surfactants, amphoteric surfactants, etc. can be used, and it is preferable to use nonionic surfactants.
  • sorbitan surfactants such as sorbitan monostearate, sorbitan distearate, sorbitan monopalmitate, sorbitan dipalmitate, sorbitan monobehenate, sorbitan dibehenate, sorbitan monolaurate, and sorbitan dilaurate; glycerin surfactants such as glycerin monolaurate, glycerin dilaurate, diglycerin monopalmitate, diglycerin dipalmitate, glycerin monostearate, glycerin distearate, diglycerin monostearate, diglycerin distearate, diglycerin monolaurate, and diglycerin dilaurate; polyethylene glycol monostearate, polyethylene glycol monopalmitate,
  • surfactants include polyethylene glycol surfactants such as dimethylamine; trimethylolpropane surfactants such as trimethylolpropane monostearate; di
  • the proportion of the anti-fogging agent in the adhesive layer (B) is preferably in the range of 0.5 to 5.0% by mass, and particularly preferably in the range of 1.0 to 4.5% by mass, based on the total mass of the layer.
  • the heat seal layer (C) of the present invention which contains a polypropylene-based resin as a main resin component and an antifogging agent, must contain a polypropylene-based resin (c1) from the viewpoint of facilitating the development of heat sealability when used as a lid material for a container or a packaging bag.
  • the polypropylene-based resin (c1) is not particularly limited as long as it can be laminated with the aforementioned layer (A) and adhesive layer (B), and examples thereof include propylene homopolymers, propylene- ⁇ -olefin random copolymers, such as propylene-ethylene copolymers, propylene-butene-1 copolymers, propylene-ethylene-butene-1 copolymers, and metallocene-catalyzed polypropylenes. These may be used alone or in combination of two or more. Propylene- ⁇ -olefin random copolymers are preferred, and as described above, propylene- ⁇ -olefin random copolymers polymerized using a metallocene catalyst are particularly preferred.
  • propylene-based resins as resins for the heat-sealable layer (C), they can be suitably used as lid materials for packaging containers, particularly those whose sealing surfaces are made of a resin layer containing a polypropylene-based resin.
  • the polypropylene resin contained in the heat seal layer (C) preferably contains propylene-butene-1 copolymer in an amount of 10 to 30% by mass.
  • the polypropylene resin (c1) preferably has an MFR (230°C) of 0.5 to 30.0 g/10 min and a melting point of 110 to 165°C, and more preferably an MFR (230°C) of 2.0 to 15.0 g/10 min and a melting point of 115 to 162°C. If the MFR and melting point are within these ranges, the film shrinks less during heat sealing, and the film's film-forming properties are also improved.
  • the polypropylene resin (c1) in the heat seal layer (C) preferably contains this resin as the main component, and more preferably contains 85% by mass or more.
  • Other resins that can be used in combination are the same as those exemplified as resins that can be used in combination in layer (A).
  • any of the anti-fogging agents exemplified above can be used, and the same applies to suitable anti-fogging agents.
  • the anti-fog agent used in the layer (A2) and the adhesive layer (B) and the heat-seal layer (C) may be the same or different.
  • the base resin be a polyethylene-based resin in the layer (A2) and the adhesive layer (B), and a polypropylene-based resin in the heat-seal layer (C).
  • the proportion of anti-fogging agent used in the heat seal layer (C) is preferably in the range of 1.0 to 6.0 mass% relative to the total mass of the layer, and particularly preferably in the range of 2.0 to 5.0 mass%. Using an anti-fogging agent in this range makes it easier to obtain a film with good anti-fogging properties and anti-fogging durability.
  • the anti-fog multilayer film of the present invention is characterized by exhibiting different seal strengths at room temperature and at high temperatures.
  • the seal strength decreases at high temperatures.
  • the seal strength at room temperature is 10 to 18 N/15 mm
  • the seal strength at 100°C is 4 to 8 N/15 mm.
  • room temperature is defined as the range of 20°C ⁇ 15°C (5 to 35°C) (JIS Z 8703 [4]).
  • Condition (X) is the following condition.
  • the polypropylene sheet and the laminate are each gripped with a jig, and the seal strength is measured as the maximum strength when peeled at a speed of 300 mm/min.
  • the peeling surface at this time is between the adhesive layer (B) and the heat seal layer (C), and the seal strength at this interface is measured.
  • the polyurethane adhesive (1) used was "DIC Dry LX500/KR90S", a urethane reactive adhesive manufactured by DIC Corporation.
  • the heat seal tester used in (2) was a "Precision Heat Sealer manufactured by Tester Sangyo.”
  • seal strength in the range of 10-18N/15mm at room temperature contents are less likely to leak due to bag rupture during distribution. Furthermore, with a seal strength in the range of 4-8N/15mm at 100°C, the container is particularly easy to open, even after microwave heating, when the rigidity of the container decreases at high temperatures and the container or lid cannot be gripped tightly. Furthermore, the risk of contents spilling due to the faster opening speed caused by seal strength that is too low is reduced.
  • the cause of the decrease in the seal strength of the antifogging multilayer film at high temperatures is presumed to be as follows.
  • Thermoplastic resins such as polyethylene, polypropylene, and their copolymers soften at temperatures above their glass transition point. Therefore, it is known that the seal strength at high temperatures is lower than at room temperature. It is also known that when heated in a microwave oven, steam emitted from the contents can reach temperatures of around 100°C.
  • adjustment of seal strength was often performed solely using copolymer resins such as propylene-butene-1 copolymer, making it difficult to control seal strength at room temperature and at high temperatures.
  • the anti-fog multilayer film of the present invention suppresses a decrease in seal strength at high temperatures and makes it possible to control strength at room temperature and at high temperatures.
  • the total thickness of the anti-fog multilayer film of the present invention is preferably in the range of 20 to 100 ⁇ m, and more preferably in the range of 25 to 80 ⁇ m, since this facilitates lamination when used in conjunction with other substrates and provides favorable heat-sealing properties and anti-fog properties.
  • the thickness ratio of each layer in the multilayer film be in the range of 60 to 90% for layer (A), 5 to 20% for adhesive layer (B), and 5 to 18% for heat seal layer (C).
  • the total amount of anti-fogging agent contained in the entire anti-fogging multilayer film of the present invention is 0.8 to 2.5 mass%, and a range of 1.0 to 2.0 mass% is particularly preferred from the standpoints of good film-forming properties, the expression of anti-fogging properties, and the durability of anti-fogging properties.
  • ingredients such as antistatic agents, heat stabilizers, nucleating agents, antioxidants, lubricants, antiblocking agents, release agents, UV absorbers, and colorants can be added to each of layers (A), (B), and (C) of the anti-fog multilayer film of the present invention, provided that the object of the present invention is not impaired.
  • the coefficient of friction of the film surface it is preferable for the coefficient of friction of the film surface to be 1.5 or less, and especially 1.0 or less. Therefore, it is preferable to add lubricants, antiblocking agents, and antistatic agents appropriately to the resin layers corresponding to the surface layers of the multilayer film.
  • the anti-fog multilayer film of the present invention may be subjected to a corona treatment, if necessary, to impart wettability.
  • a corona treatment examples include surface oxidation treatments such as corona discharge treatment, plasma treatment, flame treatment, and ozone/ultraviolet treatment, with corona discharge treatment being preferred.
  • corona discharge treatment is not particularly limited, and any known method can be used.
  • the method for producing the anti-fog multilayer film of the present invention is not particularly limited, but examples include a coextrusion method in which the resins or resin mixtures used for layer (A), adhesive layer (B), and heat-seal layer (C) are heated and melted in separate extruders, laminated in the molten state in the order (A)/(B)/(C) or (A1)/(A2)/(B)/(C) using a method such as a coextrusion multilayer die or feed block method, and then formed into a film using a method such as inflation or T-die chill roll.
  • a coextrusion method in which the resins or resin mixtures used for layer (A), adhesive layer (B), and heat-seal layer (C) are heated and melted in separate extruders, laminated in the molten state in the order (A)/(B)/(C) or (A1)/(A2)/(B)/(C) using a method such as a coextrusion
  • This coextrusion method is preferred because it allows for relatively free adjustment of the thickness ratio of each layer and produces a multilayer film that is highly hygienic and cost-effective.
  • the T-die chill roll method is preferred because it prevents deterioration of the film's appearance when coextruding resins with different melting points and Tg's, facilitates the formation of a uniform layer structure, and facilitates the production of a film with suitable transparency and gloss.
  • the inflation method is also preferred because it requires simple equipment and is suitable for small-lot, high-mix production.
  • the anti-fog multilayer film of the present invention is obtained as a substantially unstretched multilayer film using the above manufacturing method, which makes it possible to perform secondary forming such as deep drawing by vacuum forming and embossing.
  • the anti-fog multilayer film of the present invention can also be used by laminating it with another substrate.
  • the other substrate there are no particular limitations on the other substrate that can be used in this case, but from the perspective of easily achieving the effects of the present invention, it is preferable to use a thermoplastic resin film with high rigidity and high gloss, particularly a biaxially stretched resin film.
  • aluminum foil can also be used alone or in combination.
  • stretched resin films include biaxially oriented polyester (PET), biaxially oriented polypropylene (OPP), biaxially oriented polyamide (PA), co-extruded biaxially oriented polyamide (ONY) with a central layer of ethylene vinyl alcohol copolymer (EVOH), biaxially oriented ethylene vinyl alcohol copolymer (EVOH), and co-extruded biaxially oriented polypropylene coated with polyvinylidene chloride (PVDC). These may be used alone or in combination.
  • PET biaxially oriented polyester
  • OPP biaxially oriented polypropylene
  • PA biaxially oriented polyamide
  • ONY co-extruded biaxially oriented polyamide
  • EVOH ethylene vinyl alcohol copolymer
  • EVOH biaxially oriented ethylene vinyl alcohol copolymer
  • PVDC polyvinylidene chloride
  • the laminate of the present invention is a laminate film obtained by laminating the thermoplastic resin film onto the anti-fogging multilayer film obtained as described above.
  • lamination methods include dry lamination, wet lamination, non-solvent lamination, and extrusion lamination.
  • Adhesives used in the dry lamination process include, for example, polyester-polyurethane adhesives. While various other adhesives can also be used, it is preferable to use pressure-sensitive adhesives.
  • pressure-sensitive adhesives include rubber-based adhesives such as polyisobutylene rubber, butyl rubber, or mixtures of these dissolved in organic solvents such as benzene, toluene, xylene, or hexane; rubber-based adhesives containing tackifiers such as abiethylene acid rosin ester, terpene-phenol copolymer, or terpene-indene copolymer; and acrylic-based adhesives in which acrylic copolymers with a glass transition temperature of -20°C or below, such as 2-ethylhexyl acrylate-n-butyl acrylate copolymer or 2-ethylhexyl acrylate-ethyl acrylate-methyl methacrylate copolymer, are dissolved in an organic solvent
  • the laminate of the present invention may be used in any application, but it can be suitably used as a lid material for packaging containers used for food, medicines, industrial parts, miscellaneous goods, magazines, etc.
  • the outermost layer of the packaging container (the portion that adheres to the heat seal layer of the multilayer film of the present invention) contains a propylene-based resin, from the viewpoint of balancing ease of opening and seal strength.
  • the anti-fog multilayer film of the present invention and the laminate of the present invention can be used as a container lid material intended for use as a lid material for plastic containers for food, medicine, etc.
  • a lid material When used as a lid material, they may be used alone or as a laminate film, and the layer structure may vary depending on the contents, usage environment, and usage form. From the viewpoint of a balance between ease of opening and seal strength, it is preferable that the outermost layer of the packaging container (the portion that adheres to the heat seal layer of the multilayer film of the present invention) contains various propylene-based resins.
  • top-sealed container equipped with the anti-fog multilayer film or laminate of the present invention as a sealing lid is a container in which a flange protrudes from the outer periphery of the opening of a container body filled with solid or liquid food contents, and the opening is sealed by the sealing lid via this flange.
  • the anti-fog multilayer film or laminate of the present invention has sufficient seal strength to withstand distribution and to allow opening of the top-sealed container before heating in a microwave oven, but during or immediately after heating, the seal strength decreases to a strength that allows easy opening even when the container is hot, thereby reducing the risk of burns to the user and allowing food to be served safely.
  • the outermost layer (the part that adheres to the heat-sealable layer of the multilayer film of the present invention) contains various propylene-based resins from the viewpoint of balancing ease of opening and seal strength.
  • the antifogging agent was prepared by mixing 20 parts by mass of the antifogging agent with any one of the resins constituting the layers to be used, and melt-kneading the mixture in an extruder to prepare a master batch.
  • the resin for the heat seal layer (C) was a mixture of 30 parts of a propylene-butene-1 copolymer (1) having a density of 0.885 g/cm 3 and an MFR (230°C) of 7.0 g/10 min, 50 parts of a polypropylene (1) having a density of 0.900 g/cm 3 and an MFR (230°C) of 7.0 g/10 min, and 20 parts of an antifogging agent (1) prepared with the polypropylene (1).
  • the concentration of the antifogging agent in the heat seal layer (C) was 4.0% by mass.
  • the resin for adhesive layer (B) was a mixture of 65 parts of LLDPE (1) having a density of 0.937 g/cm 3 and an MFR of 4.0 g/10 min, 15 parts of polypropylene (1), and 20 parts of antifogging agent (2) prepared with LDPE (1) having a density of 0.919 g/cm 3 and an MFR of 7.0 g/10 min.
  • the antifogging agent concentration in adhesive layer (B) was 4.0 mass%.
  • As the resin for the layer (A1) containing no antifogging agent a mixture of 80 parts of LLDPE (1) and 20 parts of LDPE (1) was used.
  • Resins were supplied to the extruder for the heat-sealing layer (C), the extruder for the adhesive layer (B), and the extruder for the layer (A), and extruded from a T-die at an extrusion temperature of 250° C. by coextrusion so that the thicknesses of the layers (A)/(B)/(C) were 20 ⁇ m/6 ⁇ m/4 ⁇ m, respectively, and cooled with a water-cooled metal cooling roll at 40° C.
  • a corona discharge treatment was performed, the film was wound up on a roll, and aged in an aging chamber at 38° C.
  • Example 2 As the resin for the layer (A2) containing the antifogging agent, a mixture of LLDPE (1), LDPE (1), and antifogging agent (2) was used in a mass ratio of 80/18/2. The concentration of the antifogging agent in the layer (A2) was 0.4 mass%. Other than these, the laminate of Example 2 was obtained in the same manner as in Example 1.
  • Example 3 The resin for adhesive layer (B) was a mixture of 65 parts of LLDPE (2) having a density of 0.931 g/cm 3 and an MFR of 6.0 g/10 min, 15 parts of polypropylene (1), and 20 parts of antifogging agent (2).
  • the antifogging agent concentration in adhesive layer (B) was 4.0% by mass.
  • As the resin for the layer (A1) containing no antifogging agent a mixture of 80 parts of LLDPE (2) and 20 parts of LDPE (1) was used. Other than these, the laminate of Example 3 was obtained in the same manner as in Example 1.
  • Example 4 As the resin for the heat seal layer (C), a mixture of propylene-butene-1 copolymer (1), 58 parts of polypropylene (1), and antifogging agent (1) was used in a mass ratio of 30/58/12. The concentration of the antifogging agent in the heat seal layer (C) was 2.4 mass%. As the resin for the adhesive layer (B), LLDPE (1), LDPE (1), polypropylene (1), and antifogging agent (2) were mixed in a mass ratio of 63/12/15/10. The concentration of the antifogging agent in the adhesive layer (B) was 2.0 mass%.
  • the resin for the layer (A1) containing no antifogging agent a mixture of LLDPE (1) and LDPE (1) in a mass ratio of 80/20 was used.
  • the resin for the layer (A2) containing the antifogging agent LLDPE (1), LDPE (1), and antifogging agent (2) were mixed in a mass ratio of 80/10/10 and used.
  • the concentration of the antifogging agent in the layer (A2) was 2.0 mass%.
  • Example 4 A laminate of Example 4 was obtained in the same manner as in Example 1, except that resins were supplied to each of the extruder for the heat-sealing layer (C), the extruder for the adhesive layer (B), the extruder for the layer (A1), and the extruder for the layer (A2), and extruded from a T-die by a co-extrusion method at an extrusion temperature of 250°C so that the thicknesses of the layers (A1)/(A2)/(B)/(C) were 10 ⁇ m/12 ⁇ m/4 ⁇ m/4 ⁇ m.
  • Example 5 As the resin for the layer (A1) containing no antifogging agent, LLDPE (1) was used. As the resin for the layer (A2) containing the antifogging agent, a mixture of LLDPE (1) and antifogging agent (2) was used in a mass ratio of 90/10. The concentration of the antifogging agent in the layer (A2) was 2.0 mass%. A laminate of Example 5 was obtained in the same manner as in Example 4 except for these points.
  • Example 6 The resin for adhesive layer (B) was a mixture of 63 parts of LLDPE (3) having a density of 0.944 g/cm 3 and an MFR of 4.0 g/10 min, 12 parts of LDPE (1), 15 parts of polypropylene (1), and 10 parts of antifogging agent (2).
  • the antifogging agent concentration in adhesive layer (B) was 2.0% by mass.
  • As the resin for the layer (A1) containing no antifogging agent LLDPE (3) was used.
  • As the resin for the layer (A2) containing the antifogging agent a mixture of LLDPE (3) and antifogging agent (2) was used in a mass ratio of 90/10.
  • the concentration of the antifogging agent in the layer (A2) was 2.0 mass%.
  • the laminate of Example 6 was obtained in the same manner as in Example 4.
  • Example 7 As the resin for the adhesive layer (B), LLDPE (1), LDPE (1), propylene-butene-1 copolymer (2), and antifogging agent (2) were mixed to a mass ratio of 63/12/15/10. The concentration of the antifogging agent in the adhesive layer (B) was 2.0 mass%. Except for these, the laminate of Example 7 was obtained in the same manner as in Example 4.
  • Example 8 As the resin for the heat seal layer (C), a mixture of propylene-butene-1 copolymer (1), 58 parts of polypropylene (1), and antifogging agent (1) was used in a mass ratio of 10/78/12. The concentration of the antifogging agent in the heat seal layer (C) was 2.4 mass%. Except for these, the laminate of Example 8 was obtained in the same manner as in Example 4.
  • Example 9 As the resin for the heat seal layer (C), a mixture of propylene-butene-1 copolymer (1), 58 parts of polypropylene (1), and antifogging agent (1) was used in a mass ratio of 15/73/12. The concentration of the antifogging agent in the heat seal layer (C) was 2.4 mass%. Except for these, the laminate of Example 9 was obtained in the same manner as in Example 4.
  • Comparative Example 1 As the resin for the heat seal layer (C), a mixture of 88 parts of propylene (1) and 12 parts of the antifogging agent (1) was used. The concentration of the antifogging agent in the heat seal layer (C) was 2.4% by mass.
  • the resin for the adhesive layer (B) was a mixture of 48 parts of an ethylene-butene-1 copolymer (1) having a density of 0.886 g/cm 3 and an MFR of 4.0 g/10 min, 42 parts of LDPE (1), and 10 parts of an antifogging agent (2). The concentration of the antifogging agent in the adhesive layer (B) was 2.0% by mass. Other than these, the laminate of Comparative Example 1 was obtained in the same manner as in Example 4.
  • Comparative Example 2 As the resin for the heat seal layer (C), a mixture of propylene-butene-1 copolymer (1) and polypropylene (1) in a mass ratio of 70/30 was used. As the resin for the adhesive layer (B), a mixture of LLDPE (1), LDPE (1), and propylene (1) was used in a mass ratio of 65/20/15. Other than these, the laminate of Comparative Example 2 was obtained in the same manner as in Example 1.
  • the resin for the heat seal layer (C) was a mixture of 88 parts of a propylene-ethylene copolymer (1) having a density of 0.890 g/cm 3 and an MFR (230°C) of 7.0 g/10 min and 12 parts of an antifogging agent (3) prepared with the propylene-ethylene copolymer (1).
  • the concentration of the antifogging agent in the heat seal layer (C) was 2.4% by mass.
  • the resin for adhesive layer (B) was a mixture of 80 parts of LLDPE (4) having a density of 0.933 g/cm 3 and an MFR of 5.0 g/10 min and 20 parts of an antifogging agent (4) prepared with LLDPE (5) having a density of 0.905 g/cm 3 and an MFR of 4.0 g/10 min.
  • the antifogging agent concentration in adhesive layer (B) was 4.0 mass%.
  • a mixture of 80 parts of LLDPE (4) and 20 parts of antifogging agent (4) was used as the resin for the layer (A2) containing the antifogging agent.
  • the concentration of the antifogging agent in the layer (A2) was 4.0% by mass.
  • LLDPE (4) was used as the resin for the layer (A1) containing no antifogging agent.
  • the laminate of Comparative Example 3 was obtained in the same manner as in Example 4.
  • a laminate of Comparative Example 4 was obtained in the same manner as in Example 1, except that resins were supplied to the extruder for the heat-sealing layer (C) and the extruder for the layer (A1), and extruded from a T-die by co-extrusion at an extrusion temperature of 250°C so that the thicknesses of the layers (A1) and (C) were 25 ⁇ m and 5 ⁇ m, respectively.
  • MFR is measured at 190°C unless otherwise specified.
  • Laminate strength evaluation The behavior of the laminate strength between the biaxially oriented nylon film and the film obtained by coextrusion was evaluated using a tensile tester (manufactured by A&D Co., Ltd.) at a peeling speed of 300 mm/min, and the state of the laminate was evaluated according to the following criteria. ⁇ : Sufficient lamination strength was maintained, and strong adhesion was confirmed between the biaxially oriented nylon film and the film obtained by coextrusion. ⁇ : Easy peeling was observed between the biaxially oriented nylon film and the film obtained by coextrusion due to insufficient lamination strength.
  • the obtained laminate was aged at 40°C for 48 hours, then cut into a piece of 8 cm x 8 cm, and heat-sealed to a ⁇ 71 injection container (manufactured by Toko Co., Ltd.) containing 30 ml of water at 40°C (pressure 64 kgf/cup, temperature 160°C, time 1.0 second).
  • the laminate was then stored in a low-temperature room at 3°C for 3 hours and visually inspected for anti-fogging effect using the following criteria.
  • ⁇ A continuous water film is formed on the film surface, and visibility is good.
  • ⁇ Fine water droplets adhere to the film surface, but visibility is good.
  • ⁇ Water droplets adhere, and visibility is poor.
  • the obtained laminate was aged and heat-sealed under the above conditions, and then stored in a low-temperature room at 3°C for 3 hours. After that, a portion of the lid was opened, and the laminate was heated in a microwave oven (IMB-F186-W manufactured by Iris Ohyama Co., Ltd.) (500W for 1 minute), and the appearance immediately after heating was confirmed.
  • a microwave oven IMB-F186-W manufactured by Iris Ohyama Co., Ltd.
  • Heat seal sample creation The obtained laminate was aged under the above conditions, and then it was overlapped with a 0.3 mm thick polypropylene sheet so that the heat seal surface was on the polypropylene sheet side.
  • a heat seal tester Precision Heat Sealer manufactured by Tester Sangyo
  • the upper heat seal bar adjusted to a temperature of 180°C was set so that it was on the outermost layer side of the laminate, and the laminate was heat sealed under conditions of 0.2 MPa and 1 second.
  • the obtained laminate was aged and heat-sealed under the above conditions, and then stored in a low-temperature room at 3°C for 3 hours. After that, a portion of the lid material was opened and heated in a microwave oven (IMB-F186-W manufactured by Iris Ohyama Co., Ltd.) (500 W, 1 minute). Immediately after heating, the entire lid was opened starting from the previously opened portion and checked.
  • a microwave oven IMB-F186-W manufactured by Iris Ohyama Co., Ltd.
  • the anti-fog multilayer films of the examples have sufficient seal strength to withstand distribution and allow opening before heating in a microwave oven, but that during heating or immediately after heating, the seal strength decreases to a level that allows easy opening even when the container is hot.

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

Abstract

L'invention concerne un film multicouche anticondensation qui présente, dans l'ordre suivant, au moins une couche (A) qui comporte un polyéthylène linéaire en tant que composant de résine principal, une couche adhésive (B) qui comporte un polyéthylène linéaire et une résine de polypropylène en tant que composants de résine principaux et qui contient un agent anticondensation, et une couche de thermoscellage (C) qui comporte une résine de polypropylène en tant que composant de résine principal et qui contient un agent anticondensation, et qui a une résistance de scellage de 10 à 18 N/15 mm à température ambiante et une résistance de scellage de 4 à 8 N/15 mm à 100 °C. L'invention concerne également un stratifié, un matériau d'emballage, un matériau de couvercle et un récipient de scellage supérieur qui utilisent le film multicouche anticondensation.
PCT/JP2025/006755 2024-03-14 2025-02-27 Film multicouche anticondensation, stratifié, matériau d'emballage, matériau de couvercle et récipient de scellage supérieur Pending WO2025192296A1 (fr)

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JP2024039832 2024-03-14
JP2024-039832 2024-03-14

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WO2025192296A1 true WO2025192296A1 (fr) 2025-09-18

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0447936A (ja) * 1990-06-15 1992-02-18 Tonen Chem Corp 防曇性多層フィルム
JPH05278183A (ja) * 1992-04-06 1993-10-26 Gunze Ltd ラミネートフィルム及び包装用ラミネート袋
JP2001270053A (ja) * 2000-03-28 2001-10-02 Sekisui Chem Co Ltd ストレッチ包装用フィルム及びその製造方法
JP2005305998A (ja) * 2004-03-26 2005-11-04 Toyobo Co Ltd ヒートシール性ポリプロピレン系樹脂積層フィルム及び包装体
WO2015046132A1 (fr) * 2013-09-27 2015-04-02 Dic株式会社 Film multicouche antibuée, stratifié l'utilisant, et matériau d'emballage
WO2015046131A1 (fr) * 2013-09-27 2015-04-02 Dic株式会社 Film multicouche anticondensation, laminé l'utilisant et matériau d'emballage
JP2016210063A (ja) * 2015-05-07 2016-12-15 三菱樹脂株式会社 トップシール用蓋材フィルム
JP2020157729A (ja) * 2019-03-28 2020-10-01 大日本印刷株式会社 積層体、包装材料、包装袋およびスタンドパウチ

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0447936A (ja) * 1990-06-15 1992-02-18 Tonen Chem Corp 防曇性多層フィルム
JPH05278183A (ja) * 1992-04-06 1993-10-26 Gunze Ltd ラミネートフィルム及び包装用ラミネート袋
JP2001270053A (ja) * 2000-03-28 2001-10-02 Sekisui Chem Co Ltd ストレッチ包装用フィルム及びその製造方法
JP2005305998A (ja) * 2004-03-26 2005-11-04 Toyobo Co Ltd ヒートシール性ポリプロピレン系樹脂積層フィルム及び包装体
WO2015046132A1 (fr) * 2013-09-27 2015-04-02 Dic株式会社 Film multicouche antibuée, stratifié l'utilisant, et matériau d'emballage
WO2015046131A1 (fr) * 2013-09-27 2015-04-02 Dic株式会社 Film multicouche anticondensation, laminé l'utilisant et matériau d'emballage
JP2016210063A (ja) * 2015-05-07 2016-12-15 三菱樹脂株式会社 トップシール用蓋材フィルム
JP2020157729A (ja) * 2019-03-28 2020-10-01 大日本印刷株式会社 積層体、包装材料、包装袋およびスタンドパウチ

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