WO2015046132A1 - Film multicouche antibuée, stratifié l'utilisant, et matériau d'emballage - Google Patents

Film multicouche antibuée, stratifié l'utilisant, et matériau d'emballage Download PDF

Info

Publication number
WO2015046132A1
WO2015046132A1 PCT/JP2014/075042 JP2014075042W WO2015046132A1 WO 2015046132 A1 WO2015046132 A1 WO 2015046132A1 JP 2014075042 W JP2014075042 W JP 2014075042W WO 2015046132 A1 WO2015046132 A1 WO 2015046132A1
Authority
WO
WIPO (PCT)
Prior art keywords
multilayer film
antifogging
layer
laminate
acid
Prior art date
Application number
PCT/JP2014/075042
Other languages
English (en)
Japanese (ja)
Inventor
古根村　陽之介
森谷　貴史
智久 木田
Original Assignee
Dic株式会社
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株式会社 filed Critical Dic株式会社
Priority to KR1020167003044A priority Critical patent/KR102161563B1/ko
Priority to CN201480053407.9A priority patent/CN105593017B/zh
Priority to JP2015517541A priority patent/JP5804339B2/ja
Publication of WO2015046132A1 publication Critical patent/WO2015046132A1/fr

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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/15—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
    • B32B37/153—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state at least one layer is extruded and immediately laminated while in semi-molten state
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • B32B2310/00—Treatment by energy or chemical effects
    • B32B2310/14—Corona, ionisation, electrical discharge, plasma 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
    • B32B2323/00—Polyalkenes
    • B32B2323/04—Polyethylene
    • 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
    • B32B2435/00—Closures, end caps, stoppers
    • B32B2435/02—Closures, end caps, stoppers for containers
    • 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
    • B32B2439/00—Containers; Receptacles
    • B32B2439/70—Food packaging

Definitions

  • the present invention relates to a multilayer film having both anti-fogging properties and easy-opening properties that can be suitably used as a lid for food packaging containers, and a laminate using the same.
  • polyester containers with excellent transparency and recyclability have been widely used as wrappings for chilled foods such as cut vegetables and cut fruits.
  • These lids of the package are required to have antifogging properties in order to improve the visibility of the contents. This is because if the moisture content from the chilled food in the container becomes cloudy on the inner surface of the packaging material, the contents are difficult to see, which reduces the value of the product, that is, a consumer request for food safety and security. This is because it becomes impossible to respond.
  • the container lid While it is essential for the container lid to have a certain sealing property until the contents are taken out, the socially vulnerable (elderly, infants, people with disabilities, etc.) in the trend toward universal design As a consideration to this, a method that is easy for consumers to open, for example, easy opening, is being emphasized.
  • an antifogging agent is kneaded into a resin used for packaging materials, formed into a film, and then secondary molded for various packaging materials and resins. And a method of applying an antifogging agent to the surface in contact with the contents after forming the film into a film (for example, see Patent Document 1).
  • the surface of the antifogging agent is printed or bonded to another base film.
  • the antifogging agent that bleeds out on the surface reacts with the printing ink or adhesive to cause peeling of the printed surface or poor adhesion.
  • an antifogging agent is kneaded into the heat seal layer in the multilayer film, but the antifogging effect is not constant because the antifogging agent has the property of easily moving in the multilayer film, There is a problem that the effect is not sustainable, or the anti-fogging agent migrates to a layer adjacent to the layer containing the anti-fogging agent, thereby affecting the adhesion between the layers and causing the peeling. To do.
  • the method of applying a coating liquid containing an antifogging agent to the film surface requires a drying process of the coating film, resulting in low production efficiency, and further, the antifogging agent on the coated surface flows due to the evaporation of moisture from the contents. As a result, there is a problem that the anti-fogging effect persists.
  • the problem of the present invention is that the anti-fogging property to prevent fogging from water vapor from the contents is good and has an easy openability, and is suitable for applications such as lids for packaging containers.
  • the object is to provide a film, a laminate formed by laminating the multilayer film on a base film, and a packaging material using the laminate.
  • the present inventor has selected at least four layers of multilayer films formed by laminating an olefin-based resin and a polyester-based resin, in which an antifogging agent is kneaded.
  • the present inventors have found that a multilayer film obtained by appropriately performing the surface treatment of the multilayer film can solve the above-mentioned problems, and completed the present invention.
  • the present invention comprises a laminate layer (A) containing polyolefin (a1) as a main component and no antifogging agent, an intermediate layer (B) containing polyolefin (b1) and antifogging agent (b2), acid-modified
  • An adhesive layer (C) containing polyolefin (c1) as a main component, and a heat seal layer (D) containing a polyester resin (d1) and an antifogging agent (d2) are (A) / (B) / ( C) / (D) multilayer film, wherein the outer surface of the heat seal layer of the multilayer film is processed in the range of a wet tension of 50 to 60 mN / m.
  • An antifogging multilayer film characterized by being processed in a wet tension range of 35 to 45 mN / m, a laminate formed by laminating this and a base film, and a packaging material using the same It is to provide.
  • the heat seal layer (D) is Since the polyester-based resin is a main component, it is firmly heat-sealed to a polyester-based packaging container and exhibits an easy-open property that is suitably peeled off between the heat seal layer (D) and the adhesive layer (C) when opened. Furthermore, since the antifogging property is good, it can be suitably used as a packaging material for chilled foods such as fruits and vegetables.
  • the laminate layer (A) of the present invention is mainly composed of polyolefin (a1), and the layer does not contain an antifogging agent.
  • the main component means that a specific resin is contained in an amount of 65% by mass or more, preferably 80% by mass or more based on the total amount of resin components forming the layer.
  • polyolefin (a1) examples include various ethylene resins and propylene resins, which can effectively prevent migration of the antifogging agent in the multilayer film described later to the laminate surface, and between the layers with the base film.
  • ethylene resin examples include polyethylene resins such as very low density polyethylene (VLDPE), linear low density polyethylene (LLDPE), low density polyethylene (LDPE), linear medium density polyethylene (LMDPE), and medium density polyethylene (MDPE). And ethylene-vinyl acetate copolymer (EVA). These may be used alone or in admixture of two or more. Among these, LLDPE is preferable because it has a good balance between film formability and anti-fogging agent migration suppression.
  • VLDPE very low density polyethylene
  • LLDPE linear low density polyethylene
  • LDPE low density polyethylene
  • LLDPE low density polyethylene
  • LLDPE linear medium density polyethylene
  • MDPE medium density polyethylene
  • EVA ethylene-vinyl acetate copolymer
  • the LDPE may be a branched low density polyethylene obtained by a high pressure radical polymerization method, and is preferably a branched low density polyethylene obtained by homopolymerizing ethylene by a high pressure radical polymerization method.
  • LLDPE is a low-pressure radical polymerization method using a single-site catalyst, with ethylene monomer as the main component, and comonomer as an ⁇ -olefin such as butene-1, hexene-1, octene-1, 4-methylpentene. Are copolymerized.
  • the comonomer content in LLDPE 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 examples include various single site catalysts such as a metallocene catalyst system such as a combination of a metallocene compound of Group IV or V transition metal of the periodic table and an organoaluminum compound and / or an ionic compound.
  • the single-site catalyst has a uniform active site, so the molecular weight distribution of the resulting resin is sharper than a multi-site catalyst with a non-uniform active site. This is preferable because a resin having physical properties excellent in stability of laminate strength and anti-blocking property can be obtained.
  • the density of the ethylene-based resin is preferably 0.880 to 0.960 g / cm 3 . If the density is within this range, it has appropriate rigidity, excellent mechanical strength such as pinhole resistance, and film film formability and extrusion suitability are improved.
  • the melting point is preferably in the range of 60 to 130 ° C., more preferably 70 to 120 ° C. If melting
  • the MFR (190 ° C., 21.18 N) of the ethylene resin is preferably 2 to 20 g / 10 minutes, and more preferably 3 to 10 g / 10 minutes. When the MFR is within this range, the extrusion moldability of the film is improved.
  • Such an ethylene-based resin can maintain transparency when laminated. Further, since it has flexibility, the pinhole resistance is also good.
  • propylene resin examples include propylene homopolymer, propylene / ⁇ -olefin random copolymer, such as propylene-ethylene copolymer, propylene-butene-1 copolymer, propylene-ethylene-butene-1 copolymer.
  • propylene resin examples include propylene homopolymer, propylene / ⁇ -olefin random copolymer, such as propylene-ethylene copolymer, propylene-butene-1 copolymer, propylene-ethylene-butene-1 copolymer.
  • coalesced metallocene catalyst polypropylene These may be used alone or in combination.
  • a propylene- ⁇ -olefin random copolymer is desirable, and a propylene / ⁇ -olefin random copolymer polymerized using a single site catalyst is particularly preferable.
  • these propylene resins preferably have an MFR (230 ° C.) of 0.5 to 30.0 g / 10 min and a melting point of 110 to 165 ° C., more preferably an MFR (230 ° C.) of 2
  • the melting point is 115 to 162 ° C. at 0 to 15.0 g / 10 min. If MFR and melting
  • the laminate layer (A) is mainly composed of the polyolefin (a1).
  • the adhesive is used when laminating with another base material and an adhesive or when performing printing.
  • Other resins may be used in combination for the purpose of improving adhesion to printing ink and printing ink.
  • Other resins that can be used at this time include ethylene-vinyl acetate copolymer (EVA), ethylene-methyl methacrylate copolymer (EMMA), ethylene-ethyl acrylate copolymer (EEA), ethylene-methyl acrylate (EMA).
  • Copolymers ethylene-ethyl acrylate-maleic anhydride copolymer (E-EA-MAH), ethylene-acrylic acid copolymer (EAA), ethylene-methacrylic acid copolymer (EMAA), etc.
  • E-EA-MAH ethylene-ethyl acrylate-maleic anhydride copolymer
  • EAA ethylene-acrylic acid copolymer
  • EEMA ethylene-methacrylic acid copolymer
  • Polymers and ethylene-acrylic acid copolymer ionomers, ethylene-methacrylic acid copolymer ionomers, and copolymers of monomers having a cyclic olefin structure such as norbornene monomers and ethylene, etc. You may use individually or in mixture of 2 or more types.
  • the intermediate layer (B) in the multilayer film of the present invention contains the polyolefin (b1) and the antifogging agent (b2).
  • this polyolefin (b1) the thing similar to polyolefin (a1) used for the above-mentioned laminate layer (A) can be illustrated, and a preferable thing is also the same.
  • the polyolefin (a1) used for the laminate layer (A) and the polyolefin (b1) used for the intermediate layer (B) may be the same or different from each other. From the point of difficulty, it is preferable to use a combination of similar resins. When combining similar resins, the densities may be the same or different.
  • the resin is preferably the main component, and particularly preferably 90% by mass or more.
  • Other resin types that can be used in combination are the same as those exemplified as the resin that can be used together in the laminate layer (A).
  • the antifogging agent (b2) is not particularly limited as long as it is generally added to an olefin resin and is known to impart antifogging properties.
  • an anionic surfactant Agents nonionic surfactants, cationic surfactants, amphoteric surfactants, and the like can be used, and nonionic surfactants are preferably used.
  • sorbitan surfactants such as sorbitan monostearate, sorbitan distearate, sorbitan monopalmitate, sorbitan dipalmitate, sorbitan monobehenate, sorbitan dibehenate, sorbitan monolaurate, sorbitan dilaurate; Glycerol monolaurate, glycerol dilaurate, diglycerol monopalmitate, diglycerol dipalmitate, glycerol monostearate, glycerol distearate, diglycerol monostearate, diglycerol distearate, diglycerol monolaurate, diglycerol Glycerin surfactants such as dilaurate; Polyethylene glycol surfactants such as polyethylene glycol monostearate and polyethylene glycol monopalinate; Trimethylolpropane surfactants such as dimethylolpropane monostearate; diethanolalkylamine and diethanolalkylamide surfactants
  • the proportion of the antifogging agent (b2) used in the intermediate layer (B) is preferably in the range of 0.5 to 4.0% by mass, particularly 1.0 to 4.0%, based on the total mass of the layer.
  • the range is preferably 3.0% by mass.
  • the adhesive layer (C) in the multilayer film of the present invention contains acid-modified polyolefin (c1) as a main component.
  • the olefin component which is the main component of the acid-modified polyolefin (c1) is not particularly limited, but alkene having 2 to 6 carbon atoms such as ethylene, propylene, isobutylene, 2-butene, 1-butene, 1-pentene and 1-hexene. Are preferred, and a mixture thereof may be used. Of these, alkenes having 2 to 4 carbon atoms such as ethylene, propylene, isobutylene and 1-butene are more preferred, ethylene and propylene are more preferred, and ethylene is most preferred.
  • the acid-modified polyolefin (c1) needs to contain a (meth) acrylic acid ester component.
  • (Meth) acrylic acid ester components include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, (meth) acrylic acid Examples include octyl, decyl (meth) acrylate, lauryl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, and the like.
  • the (meth) acrylic acid ester component may be copolymerized with the olefin component, and the form thereof is not limited. Examples of the copolymerization state include random copolymerization, block copolymerization, and graft copolymerization. (Graft modification) and the like. (Note that “(meth) acrylic acid” means “acrylic acid or methacrylic acid”).
  • ethylene- (meth) acrylic acid ester copolymers include Elvalloy ( Product name: Mitsui-DuPont Polychemical Co., Ltd.), Aklift (trade name: Sumitomo Chemical Co., Ltd.), etc. These may be used alone or in combination of two or more.
  • the acid-modified polyolefin (c1) may be acid-modified with an unsaturated carboxylic acid component.
  • unsaturated carboxylic acid components include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid, crotonic acid, and the like, as well as unsaturated dicarboxylic acid half esters and half amides. It is done. Of these, acrylic acid, methacrylic acid, maleic acid, and maleic anhydride are preferable, and acrylic acid and maleic anhydride are particularly preferable.
  • the unsaturated carboxylic acid component may be copolymerized with the olefin component, and the form thereof is not limited.
  • copolymerization state examples include random copolymerization, block copolymerization, and graft copolymerization (grafting). Modification).
  • ethylene-acrylic acid copolymer examples include Mitsui, manufactured by DuPont Polychemical Co., Ltd.
  • ethylene- (meth) acrylic acid ester-maleic anhydride copolymer examples include bondine (trade name: manufactured by Arkema). These may be used alone or in combination of two or more.
  • the acid modification rate of the acid-modified polyolefin (c1) is preferably 0.5 to 40%, more preferably 0.5 to 35%, from the viewpoint of good adhesion. It is particularly preferably 5 to 30%.
  • the layer (C) in the present invention contains the acid-modified polyolefin (c1) as a main component, but other resins are used in combination as long as the adhesion between the layer (B) and the layer (D) is not impaired. Also good.
  • a polyolefin-based resin may be used in combination with the acid-modified polyolefin (c1) and easy coextrusion with the layer (B) and the layer (D).
  • the heat seal layer (D) in the multilayer film of the present invention contains a polyethylene terephthalate resin (d1) and an antifogging agent (d2).
  • the polyester resin (d1) is preferably amorphous (amorphous) or low crystalline.
  • phthalic acid, terephthalic acid, isophthalic acid, adipic acid, sevansinic acid, naphthalenedicarboxylic acid, 4,4′-diphenylsulfone dicarboxylic acid, 4,4′-biphenyl are used as dibasic acid components.
  • a lactic acid polymer can also be used, and is not particularly limited.
  • poly (D-lactic acid), poly (L-lactic acid), and a combination of D-lactic acid and L-lactic acid are not limited.
  • the polyester component obtained by copolymerization with a lactic acid component is mentioned, and polylactic acid whose main structural unit is L-lactic acid is particularly preferred from the viewpoint of film-forming stability.
  • hydroxycarboxylic acid, diol, and dicarboxylic acid examples include hydroxycaproic acids such as glycolic acid, hydroxybutyric acid, hydroxycaproic acid, and hydroxycarboxylic acids such as caprolactone, butyrolactone, lactide, glycolide, and other cyclic lactones; ethylene glycol, propylene glycol Aliphatic diols such as 1,4-butanediol and 1,4-cyclohexanedimethanol; aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid; succinic acid, adipic acid, suberic acid and sebacic acid It is an aliphatic dicarboxylic acid.
  • hydroxycaproic acids such as glycolic acid, hydroxybutyric acid, hydroxycaproic acid, and hydroxycarboxylic acids such as caprolactone, butyrolactone, lactide, glycolide, and
  • polyester-based resin (d1) used in the present invention an amorphous copolymer polyethylene terephthalate resin having a glass transition temperature Tg of about ⁇ 20 to 80 ° C. with a combination of a dibasic acid component and a glycol component is particularly suitable.
  • any of those exemplified as the antifogging agent (b2) used for the intermediate layer (B) can be used, and suitable ones are also the same. .
  • the antifogging agent (b2) used for the intermediate layer (B) and the antifogging agent (d2) used for the heat seal layer (D) may be the same or different.
  • the proportion of the antifogging agent (d2) used in the heat seal layer (D) is preferably in the range of 1.5 to 2.5% by mass, particularly 1.8 to 2%, based on the total mass of the layer. It is preferably in the range of 3% by mass.
  • the laminate layer (A), the intermediate layer (B), the adhesive layer (C) and the heat seal layer (D) are (A) / (B) / (C) / It is the multilayer film laminated
  • the anti-fogging multilayer film of the present invention does not contain an anti-fogging agent in the laminate layer (A) and contains an anti-fogging agent in both the intermediate layer (B) and the heat seal layer (D).
  • the wetting tension of the outer surface of the heat seal layer is 50 to 60 mN / m, and the coating tension of the outer surface of the laminate layer is 35 to 45 mN / m.
  • the multilayer film having the structure can realize suitable antifogging properties, can realize suitable adhesive strength when heat-sealed, and can maintain suitable easy-openability between (C) / (D) layers even when opened. .
  • the antifogging agent does not easily fall off, and the antifogging property can be stably maintained, and the printing and adhesion to other substrates can be improved.
  • the total thickness of the antifogging multilayer film of the present invention is preferably in the range of 20 to 100 ⁇ m, particularly 20 to 50 ⁇ m, from the viewpoint of easy lamination when the film is laminated with another substrate. This range is preferable from the viewpoint of easy film formation.
  • the ratio of each layer in the multilayer film is such that the thickness ratio of the laminate layer (A) is in the range of 20 to 30% from the viewpoint of sealing properties, easy opening properties, and laminate properties, and the thickness of the intermediate layer (B).
  • the ratio is preferably in the range of 30 to 40%, and the thickness ratio of the heat seal layer (D) is preferably in the range of 10 to 20%.
  • the total amount of the antifogging agent contained in the entire antifogging multilayer film of the present invention is 0.7 to 1.5% by mass, particularly 0.8 to 1.3% by mass. It is preferable from the viewpoints of good film properties, antifogging properties, and antifogging durability.
  • an antistatic agent for each layer (A), (B), (C), (D) of the antifogging multilayer film of the present invention, an antistatic agent, a heat stabilizer, a nucleating agent, an antioxidant, a lubricant, an antiblocking agent, Components such as a release agent, an ultraviolet absorber, and a colorant can be added within a range that does not impair the object of the present invention.
  • the film surface has a coefficient of friction of 1.5 or less, particularly 1.0 or less in order to impart processing suitability during film forming and packaging suitability of a filling machine, and thus corresponds to the surface layer of a multilayer film. It is preferable to add a lubricant, an antiblocking agent and an antistatic agent to the resin layer as appropriate.
  • both outer surfaces of the film are treated, the outer surface of the heat seal layer is treated in the range of 50-60 mN / m, and the outer surface of the laminate layer is the wetting tension. It must be processed within the range of 35 to 45 mN / m.
  • treatment methods include corona discharge treatment, plasma treatment, chromic acid treatment, flame treatment, hot air treatment, surface oxidation treatment such as ozone / ultraviolet treatment, and surface unevenness treatment such as sandblasting.
  • the corona discharge treatment is preferable.
  • the coating property of ink or adhesive when a post-process such as printing or applying an adhesive to the laminate layer (A) of the multilayer film and laminating it with a substrate is performed. It is excellent in adhesion with ink, aluminum, anchor coating agent, etc., and it is easy to avoid problems such as ink dropping or vapor deposition aluminum falling off or delamination. Moreover, by treating the surface of the heat seal layer (D), it becomes possible to fix the antifogging agent to the outer surface for a relatively long period of time, and a film having excellent antifogging properties and antifogging durability can be obtained.
  • the treatment method and treatment degree of the laminate layer (A) and the heat seal layer (D) may be the same or different, but from the viewpoint of productivity, the treatment is preferably carried out by the same method.
  • the method of the corona discharge treatment is not particularly limited.
  • each of JP-B-39-12838, JP-A-47-19824, JP-A-48-28067, JP-A-52-42114 It can be performed by a processing method described in the publication.
  • a solid state corona treatment machine manufactured by Pillar a LEPEL type surface treatment machine, a VETAPHON type treatment machine, or the like can be used.
  • the treatment can be performed at normal pressure in air.
  • the discharge frequency during the treatment is 5 kV to 40 kV, more preferably 10 kV to 30 kV, and the waveform is preferably an alternating sine wave.
  • the gap transparent lance between the electrode and the dielectric roll is 0.1 mm to 10 mm, more preferably 1.0 mm to 2.0 mm.
  • the discharge is processed above a dielectric support roller provided in the discharge zone, and the treatment amount is 0.34 kV ⁇ A ⁇ min / m 2 to 0.4 kV ⁇ A ⁇ min / m 2 , more preferably 0.344 kV.
  • the heat seal strength of the laminated film of the present invention may be appropriately adjusted according to the use mode.
  • the laminated film of the present invention is applied to an A-PET sheet (softening point 77 ° C., crystallization temperature 126 ° C.) After heat sealing at a temperature of 170 ° C. and a pressure of 0.2 MPa for 1.0 second, a 15 mm wide test piece was cut out and peeled in a 180 ° direction at a constant temperature of 23 ° C. and 50% RH at a tensile rate of 300 mm / min.
  • the maximum load is preferably 4 N / 15 mm or more, and more preferably 5 N / 15 mm or more.
  • the upper limit of the maximum load is preferably less than 20 N / 15 mm, and more preferably less than 15 N / 15 mm.
  • This coextrusion method is preferable because the thickness ratio of each layer can be adjusted relatively freely, and a multilayer film excellent in hygiene and cost performance can be obtained.
  • the T-die / chill roll method is easy to suppress deterioration of the film appearance and to form a uniform layer structure when coextruding resins having different melting points and Tg, and to easily obtain a film with suitable transparency and gloss. Therefore, it is preferable.
  • the inflation method is preferable because the equipment is simple, and is suitable for the production of a small variety of products.
  • the antifogging multilayer film of the present invention can be obtained as a substantially unstretched multilayer film by the above-described production method, so that secondary molding such as deep drawing by vacuum molding or embossing is also possible.
  • the antifogging multilayer film of the present invention can also be used by being bonded to other base materials.
  • Other substrates that can be used at this time are not particularly limited, but from the viewpoint of easily manifesting the effects of the present invention, a thermoplastic resin film having high rigidity and high gloss, particularly two It is preferable to use an axially stretched resin film.
  • aluminum foils can be used alone or in combination.
  • stretched resin film examples include coextrusion using, as a central layer, biaxially stretched polyester (PET), biaxially stretched polypropylene (OPP), biaxially stretched polyamide (PA), and ethylene vinyl alcohol copolymer (EVOH).
  • PET biaxially stretched polyester
  • OPP biaxially stretched polypropylene
  • PA biaxially stretched polyamide
  • EVOH ethylene vinyl alcohol copolymer
  • examples thereof include biaxially stretched polypropylene, biaxially stretched ethylene vinyl alcohol copolymer (EVOH), and coextruded biaxially stretched polypropylene coated with polyvinylidene chloride (PVDC). These may be used alone or in combination.
  • PVDC polyvinylidene chloride
  • the laminate of the present invention is a laminate film obtained by laminating the thermoplastic resin film on the antifogging multilayer film obtained as described above, and examples of the lamination method include dry lamination, wet lamination, non-solvent lamination, Examples thereof include extrusion lamination.
  • the use of the laminate of the present invention is not particularly limited, but it can be suitably used as a lid for packaging containers used for foods, medicines, industrial parts, miscellaneous goods, magazines, and the like.
  • the outermost layer of the packaging container (the part that adheres to the heat seal layer of the multilayer film of the present invention) preferably contains a polyester resin from the viewpoint of the balance between easy-openability and seal strength.
  • Preparation Example 1 [Preparation of anti-fogging agent master batch based on polyethylene terephthalate resin] Amorphous polyethylene terephthalate resin (PETG6763 manufactured by Eastman Chemical; hereinafter referred to as PETG) and 10 parts of a nonionic surfactant (Poem J-4081 manufactured by Riken Vitamin Co., Ltd.) are melt-kneaded and granulated to form an antifogging agent. Master batch pellets were obtained (hereinafter referred to as anti-fogging agent MB (1)).
  • PETG polyethylene terephthalate resin
  • Poem J-4081 manufactured by Riken Vitamin Co., Ltd.
  • Example 1 As the resin for the heat seal layer (D), a mixture of 80 parts of PETG and 20 parts of the antifoggant MB (1) was used (antifoggant concentration in the heat seal layer (D): 2% by mass).
  • As the adhesive layer (C) resin an acid-modified ethylene-propylene-butene copolymer (hereinafter referred to as adhesive resin 1) having an acid modification amount of 2.9 parts and a density of 0.89 g / cm 3 was used.
  • As the resin for the intermediate layer (B) a mixture of 80 parts of LLDPE and 20 parts of the antifogging agent MB (2) was used (antifogging agent concentration in the intermediate layer (B): 2% by mass).
  • LLDPE was used as the resin for the laminate layer (A).
  • Extruder for heat seal layer (D) (caliber 40 mm)
  • extruder for adhesive layer (C) (caliber 40 mm)
  • extruder for intermediate layer (B) (caliber 50 mm)
  • extruder for laminate layer (A) (caliber) 50 mm) and the thickness of each layer of (A) / (B) / (C) / (D) is 7.5 / 12/6 from a T die at an extrusion temperature of 230 ° C. by coextrusion. /4.5 ( ⁇ m), and cooled with a 40 ° C. water-cooled metal cooling roll.
  • Example 2 The amount of antifogging agent contained in the entire film was about 0.7% by mass in the same manner as in Example 1 except that a mixture of 90 parts of LLDPE and 10 parts of antifogging agent MB (2) was used as the intermediate layer (B). The antifogging multilayer film of Example 2 was obtained.
  • Example 3 The amount of antifogging agent contained in the entire film was about 1.5% by mass in the same manner as in Example 1 except that a mixture of 70 parts of LLDPE and 30 parts of antifogging agent MB (2) was used as the intermediate layer (B). The antifogging multilayer film of Example 3 was obtained.
  • Example 4 Low density polyethylene (density 0.92 g / cm 3 , melt flow rate 7 g / 10 min; hereinafter referred to as LDPE) is used as the laminate layer (A), and 80 parts of LDPE, 90 parts of LDPE and 10 parts of antifogging agent are used as the intermediate layer (B).
  • An antifogging multilayer film of Example 4 was obtained in the same manner as in Example 1 except that a mixture of 20 parts of a master batch obtained by melt kneading and granulating was used.
  • Example 5 Propylene-ethylene copolymer [density 0.90 g / cm 3 , melt flow rate 7 g / 10 min; hereinafter referred to as PP] was used as the laminate layer (A), and 90 parts PP and 90 parts PP were antifogged as the intermediate layer (B).
  • An antifogging multilayer film of Example 5 was obtained in the same manner as in Example 1 except that a mixture of 20 parts of master batch obtained by melt kneading and granulating 10 parts of the agent was used.
  • Example 6 An antifogging multilayer film of Example 6 was obtained in the same manner as in Example 1 except that the corona discharge treatment was performed so that the wetting tension of the heat seal layer (D) was 50 mN / m.
  • Example 7 An antifogging multilayer film of Example 7 was obtained in the same manner as in Example 1 except that the corona discharge treatment was performed so that the wetting tension of the laminate layer (A) was 35 mN / m.
  • Example 8 The antifogging multilayer film of Example 8 was prepared in the same manner as in Example 1 except that a mixture of 80 parts of crystalline PES and 20 parts of antifogging agent MB (3) was used as the resin for the heat seal layer (D). Obtained.
  • Example 9 As in Example 1, except that an acid-modified ethylene polymer having an acid modification amount of 2.5 parts and a density of 0.88 g / cm 3 (hereinafter referred to as adhesive resin 2) was used as the adhesive layer (C) resin. Thus, an antifogging multilayer film of Example 9 was obtained.
  • adhesive resin 2 an acid-modified ethylene polymer having an acid modification amount of 2.5 parts and a density of 0.88 g / cm 3
  • Example 10 (A) / (B) / (C) / (D) The same as in Example 1 except that the total thickness of extrusion was 40 ⁇ m so that the thickness of each layer was 10/16/8/6 ( ⁇ m). Thus, an antifogging multilayer film of Example 10 was obtained.
  • Comparative Example 1 A coextruded laminated film of Comparative Example 1 was obtained in the same manner as in Example 1 except that the heat seal layer was not subjected to corona discharge treatment.
  • Comparative Example 2 A coextruded laminated film of Comparative Example 2 was obtained in the same manner as in Example 1 except that the intermediate layer (B) was only LLPDE (no antifogging agent) 100%.
  • Comparative Example 3 A coextruded laminated film of Comparative Example 3 was obtained in the same manner as in Example 1 except that the heat seal layer (D) was 100% PETG alone (no antifogging agent).
  • Comparative Example 4 The coextrusion lamination of Comparative Example 4 was performed in the same manner as in Example 1 except that an ethylene-vinyl acetate copolymer (hereinafter referred to as EVA) having a density of 0.95 g / cm 3 was used as the adhesive layer (C) resin. A film was obtained.
  • EVA ethylene-vinyl acetate copolymer having a density of 0.95 g / cm 3
  • Comparative Example 5 A coextruded laminated film of Comparative Example 5 was obtained in the same manner as in Example 1 except that a mixture of 80 parts of LLDPE and 20 parts of antifoggant MB (2) was used as the resin for the laminate layer (A).
  • Comparative Example 6 A coextruded laminated film of Comparative Example 6 was obtained in the same manner as in Example 1 except that the laminate layer was not subjected to corona discharge treatment.
  • Example 7 A coextruded laminated film of Example 7 was obtained in the same manner as in Example 1 except that the corona discharge treatment was performed so that the wetting tension of the heat seal layer (D) was 45 mN / m.
  • a laminate film was prepared by laminating a 12 ⁇ m thick biaxially stretched polyester film using a urethane adhesive on the laminate layer side of the obtained film.
  • Heat of laminated film obtained by placing 30 ml of water at 40 ° C. into a square container with a capacity of 80 cm 3 consisting of an A-PET sheet, a 5 mm wide surface with a smooth buttocks and a side length of 88 mm
  • the seal layer was fitted to the container and heat sealed using a cup sealer, then stored at 3 ° C. for 3 hours, and visually confirmed the antifogging effect according to the following criteria.
  • ⁇ A continuous water film is formed on the film surface and visibility is good.
  • Fine water droplet adhesion is good visibility on the film surface.
  • Water droplet adhesion is present and visibility is deteriorated.
  • the heat seal layer of the laminate film was matched to an A-PET sheet (softening point 77 ° C., crystallization temperature 126 ° C.), and a precision heat sealer (manufactured by Tester Sangyo) was used at a temperature of 170 ° C., a pressure of 0.2 MPa, and a width of 10 mm. After heat-sealing with a seal bar for 1.0 second, the sample was allowed to cool, and then a 15 mm-wide test piece was cut out from the heat-sealed sample, in a temperature-controlled room at 23 ° C. and 50% RH, at a tensile rate of 300 mm / min.
  • the antifogging laminated films of the present invention of Examples 1 to 10 were able to realize suitable antifogging properties and heat sealing properties. Moreover, it had a suitable laminate strength and did not cause a problem of delamination practically. On the other hand, the laminated films of Comparative Examples 1 to 7 could not achieve both suitable antifogging properties and heat sealing properties.

Landscapes

  • Laminated Bodies (AREA)
  • Wrappers (AREA)

Abstract

　La présente invention porte sur un film multicouche obtenu par la stratification, dans l'ordre (A)/(B)/(C)/(D), de : une couche de stratifié (A) ayant une polyoléfine (a1) comme constituant principal et ne comprenant pas d'agent antibuée ; une couche intermédiaire (B) contenant une polyoléfine (b1) et un agent antibuée (b2) ; une couche adhésive (C) ayant une polyoléfine modifiée à l'acide (c1) comme constituant principal ; et une couche de thermoscellage (D) contenant une résine polyester (d1) et un agent antibuée (d2), la surface externe de la couche de thermoscellage du film multicouche étant traitée de façon à avoir une résistance à la traction à l'état humide à l'intérieur de la plage de 50 à 60 mN/m, et la surface externe de la couche de stratifié étant traitée de façon à avoir une résistance à la traction à l'état humide à l'intérieur de la plage de 35 à 45 mN/m.
PCT/JP2014/075042 2013-09-27 2014-09-22 Film multicouche antibuée, stratifié l'utilisant, et matériau d'emballage WO2015046132A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
KR1020167003044A KR102161563B1 (ko) 2013-09-27 2014-09-22 방담성 다층 필름, 이것을 사용하는 적층체, 및 포장재
CN201480053407.9A CN105593017B (zh) 2013-09-27 2014-09-22 防雾性多层膜、使用其的层叠体和包装材
JP2015517541A JP5804339B2 (ja) 2013-09-27 2014-09-22 防曇性多層フィルム、これを用いる積層体、及び包装材

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2013201483 2013-09-27
JP2013-201483 2013-09-27

Publications (1)

Publication Number Publication Date
WO2015046132A1 true WO2015046132A1 (fr) 2015-04-02

Family

ID=52743268

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2014/075042 WO2015046132A1 (fr) 2013-09-27 2014-09-22 Film multicouche antibuée, stratifié l'utilisant, et matériau d'emballage

Country Status (5)

Country Link
JP (1) JP5804339B2 (fr)
KR (1) KR102161563B1 (fr)
CN (1) CN105593017B (fr)
TW (1) TWI626155B (fr)
WO (1) WO2015046132A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018070191A (ja) * 2016-10-26 2018-05-10 三菱ケミカル株式会社 トップシール用蓋材フィルムおよび包装体
WO2018179689A1 (fr) * 2017-03-29 2018-10-04 東洋紡株式会社 Composition adhésive ayant des propriétés antibuée
EP3666520A1 (fr) * 2018-12-14 2020-06-17 Cryovac, LLC Film antibuée multicouches
US11273627B2 (en) 2017-01-11 2022-03-15 Bostik, Inc. Extrudable antifog copolyester heat seal resins
WO2023063091A1 (fr) * 2021-10-14 2023-04-20 Dic株式会社 Film multicouche antibuée, stratifié le comprenant et matériau d'emballage

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113681755A (zh) * 2021-09-29 2021-11-23 惠州莹光塑胶颜料有限公司 一种防雾pet母粒及其制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001310431A (ja) * 2000-04-28 2001-11-06 Dainippon Ink & Chem Inc 易開封性複合フィルム及び包装容器
JP2003170550A (ja) * 2001-12-07 2003-06-17 Dainippon Ink & Chem Inc 多層フィルム、多層シート、容器の蓋材及び容器
JP2004025825A (ja) * 2002-05-07 2004-01-29 Kureha Chem Ind Co Ltd 防曇性多層シール性ポリエステル系フィルムおよびこれを含むガスパック包装体

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100740055B1 (ko) * 1997-12-25 2007-10-18 산젠 가꼬 가부시키가이샤 흐림방지성적층체
JP2001320986A (ja) * 2000-05-12 2001-11-20 Mitsui Chemicals Inc 防曇性フィルム
JP5142470B2 (ja) * 2003-01-31 2013-02-13 三井・デュポンポリケミカル株式会社 易開封性樹脂組成物及びその用途
JP4692818B2 (ja) * 2005-08-05 2011-06-01 Ｄｉｃ株式会社 共押出積層フィルム並びにそれを用いたラミネートフィルム及び包装容器
US20110117341A1 (en) * 2008-06-06 2011-05-19 Gunze Limited Multilayered film with excellent antifogging property

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001310431A (ja) * 2000-04-28 2001-11-06 Dainippon Ink & Chem Inc 易開封性複合フィルム及び包装容器
JP2003170550A (ja) * 2001-12-07 2003-06-17 Dainippon Ink & Chem Inc 多層フィルム、多層シート、容器の蓋材及び容器
JP2004025825A (ja) * 2002-05-07 2004-01-29 Kureha Chem Ind Co Ltd 防曇性多層シール性ポリエステル系フィルムおよびこれを含むガスパック包装体

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018070191A (ja) * 2016-10-26 2018-05-10 三菱ケミカル株式会社 トップシール用蓋材フィルムおよび包装体
US11273627B2 (en) 2017-01-11 2022-03-15 Bostik, Inc. Extrudable antifog copolyester heat seal resins
US11806971B2 (en) 2017-01-11 2023-11-07 Bostik, Inc. Extrudable antifog copolyester heat seal resins
WO2018179689A1 (fr) * 2017-03-29 2018-10-04 東洋紡株式会社 Composition adhésive ayant des propriétés antibuée
JPWO2018179689A1 (ja) * 2017-03-29 2020-02-06 東洋紡株式会社 防曇性を有する接着剤組成物
EP3561019A4 (fr) * 2017-03-29 2020-06-24 Toyobo Co., Ltd. Composition adhésive ayant des propriétés antibuée
JP7067547B2 (ja) 2017-03-29 2022-05-16 東洋紡株式会社 防曇性を有する接着剤組成物
US11459492B2 (en) 2017-03-29 2022-10-04 Toyobo Co., Ltd. Adhesive composition having anti-fogging property
EP3666520A1 (fr) * 2018-12-14 2020-06-17 Cryovac, LLC Film antibuée multicouches
WO2023063091A1 (fr) * 2021-10-14 2023-04-20 Dic株式会社 Film multicouche antibuée, stratifié le comprenant et matériau d'emballage
JP7343072B1 (ja) * 2021-10-14 2023-09-12 Dic株式会社 防曇性多層フィルム、これを用いる積層体、及び包装材

Also Published As

Publication number Publication date
JP5804339B2 (ja) 2015-11-04
KR102161563B1 (ko) 2020-10-05
TWI626155B (zh) 2018-06-11
TW201520044A (zh) 2015-06-01
CN105593017A (zh) 2016-05-18
JPWO2015046132A1 (ja) 2017-03-09
KR20160063312A (ko) 2016-06-03
CN105593017B (zh) 2018-03-27

Similar Documents

Publication Publication Date Title
JP5804339B2 (ja) 防曇性多層フィルム、これを用いる積層体、及び包装材
JP6172398B2 (ja) 多層フィルム、包装材用積層フィルム、包装袋及びスタンディングパウチ
JP6057040B1 (ja) シーラントフィルム及びラミネートフィルム
JP6511713B2 (ja) 包装材用積層体
JP5991504B2 (ja) 易貫通性蓋材
JP5182183B2 (ja) 易開封性フィルム、これを用いる蓋材及び包装袋
JP5962864B2 (ja) 防曇性多層フィルム、これを用いる積層体、及び包装材
US20020122933A1 (en) Easily-peelable film
JP6972545B2 (ja) 防曇性多層フィルム、これを用いる積層体、及び包装材
JP4655703B2 (ja) 易剥離性フィルムおよび蓋材
JP6511712B2 (ja) 包装材用積層体
JP6168255B2 (ja) シーラントフィルム及びラミネートフィルム
JP7419802B2 (ja) 積層フィルム及び包装材
JP7343072B1 (ja) 防曇性多層フィルム、これを用いる積層体、及び包装材
JP6839924B2 (ja) 蓋材
US20200331242A1 (en) Sealable and easy opening polyester films
JP6554756B2 (ja) 非吸着性シーラントフィルム
JP7460036B1 (ja) 多層フィルム、蓋材及び包装材
JP2012011741A (ja) 臭気バリア性共押出多層フィルム、これを用いる包装材及び包装容器
JP2022154802A (ja) 防曇性に優れた熱融着性フィルム及びその用途
KR20240088677A (ko) 방담성 다층 필름, 이것을 사용하는 적층체, 및 포장재

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2015517541

Country of ref document: JP

Kind code of ref document: A

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14848545

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 20167003044

Country of ref document: KR

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: IDP00201601502

Country of ref document: ID

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14848545

Country of ref document: EP

Kind code of ref document: A1