WO2016003116A1 - Barrier film - Google Patents

Barrier film Download PDF

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Publication number
WO2016003116A1
WO2016003116A1 PCT/KR2015/006524 KR2015006524W WO2016003116A1 WO 2016003116 A1 WO2016003116 A1 WO 2016003116A1 KR 2015006524 W KR2015006524 W KR 2015006524W WO 2016003116 A1 WO2016003116 A1 WO 2016003116A1
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WO
WIPO (PCT)
Prior art keywords
layer
rubber
protective layer
epoxy resin
film
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PCT/KR2015/006524
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French (fr)
Korean (ko)
Inventor
김진영
김종원
Original Assignee
코오롱인더스트리 주식회사
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Priority claimed from KR1020140135222A external-priority patent/KR102218061B1/en
Application filed by 코오롱인더스트리 주식회사 filed Critical 코오롱인더스트리 주식회사
Publication of WO2016003116A1 publication Critical patent/WO2016003116A1/en

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    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L59/00—Thermal insulation in general
    • F16L59/06—Arrangements using an air layer or vacuum

Definitions

  • the present invention relates to a barrier film. More specifically, the present invention relates to a barrier film having excellent durability and long-term stability in an environment of high temperature and high humidity, and having excellent heat insulating property, gas barrier property, and water barrier property.
  • Vacuum insulation is a material that exhibits excellent insulation performance by blocking the convection phenomenon inside the insulation by vacuuming the interior.
  • the vacuum insulation material includes a core material in which a panel made of glass fibers or silica is laminated and vacuumed therebetween, and a sealing member that encloses and seals the core material to maintain the vacuum of the core material.
  • the sealing member usually has a multilayer film structure in which aluminum foil and a polymer film are laminated, and performs a function of primarily blocking internal high vacuum and external atmospheric pressure to maintain a high vacuum state inside the vacuum insulator, thereby ensuring long-term reliability of the vacuum insulator. can do.
  • the sealing member generally consists of a protective layer, a blocking layer and a heat seal layer. Insulation performance is achieved by using nylon or polyethylene terephthalate (PET) as the protective layer, aluminum metal as the barrier layer, and polyethylene (polyethylene) as the heat-sealing layer. The ingress of gas and gas can be prevented.
  • PET polyethylene terephthalate
  • polyethylene polyethylene
  • Such a sealing member may easily cause cracks in external impacts when the product is transported or applied, and such cracks may lower heat insulation performance and gas and moisture barrier properties.
  • Korean Laid-Open Patent No. 2012-0033165 discloses a vacuum insulator for a refrigerator in which aluminum foil is laminated on a polyimide film.
  • the vacuum insulator can increase the long-term durability at high temperature, but the effect of improving the thermal insulation performance and gas barrier properties is insignificant, and physical properties due to cracks may be reduced. This is because a large amount of pinholes are generated when the metal such as aluminum is coated on the polymer film, or mechanical properties due to metal lamination are reduced.
  • the present invention has been made to solve the above problems, it is possible to improve the thermal insulation performance, to prevent the performance degradation due to the generation of pinholes due to metal deposition, and to have excellent mechanical properties to ensure durability and long-term reliability
  • An object of the present invention is to provide a barrier film.
  • an object of the present invention is to provide a barrier film that can prevent the heat bridge phenomenon that can occur when the metal layer formed by metal deposition is provided in a multi-layer, and at the same time improve the moisture barrier properties and gas barrier properties. do.
  • the present invention includes a base film, a metal barrier layer on which a metal layer, a first protective layer and a second protective layer are laminated on the base film, the adhesive layer and the upper portion of the metal barrier layer; Laminating the heat seal layer in sequence,
  • the first protective layer is formed by coating and drying a first resin composition comprising an epoxy resin, a curing agent, and a solvent
  • the second protective layer is a synthetic rubber and a solvent. It may be formed by coating and drying a second resin composition comprising a.
  • the epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, cycloaliphatic epoxy resin, polyfunctional amine epoxy resin, glycidylamine Type epoxy resin, dimer acid modified epoxy resin, rubber modified epoxy resin, urethane modified epoxy resin, brominated epoxy resin, brominated phenoxy epoxy resin, hydrated bisphenol A type epoxy resin and polyol modified epoxy resin It may include any one or more than two.
  • the curing agent may include any one or two or more amine curing agents selected from the group consisting of aliphatic amines, modified amines, aromatic amines, tertiary amines and polyamine-based compounds. have.
  • the curing agent may be included 70 to 250 parts by weight based on 100 parts by weight of the epoxy resin.
  • the synthetic rubber is styrene-butadien rubber (styrene butadien rubber), polychloroprene rubber (polychloroprene rubber), nitrile rubber (acrylonitrile-butadiene rubber), butyl rubber (isoprene-isobutylene rubber, butadiene rubber, isoprene rubber, ethylene propylene rubber, polysulfide rubber, silicone rubber, fluororubber, urethane It may include any one or two or more selected from rubber (urethane rubber), acrylic rubber (acrylic rubber).
  • the base film has a thickness of 1 ⁇ 200 ⁇ m, may be made of a thermoplastic polymer film.
  • the metal layer is formed by depositing a metal oxide, the thickness may be less than 100nm, preferably 20 to 50nm.
  • the first protective layer may have a dry coating thickness of 1 to 10 ⁇ m
  • the second protective layer may have a dry coating thickness of 1 to 5 ⁇ m.
  • Barrier film is water vapor transmission rate (WVTR) of less than 0.01g / m2 / day at 38 ⁇ 2 °C and 90 ⁇ 5% relative humidity, 0.001cc / m2 / at 23 ⁇ 2 °C It may be an Oxygen Transmission Rate (OTR) of less than one day.
  • WVTR water vapor transmission rate
  • OTR Oxygen Transmission Rate
  • the barrier film according to the present invention can improve the thermal insulation performance and at the same time prevent the performance degradation caused by the pinhole generation due to metal deposition, and exhibit a synergistic effect of mechanical properties of impact resistance, heat resistance, cold resistance, scratch resistance and flexibility. There is an advantage.
  • the present invention can prevent the heat bridge (heat bridge) phenomenon by the metal layer, there is an advantage that can significantly improve the moisture barrier properties and gas barrier properties.
  • 1 to 3 show a cross-sectional view of the barrier film according to an embodiment of the present invention.
  • the barrier film according to the present invention includes a base film, a metal barrier layer in which a metal layer, a first protective layer and a second protective layer are laminated on the base film, and an adhesive layer and a heat seal layer on the metal barrier layer. Stack them sequentially,
  • the base film may be a thermoplastic polymer film, but is not necessarily limited thereto.
  • polyolefins such as homopolymers or copolymers such as ethylene, propylene, butene, amorphous polyolefins such as cyclic polyolefins, polyesters such as polyethylene terephthalate, polyethylene-2,6-naphthalate, and nylon 6, nylon 66, nylon 12, polyamides such as copolymerized nylon, ethylene-vinyl acetate copolymer partial hydrolyzate (EVOH), polyimide, polyetherimide, polysulfone, polyethersulfone, polyetheretherketone, polycarbonate, Polyvinyl butyral, polyarylate, fluorine resin, acrylate resin, biodegradable resin and the like.
  • any one or more polymer films selected from polycarbonate, polyimide, nylon, polyethylene naphthalate, and polyethylene terephthalate may be used
  • the base film may be further treated with a primer selected from a urethane-based compound, an acrylic compound, and an ester compound or a corona treatment in order to improve adhesion to the metal layer.
  • a primer selected from a urethane-based compound, an acrylic compound, and an ester compound or a corona treatment in order to improve adhesion to the metal layer.
  • the base film may be prepared by a known method.
  • the raw resin may be melted by an extruder, extruded by a cyclic die or T die, and quenched into a non-oriented film that is not oriented amorphous.
  • it may be made of a film oriented or uniaxially or biaxially, but is not limited thereto.
  • using a multilayer die it can be manufactured from the single
  • the base film may include additives such as antistatic agents, light blocking agents, ultraviolet absorbers, plasticizers, lubricants, fillers, colorants, stabilizers, lubricants, crosslinking agents, antiblocking agents, antioxidants, and the like, but are not limited thereto. .
  • the thickness of the base film in the present invention is not limited, but may be 1 ⁇ 200 ⁇ m, preferably 5 ⁇ 50 ⁇ m in terms of heat insulating performance, mechanical properties and gas and moisture barrier performance. In addition, for the workability and workability, more preferably 10 to 15 ⁇ m can be used.
  • the metal barrier layer is formed on the base film.
  • the metal blocking layer is composed of these laminates including a metal layer, a first protective layer and a second protective layer.
  • the metal blocking layer is formed on the base film, wherein a metal layer which is a constituent of the metal blocking layer is laminated on one surface of the base film, and the first protective layer and the second protective layer are laminated on the other surface where the metal layer is laminated.
  • the first protective layer or the second protective layer is laminated on the metal layer, and the first protective layer or the second protective layer is laminated on the other surface, which means that the components are sequentially laminated from the base film. It is not meant to mean limited.
  • the metal layer is formed by depositing a metal oxide to block gases such as oxygen and water vapor, and to maintain an internal vacuum degree. It can exhibit a synergistic effect of impact resistance, heat resistance, cold resistance, scratch resistance and flexibility as well as gas barrier properties and water barrier properties in combination with other components.
  • the metal barrier layer according to the present invention is characterized by including only one layer of the metal layer in order to prevent physical property degradation due to heat bridge phenomenon that may occur when it includes two or more metal layers.
  • the metal layer may be laminated regardless of the order of the first protective layer and the second protective layer to implement the above effects.
  • a metal layer, a first protective layer and a second protective layer are sequentially stacked on the base film, or a first protective layer, the second protective layer and the metal layer are sequentially stacked or the second protective layer.
  • the layer, the metal layer, and the first protective layer may be sequentially stacked.
  • a material such as evaporated polyethylene terephthalate or ethylene vinyl alcohol may be used to replace the metal, and may be used simultaneously with the metal layer.
  • the thickness of the metal layer may be 100 nm or less, preferably 20 to 50 nm. In terms of gas and moisture barrier performance, the thickness is more preferably 40 to 50 nm. If the thickness of the metal layer exceeds the above range, there is a fear that the film such as heat wrinkles.
  • the metal barrier layer is formed of a combination of a metal layer and a protective layer
  • the protective layer preferably includes a first protective layer and a second protective layer in order to implement a synergy effect of thermal insulation performance or gas and moisture blocking performance. Good to do.
  • the first protective layer and the second protective layer it is possible to prevent the thermal insulation or blocking performance deterioration due to the pinholes that may occur when the metal deposition on the base film, and when combined with the heat-sealing layer of the film mechanical The physical properties can be improved, which is better.
  • the protective layer may include a first protective layer including a resin having a gas barrier property and a second protective layer including a resin having a moisture barrier property in a more preferred embodiment for the synergistic effect of the heat insulating and blocking performance. It is not limited thereto.
  • the first protective layer and the second protective layer may be laminated without restriction in the order with the metal layer, the number of the protective layer is not limited.
  • the first protective layer has a dry coating thickness of 1 to 10 ⁇ m, more preferably 1 to 2 ⁇ m in terms of increasing mechanical properties of durability, impact resistance, heat resistance, cold resistance, scratch resistance, and flexibility. Is preferred.
  • the second protective layer satisfies the dry coating thickness of 1 to 5 ⁇ m, more preferably 1 to 2 ⁇ m, the water barrier property and the gas barrier property of the present invention can be improved.
  • the first protective layer and the second protective layer are monolayers while satisfying the thickness range, superiority of the desired effect can be realized.
  • the first protective layer may be formed using a first resin composition containing an epoxy resin, a curing agent, and a solvent.
  • the composition may be prepared by mixing in a conventional organic solvent.
  • the organic solvent may be preferably a mixed solvent of ethyl acetate and methanol.
  • the mixed weight ratio of ethyl acetate and methanol is not limited, but may be 1: 1 to 1:10, preferably 1: 5 to 1: 7.
  • the first resin composition may have a solid content of 10 to 50% by weight, preferably 30 to 40% by weight.
  • the first protective layer may be formed by applying a film prepared by curing the first resin composition or by coating the upper portion of the metal barrier layer, and includes mechanical properties including thermal insulation and gas barrier properties.
  • a coating method using a composition rather than inserting a film because pinholes may occur on the upper surface of the metal barrier layer when the metal layer is laminated on the base film or when the product is exposed to the outside.
  • the epoxy resin is bisphenol A epoxy resin, bisphenol F epoxy resin, novolac epoxy resin, cycloaliphatic epoxy resin, polyfunctional amine epoxy resin, glycidylamine epoxy resin, dimer acid modified epoxy resin, rubber modified Epoxy resins, urethane-modified epoxy resins, brominated epoxy resins, brominated phenoxy epoxy resins, hydrated bisphenol A-type epoxy resin and polyol modified epoxy resin may include any one or two or more It is not limited.
  • the epoxy resin may be any one or more of a saturated or unsaturated aliphatic compound, an alicyclic compound, an aromatic compound, or a heterocyclic compound, but preferably an epoxy resin containing an aromatic functional group in a molecule.
  • an epoxy resin having a glycidylamine moiety derived from metha xylylenediamine an epoxy resin having a glycidylamine moiety derived from 1,3-bis (aminomethyl) cyclohexane, diaminodiphenyl Epoxy resins having glycidylamine moieties derived from methane, epoxy resins having glycidylamine moieties derived from paraaminophenol and / or glycidyl ether moieties, having glycidylether moieties derived from bisphenol A Epoxy resins, epoxy resins having glycidyl ether moieties derived from bisphenol F, epoxy resins having glycidyl ether moie
  • the epoxy resin may be a dimer acid (modified acid) modified epoxy resin.
  • the dimer acid-modified epoxy resin may improve the adhesive strength to improve the performance of the protective layer, and may express synergistic effects of mechanical properties such as durability, flexibility, impact resistance, and heat resistance of the film.
  • the dimer acid-modified epoxy resin may be formed by reacting one or more carboxyl groups of the dimer acid structure with the polyfunctional epoxy resin.
  • the curing agent may include any one or two or more amine curing agents selected from the group consisting of aliphatic amines, modified amines, aromatic amines, tertiary amines and polyamine compounds.
  • a polyamine curing agent can be used.
  • aliphatic amines having 1,3-bis with aromatic rings such as aliphatic amines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, methaxylylenediamine, and paraxylylenediamine
  • Alicyclic amines such as (aminomethyl) cyclohexane, isophoronediamine, norbornenediamine, and aromatic amines such as diaminodiphenylmethane, metaphenylenediamine, and the like.
  • the curing agent may contain 70 to 250 parts by weight, preferably 100 to 250 parts by weight, and more preferably 150 to 200 parts by weight based on 100 parts by weight of the epoxy resin. If the content of the curing agent is less than 70 parts by weight, the curing rate is slow, blocking may occur. If the content of the curing agent is greater than 250 parts by weight, the curing time is short, the usability time is short, the processability is not good, and the viscosity may be increased.
  • the first resin composition is not limited, but may be one having a viscosity of 1,000 to 3,000 cP (25 ° C.), preferably 1,500 to 2,500 cP (25 ° C.).
  • the thickness of the first protective layer may be 5 ⁇ 10 ⁇ m.
  • the second protective layer may be formed using a second resin composition containing a synthetic rubber and a solvent.
  • the solvent is not particularly limited as long as it can dissolve synthetic rubber, and specifically, for example, methylcyclohexane may be used.
  • the second resin composition may easily form a desired thickness in the range of 10 to 50% by weight, preferably 10 to 20% by weight of solid content.
  • the second protective layer in one embodiment, may be formed by inserting a film prepared by curing the second resin composition or by coating the upper portion of the metal barrier layer, and includes mechanical properties including thermal insulation and gas barrier properties. In order to improve this, it is preferable to apply
  • the synthetic rubber is styrene butadien rubber, styrene-butadiene-styrene block copolymer (SBS, Styrene-Butadiene-Styrene block copolymer), styrene-isoprene-styrene block copolymer (SIS, Styrene-Isoprene) -Styrene Block copolymer), Styrene-Ethylene-Butadiene-Styrene Block copolymer (SEBS), Ethylene propylene diene rubber (EPDM), Polychloroprene rubber ), Nitrile rubber (acrylonitrile-butadiene rubber), isoprene-isobutylene rubber, isadirene rubber, butadiene rubber, isoprene rubber, ethylene propylene rubber, polysulfide Any one or two selected from rubber (polysulfide rubber), silicone rubber (silicone rubber), flu
  • the second resin composition is not limited, the viscosity is preferably in the range of 100 to 200 cP (25 ° C.), more preferably 120 to 180 cP (25 ° C.), and the second resin composition may be It is possible to secure excellent moisture barrier properties by forming a coating on the metal layer.
  • the thickness of the second protective layer may be 1 ⁇ 5 ⁇ m.
  • the adhesive layer may be used to laminate the metal barrier layer and the heat seal layer. This may be formed by applying an adhesive or may be formed by laminating an adhesive film between the heat seal layer and the metal barrier layer, but is not limited thereto.
  • thermosetting adhesives such as polyester resin, urethane resin, acrylic resin, ether resin, phenol resin, furan resin, urea resin and melamine resin may be used alone or in combination of two or more kinds thereof. However, it is not necessarily limited thereto.
  • the adhesive layer may preferably have an interlayer adhesive strength of 400 gf / inch or more in order to prevent peeling.
  • the heat-sealing layer provides heat insulation at high temperature, and can be used to maintain the internal vacuum while simultaneously blocking gas.
  • the heat-sealing layer includes linear low density polyethylene, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, cyclic polyolefin, polypropylene, casting polypropylene, ethylene-vinyl acetate copolymer, ionomer A resin, an ethylene-ethyl acrylate copolymer, an ethylene-acrylic acid copolymer, an ethylene-methacrylic acid copolymer, and an ethylene-propylene copolymer can be used.
  • heat-sealing of the co-extrusion structure such as linear low density polyethylene resin layer (LLDPE) / ethylene vinyl alcohol resin layer (EVOH) / linear low density polyethylene resin layer (LLDPE), EVOH / LLDPE / EVOH or LLDPE / EVOH Film may be included.
  • the ethylene vinyl alcohol resin layer may increase the thickness to improve gas and moisture barrier properties, and may reduce the thickness of the linear low density polyethylene resin layer to control the thermal fusion temperature.
  • the thickness of the heat-sealing layer is not limited, but may be, for example, 10 ⁇ 100 ⁇ m, implements excellent heat insulating properties, gas and water blocking performance within the thickness range, improves the internal vacuum degree and excellent economy due to cost reduction .
  • the heat-sealing layer may be formed in a multi-layer, for example, a portion in contact with the blocking layer may use a modified polyolefin resin having excellent adhesion.
  • FIG. 1 to 4 show a cross-sectional view of the barrier film according to an embodiment of the present invention.
  • the first protective layer 310, the base film 100, the metal layer 210, and the second protective layer 320 are sequentially stacked from the top, and the second The adhesive layer 400 and the heat seal layer 500 may be stacked on one surface of the protective layer 320.
  • FIG. 2 Another embodiment is as shown in Figure 2, from the top of the base film 100, the metal layer 210, the first protective layer 310 and the second protective layer 320 of the metal blocking layer 200, the metal blocking layer
  • the adhesive layer 400 and the heat seal layer 500 may be stacked on one surface of the 200.
  • the adhesive layer 400 and the heat seal layer 500 may be stacked on one surface of the layer 200.
  • FIG. 4 Another embodiment is as shown in Figure 4, from the top of the base film 100, the first protective layer 310, the second protective layer 320 and the metal layer 210 of the metal layer 210, the metal blocking
  • the adhesive layer 400 and the heat seal layer 500 may be stacked on one surface of the layer 200.
  • the present invention can improve the thermal insulation performance and prevent the performance degradation caused by the pinholes due to the metal deposition due to the laminated structure as described above, and the mechanical properties of impact resistance, heat resistance, cold resistance, scratch resistance and flexibility There is an advantage that can provide a barrier film that can implement a synergistic effect.
  • the barrier film according to the present invention can prevent the heat bridge phenomenon by the metal layer, significantly reducing the use of the adhesive layer to block moisture and gas that can be introduced through the contact layer to prevent moisture barrier and gas There is an advantage to maximize the blocking.
  • Barrier film is water vapor transmission rate (WVTR) of less than 0.01g / m2 / day at 38 ⁇ 2 °C and 90 ⁇ 5% relative humidity, 0.001cc / m2 / at 23 ⁇ 2 °C It may be an Oxygen Transmission Rate (OTR) of less than one day.
  • WVTR water vapor transmission rate
  • OTR Oxygen Transmission Rate
  • the physical properties were measured by the following method.
  • Measuring range 0.1 to 145 g / (m 2 ⁇ day)
  • Synthetic rubber (LBR Chemical Co., NBR 3250) was prepared by adding water to a solid content of 30 wt%.
  • Polyurethane adhesive resin (Gangnam Hwaseong Co., Ltd. 338S) and hardener (Gangnam Hwaseong Co., Ltd. CL-100) were mixed with ethyl acetate in a 10: 1 weight ratio to prepare a solid content of 33% by weight.
  • a 12 ⁇ m thick urethane primer-treated polyethylene terephthalate film (Kolon Industries, Inc., CD311) was prepared as a base film.
  • Aluminum was deposited to a thickness of 50 nm on the urethane primer layer of the base film. After deposition, it was aged for 6 hours at room temperature. After coating the first protective layer composition prepared in Preparation Example 1 on the opposite side of the aluminum deposition surface using a gravure coater, and dried at 80 °C to form a first protective layer. The thickness was 2 micrometers. Thereafter, the second protective layer composition prepared in Preparation Example 2 was coated on the aluminum deposition surface by using a gravure coater, and then dried at 80 ° C.
  • first protective layer / PET / Al / second protective layer / adhesive layer / LLDPE was manufactured by laminating with an LLDPE film (Daewon, B002, 50 ⁇ m thick).
  • the base film was prepared from the 12-micrometer-thick urethane primer-treated polyethylene terephthalate film (Kolon Industries, Inc., CD311). Aluminum was deposited to a thickness of 50 nm on the urethane primer layer of the base film. After deposition, it was aged for 6 hours at room temperature.
  • the first protective layer composition prepared in Preparation Example 1 was coated on the aluminum deposition surface using a gravure coater, and then dried at 80 ° C. to form a first protective layer. The thickness was 2 micrometers. Thereafter, the second protective layer composition prepared in Preparation Example 2 was coated on the upper surface of the first protective layer using a gravure coater, and then dried at 80 ° C.
  • the adhesive layer composition prepared in Preparation Example 3 was coated on the upper surface of the metal barrier layer using a gravure coater and dried at 120 ° C. The thickness of the said contact bonding layer was 2 micrometers. Thereafter, the film for lamination (PET / Al layer / first protective layer / second protective layer / adhesive layer / LLDPE) was prepared by laminating with an LLDPE film (Daewon, B002, 50 ⁇ m thick).
  • the base film was prepared from the 12-micrometer-thick urethane primer-treated polyethylene terephthalate film (Kolon Industries, Inc., CD311).
  • the second protective layer composition prepared in Preparation Example 2 was coated on one surface of the base film using a gravure coater, and then dried at 80 ° C. to form a second protective layer.
  • the thickness of the said 2nd protective layer was 2 micrometers.
  • Aluminum was deposited to a thickness of 50 nm on the upper surface of the second protective layer. After deposition, it was aged for 6 hours at room temperature.
  • the first protective layer composition prepared in Preparation Example 1 was coated on the aluminum deposition surface using a gravure coater, and then dried at 80 ° C. to form a first protective layer.
  • the thickness of the said 1st protective layer was 2 micrometers.
  • a metal blocking layer formed of the second protective layer, the metal layer and the first protective layer was formed on the base film.
  • the adhesive layer composition prepared in Preparation Example 3 was coated on the upper surface of the metal barrier layer using a gravure coater and dried at 120 ° C. The thickness of the said contact bonding layer was 2 micrometers. Thereafter, the film for lamination (PET / second protective layer / Al layer / first protective layer / adhesive layer / LLDPE) was manufactured by laminating with an LLDPE film (Daewon, B002, 50 ⁇ m thick).
  • the base film was prepared from the 12-micrometer-thick urethane primer-treated polyethylene terephthalate film (Kolon Industries, Inc., CD311).
  • the first protective layer composition prepared in Preparation Example 1 was coated on one surface of the base film using a gravure coater, and then dried at 80 ° C. to form a first protective layer.
  • the thickness of the said 1st protective layer was 2 micrometers.
  • the second protective layer composition prepared in Preparation Example 2 was coated on the upper surface of the first protective layer using a gravure coater, and then dried at 80 ° C. to form a second protective layer.
  • the thickness of the said 2nd protective layer was 2 micrometers.
  • Aluminum was deposited to a thickness of 50 nm on the upper surface of the second protective layer.
  • a metal blocking layer including a first protective layer, a second protective layer, and a metal layer was formed on the base film.
  • the adhesive layer composition prepared in Preparation Example 3 was coated on the upper surface of the metal barrier layer using a gravure coater and dried at 120 ° C. The thickness of the said contact bonding layer was 2 micrometers. Thereafter, the film for lamination (PET / first protective layer / second protective layer / Al layer / adhesive layer / LLDPE) was prepared by laminating with an LLDPE film (Daewon, B002, thickness of 50 ⁇ m).
  • the base film was prepared from the 12-micrometer-thick urethane primer-treated polyethylene terephthalate film (Kolon Industries, Inc., CD311). Aluminum was deposited to a thickness of 50 nm on the urethane primer layer of the base film. After deposition, it was aged for 6 hours at room temperature.
  • the adhesive composition prepared in Preparation Example 3 was coated on the aluminum deposition surface using a gravure coater, and dried at 80 ° C. (the thickness of the adhesive layer was 2 ⁇ m.). Was deposited to a thickness of 50 nm. After deposition, it was aged for 6 hours at room temperature. Thereafter, a 12 ⁇ m-thick urethane primer-treated polyethylene terephthalate film was laminated on the deposition surface.
  • the adhesive composition prepared in Preparation Example 3 was coated on the upper surface of the polyethylene terephthalate film using a gravure coater, and dried at 80 ° C. (the thickness of the adhesive layer was 2 ⁇ m). Aluminum was deposited to a thickness of 50 nm. After deposition, it was aged for 6 hours at room temperature. Thereafter, a 12 ⁇ m thick urethane primer-treated polyethylene terephthalate film was laminated.
  • the adhesive composition prepared in Preparation Example 3 was coated on the upper surface of the polyethylene terephthalate film using a gravure coater, dried at 80 ° C. (the thickness of the adhesive layer was 2 ⁇ m), and an LLDPE film.
  • a barrier film (PET / Al layer / adhesive layer / Al layer / PET / adhesive layer / Al layer / PET / adhesive layer / LLDPE) was produced by laminating with Industry, B002, 50 ⁇ m thick.
  • the base film was prepared from the 12-micrometer-thick urethane primer-treated polyethylene terephthalate film (Kolon Industries, Inc., CD311). Aluminum was deposited to a thickness of 50 nm on the urethane primer layer of the base film. After deposition, it was aged for 6 hours at room temperature.
  • the first protective layer composition prepared in Preparation Example 1 was coated on the aluminum deposition surface using a gravure coater, and then dried at 80 ° C. to form a first protective layer. The thickness of the said 1st protective layer was 2 micrometers.
  • the adhesive composition prepared in Preparation Example 3 was coated on the upper surface of the first protective layer using a gravure coater, dried at 80 ° C.
  • the thickness of the adhesive layer was 2 ⁇ m
  • aluminum was deposited to a thickness of 50 nm. It was. After deposition, it was aged for 24 hours at room temperature. Next, a 12 ⁇ m thick urethane primer-treated polyethylene terephthalate film was laminated on the aluminum deposition surface.
  • the adhesive composition prepared in Preparation Example 3 was coated on the upper surface of the polyethylene terephthalate film using a gravure coater, dried at 80 ° C. (the thickness of the adhesive layer was 2 ⁇ m), and Preparation Example 2
  • the second protective layer composition prepared in the above was coated using a gravure coater and dried at 80 ° C. to form a second protective layer. The thickness of the said 2nd protective layer was 2 micrometers.
  • Examples 1 to 4 according to the present invention was confirmed that the excellent oxygen and moisture barrier properties.
  • the mechanical properties of the embodiments according to the present invention having a base film having a metal layer formed on one surface thereof were similar to each other. As a result, it was confirmed that the blocking property and the mechanical property synergy effect could be realized.
  • Comparative Examples 1 and 2 may increase the thermal conductivity generated from a multi-layered aluminum layer as the number of aluminum layers to three layers, the film according to the embodiment can significantly reduce the thermal conductivity made of a single layer of aluminum, Accordingly, there is an effect to prevent thermal bridge phenomenon.
  • the embodiments according to the present invention although the aluminum layer on the base film is formed as a single layer, the mechanical properties such as tensile strength and elongation are formed in a multi-layered to a similar level compared to the comparative examples having a high thickness Implemented physical properties, and at the same time it was confirmed that the oxygen and water barrier properties are excellent.

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Abstract

The present invention relates to a barrier film and, more specifically, to a barrier film having excellent durability and long-term stability in a high-temperature and high-humidity environment and excellent heat-insulating properties, gas barrier properties and water barrier properties.

Description

배리어용 필름Barrier Film
본 발명은 배리어용 필름에 관한 것이다. 보다 상세하게는 고온 다습의 환경에서 내구성 및 장기 안정성이 뛰어나며, 단열성, 가스차단성 및 수분차단성이 우수한 배리어용 필름에 관한 것이다.The present invention relates to a barrier film. More specifically, the present invention relates to a barrier film having excellent durability and long-term stability in an environment of high temperature and high humidity, and having excellent heat insulating property, gas barrier property, and water barrier property.
진공 단열재는 내부를 진공 처리함으로써 단열재 내부의 대류 현상을 차단시켜 우수한 단열성능을 나타내는 소재이다. 이러한 진공 단열재는 유리섬유 또는 실리카로 된 패널이 적층되고 그 사이에 진공으로 형성되는 코어재와 상기 코어재의 진공을 유지하기 위하여 코어재를 감싸서 밀봉하는 밀봉부재를 포함하여 이루어진다. 상기 밀봉부재는 통상 알루미늄 호일과 고분자 필름이 적층된 다층 필름 구조를 가지며, 내부 고진공과 외부 대기압을 1차적으로 차단하는 기능을 수행하여 진공 단열재 내부의 고진공 상태를 유지시킴으로써 진공 단열재의 장기 신뢰성을 확보할 수 있다. Vacuum insulation is a material that exhibits excellent insulation performance by blocking the convection phenomenon inside the insulation by vacuuming the interior. The vacuum insulation material includes a core material in which a panel made of glass fibers or silica is laminated and vacuumed therebetween, and a sealing member that encloses and seals the core material to maintain the vacuum of the core material. The sealing member usually has a multilayer film structure in which aluminum foil and a polymer film are laminated, and performs a function of primarily blocking internal high vacuum and external atmospheric pressure to maintain a high vacuum state inside the vacuum insulator, thereby ensuring long-term reliability of the vacuum insulator. can do.
밀봉부재는 일반적으로 보호층, 차단층 및 열융착층으로 이루어진다. 보호층으로는 나일론(Nylon)이나 폴리에틸렌 테레프탈레이트(Polyethylene Terephthalate, PET)를, 차단층으로는 알루미늄 (Aluminum) 금속을, 열융착층으로는 폴리에틸렌(Polyethylene)을 사용하여 단열 성능을 발현하고, 습기와 가스의 침투를 방지할 수 있다. The sealing member generally consists of a protective layer, a blocking layer and a heat seal layer. Insulation performance is achieved by using nylon or polyethylene terephthalate (PET) as the protective layer, aluminum metal as the barrier layer, and polyethylene (polyethylene) as the heat-sealing layer. The ingress of gas and gas can be prevented.
이러한 밀봉부재는 제품의 이송이나 적용 시 외부 충격에 쉽게 크랙이 발생할 수 있으며, 이러한 크랙으로 단열성능 및 가스 및 수분 차단성이 저하될 수 있다.Such a sealing member may easily cause cracks in external impacts when the product is transported or applied, and such cracks may lower heat insulation performance and gas and moisture barrier properties.
한국공개특허 제2012-0033165호에는 알루미늄 호일을 폴리이미드 필름에 적층한 냉장고용 진공 단열재가 개시되어 있다. 상기 진공 단열재는 고온에서의 장기 내구성을 높일 수 있으나, 단열 성능 및 가스 차단성 개선 효과가 미미하며, 크랙 발생에 따른 물성이 저하될 수 있다. 이는 고분자 필름 상에 알루미늄과 같은 금속을 코팅 시 다량의 핀홀이 발생되거나, 금속 적층에 따른 기계적 물성이 저하되기 때문이다. Korean Laid-Open Patent No. 2012-0033165 discloses a vacuum insulator for a refrigerator in which aluminum foil is laminated on a polyimide film. The vacuum insulator can increase the long-term durability at high temperature, but the effect of improving the thermal insulation performance and gas barrier properties is insignificant, and physical properties due to cracks may be reduced. This is because a large amount of pinholes are generated when the metal such as aluminum is coated on the polymer film, or mechanical properties due to metal lamination are reduced.
따라서, 외부 충격에 의한 기계적 물성이 저하되지 않으면서 단열 성능뿐만 아니라 가스 및 수분 차단성을 높일 수 있으며, 특히, 고분자 필름 상에 금속 증착 시 발생할 수 있는 핀홀을 방지할 수 있는 배리어용 필름에 대한 연구 개발이 필요한 실정이다.Therefore, it is possible to increase not only thermal insulation performance but also gas and moisture barrier properties without deteriorating mechanical properties due to external impact, and in particular, for barrier films that can prevent pinholes that may occur during metal deposition on polymer films. Research and development is needed.
본 발명은 상기와 같은 문제점을 해결하기 위하여 안출된 것으로서, 단열 성능을 향상시키고, 금속 증착에 따른 핀홀 발생으로 인한 성능 저하를 방지할 수 있으며, 우수한 기계적 물성을 갖고 있어 내구성 및 장기 신뢰성을 확보할 수 있는 배리어용 필름을 제공하는 것을 목적으로 한다.The present invention has been made to solve the above problems, it is possible to improve the thermal insulation performance, to prevent the performance degradation due to the generation of pinholes due to metal deposition, and to have excellent mechanical properties to ensure durability and long-term reliability An object of the present invention is to provide a barrier film.
또한, 본 발명은 금속 증착으로 형성된 금속층이 다층으로 구비 시 발생할 수 있는 열교(heat bridge) 현상을 방지하는 것과 동시에 수분 차단성 및 가스 차단성을 향상시킬 수 있는 배리어용 필름을 제공하는 것을 목적으로 한다.In addition, an object of the present invention is to provide a barrier film that can prevent the heat bridge phenomenon that can occur when the metal layer formed by metal deposition is provided in a multi-layer, and at the same time improve the moisture barrier properties and gas barrier properties. do.
상기와 같은 목적을 달성하기 위하여, 본 발명은 기재필름, 상기 기재필름 상에 금속층, 제1 보호층 및 제2 보호층을 적층한 금속차단층을 포함하며, 상기 금속차단층의 상부에 접착층 및 열융착층을 순차적으로 적층하되,In order to achieve the above object, the present invention includes a base film, a metal barrier layer on which a metal layer, a first protective layer and a second protective layer are laminated on the base film, the adhesive layer and the upper portion of the metal barrier layer; Laminating the heat seal layer in sequence,
기재필름의 일면에 형성된 금속층 또는 상기 금속층의 반대면의 기재필름 상에 제1 보호층 및 제2 보호층 중에서 선택된 어느 하나 층을 일층 또는 다층으로 적층하며, 상기 일면에 금속층을 형성한 기재필름을 단층으로 구비하는 것을 특징으로 하는 배리어용 필름을 제공한다. A base film having a metal layer formed on one surface of the metal layer formed on one surface of the base film or the base film on the opposite side of the metal layer by laminating any one selected from the first protective layer and the second protective layer in one layer or multiple layers. It is provided with a single layer, The film for barriers characterized by the above-mentioned.
본 발명의 일 실시예에 따른 배리어용 필름에 있어서, 제 1 보호층은 에폭시수지, 경화제 및 용매를 포함하는 제 1 수지 조성물을 코팅 및 건조하여 형성한 것이고, 제 2 보호층은 합성고무와 용매를 포함하는 제 2 수지 조성물을 코팅 및 건조하여 형성한 것일 수 있다.In the barrier film according to an embodiment of the present invention, the first protective layer is formed by coating and drying a first resin composition comprising an epoxy resin, a curing agent, and a solvent, and the second protective layer is a synthetic rubber and a solvent. It may be formed by coating and drying a second resin composition comprising a.
본 발명의 일 실시예에 따른 배리어용 필름에 있어서, 에폭시수지는 비스페놀 A형 에폭시 수지, 비스페놀 F형 에폭시 수지, 노볼락형 에폭시 수지, 고리지방족 에폭시 수지, 다관능형 아민 에폭시 수지, 글리시딜아민형 에폭시 수지, 다이머산 변성 에폭시 수지, 고무 변성 에폭시 수지, 우레탄 변성 에폭시 수지, 브롬화 에폭시 수지, 브롬화 페녹시 에폭시 수지,하이드리지네이티드 비스페놀 A형 에폭시 수지 및 폴리올 변성 에폭시 수지로 이루어진 군으로부터 선택되는 어느 하나 또는 둘 이상을 포함할 수 있다.In the barrier film according to an embodiment of the present invention, the epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, cycloaliphatic epoxy resin, polyfunctional amine epoxy resin, glycidylamine Type epoxy resin, dimer acid modified epoxy resin, rubber modified epoxy resin, urethane modified epoxy resin, brominated epoxy resin, brominated phenoxy epoxy resin, hydrated bisphenol A type epoxy resin and polyol modified epoxy resin It may include any one or more than two.
본 발명의 일 실시예에 따른 배리어용 필름에 있어서, 경화제는 지방족 아민, 변성 아민, 방향족 아민, 3급 아민 및 폴리아민계 화합물로 이루어진 군으로부터 선택되는 어느 하나 또는 둘 이상의 아민계 경화제를 포함할 수 있다.In the barrier film according to an embodiment of the present invention, the curing agent may include any one or two or more amine curing agents selected from the group consisting of aliphatic amines, modified amines, aromatic amines, tertiary amines and polyamine-based compounds. have.
본 발명의 일 실시예에 따른 배리어용 필름에 있어서, 경화제는 에폭시계 수지 100중량부에 대하여 70 ~ 250중량부 포함될 수 있다.In the barrier film according to an embodiment of the present invention, the curing agent may be included 70 to 250 parts by weight based on 100 parts by weight of the epoxy resin.
본 발명의 일 실시예에 따른 배리어용 필름에 있어서, 합성고무는 스티렌-부타디엔고무(styrene butadien rubber), 폴리클로로프렌고무(polychloroprene rubber), 니트릴고무(acrylonitrile-butadiene rubber), 부틸고무(isoprene-isobutylene rubber), 부타디엔고무(butadiene rubber), 이소프렌고무(isoprene rubber), 에틸렌프로필렌고무(ethylene propylene rubber), 다황화물계 고무(polysulfide rubber), 실리콘고무(silicone rubber), 플루오로고무(fluororubber), 우레탄고무(urethane rubber), 아크릴고무(acrylic rubber)에서 선택되는 어느 하나 또는 둘 이상을 포함할 수 있다.In the barrier film according to an embodiment of the present invention, the synthetic rubber is styrene-butadien rubber (styrene butadien rubber), polychloroprene rubber (polychloroprene rubber), nitrile rubber (acrylonitrile-butadiene rubber), butyl rubber (isoprene-isobutylene rubber, butadiene rubber, isoprene rubber, ethylene propylene rubber, polysulfide rubber, silicone rubber, fluororubber, urethane It may include any one or two or more selected from rubber (urethane rubber), acrylic rubber (acrylic rubber).
본 발명의 일 실시예에 따른 배리어용 필름에 있어서, 기재필름은 두께가 1 ~ 200㎛이고, 열가소성 고분자 필름으로 이루어질 수 있다.In the barrier film according to an embodiment of the present invention, the base film has a thickness of 1 ~ 200㎛, may be made of a thermoplastic polymer film.
본 발명의 일 실시예에 따른 배리어용 필름에 있어서, 금속층은 금속 산화물을 증착하여 형성된 것으로, 두께가 100nm이하, 바람직하게는 20 ~ 50nm일 수 있다. In the barrier film according to an embodiment of the present invention, the metal layer is formed by depositing a metal oxide, the thickness may be less than 100nm, preferably 20 to 50nm.
본 발명의 일 실시예에 따른 배리어용 필름에 있어서, 제 1 보호층은 건조도포두께가 1 ~ 10㎛이고, 제 2 보호층은 건조도포두께가 1 ~ 5㎛일 수 있다. In the barrier film according to an embodiment of the present invention, the first protective layer may have a dry coating thickness of 1 to 10 μm, and the second protective layer may have a dry coating thickness of 1 to 5 μm.
본 발명의 일 실시예에 따른 배리어용 필름은 38± 2℃ 및 90± 5% 상대 습도에서 0.01g/㎡/day 이하의 WVTR(Water vapor transmission rate), 23± 2℃에서 0.001cc/㎡/day 이하의 OTR(Oxygen Transmission Rate)일 수 있다.Barrier film according to an embodiment of the present invention is water vapor transmission rate (WVTR) of less than 0.01g / ㎡ / day at 38 ± 2 ℃ and 90 ± 5% relative humidity, 0.001cc / ㎡ / at 23 ± 2 ℃ It may be an Oxygen Transmission Rate (OTR) of less than one day.
본 발명에 따른 배리어용 필름은 단열 성능을 향상시키는 것과 동시에 금속 증착에 따른 핀홀 발생에 따른 성능 저하를 방지하고, 내충격성, 내열성, 내한성, 내스크래치성 및 유연성의 기계적 물성의 상승효과를 나타낼 수 있는 장점이 있다. The barrier film according to the present invention can improve the thermal insulation performance and at the same time prevent the performance degradation caused by the pinhole generation due to metal deposition, and exhibit a synergistic effect of mechanical properties of impact resistance, heat resistance, cold resistance, scratch resistance and flexibility. There is an advantage.
또한, 본 발명은 금속층에 의한 열교(heat bridge) 현상을 방지할 수 있으며, 수분 차단성 및 가스 차단성을 획기적으로 향상시킬 수 있는 장점이 있다. In addition, the present invention can prevent the heat bridge (heat bridge) phenomenon by the metal layer, there is an advantage that can significantly improve the moisture barrier properties and gas barrier properties.
또한, 우수한 기계적 물성 및 장기 내구성으로 제품의 신뢰성을 확보할 수 있는 장점이 있다.In addition, there is an advantage that can ensure the reliability of the product with excellent mechanical properties and long-term durability.
도 1 내지 3은 본 발명의 일 실시예에 따른 배리어용 필름의 단면도를 나타낸 것이다.1 to 3 show a cross-sectional view of the barrier film according to an embodiment of the present invention.
(부호의 설명)(Explanation of the sign)
100 : 기재필름, 200 : 금속차단층, 210 : 금속층, 310 : 제1 보호층100: base film, 200: metal blocking layer, 210: metal layer, 310: first protective layer
320 : 제2 보호층, 400 : 접착층, 500 : 열융착층320: second protective layer, 400: adhesive layer, 500: heat seal layer
이하 본 발명의 배리어용 필름을 상세히 설명한다. 다음에 소개되는 실시예들은 당업자에게 본 발명의 사상이 충분히 전달될 수 있도록 하기 위해 예로서 제공되는 것이다. 또한, 사용되는 기술 용어 및 과학 용어에 있어서 다른 정의가 없다면, 이 발명이 속하는 기술 분야에서 통상의 지식을 가진 자가 통상적으로 이해하고 있는 의미를 가지며, 하기의 설명 및 첨부 도면에서 본 발명의 요지를 불필요하게 흐릴 수 있는 공지 기능 및 구성에 대한 설명은 생략한다.Hereinafter, the barrier film of the present invention will be described in detail. The following embodiments are provided as examples to ensure that the spirit of the present invention can be fully conveyed to those skilled in the art. In addition, if there is no other definition in the technical terms and scientific terms used, it has a meaning commonly understood by those of ordinary skill in the art to which this invention belongs, and the gist of the present invention in the following description and the accompanying drawings. Descriptions of well-known functions and configurations that may be unnecessarily blurred are omitted.
본 발명에 따른 배리어용 필름은 기재필름, 상기 기재필름 상에 금속층, 제1 보호층 및 제2 보호층을 적층한 금속차단층을 포함하며, 상기 금속차단층의 상부에 접착층 및 열융착층을 순차적으로 적층하되,The barrier film according to the present invention includes a base film, a metal barrier layer in which a metal layer, a first protective layer and a second protective layer are laminated on the base film, and an adhesive layer and a heat seal layer on the metal barrier layer. Stack them sequentially,
기재필름의 일면에 형성된 금속층 또는 상기 금속층의 반대면의 기재필름 상에 제1 보호층 및 제2 보호층 중에서 선택된 어느 하나 층을 일층 또는 다층으로 적층하며, 상기 일면에 금속층을 형성한 기재필름을 단층으로 구비하는 것을 특징으로 한다. A base film having a metal layer formed on one surface of the metal layer formed on one surface of the base film or the base film on the opposite side of the metal layer by laminating any one selected from the first protective layer and the second protective layer in one layer or multiple layers. It is characterized by comprising a single layer.
이하, 각 구성성분에 대하여 상세히 설명한다.Hereinafter, each component is demonstrated in detail.
(1) 기재필름(1) base film
상기 기재필름은 열가소성 고분자 필름을 사용할 수 있으며, 반드시 이에 한정되지 않는다. 상기 기재필름의 바람직한 일예로, 에틸렌, 프로필렌, 부텐 등의 단독 중합체 또는 공중합체 등의 폴리올레핀, 고리형 폴리올레핀 등의 비정질 폴리올레핀, 폴리에틸렌테레프탈레이트, 폴리에틸렌-2,6-나프탈레이트 등의 폴리에스테르, 나일론 6, 나일론 66, 나일론 12, 공중합 나일론 등의 폴리아미드, 에틸렌-아세트산비닐 공중합체 부분 가수 분해물 (EVOH), 폴리이미드, 폴리에테르이미드, 폴리설폰, 폴리에테르설폰, 폴리에테르에테르케톤, 폴리카보네이트, 폴리비닐부티랄, 폴리아릴레이트, 불소 수지, 아크릴레이트 수지, 생분해성 수지 등을 들 수 있다. 이들 중에서 물성 및 비용 등을 고려하여 보다 바람직하게는 폴리카보네이트, 폴리이미드, 나일론, 폴리에틸렌나프탈레이트 및 폴리에틸렌테레프탈레이트 중에서 선택되는 어느 하나 이상의 고분자 필름을 사용할 수 있다.The base film may be a thermoplastic polymer film, but is not necessarily limited thereto. As a preferable example of the base film, polyolefins such as homopolymers or copolymers such as ethylene, propylene, butene, amorphous polyolefins such as cyclic polyolefins, polyesters such as polyethylene terephthalate, polyethylene-2,6-naphthalate, and nylon 6, nylon 66, nylon 12, polyamides such as copolymerized nylon, ethylene-vinyl acetate copolymer partial hydrolyzate (EVOH), polyimide, polyetherimide, polysulfone, polyethersulfone, polyetheretherketone, polycarbonate, Polyvinyl butyral, polyarylate, fluorine resin, acrylate resin, biodegradable resin and the like. Among these, any one or more polymer films selected from polycarbonate, polyimide, nylon, polyethylene naphthalate, and polyethylene terephthalate may be used in consideration of physical properties and cost.
상기 기재필름은 금속층과의 접착력을 향상시키기 위하여 우레탄계 화합물, 아크릴계 화합물 및 에스테르 화합물 중에서 선택되는 프라이머로 처리하거나 코로나 처리한 것을 사용하면 더욱 좋다. The base film may be further treated with a primer selected from a urethane-based compound, an acrylic compound, and an ester compound or a corona treatment in order to improve adhesion to the metal layer.
상기 기재필름은 공지된 방법으로 제조된 것일 수 있다. 예를 들어, 원료 수지를 압출기에 의해 용융하고, 고리형 다이나 T 다이에 의해 압출하여, 급냉시킴으로써 무정형으로 배향되지 않은 미연신 필름으로 제조될 수 있다. 또한, 일축 또는 이축으로 배향 연신된 필름으로 제조된 것일 수 있으며, 이에 제한되는 것은 아니다. 또한, 다층 다이를 사용하여, 1 종의 수지로 이루어지는 단층 필름, 1 종의 수지로 이루어지는 다층 필름, 다종의 수지로 이루어지는 다층 필름으로 제조될 수 있다. The base film may be prepared by a known method. For example, the raw resin may be melted by an extruder, extruded by a cyclic die or T die, and quenched into a non-oriented film that is not oriented amorphous. In addition, it may be made of a film oriented or uniaxially or biaxially, but is not limited thereto. Moreover, using a multilayer die, it can be manufactured from the single | mono layer film which consists of 1 type of resin, the multilayer film which consists of 1 type of resin, and the multilayer film which consists of multiple types of resin.
상기 기재필름은 필요에 따라 대전 방지제, 광선 차단제, 자외선 흡수제, 가소제, 활제, 필러, 착색제, 안정제, 윤활제, 가교제, 블로킹 방지제, 산화 방지제 등의 첨가제를 포함한 것을 사용할 수 있으며, 이에 제한되지는 않는다. The base film may include additives such as antistatic agents, light blocking agents, ultraviolet absorbers, plasticizers, lubricants, fillers, colorants, stabilizers, lubricants, crosslinking agents, antiblocking agents, antioxidants, and the like, but are not limited thereto. .
본 발명에서 기재필름의 두께는 제한되지는 않지만 1 ~ 200㎛일 수 있으며, 단열 성능, 기계적 물성과 동시에 가스 및 수분 차단성능 등의 면에서 바람직하게는 5 ~ 50㎛일 수 있다. 또한, 가공성 및 작업성을 위하여 보다 바람직하게는 10 ~ 15㎛인 것을 사용할 수 있다. The thickness of the base film in the present invention is not limited, but may be 1 ~ 200㎛, preferably 5 ~ 50㎛ in terms of heat insulating performance, mechanical properties and gas and moisture barrier performance. In addition, for the workability and workability, more preferably 10 to 15 μm can be used.
(2) 금속차단층(2) metal barrier layer
본 발명에서 금속차단층은 기재필름 상에 형성된다. 상기 금속차단층은 금속층, 제1 보호층 및 제2 보호층을 포함하여 이들 적층체로 이루어진다. 본 발명에서 상기 금속차단층이 기재필름 상에 형성된다는 것은 기재필름 일면에 금속차단층의 구성성분인 금속층이 적층되고, 금속층이 적층된 다른 일면에 제1 보호층 및 제2 보호층이 적층되거나, 상기 금속층 상부에 제1 보호층 또는 제2 보호층이 적층되고, 다른 일면에 제1 보호층 또는 제2 보호층이 적층되는 것을 의미하는 것으로, 기재필름에서부터 순차적으로 상기 구성성분을 적층한다는 것을 의미하는 것으로 제한하여 의미하는 것은 아니다. In the present invention, the metal barrier layer is formed on the base film. The metal blocking layer is composed of these laminates including a metal layer, a first protective layer and a second protective layer. In the present invention, the metal blocking layer is formed on the base film, wherein a metal layer which is a constituent of the metal blocking layer is laminated on one surface of the base film, and the first protective layer and the second protective layer are laminated on the other surface where the metal layer is laminated. The first protective layer or the second protective layer is laminated on the metal layer, and the first protective layer or the second protective layer is laminated on the other surface, which means that the components are sequentially laminated from the base film. It is not meant to mean limited.
상기 금속층은 금속 산화물을 증착하여 형성된 것으로, 산소 및 수증기와 같은 가스를 차단하며, 내부 진공도를 유지할 수 있도록 한다. 이는 다른 구성성분과의 조합으로 가스 차단성 및 수분 차단성뿐만 아니라 내충격성, 내열성, 내한성, 내스크래치성 및 유연성의 상승효과를 나타낼 수 있다. The metal layer is formed by depositing a metal oxide to block gases such as oxygen and water vapor, and to maintain an internal vacuum degree. It can exhibit a synergistic effect of impact resistance, heat resistance, cold resistance, scratch resistance and flexibility as well as gas barrier properties and water barrier properties in combination with other components.
본 발명에 따른 금속차단층은 둘 이상의 금속층을 포함할 경우 발생할 수 있는 열교(heat bridge) 현상으로 인한 물성 저하를 방지하기 위해서 금속층을 한층만 구비하는 것을 특징으로 한다. 이때, 상기 금속층은 제1 보호층 및 제2 보호층과 순서에 관계없이 적층되어 상기와 같은 효과를 구현할 수 있다. The metal barrier layer according to the present invention is characterized by including only one layer of the metal layer in order to prevent physical property degradation due to heat bridge phenomenon that may occur when it includes two or more metal layers. In this case, the metal layer may be laminated regardless of the order of the first protective layer and the second protective layer to implement the above effects.
상기 금속차단층의 바람직한 일 양태는 기재필름 상에, 금속층, 제1 보호층 및 제2 보호층이 순차적으로 적층되거나, 제1 보호층, 제2 보호층 및 금속층이 순차적으로 적층되거나 제2보호층, 금속층 및 제1 보호층이 순차적으로 적층된 것일 수 있다. According to one preferred aspect of the metal blocking layer, a metal layer, a first protective layer and a second protective layer are sequentially stacked on the base film, or a first protective layer, the second protective layer and the metal layer are sequentially stacked or the second protective layer. The layer, the metal layer, and the first protective layer may be sequentially stacked.
이때, 금속층은 제한되지는 않지만 바람직하게는 알루미늄 호일(aluminum foil)을 사용할 수 있다. 더욱 좋게는 알루미늄 산화물(AlOx , x= 2 ~3), 실리카 산화물(SiOx , x= 2 ~ 3) 등의 금속 산화물을 기재필름 상에 증착하여 형성할 수 있다. 또는 필요에 따라 증착 폴리에틸렌테레프탈레이트, 에틸렌비닐알콜과 같은 소재를 사용하여 금속을 대체할 수 있으며, 금속층과 동시에 사용할 수 있다. At this time, the metal layer is not limited but may preferably use aluminum foil. More preferably, metal oxides such as aluminum oxide (AlO x , x = 2 to 3) and silica oxide (SiO x , x = 2 to 3) may be formed by depositing on a base film. Alternatively, if necessary, a material such as evaporated polyethylene terephthalate or ethylene vinyl alcohol may be used to replace the metal, and may be used simultaneously with the metal layer.
상기 금속층의 두께는 100nm이하, 바람직하게는 20 ~ 50nm일 수 있다. 가스 및 수분 차단 성능면에서 40 ~ 50nm의 두께인 것이 더욱 좋다. 상기 금속층의 두께가 상기 범위를 초과하면 열주름 등 필름이 손상될 우려가 있다. The thickness of the metal layer may be 100 nm or less, preferably 20 to 50 nm. In terms of gas and moisture barrier performance, the thickness is more preferably 40 to 50 nm. If the thickness of the metal layer exceeds the above range, there is a fear that the film such as heat wrinkles.
(3) 보호층(3) protective layer
본 발명에서 금속차단층은 금속층과 보호층의 조합으로 이루어지며, 상기 보호층은 단열 성능 또는 가스 및 수분 차단 성능의 상승 효과를 구현하기 위하여 바람직하게는 제1 보호층 및 제2 보호층을 포함하는 것이 좋다. 또한, 제1 보호층 및 제2 보호층을 포함하는 경우, 기재필름 상에 금속 증착 시 발생할 수 있는 핀홀에 의한 단열 또는 차단 성능 저하를 방지할 수 있으며, 열융착층과 조합하는 경우 필름의 기계적 물성을 향상시킬 수 있어 더욱 좋다.In the present invention, the metal barrier layer is formed of a combination of a metal layer and a protective layer, and the protective layer preferably includes a first protective layer and a second protective layer in order to implement a synergy effect of thermal insulation performance or gas and moisture blocking performance. Good to do. In addition, in the case of including the first protective layer and the second protective layer, it is possible to prevent the thermal insulation or blocking performance deterioration due to the pinholes that may occur when the metal deposition on the base film, and when combined with the heat-sealing layer of the film mechanical The physical properties can be improved, which is better.
본 발명에서 보호층은 단열 및 차단 성능의 상승 효과를 위하여 더욱 바람직한 양태로 가스 차단성을 갖는 수지를 포함하는 제 1 보호층 및 수분 차단성을 갖는 수지를 포함하는 제 2 보호층을 포함할 수 있으며, 이에 제한되지는 않는다. 또한, 상기 제1 보호층 및 제2 보호층은 금속층과의 순서에 제한없이 적층될 수 있으며, 적층되는 보호층은 수는 제한되지는 않는다. In the present invention, the protective layer may include a first protective layer including a resin having a gas barrier property and a second protective layer including a resin having a moisture barrier property in a more preferred embodiment for the synergistic effect of the heat insulating and blocking performance. It is not limited thereto. In addition, the first protective layer and the second protective layer may be laminated without restriction in the order with the metal layer, the number of the protective layer is not limited.
상기 제1 보호층 및 제2보호층은 두께가 두꺼워질수록, 각 보호층의 개수가 증가할수록 단열 및 가스 차단 성능을 상승시킬 수 있다. 바람직하게는 상기 제 1 보호층은 건조도포두께가 1 ~ 10㎛인 것이 좋고, 더욱 좋게는 1~ 2㎛인 것이 내구성, 내충격성, 내열성, 내한성, 내스크래치성 및 유연성의 기계적 물성 상승면에서 선호된다. 이와 동시에 제 2 보호층은 건조도포두께가 1 ~ 5㎛, 더욱 좋게는 1~ 2㎛인 범위를 만족하는 경우 본 발명에서 목적으로 하는 수분차단성 및 가스차단성 향상을 구현할 수 있다. 본 발명에서 보다 바람직한 일 양태로 제1 보호층 및 제2 보호층이 상기 두께 범위를 만족하면서 단층인 경우 더욱 목적하는 효과의 우수성을 구현할 수 있다. As the thickness of the first protective layer and the second protective layer increases, and as the number of each protective layer increases, the insulation and gas barrier performance may be increased. Preferably, the first protective layer has a dry coating thickness of 1 to 10 μm, more preferably 1 to 2 μm in terms of increasing mechanical properties of durability, impact resistance, heat resistance, cold resistance, scratch resistance, and flexibility. Is preferred. At the same time, when the second protective layer satisfies the dry coating thickness of 1 to 5 μm, more preferably 1 to 2 μm, the water barrier property and the gas barrier property of the present invention can be improved. In a more preferred embodiment of the present invention, when the first protective layer and the second protective layer are monolayers while satisfying the thickness range, superiority of the desired effect can be realized.
본 발명에서 제1 보호층은 에폭시수지 수지, 경화제 및 용매를 포함하는 제1 수지 조성물을 이용하여 형성할 수 있다. 이때, 상기 조성물은 통상의 유기 용매에 혼합하여 제조할 수 있다. 상기 유기용매는 바람직하게는 에틸아세테이트 및 메탄올을 혼합한 혼합 용매를 사용할 수 있다. 이때, 에틸아세테이트 및 메탄올의 혼합중량비는 제한되는 것은 아니지만 1 : 1 ~ 1 : 10일 수 있으며, 바람직하게는 1 : 5 ~ 1 : 7일 수 있다. 상기 제1 수지 조성물은 고형분 함량이 10 ~ 50중량%, 바람직하게는 30 ~ 40중량%일 수 있다. In the present invention, the first protective layer may be formed using a first resin composition containing an epoxy resin, a curing agent, and a solvent. In this case, the composition may be prepared by mixing in a conventional organic solvent. The organic solvent may be preferably a mixed solvent of ethyl acetate and methanol. At this time, the mixed weight ratio of ethyl acetate and methanol is not limited, but may be 1: 1 to 1:10, preferably 1: 5 to 1: 7. The first resin composition may have a solid content of 10 to 50% by weight, preferably 30 to 40% by weight.
본 발명에서 제1 보호층은 일 양태로, 상기 제 1 수지 조성물을 경화시켜 제조한 필름을 삽입하는 방법이나 금속차단층 상부에 도포하여 형성할 수 있으며, 단열 및 가스 차단 특성을 포함하여 기계적 물성을 향상시키기 위하여 바람직하게는 도포하여 형성하는 것이 좋다. 이는 기재필름에 금속층을 적층 시 또는 제품의 이송 등의 외부 노출 시 금속차단층의 상부 표면에 핀홀이 발생할 수 있으므로 필름 삽입보다는 조성물을 이용한 코팅 방법을 사용하는 것이 바람직하다.In one embodiment of the present invention, the first protective layer may be formed by applying a film prepared by curing the first resin composition or by coating the upper portion of the metal barrier layer, and includes mechanical properties including thermal insulation and gas barrier properties. In order to improve this, it is preferable to apply | coat and form. It is preferable to use a coating method using a composition rather than inserting a film because pinholes may occur on the upper surface of the metal barrier layer when the metal layer is laminated on the base film or when the product is exposed to the outside.
상기 에폭시계 수지는 비스페놀 A형 에폭시 수지, 비스페놀 F형 에폭시 수지, 노볼락형 에폭시 수지, 고리지방족 에폭시 수지, 다관능형 아민 에폭시 수지, 글리시딜아민형 에폭시 수지, 다이머산 변성 에폭시 수지, 고무 변성 에폭시 수지, 우레탄 변성 에폭시 수지, 브롬화 에폭시 수지, 브롬화 페녹시 에폭시 수지,하이드리지네이티드 비스페놀 A형 에폭시 수지 및 폴리올 변성 에폭시 수지로 이루어진 군으로부터 선택되는 어느 하나 또는 둘 이상을 포함할 수 있으며, 이에 한정되지 않는다. The epoxy resin is bisphenol A epoxy resin, bisphenol F epoxy resin, novolac epoxy resin, cycloaliphatic epoxy resin, polyfunctional amine epoxy resin, glycidylamine epoxy resin, dimer acid modified epoxy resin, rubber modified Epoxy resins, urethane-modified epoxy resins, brominated epoxy resins, brominated phenoxy epoxy resins, hydrated bisphenol A-type epoxy resin and polyol modified epoxy resin may include any one or two or more It is not limited.
상기 에폭시계 수지는 포화 또는 불포화 지방족 화합물이나 지환식 화합물, 방향족 화합물 또는 복소환식 화합물 중 어느 하나 이상일 수 있으나, 바람직하게는 방향족 관능기를 분자 내에 포함하는 에폭시 수지일 수 있다. 예를 들어, 메타크실릴렌디아민으로부터 유도된 글리시딜아민 부위를 갖는 에폭시 수지, 1,3-비스(아미노메틸)시클로헥산으로부터 유도된 글리시딜아민 부위를 갖는 에폭시 수지, 디아미노디페닐메탄으로부터 유도된 글리시딜아민 부위를 갖는 에폭시 수지, 파라아미노페놀로부터 유도된 글리시딜아민 부위 및/또는 글리시딜에테르 부위를 갖는 에폭시 수지, 비스페놀 A에서 유도된 글리시딜에테르 부위를 갖는 에폭시 수지, 비스페놀 F에서 유도된 글리시딜에테르 부위를 갖는 에폭시 수지, 페놀노볼락으로부터 유도된 글리시딜에테르 부위를 갖는 에폭시 수지 및 레조르시놀로부터 유도된 글리시딜에테르 부위를 갖는 에폭시 수지 등을 사용할 수 있으며, 바람직하게는 메타크실릴렌디아민으로부터 유도된 글리시딜아민 부위를 갖는 에폭시 수지, 1,3-비스(아미노메틸)시클로헥산으로부터 유도된 글리시딜아민 부위를 갖는 에폭시 수지, 비스페놀 F에서 유도된 글리시딜에테르 부위를 갖는 에폭시 수지 및 레조르시놀로부터 유도된 글리시딜에테르 부위를 갖는 에폭시 수지 중에서 선택된 어느 하나 이상을 사용할 수 있다. The epoxy resin may be any one or more of a saturated or unsaturated aliphatic compound, an alicyclic compound, an aromatic compound, or a heterocyclic compound, but preferably an epoxy resin containing an aromatic functional group in a molecule. For example, an epoxy resin having a glycidylamine moiety derived from metha xylylenediamine, an epoxy resin having a glycidylamine moiety derived from 1,3-bis (aminomethyl) cyclohexane, diaminodiphenyl Epoxy resins having glycidylamine moieties derived from methane, epoxy resins having glycidylamine moieties derived from paraaminophenol and / or glycidyl ether moieties, having glycidylether moieties derived from bisphenol A Epoxy resins, epoxy resins having glycidyl ether moieties derived from bisphenol F, epoxy resins having glycidyl ether moieties derived from phenol novolac, epoxy resins having glycidyl ether moieties derived from resorcinol, and the like. Epoxy resins having a glycidylamine moiety derived from methacrylicylenediamine, 1,3 Epoxy resins with glycidylamine moieties derived from bis (aminomethyl) cyclohexane, epoxy resins with glycidylether moieties derived from bisphenol F and epoxy with glycidylether moieties derived from resorcinol Any one or more selected from resins can be used.
또한, 상기 에폭시 수지는 다이머산(dimer acid) 변성 에폭시 수지를 사용할 수 있다. 상기 다이머산 변성 에폭시 수지는 접착강도를 향상시켜 보호층의 성능을 향상시키고, 필름의 내구성, 유연성, 내충격성, 내열성 등의 기계적 물성의 상승효과를 발현시킬 수 있다. 상기 다이머산 변성 에폭시 수지는 다이머산 구조 중 하나 이상의 카르복실기와 다관능 에폭시 수지가 반응하여 이루어진 것일 수 있다.In addition, the epoxy resin may be a dimer acid (modified acid) modified epoxy resin. The dimer acid-modified epoxy resin may improve the adhesive strength to improve the performance of the protective layer, and may express synergistic effects of mechanical properties such as durability, flexibility, impact resistance, and heat resistance of the film. The dimer acid-modified epoxy resin may be formed by reacting one or more carboxyl groups of the dimer acid structure with the polyfunctional epoxy resin.
상기 경화제는 지방족 아민, 변성 아민, 방향족 아민, 3급 아민 및 폴리아민계 화합물으로 이루어진 군으로부터 선택되는 어느 하나 또는 둘 이상의 아민계 경화제를 포함할 수 있다.The curing agent may include any one or two or more amine curing agents selected from the group consisting of aliphatic amines, modified amines, aromatic amines, tertiary amines and polyamine compounds.
바람직하게는 폴리아민계 경화제를 사용할 수 있다. 일예로, 에틸렌디아민, 디에틸렌트리아민, 트리에틸렌테트라민, 테트라에틸렌펜타민 등의 지방족 아민, 메타크실릴렌디아민, 파라크실릴렌디아민 등의 방향환을 갖는 지방족 아민, 1,3-비스(아미노메틸)시클로헥산, 이소포론디아민, 노르보르넨디아민 등의 지환식 아민, 디아미노디페닐메탄, 메타페닐렌디아민 등의 방향족 아민을 들 수 있으며, 이에 제한되지 않는다.Preferably, a polyamine curing agent can be used. For example, aliphatic amines having 1,3-bis with aromatic rings such as aliphatic amines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, methaxylylenediamine, and paraxylylenediamine Alicyclic amines such as (aminomethyl) cyclohexane, isophoronediamine, norbornenediamine, and aromatic amines such as diaminodiphenylmethane, metaphenylenediamine, and the like.
상기 경화제는 에폭시계 수지 100중량부에 대하여 70 ~ 250중량부, 바람직하게는 100 ~ 250 중량부, 보다 바람직하게는 150 ~ 200중량부 함유할 수 있다. 상기 경화제의 함량이 70중량부 미만이면 경화속도가 느리며, 블록킹이 발생할 수 있으며, 250중량부 초과이면 경화속도가 빨라 가용시간이 짧고 공정성이 좋지 않으며, 점도가 상승할 수 있다. The curing agent may contain 70 to 250 parts by weight, preferably 100 to 250 parts by weight, and more preferably 150 to 200 parts by weight based on 100 parts by weight of the epoxy resin. If the content of the curing agent is less than 70 parts by weight, the curing rate is slow, blocking may occur. If the content of the curing agent is greater than 250 parts by weight, the curing time is short, the usability time is short, the processability is not good, and the viscosity may be increased.
상기 제1 수지 조성물은 제한되지는 않지만 점도가 1,000 ~ 3,000cP(25℃), 바람직하게는 1,500 ~ 2,500cP(25℃)인 것을 사용하는 것일 수 있다. 상기 제1 수지 조성물을 금속차단층의 금속층 상부에 코팅하여 형성함으로써 우수한 가스차단성을 확보할 수 있다. 상기 제1 보호층의 두께는 5 ~ 10㎛일 수 있다. The first resin composition is not limited, but may be one having a viscosity of 1,000 to 3,000 cP (25 ° C.), preferably 1,500 to 2,500 cP (25 ° C.). By coating the first resin composition on the metal layer of the metal barrier layer and forming the first resin composition, excellent gas barrier properties can be ensured. The thickness of the first protective layer may be 5 ~ 10㎛.
본 발명에서 제2 보호층은 합성고무와 용매를 포함하는 제2 수지 조성물을 을 이용하여 형성할 수 있다. 이때, 상기 용매는 바람직하게는 합성고무를 용해할 수 있는 것이라면 제한되지 않으며, 구체적으로 예를 들면, 메틸사이클로헥산 등을 사용할 수 있다. 상기 제2 수지 조성물은 고형분 함량이 10 ~ 50중량%, 바람직하게는 10 ~ 20중량%인 범위에서 목적으로 하는 두께를 용이하게 형성할 수 있다.In the present invention, the second protective layer may be formed using a second resin composition containing a synthetic rubber and a solvent. In this case, the solvent is not particularly limited as long as it can dissolve synthetic rubber, and specifically, for example, methylcyclohexane may be used. The second resin composition may easily form a desired thickness in the range of 10 to 50% by weight, preferably 10 to 20% by weight of solid content.
본 발명에서 제2 보호층은 일 양태로, 상기 제 2 수지 조성물을 경화시켜 제조한 필름을 삽입하는 방법이나 금속차단층 상부에 도포하여 형성할 수 있으며, 단열 및 가스 차단 특성을 포함하여 기계적 물성을 향상시키기 위하여 바람직하게는 도포하여 형성하는 것이 좋다. 이는 기재필름에 금속층을 적층 시 또는 제품의 이송 등의 외부 노출 시 금속차단층의 상부 표면에 핀홀이 발생할 수 있으므로 필름 삽입보다는 조성물을 이용한 코팅 방법을 사용하는 것이 바람직하다.In the present invention, the second protective layer, in one embodiment, may be formed by inserting a film prepared by curing the second resin composition or by coating the upper portion of the metal barrier layer, and includes mechanical properties including thermal insulation and gas barrier properties. In order to improve this, it is preferable to apply | coat and form. It is preferable to use a coating method using a composition rather than inserting a film because pinholes may occur on the upper surface of the metal barrier layer when the metal layer is laminated on the base film or when the product is exposed to the outside.
상기 합성고무는 스티렌-부타디엔고무(styrene butadien rubber), 스티렌-부타디엔-스티렌 블록 코폴리머(SBS, Styrene-Butadiene-Styrene block copolymer), 스티렌-이소플렌-스티렌 블록 코폴리머((SIS, Styrene-Isoprene-Styrene Block copolymer), 스티렌-에틸렌-부타디엔-스티렌 블록 코폴리머((SEBS, Styrene-Ethylene-Butadiene-Styrene Block copolymer), 에틸렌 프로필렌 디엔 고무(EPDM, Ethylene propylene diene rubber), 폴리클로로프렌고무(polychloroprene rubber), 니트릴고무(acrylonitrile-butadiene rubber), 이소플렌이소부틸렌고무(isoprene-isobutylene rubber), 부타디엔고무(butadiene rubber), 이소프렌고무(isoprene rubber), 에틸렌프로필렌고무(ethylene propylene rubber), 다황화물계 고무(polysulfide rubber), 실리콘고무(silicone rubber), 플루오로고무(fluororubber), 우레탄고무(urethane rubber), 아크릴고무(acrylic rubber)에서 선택되는 어느 하나 또는 둘 이상을 포함할 수 있으며, 이에 한정되지 않는다. The synthetic rubber is styrene butadien rubber, styrene-butadiene-styrene block copolymer (SBS, Styrene-Butadiene-Styrene block copolymer), styrene-isoprene-styrene block copolymer (SIS, Styrene-Isoprene) -Styrene Block copolymer), Styrene-Ethylene-Butadiene-Styrene Block copolymer (SEBS), Ethylene propylene diene rubber (EPDM), Polychloroprene rubber ), Nitrile rubber (acrylonitrile-butadiene rubber), isoprene-isobutylene rubber, isadirene rubber, butadiene rubber, isoprene rubber, ethylene propylene rubber, polysulfide Any one or two selected from rubber (polysulfide rubber), silicone rubber (silicone rubber), fluororubber (fluororubber), urethane rubber (urethane rubber), acrylic rubber (acrylic rubber) It may include the above, but is not limited thereto.
상기 제2 수지 조성물은 제한되지는 않지만, 점도가 100 ~ 200cP(25℃), 보다 바람직하게는 점도가 120 ~ 180cP(25℃)인 범위인 것이 좋으며, 상기 제2 수지 조성물을 금속차단층의 금속층 상부에 코팅하여 형성함으로써 우수한 수분차단 특성을 확보할 수 있다. 상기 제2 보호층의 두께는 1 ~ 5㎛일 수 있다. Although the second resin composition is not limited, the viscosity is preferably in the range of 100 to 200 cP (25 ° C.), more preferably 120 to 180 cP (25 ° C.), and the second resin composition may be It is possible to secure excellent moisture barrier properties by forming a coating on the metal layer. The thickness of the second protective layer may be 1 ~ 5㎛.
(4) 접착층(4) adhesive layer
본 발명에서 접착층은 금속차단층 및 열융착층를 적층하기 위하여 사용할 수 있다. 이는 접착제를 도포하여 형성하거나 접착성 필름을 열융착층과 금속차단층 사이에 적층하여 형성할 수 있으며, 반드시 이에 제한되지 않는다. In the present invention, the adhesive layer may be used to laminate the metal barrier layer and the heat seal layer. This may be formed by applying an adhesive or may be formed by laminating an adhesive film between the heat seal layer and the metal barrier layer, but is not limited thereto.
상기 접착제로는 폴리에스테르계 수지, 우레탄계 수지계, 아크릴계 수지, 에테르계 수지, 페놀계 수지, 푸란계 수지, 우레아계 수지, 멜라민계 수지 등의 열경화형 접착제를 단독 또는 2종 이상 혼용하여 사용할 수 있으며, 반드시 이에 제한되지 않는다.As the adhesive, thermosetting adhesives such as polyester resin, urethane resin, acrylic resin, ether resin, phenol resin, furan resin, urea resin and melamine resin may be used alone or in combination of two or more kinds thereof. However, it is not necessarily limited thereto.
상기 접착층은 박리 현상을 방지하기 위하여 바람직하게는 층간 접착 강도가 400 gf/inch 이상일 수 있다.The adhesive layer may preferably have an interlayer adhesive strength of 400 gf / inch or more in order to prevent peeling.
(5) 열융착층(5) heat seal layer
본 발명에서 열융착층은 고온에서의 단열 성능을 부여하며, 가스 차단과 동시에 내부 진공도를 유지하기 위하여 사용할 수 있다. 상기 열융착층으로는 선형 저밀도 폴리에틸렌, 저밀도 폴리에틸렌, 중밀도 폴리에틸렌, 고밀도 폴리에틸렌, 직사슬형 저밀도 폴리에틸렌, 고리형 폴리올레핀, 폴리프로필렌, 캐스팅 폴리프로필렌(Casting Polypropylene), 에틸렌-아세트산비닐 공중합체, 아이오노머 수지, 에틸렌-아크릴산에틸 공중합체, 에틸렌-아크릴산 공중합체, 에틸렌-메타크릴산 공중합체, 에틸렌-프로필렌 공중합체를 사용할 수 있다. 또한, 폴리에틸렌 또는 폴리프로필렌 등의 폴리올레핀계 수지를 아크릴산, 메타크릴산, 말레산, 무수 말레산, 푸말산, 이타콘산, 그 외 등의 불포화 카르복실산으로 변성한 산변성 폴리올레핀계 수지, 폴리에스테르계 수지, 폴리스티렌계 수지 및 이들의 혼합물 중에서 선택되는 어느 하나를 사용할 수 있으며, 이에 제한되지는 않는다. In the present invention, the heat-sealing layer provides heat insulation at high temperature, and can be used to maintain the internal vacuum while simultaneously blocking gas. The heat-sealing layer includes linear low density polyethylene, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, cyclic polyolefin, polypropylene, casting polypropylene, ethylene-vinyl acetate copolymer, ionomer A resin, an ethylene-ethyl acrylate copolymer, an ethylene-acrylic acid copolymer, an ethylene-methacrylic acid copolymer, and an ethylene-propylene copolymer can be used. Acid-modified polyolefin resins and polyesters in which polyolefin resins such as polyethylene or polypropylene are modified with unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, and the like Any one selected from resins, polystyrene resins, and mixtures thereof may be used, but is not limited thereto.
본 발명에서 더욱 좋게는 선형저밀도폴리에틸렌 수지층(LLDPE)/에틸렌비닐알콜 수지층(EVOH)/선형저밀도폴리에틸렌 수지층(LLDPE), EVOH/LLDPE/EVOH 또는 LLDPE/EVOH 등의 공압출 구조의 열융착 필름을 포함할 수 있다. 이때, 에틸렌비닐알콜 수지층은 두께를 증가시켜 가스 및 수분 차단성을 향상시킬 수 있으며, 선형저밀도폴리에틸렌 수지층의 두께를 감소시켜 열융착 온도를 조절할 수 있다. More preferably in the present invention, heat-sealing of the co-extrusion structure, such as linear low density polyethylene resin layer (LLDPE) / ethylene vinyl alcohol resin layer (EVOH) / linear low density polyethylene resin layer (LLDPE), EVOH / LLDPE / EVOH or LLDPE / EVOH Film may be included. In this case, the ethylene vinyl alcohol resin layer may increase the thickness to improve gas and moisture barrier properties, and may reduce the thickness of the linear low density polyethylene resin layer to control the thermal fusion temperature.
상기 열융착층의 두께는 제한되지는 않지만 일예로 10 ~ 100㎛일 수 있으며, 상기 두께범위 내에서 우수한 단열성, 가스 및 수분 차단 성능을 구현하며, 내부 진공도를 향상시키고 비용 절감으로 인한 경제성이 뛰어나다.The thickness of the heat-sealing layer is not limited, but may be, for example, 10 ~ 100㎛, implements excellent heat insulating properties, gas and water blocking performance within the thickness range, improves the internal vacuum degree and excellent economy due to cost reduction .
상기 열융착층은 다층으로 형성할 수 있으며, 일예로, 차단층에 접하는 부분은 접착성이 우수한 변성 폴리올레핀계 수지를 사용할 수 있다. The heat-sealing layer may be formed in a multi-layer, for example, a portion in contact with the blocking layer may use a modified polyolefin resin having excellent adhesion.
도 1 내지 4는 본 발명의 일 실시예에 따른 배리어용 필름의 단면도를 나타낸 것이다. 본 발명의 일 양태는 도 1에서 보이는 바와 같이, 상부로부터 제1보호층(310), 기재필름(100), 금속층(210) 및 제2 보호층(320)이 순차적으로 적층되고, 상기 제2 보호층(320)의 일면에 접착층(400) 및 열융착층(500)이 적층된 것일 수 있다. 1 to 4 show a cross-sectional view of the barrier film according to an embodiment of the present invention. In an aspect of the present invention, as shown in FIG. 1, the first protective layer 310, the base film 100, the metal layer 210, and the second protective layer 320 are sequentially stacked from the top, and the second The adhesive layer 400 and the heat seal layer 500 may be stacked on one surface of the protective layer 320.
다른 양태는 도 2에서 보이는 바와 같이, 상부로부터 기재필름(100), 금속층(210), 제1 보호층(310) 및 제2 보호층(320)의 금속차단층(200), 상기 금속차단층(200)의 일면에 접착층(400) 및 열융착층(500)이 적층된 것일 수 있다. Another embodiment is as shown in Figure 2, from the top of the base film 100, the metal layer 210, the first protective layer 310 and the second protective layer 320 of the metal blocking layer 200, the metal blocking layer The adhesive layer 400 and the heat seal layer 500 may be stacked on one surface of the 200.
또 다른 양태는 도 3에서 보이는 바와 같이, 상부로부터 기재필름(100), 제2 보호층(320), 금속층(210) 및 제1보호층(310)의 금속차단층(200), 상기 금속차단층(200)의 일면에 접착층(400) 및 열융착층(500)이 적층된 것일 수 있다. In another embodiment, as shown in FIG. 3, the metal blocking layer 200, the metal blocking layer of the base film 100, the second protective layer 320, the metal layer 210 and the first protective layer 310 from the top. The adhesive layer 400 and the heat seal layer 500 may be stacked on one surface of the layer 200.
또 다른 양태는 도 4에서 보이는 바와 같이, 상부로부터 기재필름(100), 제1보호층(310), 제2 보호층(320) 및 금속층(210)의 금속차단층(200), 상기 금속차단층(200)의 일면에 접착층(400) 및 열융착층(500)이 적층된 것일 수 있다. Another embodiment is as shown in Figure 4, from the top of the base film 100, the first protective layer 310, the second protective layer 320 and the metal layer 210 of the metal layer 210, the metal blocking The adhesive layer 400 and the heat seal layer 500 may be stacked on one surface of the layer 200.
본 발명은 상술한 바와 같은 적층구조로 인하여 단열 성능을 향상시키는 것과 동시에 금속 증착에 따른 핀홀 발생에 따른 성능 저하를 방지할 수 있으며, 내충격성, 내열성, 내한성, 내스크래치성 및 유연성의 기계적 물성의 상승효과를 구현할 수 있는 배리어용 필름을 제공할 수 있는 장점이 있다. 더구나, 본 발명에 따른 배리어용 필름은 금속층에 의한 열교(heat bridge) 현상을 방지할 수 있으며, 접착층의 사용을 현저히 줄여 접측층을 통해 유입될 수 있는 수분 및 가스를 차단함으로써 수분 차단성 및 가스 차단성을 극대화할 수 있는 장점이 있다. The present invention can improve the thermal insulation performance and prevent the performance degradation caused by the pinholes due to the metal deposition due to the laminated structure as described above, and the mechanical properties of impact resistance, heat resistance, cold resistance, scratch resistance and flexibility There is an advantage that can provide a barrier film that can implement a synergistic effect. In addition, the barrier film according to the present invention can prevent the heat bridge phenomenon by the metal layer, significantly reducing the use of the adhesive layer to block moisture and gas that can be introduced through the contact layer to prevent moisture barrier and gas There is an advantage to maximize the blocking.
본 발명의 일 실시예에 따른 배리어용 필름은 38± 2℃ 및 90± 5% 상대 습도에서 0.01g/㎡/day 이하의 WVTR(Water vapor transmission rate), 23± 2℃에서 0.001cc/㎡/day 이하의 OTR(Oxygen Transmission Rate)일 수 있다.Barrier film according to an embodiment of the present invention is water vapor transmission rate (WVTR) of less than 0.01g / ㎡ / day at 38 ± 2 ℃ and 90 ± 5% relative humidity, 0.001cc / ㎡ / at 23 ± 2 ℃ It may be an Oxygen Transmission Rate (OTR) of less than one day.
이하, 본 발명의 구체적인 설명을 위하여 일예를 들어 설명하는 바, 본 발명이 하기 실시예에 한정되는 것은 아니다.Hereinafter, the present invention will be described by way of example for specific description of the present invention, but the present invention is not limited to the following examples.
이하 물성을 하기 방법으로 측정을 하였다.The physical properties were measured by the following method.
(1) 산소 투과도(1) oxygen permeability
- 시험방법: ASTM D3985 (Standard Test Method for Oxygen Gas Transmission Rate Through Plastic Film and Sheeting Using a Coulometric Sensor)-Test method: ASTM D3985 (Standard Test Method for Oxygen Gas Transmission Rate Through Plastic Film and Sheeting Using a Coulometric Sensor)
- 시험기기: OX-TRAN Model 2/21 (미국 Mocon 社)-Tester: OX-TRAN Model 2/21 (Mocon, USA)
- 시험온도: (23± 2) ℃-Test temperature: (23 ± 2) ℃
- 측정범위: 0.05 ~ 2 000 (cm3/(m2· 24hr·atm))Measuring range: 0.05 ~ 2 000 (cm 3 / (m 2 · 24hr · atm))
- 가스배리어 평가Gas barrier evaluation
○ : 0.0005cc/㎡·day이하, 기타물성 만족○: 0.0005cc / ㎡ · day or less, satisfying other physical properties
× : 0.0005cc/㎡·day이상, 기타물성 불만족×: 0.0005cc / ㎡ · day or more, dissatisfied with other physical properties
(2) 수분 투과도(2) moisture permeability
- 시험방법: ASTM F1249 (Standard Test Method for Water Vapor Transmission Rate Through Plastic Film and Sheeting Using a Modulated Infrared Sensor)Test Method: ASTM F1249 (Standard Test Method for Water Vapor Transmission Rate Through Plastic Film and Sheeting Using a Modulated Infrared Sensor)
- 시험기기: Permatran-W 3/33 MA (미국 Mocon 社)-Tester: Permatran-W 3/33 MA (Mocon, USA)
- 시험환경: (38± 2) ℃, (90± 5) % R.H-Test environment: (38 ± 2) ℃, (90 ± 5)% R.H
- 측정범위: 0.1 ~ 145 g/(m2· day)Measuring range: 0.1 to 145 g / (m 2 · day)
- 수분 배리어 평가-Moisture barrier evaluation
○ : 0.01g/㎡·day이하, 기타물성 만족○: 0.01g / ㎡ · day or less, satisfying other physical properties
× : 0.01g/㎡·day이상, 기타물성 불만족×: 0.01g / ㎡ · day or more, dissatisfied with other physical properties
(3) 인장강도(Tensile Strength), 신장율(Elongation)(3) Tensile Strength, Elongation
ASTM D-882에 따라 측정하였다.It was measured according to ASTM D-882.
(4) 가열밀봉강도(Heat seal strength)(4) Heat seal strength
ASTM D-882에 따라 측정하였다.It was measured according to ASTM D-882.
(제조예 1) (Manufacture example 1)
제1 보호층 조성물의 제조Preparation of First Protective Layer Composition
에폭시 수지(코오롱인더스트리(주), KEC-2185)100중량부에 대하여, 경화제(코오롱인더스트리(주), KPH-F2002)150중량부를 MEK 용매에 고형분 함량이 30 중량%가 되도록 제조하였다.To 100 parts by weight of epoxy resin (Kolon Industries, Ltd., KEC-2185), 150 parts by weight of a curing agent (Kolon Industries, Ltd., KPH-F2002) was prepared in a MEK solvent so that the solid content was 30% by weight.
(제조예 2) (Manufacture example 2)
제2 보호층 조성물의 제조Preparation of Second Protective Layer Composition
합성고무(LG 화학社 NBR 3250)에 물을 첨가하여 고형분 30 wt%가 되도록 제조하였다. Synthetic rubber (LBR Chemical Co., NBR 3250) was prepared by adding water to a solid content of 30 wt%.
(제조예 3) (Manufacture example 3)
접착층 조성물의 제조Preparation of Adhesive Layer Composition
폴리우레탄계 접착제 수지(강남화성社 338S) 및 경화제(강남화성社 CL-100)를 10 : 1 중량비로 에틸아세테이트와 혼합하여 고형분 함량이 33 중량%가 되도록 제조하였다. Polyurethane adhesive resin (Gangnam Hwaseong Co., Ltd. 338S) and hardener (Gangnam Hwaseong Co., Ltd. CL-100) were mixed with ethyl acetate in a 10: 1 weight ratio to prepare a solid content of 33% by weight.
(실시예1)Example 1
12㎛ 두께의 우레탄프라이머 처리된 폴리에틸렌테레프탈레이트 필름(코오롱인더스트리㈜, CD311)을 기재필름으로 준비하였다. 상기 기재필름의 우레탄프라이머층 상부에 알루미늄을 50nm 두께로 증착하였다. 증착 후 상온에서 6시간 동안 숙성시켰다. 상기 알루미늄 증착면의 반대면에 제조예 1에서 제조한 제1 보호층 조성물을 그라비아 코터를 이용하여 코팅한 후, 80℃에서 건조하여 제1 보호층을 형성하였다. 그 두께는 2㎛였다. 이후, 상기 알루미늄 증착면에 제조예 2에서 제조한 제2 보호층 조성물을 그라비아 코터를 이용하여 코팅한 다음, 80℃에서 건조하여 기재필름 상에 금속층, 제1 보호층 및 제2 보호층으로 이루어진 금속차단층을 형성하였다. 상기 제2 보호층의 두께는 2㎛였다. 상기 금속차단층의 상부면에 제조예 3에서 제조한 접착층 조성물을 그라비아 코터를 이용하여 코팅하고 120℃에서 건조하였다. 상기 접착층의 두께는 2㎛였다. 이후, LLDPE 필름(대원산업, B002, 두께 50㎛)과 합지하여 배리어용 필름(제1 보호층/PET/Al/제2 보호층/접착층/LLDPE)을 제조하였다. A 12 μm thick urethane primer-treated polyethylene terephthalate film (Kolon Industries, Inc., CD311) was prepared as a base film. Aluminum was deposited to a thickness of 50 nm on the urethane primer layer of the base film. After deposition, it was aged for 6 hours at room temperature. After coating the first protective layer composition prepared in Preparation Example 1 on the opposite side of the aluminum deposition surface using a gravure coater, and dried at 80 ℃ to form a first protective layer. The thickness was 2 micrometers. Thereafter, the second protective layer composition prepared in Preparation Example 2 was coated on the aluminum deposition surface by using a gravure coater, and then dried at 80 ° C. to form a metal layer, a first protective layer, and a second protective layer on the base film. A metal barrier layer was formed. The thickness of the said 2nd protective layer was 2 micrometers. The adhesive layer composition prepared in Preparation Example 3 was coated on the upper surface of the metal barrier layer using a gravure coater and dried at 120 ° C. The thickness of the said contact bonding layer was 2 micrometers. Thereafter, the film for lamination (first protective layer / PET / Al / second protective layer / adhesive layer / LLDPE) was manufactured by laminating with an LLDPE film (Daewon, B002, 50 μm thick).
(실시예 2)(Example 2)
12㎛ 두께의 우레탄프라이머 처리된 폴리에틸렌테레프탈레이트 필름(코오롱인더스트리㈜, CD311)을 기재필름을 준비하였다. 상기 기재필름의 우레탄프라이머층 상부에 알루미늄을 50nm 두께로 증착하였다. 증착 후 상온에서 6시간 동안 숙성시켰다. 상기 알루미늄 증착면에 제조예 1에서 제조한 제1 보호층 조성물을 그라비아 코터를 이용하여 코팅한 후, 80℃에서 건조하여 제1 보호층을 형성하였다. 그 두께는 2㎛였다. 이후, 제조예 2에서 제조한 제2 보호층 조성물을 상기 제1 보호층의 상부면에 그라비아 코터를 이용하여 코팅한 다음, 80℃에서 건조하여 기재필름 상에 금속층, 제1 보호층 및 제2 보호층으로 이루어진 금속차단층을 형성하였다. 상기 제2 보호층의 두께는 2㎛였다. 상기 금속차단층의 상부면에 제조예 3에서 제조한 접착층 조성물을 그라비아 코터를 이용하여 코팅하고 120℃에서 건조하였다. 상기 접착층의 두께는 2㎛였다. 이후, LLDPE 필름(대원산업, B002, 두께 50㎛)과 합지하여 배리어용 필름(PET/Al층/제1 보호층/제2 보호층/접착층/LLDPE)을 제조하였다. The base film was prepared from the 12-micrometer-thick urethane primer-treated polyethylene terephthalate film (Kolon Industries, Inc., CD311). Aluminum was deposited to a thickness of 50 nm on the urethane primer layer of the base film. After deposition, it was aged for 6 hours at room temperature. The first protective layer composition prepared in Preparation Example 1 was coated on the aluminum deposition surface using a gravure coater, and then dried at 80 ° C. to form a first protective layer. The thickness was 2 micrometers. Thereafter, the second protective layer composition prepared in Preparation Example 2 was coated on the upper surface of the first protective layer using a gravure coater, and then dried at 80 ° C. to form a metal layer, a first protective layer, and a second on the base film. A metal blocking layer formed of a protective layer was formed. The thickness of the said 2nd protective layer was 2 micrometers. The adhesive layer composition prepared in Preparation Example 3 was coated on the upper surface of the metal barrier layer using a gravure coater and dried at 120 ° C. The thickness of the said contact bonding layer was 2 micrometers. Thereafter, the film for lamination (PET / Al layer / first protective layer / second protective layer / adhesive layer / LLDPE) was prepared by laminating with an LLDPE film (Daewon, B002, 50 μm thick).
(실시예 3)(Example 3)
12㎛ 두께의 우레탄프라이머 처리된 폴리에틸렌테레프탈레이트 필름(코오롱인더스트리㈜, CD311)을 기재필름을 준비하였다. 상기 기재필름의 일면에 제조예 2에서 제조한 제2 보호층 조성물을 그라비아 코터를 이용하여 코팅한 다음, 80℃에서 건조하여 제2 보호층을 형성하였다. 상기 제2 보호층의 두께는 2㎛였다. 상기 제2 보호층의 상부면에 알루미늄을 50nm 두께로 증착하였다. 증착 후 상온에서 6시간 동안 숙성시켰다. 상기 알루미늄 증착면에 제조예 1에서 제조한 제1 보호층 조성물을 그라비아 코터를 이용하여 코팅한 다음, 80℃에서 건조하여 제1 보호층을 형성하였다. 상기 제1 보호층의 두께는 2㎛였다. 이렇게 기재필름 상에 제2보호층, 금속층 및 제1보호층으로 이루어진 금속차단층을 형성하였다. 상기 금속차단층의 상부면에 제조예 3에서 제조한 접착층 조성물을 그라비아 코터를 이용하여 코팅하고 120℃에서 건조하였다. 상기 접착층의 두께는 2㎛였다. 이후, LLDPE 필름(대원산업, B002, 두께 50㎛)과 합지하여 배리어용 필름(PET/제2 보호층/Al층/제1 보호층/접착층/LLDPE)을 제조하였다. The base film was prepared from the 12-micrometer-thick urethane primer-treated polyethylene terephthalate film (Kolon Industries, Inc., CD311). The second protective layer composition prepared in Preparation Example 2 was coated on one surface of the base film using a gravure coater, and then dried at 80 ° C. to form a second protective layer. The thickness of the said 2nd protective layer was 2 micrometers. Aluminum was deposited to a thickness of 50 nm on the upper surface of the second protective layer. After deposition, it was aged for 6 hours at room temperature. The first protective layer composition prepared in Preparation Example 1 was coated on the aluminum deposition surface using a gravure coater, and then dried at 80 ° C. to form a first protective layer. The thickness of the said 1st protective layer was 2 micrometers. Thus, a metal blocking layer formed of the second protective layer, the metal layer and the first protective layer was formed on the base film. The adhesive layer composition prepared in Preparation Example 3 was coated on the upper surface of the metal barrier layer using a gravure coater and dried at 120 ° C. The thickness of the said contact bonding layer was 2 micrometers. Thereafter, the film for lamination (PET / second protective layer / Al layer / first protective layer / adhesive layer / LLDPE) was manufactured by laminating with an LLDPE film (Daewon, B002, 50 μm thick).
(실시예 4)(Example 4)
12㎛ 두께의 우레탄프라이머 처리된 폴리에틸렌테레프탈레이트 필름(코오롱인더스트리㈜, CD311)을 기재필름을 준비하였다. 상기 기재필름의 일면에 제조예 1에서 제조한 제1 보호층 조성물을 그라비아 코터를 이용하여 코팅한 다음, 80℃에서 건조하여 제1 보호층을 형성하였다. 상기 제1 보호층의 두께는 2㎛였다. 상기 제1 보호층의 상부면에 제조예 2에서 제조한 제2 보호층 조성물을 그라비아 코터를 이용하여 코팅한 다음, 80℃에서 건조하여 제2 보호층을 형성하였다. 상기 제2 보호층의 두께는 2㎛였다. 상기 제2 보호층 상부면에 알루미늄을 50nm 두께로 증착하였다. 증착 후 상온에서 6시간 동안 숙성시켰다. 이로써 기재필름 상에 제1 보호층, 제2 보호층 및 금속층으로 이루어진 금속차단층을 형성하였다. 상기 금속차단층의 상부면에 제조예 3에서 제조한 접착층 조성물을 그라비아 코터를 이용하여 코팅하고 120℃에서 건조하였다. 상기 접착층의 두께는 2㎛였다. 이후, LLDPE 필름(대원산업, B002, 두께 50㎛)과 합지하여 배리어용 필름(PET/제1 보호층/제2 보호층/Al층/접착층/LLDPE)을 제조하였다. The base film was prepared from the 12-micrometer-thick urethane primer-treated polyethylene terephthalate film (Kolon Industries, Inc., CD311). The first protective layer composition prepared in Preparation Example 1 was coated on one surface of the base film using a gravure coater, and then dried at 80 ° C. to form a first protective layer. The thickness of the said 1st protective layer was 2 micrometers. The second protective layer composition prepared in Preparation Example 2 was coated on the upper surface of the first protective layer using a gravure coater, and then dried at 80 ° C. to form a second protective layer. The thickness of the said 2nd protective layer was 2 micrometers. Aluminum was deposited to a thickness of 50 nm on the upper surface of the second protective layer. After deposition, it was aged for 6 hours at room temperature. As a result, a metal blocking layer including a first protective layer, a second protective layer, and a metal layer was formed on the base film. The adhesive layer composition prepared in Preparation Example 3 was coated on the upper surface of the metal barrier layer using a gravure coater and dried at 120 ° C. The thickness of the said contact bonding layer was 2 micrometers. Thereafter, the film for lamination (PET / first protective layer / second protective layer / Al layer / adhesive layer / LLDPE) was prepared by laminating with an LLDPE film (Daewon, B002, thickness of 50 μm).
(비교예 1)(Comparative Example 1)
12㎛ 두께의 우레탄프라이머 처리된 폴리에틸렌테레프탈레이트 필름(코오롱인더스트리㈜, CD311)을 기재필름을 준비하였다. 상기 기재필름의 우레탄프라이머층 상부에 알루미늄을 50nm 두께로 증착하였다. 증착 후 상온에서 6시간 동안 숙성시켰다. 상기 알루미늄 증착면에 상기 알루미늄 증착면에 제조예 3에서 제조한 접착제 조성물을 그라비아 코터를 이용하여 코팅하고, 이를 80℃에서 건조한 다음(상기 접착층의 두께는 2㎛였다.) 상기 접착층 상부면에 알루미늄을 50nm 두께로 증착하였다. 증착 후 상온에서 6시간 동안 숙성시켰다. 이후, 증착면 상부에 12㎛ 두께의 우레탄프라이머 처리된 폴리에틸렌테레프탈레이트 필름을 적층하였다. 다음으로, 상기 폴리에틸렌테레프탈레이트 필름의 상부면에 제조예 3에서 제조한 접착제 조성물을 그라비아 코터를 이용하여 코팅하고, 이를 80℃에서 건조한 다음(상기 접착층의 두께는 2㎛였다.) 접착층 상부면에 알루미늄을 50nm 두께로 증착하였다. 증착 후 상온에서 6시간 동안 숙성시켰다. 이후, 다시 12㎛ 두께의 우레탄프라이머 처리된 폴리에틸렌테레프탈레이트 필름을 적층하였다. 다음으로, 상기 폴리에틸렌테레프탈레이트 필름의 상부면에 제조예 3에서 제조한 접착제 조성물을 그라비아 코터를 이용하여 코팅하고, 이를 80℃에서 건조한 다음(상기 접착층의 두께는 2㎛였다.) LLDPE 필름(대원산업, B002, 두께 50㎛)과 합지하여 배리어용 필름(PET/Al층/접착층/Al층/PET/접착층/Al층/PET/접착층/LLDPE)을 제조하였다. The base film was prepared from the 12-micrometer-thick urethane primer-treated polyethylene terephthalate film (Kolon Industries, Inc., CD311). Aluminum was deposited to a thickness of 50 nm on the urethane primer layer of the base film. After deposition, it was aged for 6 hours at room temperature. The adhesive composition prepared in Preparation Example 3 was coated on the aluminum deposition surface using a gravure coater, and dried at 80 ° C. (the thickness of the adhesive layer was 2 μm.). Was deposited to a thickness of 50 nm. After deposition, it was aged for 6 hours at room temperature. Thereafter, a 12 μm-thick urethane primer-treated polyethylene terephthalate film was laminated on the deposition surface. Next, the adhesive composition prepared in Preparation Example 3 was coated on the upper surface of the polyethylene terephthalate film using a gravure coater, and dried at 80 ° C. (the thickness of the adhesive layer was 2 μm). Aluminum was deposited to a thickness of 50 nm. After deposition, it was aged for 6 hours at room temperature. Thereafter, a 12 μm thick urethane primer-treated polyethylene terephthalate film was laminated. Next, the adhesive composition prepared in Preparation Example 3 was coated on the upper surface of the polyethylene terephthalate film using a gravure coater, dried at 80 ° C. (the thickness of the adhesive layer was 2 μm), and an LLDPE film. A barrier film (PET / Al layer / adhesive layer / Al layer / PET / adhesive layer / Al layer / PET / adhesive layer / LLDPE) was produced by laminating with Industry, B002, 50 μm thick.
(비교예 2)(Comparative Example 2)
12㎛ 두께의 우레탄프라이머 처리된 폴리에틸렌테레프탈레이트 필름(코오롱인더스트리㈜, CD311)을 기재필름을 준비하였다. 상기 기재필름의 우레탄프라이머층 상부에 알루미늄을 50nm 두께로 증착하였다. 증착 후 상온에서 6시간 동안 숙성시켰다. 상기 알루미늄 증착면에 제조예 1에서 제조한 제1 보호층 조성물을 그라비아 코터를 이용하여 코팅한 다음, 80℃에서 건조하여 제1 보호층을 형성하였다. 상기 제1 보호층의 두께는 2㎛였다. 상기 제1 보호층의 상부면에 제조예 3에서 제조한 접착제 조성물을 그라비아 코터를 이용하여 코팅하고, 이를 80℃에서 건조한 다음(상기 접착층의 두께는 2㎛였다.), 알루미늄을 50nm 두께로 증착하였다. 증착 후 상온에서 24시간 동안 숙성시켰다. 다음으로, 상기 알루미늄 증착면에 12㎛ 두께의 우레탄프라이머 처리된 폴리에틸렌테레프탈레이트 필름을 적층하였다. 다음으로, 상기 폴리에틸렌테레프탈레이트 필름의 상부면에 제조예 3에서 제조한 접착제 조성물을 그라비아 코터를 이용하여 코팅하고, 이를 80℃에서 건조한 다음(상기 접착층의 두께는 2㎛였다.), 제조예 2에서 제조한 제2 보호층 조성물을 그라비아 코터를 이용하여 코팅하고, 이를 80℃에서 건조하여 제2 보호층을 형성하였다. 상기 제2 보호층의 두께는 2㎛였다. 다음으로, 상기 제2 보호층의 상부면에 알루미늄을 50nm 두께로 증착하였다. 증착 후 상온에서 24시간 동안 숙성시켰다. 다음으로, 12㎛ 두께의 우레탄프라이머 처리된 폴리에틸렌테레프탈레이트 필름을 적층하였다. 다음으로, 상기 폴리에틸렌테레프탈레이트 필름의 상부면에 제조예 3에서 제조한 접착제 조성물을 그라비아 코터를 이용하여 코팅하고, 이를 80℃에서 건조하였다. 상기 접착층의 두께는 2㎛였다. 이후, LLDPE 필름(대원산업, B002, 두께 50㎛)과 합지하여 배리어용 필름(PET/Al층/제1 보호층/접착층/Al층/PET/접착층/제2 보호층/Al층/PET/접착층/LLDPE)을 제조하였다.The base film was prepared from the 12-micrometer-thick urethane primer-treated polyethylene terephthalate film (Kolon Industries, Inc., CD311). Aluminum was deposited to a thickness of 50 nm on the urethane primer layer of the base film. After deposition, it was aged for 6 hours at room temperature. The first protective layer composition prepared in Preparation Example 1 was coated on the aluminum deposition surface using a gravure coater, and then dried at 80 ° C. to form a first protective layer. The thickness of the said 1st protective layer was 2 micrometers. The adhesive composition prepared in Preparation Example 3 was coated on the upper surface of the first protective layer using a gravure coater, dried at 80 ° C. (the thickness of the adhesive layer was 2 μm), and aluminum was deposited to a thickness of 50 nm. It was. After deposition, it was aged for 24 hours at room temperature. Next, a 12 μm thick urethane primer-treated polyethylene terephthalate film was laminated on the aluminum deposition surface. Next, the adhesive composition prepared in Preparation Example 3 was coated on the upper surface of the polyethylene terephthalate film using a gravure coater, dried at 80 ° C. (the thickness of the adhesive layer was 2 μm), and Preparation Example 2 The second protective layer composition prepared in the above was coated using a gravure coater and dried at 80 ° C. to form a second protective layer. The thickness of the said 2nd protective layer was 2 micrometers. Next, aluminum was deposited to a thickness of 50 nm on the upper surface of the second protective layer. After deposition, it was aged for 24 hours at room temperature. Next, a 12 μm thick urethane primer-treated polyethylene terephthalate film was laminated. Next, the adhesive composition prepared in Preparation Example 3 was coated on the upper surface of the polyethylene terephthalate film using a gravure coater and dried at 80 ° C. The thickness of the said contact bonding layer was 2 micrometers. After that, the film for lamination (PET / Al layer / first protective layer / adhesive layer / Al layer / PET / adhesive layer / second protective layer / Al layer / PET / Adhesive layer / LLDPE).
제조된 필름의 물성을 측정하여 하기 표 1에 나타내었다. The physical properties of the produced film were measured and shown in Table 1 below.
구분division 실시예1Example 1 실시예2Example 2 실시예3Example 3 실시예4Example 4 비교예1Comparative Example 1 비교예2Comparative Example 2
Gas barrierGas barrier ◎◎ ◎◎ ○○ ○○ ○○ ○○
Moisture barrierMoisture barrier ◎◎ ◎◎ ○○ ○○ ○○ ○○
Tensile Strength(MD/TD, MPa)Tensile Strength (MD / TD, MPa) 79/7579/75 75/7675/76 78/7778/77 78/7678/76 95/9295/92 97/9497/94
Elongation(MD/TD,%)Elongation (MD / TD,%) 93/7093/70 93/7293/72 93/7093/70 94/7294/72 85/6685/66 85/6685/66
Heat Seal Strength(N/㎜)Heat Seal Strength (N / mm) 4.14.1 4.54.5 4.44.4 4.54.5 4.24.2 4.24.2
OTR(cc/㎡·day)OTR (cc / ㎡day) 0.0005이하Less than 0.0005 0.0005이하Less than 0.0005 0.0005이하Less than 0.0005 0.0005이하Less than 0.0005 0.0005이하Less than 0.0005 0.0005이하Less than 0.0005
MVTR(g/㎡·day)MVTR (g / ㎡day) 0.01이하0.01 or less 0.01이하0.01 or less 0.01이하0.01 or less 0.01이하0.01 or less 0.01이하0.01 or less 0.01이하0.01 or less
표 1에서 볼 수 있는 바와 같이, 본 발명에 따른 실시예 1 내지 실시예 4는은 산소 및 수분 차단 특성이 우수함을 확인할 수 있었다. 뿐만 아니라, 기재필름 및 금속층을 다층으로 구비한 비교예 1 및 2와 비교하여도 금속층을 일면에 형성한 기재필름을 단층으로 구비한 본 발명에 따른 실시예들의 기계적 물성은 유사하게 나타나 상기 조합에 따른 차단 특성 및 기계적 물성 상승 효과를 구현할 수 있음을 확인할 수 있었다. 또한, 비교예 1 및 2는 알루미늄층의 수가 3층으로 다층의 알루미늄층으로부터 발생하는 열전도도가 높아질 수 있으나, 실시예에 따른 필름은 알루미늄층이 단층으로 이루어져 열전도도를 획기적으로 줄일 수 있고, 이에 따른 열교현상을 방지할 수 있는 효과가 있습니다. 즉, 본원발명에 따른 실시예들은 기재필름 상 알루미늄층이 단층으로 형성됨에도 불구하고, 인장강도 및 신율 등의 기계적 물성이 다층으로 형성되어 높은 두께를 갖는 비교예들과 비교하여 볼 때 비슷한 수준의 물성을 구현하고, 동시에 산소 및 수분 차단성이 우수함을 확인할 수 있었다. As can be seen in Table 1, Examples 1 to 4 according to the present invention was confirmed that the excellent oxygen and moisture barrier properties. In addition, compared with Comparative Examples 1 and 2 having a base film and a metal layer in multiple layers, the mechanical properties of the embodiments according to the present invention having a base film having a metal layer formed on one surface thereof were similar to each other. As a result, it was confirmed that the blocking property and the mechanical property synergy effect could be realized. In addition, Comparative Examples 1 and 2 may increase the thermal conductivity generated from a multi-layered aluminum layer as the number of aluminum layers to three layers, the film according to the embodiment can significantly reduce the thermal conductivity made of a single layer of aluminum, Accordingly, there is an effect to prevent thermal bridge phenomenon. That is, the embodiments according to the present invention, although the aluminum layer on the base film is formed as a single layer, the mechanical properties such as tensile strength and elongation are formed in a multi-layered to a similar level compared to the comparative examples having a high thickness Implemented physical properties, and at the same time it was confirmed that the oxygen and water barrier properties are excellent.

Claims (10)

  1. 기재필름, 상기 기재필름 상에 금속층, 제1 보호층 및 제2 보호층을 적층한 금속차단층을 포함하며, A base film, a metal blocking layer comprising a metal layer, a first protective layer, and a second protective layer laminated on the base film;
    상기 금속차단층의 상부에 접착층 및 열융착층을 순차적으로 적층하되,While laminating the adhesive layer and the heat-sealing layer on top of the metal blocking layer,
    기재필름의 일면에 형성된 금속층 또는 상기 금속층의 반대면의 기재필름 상에 제1 보호층 및 제2 보호층 중에서 선택된 어느 하나 층을 일층 또는 다층으로 적층하며, 상기 일면에 금속층을 형성한 기재필름을 단층으로 구비하는 것을 특징으로 하는 배리어용 필름.A base film having a metal layer formed on one surface of the metal layer formed on one surface of the base film or the base film on the opposite side of the metal layer by laminating any one selected from the first protective layer and the second protective layer in one layer or multiple layers. It is provided with a single | mono layer, The film for barriers characterized by the above-mentioned.
  2. 제1항에 있어서,The method of claim 1,
    상기 제 1 보호층은 에폭시수지, 경화제 및 용매를 포함하는 제 1 수지 조성물을 코팅 및 건조하여 형성한 것이고, 제 2 보호층은 합성고무와 용매를 포함하는 제 2 수지 조성물을 코팅 및 건조하여 형성한 것인 배리어용 필름. The first protective layer is formed by coating and drying a first resin composition comprising an epoxy resin, a curing agent and a solvent, and the second protective layer is formed by coating and drying a second resin composition including a synthetic rubber and a solvent. Barrier film which is one.
  3. 제2항에 있어서,The method of claim 2,
    상기 에폭시수지는 비스페놀 A형 에폭시 수지, 비스페놀 F형 에폭시 수지, 노볼락형 에폭시 수지, 고리지방족 에폭시 수지, 다관능형 아민 에폭시 수지, 글리시딜아민형 에폭시 수지, 다이머산 변성 에폭시 수지, 고무 변성 에폭시 수지, 우레탄 변성 에폭시 수지, 브롬화 에폭시 수지, 브롬화 페녹시 에폭시 수지,하이드리지네이티드 비스페놀 A형 에폭시 수지 및 폴리올 변성 에폭시 수지로 이루어진 군으로부터 선택되는 어느 하나 또는 둘 이상을 포함하는 배리어용 필름.The epoxy resin is bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, cycloaliphatic epoxy resin, polyfunctional amine epoxy resin, glycidylamine type epoxy resin, dimer acid modified epoxy resin, rubber modified epoxy A barrier film comprising any one or two or more selected from the group consisting of a resin, a urethane-modified epoxy resin, a brominated epoxy resin, a brominated phenoxy epoxy resin, a hydrated bisphenol A-type epoxy resin and a polyol-modified epoxy resin.
  4. 제2항에 있어서,The method of claim 2,
    상기 경화제는 지방족 아민, 변성 아민, 방향족 아민, 3급 아민 및 폴리아민계 화합물로 이루어진 군으로부터 선택되는 어느 하나 또는 둘 이상의 아민계 경화제를 포함하는 배리어용 필름. The curing agent is a barrier film comprising any one or two or more amine curing agents selected from the group consisting of aliphatic amines, modified amines, aromatic amines, tertiary amines and polyamine compounds.
  5. 제2항에 있어서,The method of claim 2,
    상기 경화제는 에폭시계 수지 100중량부에 대하여 70 ~ 250중량부 포함되는 배리어용 필름. The curing agent is a barrier film containing 70 to 250 parts by weight based on 100 parts by weight of epoxy resin.
  6. 제2항에 있어서,The method of claim 2,
    상기 합성고무는 스티렌-부타디엔고무(styrene butadien rubber), 폴리클로로프렌고무(polychloroprene rubber), 니트릴고무(acrylonitrile-butadiene rubber), 부틸고무(isoprene-isobutylene rubber), 부타디엔고무(butadiene rubber), 이소프렌고무(isoprene rubber), 에틸렌프로필렌고무(ethylene propylene rubber), 다황화물계 고무(polysulfide rubber), 실리콘고무(silicone rubber), 플루오로고무(fluororubber), 우레탄고무(urethane rubber), 아크릴고무(acrylic rubber)에서 선택되는 어느 하나 또는 둘 이상을 포함하는 배리어용 필름.The synthetic rubber is styrene butadien rubber, polychloroprene rubber, nitrile rubber (acrylonitrile-butadiene rubber), butyl rubber (isoprene-isobutylene rubber), butadiene rubber, isoprene rubber (isoprene rubber) from isoprene rubber, ethylene propylene rubber, polysulfide rubber, silicone rubber, fluororubber, urethane rubber, acrylic rubber Barrier film containing any one or two or more selected.
  7. 제1항에 있어서, The method of claim 1,
    상기 기재필름은 두께가 1 ~ 200㎛이고, 열가소성 고분자 필름으로 이루어진 배리어용 필름.The base film has a thickness of 1 ~ 200㎛, barrier film made of a thermoplastic polymer film.
  8. 제1항에 있어서,The method of claim 1,
    상기 금속층은 두께가 100nm이하이고, 금속산화물을 증착하여 형성된 것인 배리어용 필름.The metal layer has a thickness of 100nm or less, the barrier film formed by depositing a metal oxide.
  9. 제1항에 있어서,The method of claim 1,
    상기 제1 보호층은 건조도포두께가 1 ~ 10㎛이고, 제 2 보호층은 건조도포두께가 1 ~ 5㎛인 배리어용 필름.The first protective layer has a dry coating thickness of 1 ~ 10㎛, the second protective layer has a dry coating thickness of 1 ~ 5㎛.
  10. 제1항에 있어서,The method of claim 1,
    상기 배리어용 필름은 38± 2℃ 및 90± 5% 상대 습도에서 0.01g/㎡/day 이하의 WVTR(Water vapor transmission rate), 23± 2℃에서 0.001cc/㎡/day 이하의 OTR(Oxygen Transmission Rate)을 갖는 배리어용 필름.The barrier film has a water vapor transmission rate (WVTR) of 0.01 g / m 2 / day or less at 38 ± 2 ° C. and 90 ± 5% relative humidity, and OTR (Oxygen Transmission) of 0.001 cc / m 2 / day or less at 23 ± 2 ° C. A barrier film having a rate).
PCT/KR2015/006524 2014-06-30 2015-06-26 Barrier film WO2016003116A1 (en)

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KR10-2014-0081104 2014-06-30
KR20140081104 2014-06-30
KR10-2014-0135222 2014-10-07
KR1020140135222A KR102218061B1 (en) 2014-06-30 2014-10-07 Film for vacuum heat insulating material

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108192288A (en) * 2017-12-29 2018-06-22 定远县丹宝树脂有限公司 A kind of resistance to oil epoxy resin and preparation method thereof
EP3354959B1 (en) 2017-01-31 2019-11-06 Powerpipe Systems AB Improved pipe insulation

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Publication number Priority date Publication date Assignee Title
JPH1122896A (en) * 1997-07-04 1999-01-26 Mitsubishi Chem Corp Vacuum heat insulating material
KR20100119937A (en) * 2009-05-04 2010-11-12 한국과학기술원 Vacuum insulator and envelope for vacuum insulator
KR20110044699A (en) * 2009-10-23 2011-04-29 (주)엘지하우시스 Vacuum insulation panel
JP2011143692A (en) * 2010-01-18 2011-07-28 Dainippon Printing Co Ltd Laminate for vacuum heat insulating material and vacuum heat insulating material
KR20120038618A (en) * 2010-10-14 2012-04-24 주식회사 케이씨씨 Multilayered super barrier sealing member for vacuum insulation materials having excellent gas barrier property

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Publication number Priority date Publication date Assignee Title
JPH1122896A (en) * 1997-07-04 1999-01-26 Mitsubishi Chem Corp Vacuum heat insulating material
KR20100119937A (en) * 2009-05-04 2010-11-12 한국과학기술원 Vacuum insulator and envelope for vacuum insulator
KR20110044699A (en) * 2009-10-23 2011-04-29 (주)엘지하우시스 Vacuum insulation panel
JP2011143692A (en) * 2010-01-18 2011-07-28 Dainippon Printing Co Ltd Laminate for vacuum heat insulating material and vacuum heat insulating material
KR20120038618A (en) * 2010-10-14 2012-04-24 주식회사 케이씨씨 Multilayered super barrier sealing member for vacuum insulation materials having excellent gas barrier property

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3354959B1 (en) 2017-01-31 2019-11-06 Powerpipe Systems AB Improved pipe insulation
CN108192288A (en) * 2017-12-29 2018-06-22 定远县丹宝树脂有限公司 A kind of resistance to oil epoxy resin and preparation method thereof

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