WO2017018707A1 - Barrier film and manufacturing method therefor - Google Patents

Barrier film and manufacturing method therefor Download PDF

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Publication number
WO2017018707A1
WO2017018707A1 PCT/KR2016/007786 KR2016007786W WO2017018707A1 WO 2017018707 A1 WO2017018707 A1 WO 2017018707A1 KR 2016007786 W KR2016007786 W KR 2016007786W WO 2017018707 A1 WO2017018707 A1 WO 2017018707A1
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WIPO (PCT)
Prior art keywords
layer
resin
resins
overcoating
barrier
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PCT/KR2016/007786
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French (fr)
Korean (ko)
Inventor
김종원
김진영
Original Assignee
코오롱인더스트리 주식회사
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Publication of WO2017018707A1 publication Critical patent/WO2017018707A1/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
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/02—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by a sequence of laminating steps, e.g. by adding new layers at consecutive laminating stations
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/24—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate

Definitions

  • the present invention relates to a barrier film and a method of manufacturing the same.
  • a quantum dot is a semiconductor material having a crystal structure of several nano-sizes, and has a characteristic of emitting wavelengths different according to its size.
  • the quantum dot is used as a fluorescent material or a light emitting material to improve display characteristics. It is known that it can be used as a display or itself.
  • the quantum dots are used in combination in a small amount in the polymer optical sheet, for example to enter the backlight unit (BLU).
  • the quantum dot has a problem of oxidation due to surface oxidation when exposed to moisture and oxygen in the air.
  • the quantum dot is dispersed and cured by dispersing a polymer resin having quantum dots dispersed between two barrier films to produce an optical sheet.
  • the optical sheet is disposed on a light guide plate of a blue BLU module (on-surface method).
  • the optical sheet may correspond to various display screen sizes from small to large.
  • the optical sheet as described above has a certain barrier performance against moisture and oxygen due to the barrier film, but there is a problem that the barrier performance of the barrier film is sharply dropped when exposed to high temperature and high humidity conditions, accordingly, the optical sheet There is a problem in that the luminance of the crystal cannot be maintained stably.
  • the inorganic layer which is a major component of the barrier film, generally has hydrophilicity
  • the polymer resin layer in which the quantum dots are dispersed generally has hydrophobicity, so that the overcoating layer inserted between the inorganic layer and the polymer resin layer is an inorganic layer and a polymer. The adhesive force to both resin layers is required.
  • the present invention is to provide a barrier film that maintains sufficient adhesion to the inorganic material layer and the polymer resin layer under high temperature and high humidity conditions by including an overcoat layer having excellent stability under high temperature and high humidity conditions. Furthermore, by including an undercoat layer, it is possible to prevent the occurrence of cracks in the inorganic layer under high temperature and high humidity conditions, thereby maintaining barrier performance continuously, and further providing a barrier film that prevents a decrease in luminance of the optical sheet.
  • the substrate In one embodiment of the present invention for achieving the above object, the substrate; An undercoat layer formed on the substrate; An inorganic layer formed on the undercoat layer; And an overcoat layer formed on the inorganic layer and including a thermoplastic resin and a thermosetting resin.
  • the two barrier films facing each other; And a polymer resin layer in which a quantum dot is formed between the overcoating layers of the two barrier films.
  • the barrier film according to the present invention includes an overcoating layer having excellent stability under high temperature and high humidity conditions, thereby maintaining sufficient adhesive force with the inorganic material layer and the polymer resin layer under high temperature and high humidity conditions.
  • the barrier film according to the present invention includes an undercoating layer to prevent cracks in the inorganic layer under high temperature and high humidity conditions, thereby maintaining barrier performance continuously, and further preventing a decrease in luminance of the optical sheet.
  • FIG. 1 is a diagram illustrating a structure of a barrier film according to an embodiment of the present invention.
  • Figure 2 illustrates the structure of an optical sheet according to an embodiment of the present invention.
  • Barrier film according to the invention is a substrate 10 as shown in Figure 1; An undercoat layer 20 formed on the substrate; An inorganic layer 30 formed on the undercoat layer; And an overcoat layer 40 formed on the inorganic layer and including a thermoplastic resin and a thermosetting resin (see FIG. 1).
  • the barrier film according to the present invention was applied to the mixed composition of the thermoplastic resin and the thermosetting resin to form an overcoating layer, the overcoating layer has a good adhesive strength with the inorganic layer and the polymer resin layer under high temperature and high humidity conditions.
  • the undercoat layer having excellent heat resistance barrier performance can be continuously maintained even under high temperature and high humidity conditions.
  • the layer may mean to be formed in a single layer or a multilayer structure of one or more layers.
  • the base material is excellent in chemical and physical strength, can withstand the conditions for forming the inorganic layer, and can be satisfactorily preserved without impairing the properties of the inorganic layer, etc., which are formed, and also has transparency. It may be to have.
  • the substrate is a cyclic polyolefin-based resin; Polystyrene resin; Acrylonitrile-styrene copolymer (AS resin); Acrylonitrile-butadiene-styrene copolymer (ABS resin); Poly (meth) acrylic resins; Polyester-based resins including polycarbonate-based resins, polyethylene terephthalate and polyethylene naphthalate; Polyamide-based resins including nylon; Polyurethane-based resins; Acetal resins; And cellulose-based resin; may be in the form of a film or sheet made of one or more resins selected from the group consisting of.
  • the base material is a method of forming a film of the various resins alone using a film forming method such as extrusion method, cast molding method, T-die method, cutting method, inflation method using one or more of the polymer resin, or 2 It may be prepared by a method of forming a multilayer coextrusion film using at least one polymer resin, or further, by mixing and forming a film before forming a film by using at least two resins, and also using a tenter method or a tube. It may be manufactured by stretching in the uniaxial or biaxial direction using a blur (tubular) method.
  • a film forming method such as extrusion method, cast molding method, T-die method, cutting method, inflation method using one or more of the polymer resin, or 2 It may be prepared by a method of forming a multilayer coextrusion film using at least one polymer resin, or further, by mixing and forming a film before forming a film by using at least two resins, and also using a tenter method or
  • the substrate may be surface treated after the film forming process and the film forming process, if necessary, the surface treatment may be corona treatment, plasma treatment, ion beam treatment, sputtering treatment or coating treatment.
  • the coating resin it can be selectively applied to both sides of the substrate among the urethane, acrylic, and polyester.
  • the thickness of the substrate may be, for example, 25 to 188 ⁇ m, more specifically 50 to 125 ⁇ m, it can be adjusted to ensure sufficient heat resistance, mechanical properties and gas barrier performance within the above range.
  • the substrate according to an embodiment of the present invention may be one or both surfaces of the mat coating (Matt coating), in detail, the surface of the substrate is a mat coating on the opposite surface of the contact surface with the undercoat layer Can be.
  • the contact area is reduced when it is in contact with another optical sheet, thereby reducing the occurrence of wet-out, and due to the haze imparted by the matte coating, The effect of making a defect invisible to the naked eye can be given.
  • the matte coating can make light efficiency of each position uniform by increasing light diffusion.
  • the undercoat in the barrier film serves as a planarization layer to lower the roughness of the substrate to form an inorganic layer without a defect as a dense structure when forming the inorganic layer.
  • the undercoating layer prevents the occurrence of cracking of the inorganic layer caused by flow and lowering of the inorganic layer due to thermal expansion or thermal contraction under high temperature and high humidity conditions by controlling the glass transition temperature (T g ). It also plays a role.
  • the barrier film of the present invention maintains barrier performance uniformly even under high temperature and high humidity conditions, and effectively reduces the brightness of the optical sheet.
  • the polymer resin included in the undercoat composition forming the undercoat layer in the present invention is characterized by having a relatively high glass transition temperature (T g ) compared to the polymer resin constituting the substrate.
  • T g glass transition temperature
  • the polymer resin included in the undercoat layer composition may have a glass transition temperature of 80 to 250 °C, more specifically, a glass transition temperature of 80 to 200 °C.
  • the polymer resin included in the undercoat layer has a relatively higher glass transition temperature than the polymer resin constituting the substrate as described above to prevent the undercoat layer from shrinking when the inorganic layer is formed at a high temperature to minimize the occurrence of cracks in the inorganic layer. Accordingly, the barrier performance may be prevented from being reduced, and heat resistance may be ensured at the high temperature reliability evaluation to prevent cracks in the inorganic layer.
  • the undercoat layer is a urethane acrylate including bisphenol A-based acrylate, naphthalene-based acrylate, isobornyl-based acrylate and ammanthyl-based acrylate; Bisphenols such as bisphenol A, bisphenol F, methylene bis (4-hydroxyphenyl), resorcinol, dihydroxy naphthalene, dihydroxy biphenyl, dihydroxy phenyl ethanol, dihydroxy pyridine, dihydroxyquino Aromatic polyol compounds including saline, dihydroxy tetrahydronaphthalene and dihydroxypyrimidine; And 1,3-propane diol, 1,4-butane diol, 1,5-pentane diol, 1,6-hexane diol, 3-methyl-1,5-pentane diol, Aliphatic polyol compounds comprising 1,8-octane diol, 2-methyl-1,8-octane diol, 1,
  • the undercoat layer may include at least one polymer resin selected from the group consisting of urethane acrylate oligomer, dipentaerythritol pentaacrylate and trihydroxyethyl isocyanurate triacrylate or a combination thereof.
  • the thickness of the formed undercoat layer may have a range of 0.01 to 100 ⁇ m, more specifically may have a range of 0.1 to 10 ⁇ m.
  • the thickness of the undercoat layer is formed within the above range, it is possible to ensure a flattening function and heat resistance at the same time.
  • the inorganic layer should have moisture and oxygen shielding properties. Since the quantum dots included in the optical sheet of the present invention are vulnerable to moisture and oxygen, the surface is oxidized when exposed to moisture and oxygen, which shortens the lifespan of the optical sheet and decreases the brightness. Thus, the inorganic layer blocks moisture and oxygen. This prevents the quantum dots from oxidizing.
  • the inorganic material included in the inorganic layer is silicon (Si), aluminum (Al), indium (In), tin (Sn), zinc (Zn), zirconium (Zr), titanium (Ti) , Copper (Cu), cerium (Ce), yttrium (Yt), lanthanum (La), barium (Ba), magnesium (Mg), fluorine (F 2 ), antimony (Sb), strontium (Sr) and tantalum (Ta) It may be an oxide, nitride, carbide, oxynitride, oxidized carbide, nitride carbide, or oxynitride carbide containing at least one metal selected from the group consisting of.
  • the thickness of the inorganic layer formed may be, for example, 10 to 1000nm, the thickness of the inorganic layer may be relatively thin compared to the conventional barrier film due to the undercoat as described above.
  • the inorganic layer may have a multilayer structure of one or more layers, and may further include a layer for improving tie or layer or permeability to improve adhesion when formed into a multilayer structure.
  • the overcoat layer protects the inorganic layer from scratches and at the same time secures sufficient adhesion to the polymer resin layer including an inorganic layer in contact with the bottom of the overcoating layer and a quantum dot in contact with the top of the overcoating layer. It is to. In addition, the barrier performance is improved by preventing fine pinholes present in the inorganic layer.
  • the overcoat layer includes a thermoplastic resin and a thermosetting resin together.
  • the thermoplastic resin may be at least one polymer resin selected from the group consisting of polyether resin, polyurethane resin, polyester resin, polyvinyl butyral resin and polyvinyl alcohol resin. have.
  • the thermoplastic resin is applied to secure adhesion to the polymer resin layer in which the quantum dots are dispersed.
  • the thermosetting resin is a group consisting of epoxy resin, unsaturated polyester resin, polyurethane resin, polycarbonate polyurethane, polyester polyurethane, phenol resin, melamine resin, urea resin and silicon resin It may be at least one polymer resin selected from.
  • the thermosetting resin is applied to ensure long-term reliability under high temperature and high humidity conditions.
  • the solid content weight ratio of the thermoplastic resin to the thermosetting resin included in the overcoating layer may have a range of 2: 8 to 8: 2.
  • the thermoplastic resin when the thermoplastic resin is included in the above range, adhesion to the polymer resin layer in which the quantum dots are dispersed is improved, but it is difficult to secure adhesion and long-term reliability under high temperature and high humidity conditions.
  • the thermoplastic resin When included in excess, it is easy to secure long-term reliability under high temperature and high humidity conditions, but there is a problem in that adhesion to the polymer resin in which the quantum dots are dispersed may be degraded.
  • the method of forming the overcoating layer is not particularly limited, but may be formed by applying the overcoating composition on the inorganic layer using a coater such as a bar coater, a roll coater or a die coater, optionally the plasma on the inorganic layer After treatment, such as treatment, corona treatment, acid treatment, etc. may be applied to the overcoating composition.
  • the overcoating composition may be formed by stirring a thermoplastic resin and a thermosetting resin in a solvent, and as necessary, a reaction accelerator, an antistatic agent, a sunscreen agent, an ultraviolet absorber, a plasticizer, a lubricant, a filler, a colorant, a stabilizer, a lubricant, a crosslinking agent. It may be prepared by additionally adding an additive, such as an antiblocking agent, an antioxidant, an adhesion promoter, and the like.
  • the overcoating layer may be patterned to implement additional functions such as transmittance, haze control, or the like, and may be formed of one or more layers.
  • the overcoating layer may be formed in a lattice form on the inorganic layer, or may be patterned in a line shape or various shapes. In the case of the patterning, the overcoating layer may be adjusted in consideration of economical efficiency and transmittance and haze of the overcoating layer. According to the present invention.
  • the overcoating composition may further include at least one additive selected from a coupling agent and a hydrolysis inhibitor and an adhesion promoter.
  • the coupling agent serves to further improve the adhesion between the overcoating layer and the inorganic layer, and more specifically, by modifying the surface by reacting with hydroxy groups present on the surface of the inorganic layer to improve the adhesion between the overcoating layer and the inorganic layer. Let's go.
  • the coupling agent is methoxy, ethoxy, amino, epoxy, acryl, mercapto, vinyl and meta. It may be one or more materials selected from the group consisting of Methacryl-based silane coupling agents or a combination thereof.
  • the hydrolysis inhibitor serves to improve the high-temperature and high-humidity adhesion reliability by generating a stable state compound of the polymer, and more specifically, the hydrolysis inhibitor reacts with water to form a urea structure, It prevents the aging caused by the adhesion and the durability is excellent.
  • the hydrolysis inhibitor may be one or more substances selected from the group consisting of aromatic carbodiimide series or a combination thereof.
  • the adhesion promoter is not particularly limited as long as it can help to secure the adhesive force with the polymer resin layer or the adhesive force with the inorganic material layer, it may be generally used in the art.
  • the thickness of the overcoat layer may be, for example, 0.1 to 10 ⁇ m, more specifically 0.5 to 2 ⁇ m. If the thickness of the overcoating layer is less than 0.1 ⁇ m may have a problem with the adhesive strength with the polymer resin layer, if it exceeds 10 ⁇ m there may be a problem that the barrier performance deteriorates due to the penetration of water and gas to the side.
  • the barrier film of the present invention includes an overcoating layer having excellent stability under high temperature and high humidity conditions, thereby maintaining sufficient adhesion to the inorganic material layer and the polymer resin layer under high temperature and high humidity conditions, and further including an undercoating layer.
  • an overcoating layer having excellent stability under high temperature and high humidity conditions, thereby maintaining sufficient adhesion to the inorganic material layer and the polymer resin layer under high temperature and high humidity conditions, and further including an undercoating layer.
  • the overcoating layer secures sufficient adhesion with the inorganic material layer and the polymer resin layer, and the undercoating layer maintains barrier performance under high temperature and high humidity conditions, thereby improving reliability under high temperature and high humidity conditions.
  • Optical sheet according to an embodiment of the present invention the two barrier film facing each other; And a polymer resin layer 50 in which quantum dots formed between the overcoating layers 40 of the two barrier films are dispersed (see FIG. 2).
  • a substrate is prepared, and an undercoat composition is applied on the substrate to form an undercoat layer (step a).
  • the method of forming the undercoat layer is not particularly limited, but may be formed by applying the undercoat composition on the substrate using a coater such as a roll coater, the undercoat composition is a polymer resin And it may be formed by putting a polymerization initiator in a solvent and stirred.
  • the polymer resin included in the undercoat composition corresponds to the polymer resin included in the undercoat layer as described above, and may further include an additive such as a polymerization initiator as necessary.
  • step b to form an inorganic layer on the undercoat layer.
  • the inorganic layer may be formed by various methods such as a deposition method and a coating method.
  • the deposition method may be used to sufficiently secure a gas barrier property and obtain a uniform thin film.
  • the deposition method may include all methods such as physical vapor deposition (PVD), chemical vapor deposition (CVD), and the like, such as vacuum deposition, ion plating, and sputtering.
  • PVD physical vapor deposition
  • CVD chemical vapor deposition
  • a target is provided in a vacuum chamber, and a rare gas element (normally argon) ionized by applying a high voltage is collided with the target to drop atoms on the target surface and adhere to the substrate.
  • a reactive sputtering method may be used in which a gas barrier layer is formed by reacting nitrogen or oxygen with an element separated from the target by argon gas by flowing nitrogen gas or oxygen gas into the chamber.
  • a pretreatment may be additionally performed.
  • the pretreatment may be plasma treatment, corona treatment, or acid treatment, and removes various adsorbed impurities.
  • the adhesion between the coating layers can be further improved.
  • the plasma treatment or the corona treatment can effectively remove the low molecular weight impurities present on the inorganic layer.
  • an overcoating composition comprising a thermoplastic resin and a thermosetting resin is applied on the inorganic layer to form an overcoating layer and thermally cured to produce a barrier film (step c).
  • the post-curing step may be further roughened as needed immediately after the barrier film is manufactured.
  • the overcoating composition may further include at least one additive selected from the group consisting of a coupling agent, a hydrolysis inhibitor, and an adhesion promoter in addition to the thermoplastic resin and the thermosetting resin.
  • the reaction accelerator, the antistatic agent, the sunscreen, the ultraviolet absorber, the plasticizer, the lubricant, the filler, the colorant, the stabilizer, the lubricant, the crosslinking agent, the antiblocking agent, the antioxidant or the adhesion promoter, etc. may be prepared by adding the same additives.
  • the solids weight ratio of the thermoplastic resin to the thermosetting resin included in the overcoating composition may be 2: 8 to 8: 2.
  • the coupling agent may be included in 1 to 20wt% based on the total weight of the composition, more specifically may be included in 1 to 10wt%.
  • the hydrolysis inhibitor may be included in 1 to 20wt% based on the total weight of the composition, more specifically may be included in 1 to 5wt%.
  • the adhesion promoter may be included in 1 to 20wt% based on the total weight of the composition, more specifically may be included in 1 to 5wt%.
  • a chemical treatment for removing impurities on the surface of the inorganic layer may be additionally performed, and the chemical treatment is sodium hydroxide and potassium hydrdoxide.
  • Caustics including; Silicates, including sodium meta silicate; Amines including triethanolamine and monoethanolamine; Phosphates including trisodium phophate, tetra potaasium pyro phosphate; Acids, including phosphoric, hydrofluoric, and citric; And chelates including EDTA; and one or more chemical cleaners selected from the group including chelates.
  • thermosetting process is a process of curing the thermoplastic and the thermosetting resin in the overcoating composition by applying heat
  • specific conditions for the thermosetting is a solvent (Solvent) for 30 seconds to 5 minutes at a temperature of 80 to 150 °C
  • the post-curing may be performed for 1 to 3 days at a temperature condition of 30 to 60 °C. More specifically, after drying and curing the solvent (Solvent) for 30 seconds to 60 seconds at a temperature of 100 to 120 °C, after curing may be performed for 24 to 72 hours at a temperature of 40 to 60 °C. .
  • the overcoating layers of the barrier film were disposed to face each other, and then the optical sheet was applied by UV curing by applying a polymer composition having quantum dots dispersed between the two barrier films.
  • the optical sheet was applied by UV curing by applying a polymer composition having quantum dots dispersed between the two barrier films.
  • the polymer resin included in the polymer composition in which the quantum dots are dispersed may serve as a matrix including quantum dots, and may have a layer structure of one or more layers, and preferably have low oxygen and moisture permeability, and also have high light stability and It is desirable to have chemical stability.
  • the polymer resin for example, epoxy, epoxy acrylate, lauryl acrylate, norborene, polyethylene, polystyrene, ethylene-styrene copolymer, bisphenol A and bisphenol A derivatives are included Acrylate, acrylate containing fluorene derivative, isobornyl acrylate, polyphenylalkylsiloxane, polydiphenylsiloxane, polydialkylsiloxane, silsesquioxane, fluorinated silicone, vinyl and hydride substituted silicone It may be at least one polymer resin selected from.
  • the quantum dots refer to nanostructures that are substantially monocrystalline, and the quantum dots absorb primary light emitted from a light source and then emit secondary light, and have different wavelengths depending on the size of the quantum dot. It can emit light.
  • the typical size of the quantum dot may be 1 to 10 nm, when the size of the quantum dot is 4 to 5 nm may absorb the secondary light from the light source and then emit a secondary light having a red, 2 to In the case of 3 nm, the secondary light having green color may be emitted after absorbing the primary light from the light source.
  • the quantum dots may be uniformly dispersed in the polymer matrix, when the polymer resin layer is a multi-layer structure, quantum dots of different sizes may be arranged for each layer layer, quantum dots of different sizes are mixed and dispersed in a single layer It may have a form.
  • the quantum dot according to an embodiment of the present invention may be a non-cadmium-based quantum dot
  • the quantum dots for use in the present invention may include any suitable inorganic material.
  • the non-cadmium-based quantum dots may include an inorganic material selected from the group consisting of Group II-VI, III-V, IV-VI and Group IV semiconductors.
  • the non-cadmium-based quantum dot is Si, Ge, Sn, Se, Te, B, C, P, BN, BP, BAs, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, ZnO, ZnS, ZnSe, ZnTe, HgS, HgSe, HgTe, BeS, BeSe, BeTe, MgS, MgSe, At least one selected from the group consisting of GeS, GeSe, GeTe, SnS, SnSe, SnTe, PbO, PbS, PbSe, PbTe, CuF, CuCl, CuBr, CuI, Si 3 N 4 , Ge 3 N 4, and combinations thereof Inorganic materials.
  • the optical sheet may be prepared by applying the polymer composition as described above between the barrier films and undergoing UV curing.
  • the UV curing step may be performed under exposure conditions of 100 to 5000mJ / cm 2 .
  • UV curing may not be performed effectively under exposure conditions other than the above range, and thus may not have adhesive strength enough to be deposited between the barrier film and the polymer resin layer.
  • the degree of hardening (the rate at which the peak decreases when the state is not exposed to 100%) is 60 to 80%. Can be.
  • the process of applying the polymer composition between the barrier film is not particularly limited, for example, may be performed by a roll-to-roll process.
  • the optical sheet manufactured according to the present invention maintains the same adhesive strength even if left for a long time under high temperature conditions of 60 °C high temperature, 90% relative humidity, a significant improvement effect compared to the optical sheet manufactured according to the prior art in terms of reliability There is.
  • thermoplastic polyurethane Ellas / KOLON
  • thermosetting polyurethane Polyurethane, PCB3200 / Piltec
  • hardener isocyanate, P300 / Piltec
  • the undercoating composition was coated on one surface of a polyethylene terephthalate (KOLON U43R grade) having a thickness of 125 ⁇ m, dried in an oven at 80 ° C. for 3 minutes, and a type-D bulb was applied to an ultraviolet irradiation device (Fusion). It mounted and irradiated with the exposure amount of 500mJ / cm ⁇ 2> in the direction which apply
  • a polyethylene terephthalate KOLON U43R grade
  • the overcoating composition was formed on the substrate on which the inorganic layer was formed using microgravure. Next, dried and cured at 120 ° C. for 1 minute to form an overcoat layer having a thickness of 1 ⁇ m. Thereafter, after curing for 3 days at 40 °C to produce a final barrier film.
  • the urethane acrylic resin polymer crude liquid in which a cadmium-based quantum dot was dispersed between the two barrier films prepared above was applied to a thickness of 100 ⁇ m, and UV cured under 1000 mJ / cm 2 exposure conditions to prepare an optical sheet.
  • thermoplastic polyurethane Ellas / KOLON
  • thermosetting polyurethane Polyurethane, PCB3200 / Piltec
  • An optical sheet was manufactured under the same conditions as in Example 1, but 20 wt% of thermoplastic polyurethane (Ellas / KOLON) and 72 wt% of thermosetting polyurethane (Polyurethane, PCB3200 / Piltec) based on the total solid weight of the overcoating composition %, 8 wt% of a curing agent (isocyanate, P300 / filtec) was mixed with a solvent, methyl ethyl ketone (Methyl Ethyl Ketone), and then applied only to the overcoating composition of 20wt% of the solid content prepared by stirring.
  • a curing agent isocyanate, P300 / filtec
  • thermoplastic polyurethane Polyurethane, Ellas / KOLON
  • 41wt of thermosetting polyurethane Polyurethane, PCB3200 / piltech
  • 4 wt% of isocyanate P300 / Piltec
  • 10 wt% of silane coupling agent OFS6020 / DOW
  • thermoplastic polyurethane Ellas / KOLON
  • thermosetting polyurethane Polyurethane, PCB3200 / Piltec
  • %, 5 wt% of hardener isocyanate, P300 / filtec
  • 1 wt% of adhesion promoter Librizol 2061, / Lubrizol
  • thermoplastic polyurethane Ellas / KOLON
  • thermosetting polyurethane Polyurethane, PCB3200 / Piltec
  • wt%, 4.4 wt% of a curing agent isocyanate, P300 / filtec
  • 2 wt% of an anti-hydrolysis agent Altfona5151 / Green Chem
  • thermoplastic polyurethane (Polyurethane, Ellas / KOLON) based on the total solid weight of the overcoating composition, 36wt of thermosetting polyurethane (Polyurethane, PCB3200 / piltech) %, 4 wt% of hardener (isocyanate, P300 / filtec), 10 wt% of silane coupling agent (Silan coupling gent, OFS6020 / DOW), 1 wt% of hydrolysis inhibitor (Altfona5151 / Green Chem), adhesion promoter (Lubrizol 2061, / Lubrizol) was mixed with 2 wt% of methyl ethyl ketone (Methyl Ethyl Ketone) as a solvent, and only the application of the overcoating composition prepared by stirring was different.
  • thermosetting polyurethane Polyurethane, PCB3200 / piltech
  • hardener isocyanate, P300 / filtec
  • the optical sheet was manufactured under the same conditions as in Example 1, but after plasma pretreatment using a roll to roll sputter on the undercoat layer, dry coating was performed on a total thickness of 40 nm in SiN x 10 nm / SiO x 30 nm. Only the inorganic layer was formed by (Dry Coating).
  • An optical sheet was manufactured under the same conditions as in Example 1, but the undercoating layer composition was changed.
  • the undercoat composition was mixed with Negami's UN9000grade acrylate and an acrylate resin (Aica Kogyo, Z-711 grade) at a solid ratio of 5: 5, diluted with methyl ethyl ketone solvent, and then a photoinitiator (Igacure). 184) was added to 3 parts of acrylate resin solids to fully dissolve a 20 wt% undercoating composition.
  • the optical sheet is manufactured under the same conditions as in Example 1, but 100 wt% of thermoplastic polyurethane (Elur / KOLON) and 0 wt% of thermosetting polyurethane (Polyurethane, PCB3200 / Piltec) based on the total solid weight of the overcoating composition. % was mixed with the solvent methyl ethyl ketone (Methyl Ethyl Ketone), and then applied only to the overcoating composition prepared by stirring.
  • thermoplastic polyurethane Elur / KOLON
  • thermosetting polyurethane Polyurethane, PCB3200 / Piltec
  • thermoplastic polyurethane Polyurethane, Ellas / KOLON
  • thermosetting polyurethane Polyurethane, PCB3200 / Piltec
  • Wt% the curing agent (isocyanate, P300 / filtec) was 0.5 wt%, and mixed with a solvent, methyl ethyl ketone (Methyl Ethyl Ketone), followed by applying only the overcoating composition prepared by stirring.
  • thermoplastic polyurethane Ellas / KOLON
  • thermosetting polyurethane Polyurethane, PCB3200 / Piltec
  • An optical sheet was manufactured under the same conditions as in Example 1 except that there was no undercoat layer.
  • the undercoating layer composition was an undercoating composition of 20 wt% of solids prepared by adding 3 parts of photoinitiator (Igacure 184) to Negami KY-11grade acrylate and sufficiently dissolving it.
  • the optical sheet was manufactured under the same conditions as in Example 1, but there was no undercoating layer, and the inorganic layer was subjected to plasma pretreatment using a roll to roll sputter, followed by SiN x 10 nm / SiO x 30 nm in total 40 nm. Dry coating to a thickness (Dry Coating) to form an inorganic layer.
  • optical sheets prepared in Examples and Comparative Examples were evaluated through the following evaluation method, and the results are shown in Table 1 below.
  • the base film is torn in four or more specimens out of five specimens.
  • the optical sheet is placed in a high temperature and high humidity chamber (60 ° C., 90%), and then taken out every 24 hours to evaluate the above adhesive strength.
  • Defective Destroys adherend less than 500 hours
  • the undercoating layer composition is produced with a thickness of 100 ⁇ m on a PET release coating film fabric.
  • the PET release film was removed from the produced sample, and only the undercoating layer was taken as a sample to measure the glass transition temperature.
  • the glass transition temperature was measured by using TA AR AR G2 rheometer.
  • the sample kept for 500 hours in a barrier film in an 85 °C oven is left at room temperature (25 °C) for 1 hour.
  • the barrier properties of the samples before high temperature and after high temperature were measured using a MOCON Permatran-W700 instrument to measure the WVTR value at 37.8 ° C and 100% humidity.
  • the optical sheet manufactured according to the embodiment of the present invention exhibits a deposition failure level of 500 h or more under high temperature and high humidity conditions, and exhibits stable barrier performance even after being left for 500 hours at a high temperature.
  • the solid weight ratio of the thermoplastic resin: the thermosetting resin (curing agent) resin should be included in the range of 2: 8 to 8: 2, and the barrier performance is stably maintained even after high temperature standing.
  • the present invention can be used for the barrier film and its manufacturing method.

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Abstract

The present invention relates to a barrier film and an optical sheet, wherein the barrier film comprises: a substrate; an under-coating layer formed on the substrate; an inorganic layer formed on the under-coating layer; and an over-coating layer formed on the inorganic layer and containing a thermoplastic resin and a thermosetting resin together, and the optical sheet comprises: two barrier films facing each other; and a polymer resin layer in which quantum dots formed between the two barrier films and the over-coating layer are dispersed. The optical sheet of the present invention includes the over-coating layer exhibiting excellent stability under a high-temperature and high-humidity condition to maintain a sufficient adhesive force with the inorganic layer and the polymer resin layer under the high-temperature and high-humidity condition, and includes the under-coating layer to prevent cracks in the inorganic layer under the high-temperature and high-humidity condition, thereby continually maintaining the barrier performance and preventing a degradation in the luminance of the optical sheet.

Description

배리어필름 및 그 제조방법Barrier Film and Manufacturing Method
본 발명은 배리어필름 및 그 제조방법에 관한 것이다.The present invention relates to a barrier film and a method of manufacturing the same.
양자점(quantum dot)은 수 나노 크기의 결정 구조를 가진 반도체 물질로서, 그 크기에 따라 방출하는 파장이 다른 특성을 지니며, 이러한 양자점을 형광물질 또는 발광물질로 사용하여, 디스플레이의 특성을 향상시키거나 디스플레이 자체로 활용할 수 있음이 알려져 있다. 한편, 상기 양자점은 예를 들어 백라이트 유닛(BLU)에 들어가는 고분자 광학시트 내에 소량으로 결합되어 사용되고 있다.A quantum dot is a semiconductor material having a crystal structure of several nano-sizes, and has a characteristic of emitting wavelengths different according to its size. The quantum dot is used as a fluorescent material or a light emitting material to improve display characteristics. It is known that it can be used as a display or itself. On the other hand, the quantum dots are used in combination in a small amount in the polymer optical sheet, for example to enter the backlight unit (BLU).
그러나 상기 양자점은 공기 중의 수분과 산소에 노출되면 표면산화에 의한 산화 문제점이 있어, 이를 보완하기 위한 방법으로 2장의 배리어필름 사이에 양자점이 분산된 고분자 수지를 분산시킨 후 경화시켜 광학시트로 제조하는 것이 일반적이며, 상기 광학시트는 청색 BLU 모듈의 도광판 위에 배치(on-surface 방식)되고 있다. 한편 상기 광학시트는 소형부터 대형까지 다양한 디스플레이 화면 크기에 대응할 수 있다.However, the quantum dot has a problem of oxidation due to surface oxidation when exposed to moisture and oxygen in the air. As a method for compensating for this, the quantum dot is dispersed and cured by dispersing a polymer resin having quantum dots dispersed between two barrier films to produce an optical sheet. In general, the optical sheet is disposed on a light guide plate of a blue BLU module (on-surface method). The optical sheet may correspond to various display screen sizes from small to large.
한편, 상기와 같은 광학시트는 배리어필름으로 인하여 수분과 산소에 대한 어느 정도의 배리어성능은 가지고 있으나, 고온·고습 조건에 노출 시 배리어필름의 배리어성능이 급격히 떨어지게 되는 문제점이 있고, 이에 따라 광학시트의 휘도를 안정적으로 유지할 수 없는 문제점이 있다. 또한, 배리어필름의 주요 구성인 무기물층은 일반적으로 친수성을 가지고, 양자점이 분산된 고분자 수지층은 일반적으로 소수성을 가지므로, 상기 무기물층과 고분자 수지층 사이에 삽입되는 오버코팅층은 무기물층 및 고분자 수지층 양쪽 모두에 대한 접착력을 필요로 한다. 한편, 상기 오버코팅층 조성의 완성도가 떨어지는 경우 충분한 접착력을 확보하기 어렵고, 이에 따라 고온·고습 조건에 노출 시 고분자 수지층으로부터 무기물층을 비롯한 배리어층이 박리되는 문제점이 있으며, 이는 광학시트의 수명과 안정성에 악영향을 미치기 때문에 이를 개선하기 위한 노력이 필요한 실정이다.On the other hand, the optical sheet as described above has a certain barrier performance against moisture and oxygen due to the barrier film, but there is a problem that the barrier performance of the barrier film is sharply dropped when exposed to high temperature and high humidity conditions, accordingly, the optical sheet There is a problem in that the luminance of the crystal cannot be maintained stably. In addition, the inorganic layer, which is a major component of the barrier film, generally has hydrophilicity, and the polymer resin layer in which the quantum dots are dispersed generally has hydrophobicity, so that the overcoating layer inserted between the inorganic layer and the polymer resin layer is an inorganic layer and a polymer. The adhesive force to both resin layers is required. On the other hand, when the completeness of the overcoating layer composition is poor, it is difficult to secure sufficient adhesive strength, and thus, when exposed to high temperature and high humidity conditions, there is a problem in that a barrier layer including an inorganic layer is peeled from the polymer resin layer. As it adversely affects stability, efforts to improve the situation are required.
본 발명은 고온·고습 조건 하에서 안정성이 뛰어난 오버코팅층을 포함함으로써 고온·고습 조건 하에서 무기물층 및 고분자 수지층과의 충분한 접착력을 유지하는 배리어필름을 제공하고자 한다. 더 나아가, 언더코팅층을 포함함으로써 고온·고습 조건 하에서 무기물층에 크랙(crack)이 발생하는 것을 방지하여 배리어 성능을 지속적으로 유지하고, 나아가 광학시트의 휘도 저하를 방지하는 배리어필름을 제공한다.The present invention is to provide a barrier film that maintains sufficient adhesion to the inorganic material layer and the polymer resin layer under high temperature and high humidity conditions by including an overcoat layer having excellent stability under high temperature and high humidity conditions. Furthermore, by including an undercoat layer, it is possible to prevent the occurrence of cracks in the inorganic layer under high temperature and high humidity conditions, thereby maintaining barrier performance continuously, and further providing a barrier film that prevents a decrease in luminance of the optical sheet.
상기 과제를 달성하기 위한 본 발명의 일실시예에서, 기재; 상기 기재 상에 형성된 언더코팅층; 상기 언더코팅층 상에 형성된 무기물층; 및 상기 무기물층 상에 형성되며 열가소성 수지 및 열경화성 수지를 함께 포함하는 오버코팅층;을 포함하는 배리어필름을 제공한다.In one embodiment of the present invention for achieving the above object, the substrate; An undercoat layer formed on the substrate; An inorganic layer formed on the undercoat layer; And an overcoat layer formed on the inorganic layer and including a thermoplastic resin and a thermosetting resin.
본 발명의 또 다른 일실시예에서, 서로 대향하는 상기 2장의 배리어필름; 및 상기 2장의 배리어필름의 오버코팅층 사이에 형성되는 양자점이 분산된 고분자 수지층;을 포함하는 광학시트를 제공한다.In another embodiment of the present invention, the two barrier films facing each other; And a polymer resin layer in which a quantum dot is formed between the overcoating layers of the two barrier films.
본 발명의 또 다른 일실시예에서, a) 준비된 기재 상에 언더코팅 조성물을 도포하여 언더코팅층을 형성하는 단계; b) 상기 언더코팅층 상에 무기물층을 형성하는 단계; c) 열가소성 수지 및 열경화성 수지를 포함하는 오버코팅 조성물을 상기 무기물층 상에 도포하여 오버코팅층을 형성하고, 열경화하여 배리어필름을 제조하는 단계; 및 d) 상기 2장의 배리어필름 사이에 양자점이 분산된 고분자 조성물을 도포하고 UV 경화하는 단계;를 더 포함하는 광학시트 제조방법을 제공한다. In another embodiment of the present invention, a) applying an undercoat composition on the prepared substrate to form an undercoat layer; b) forming an inorganic layer on the undercoat layer; c) applying an overcoating composition comprising a thermoplastic resin and a thermosetting resin on the inorganic layer to form an overcoating layer, and thermosetting to prepare a barrier film; And d) applying a polymer composition in which a quantum dot is dispersed between the two barrier films and UV curing.
본 발명에 따른 배리어필름은 고온·고습 조건 하에서 안정성이 뛰어난 오버코팅층을 포함함으로써 고온·고습 조건 하에서 무기물층 및 고분자 수지층과의 충분한 접착력을 유지하게 된다.The barrier film according to the present invention includes an overcoating layer having excellent stability under high temperature and high humidity conditions, thereby maintaining sufficient adhesive force with the inorganic material layer and the polymer resin layer under high temperature and high humidity conditions.
또한, 본 발명에 따른 배리어필름은 언더코팅층을 포함함으로써 고온·고습 조건 하에서 무기물층에 크랙(crack)이 발생하는 것을 방지하여 배리어 성능을 지속적으로 유지하고, 나아가 광학시트의 휘도 저하를 방지한다.In addition, the barrier film according to the present invention includes an undercoating layer to prevent cracks in the inorganic layer under high temperature and high humidity conditions, thereby maintaining barrier performance continuously, and further preventing a decrease in luminance of the optical sheet.
도 1은 본 발명의 일실시예에 따른 배리어필름의 구조를 도식화한 것이다.1 is a diagram illustrating a structure of a barrier film according to an embodiment of the present invention.
도 2는 본 발명의 일실시예에 따른 광학시트의 구조를 도식화한 것이다.Figure 2 illustrates the structure of an optical sheet according to an embodiment of the present invention.
본 발명에 따른 배리어필름은 도 1에 도시된 바와 같이 기재(10); 상기 기재 상에 형성된 언더코팅층(20); 상기 언더코팅층 상에 형성된 무기물층(30); 및 상기 무기물층 상에 형성되며 열가소성 수지 및 열경화성 수지를 함께 포함하는 오버코팅층(40);을 포함한다(도 1 참조). Barrier film according to the invention is a substrate 10 as shown in Figure 1; An undercoat layer 20 formed on the substrate; An inorganic layer 30 formed on the undercoat layer; And an overcoat layer 40 formed on the inorganic layer and including a thermoplastic resin and a thermosetting resin (see FIG. 1).
종래의 기술에 따른 배리어필름의 경우 일반적으로 UV 경화 타입의 오버코팅층을 적용함으로써, 경화 시 급격한 수축에 의해 무기물층에 크랙(crack)이 발생하거나 미반응 모노머(monomer)의 표면 마이그레이션(migration)에 의한 접착불량 등의 문제점이 있었다. In the case of the barrier film according to the prior art, by applying an UV-curable type overcoat layer, cracks may occur in the inorganic layer due to rapid shrinkage during curing, or may be applied to surface migration of unreacted monomers. There was a problem such as poor adhesion.
반면, 본 발명에 따른 배리어필름은 열가소성 수지와 열경화성 수지의 혼합 조성을 적용하여 오버코팅층을 구성하였는 바, 상기 오버코팅층은 고온·고습 조건 하에서 무기물층 및 고분자 수지층과 양호한 접착력을 지속적으로 가진다. 또한, 내열성이 우수한 언더코팅층을 포함함으로써 고온·고습 조건 하에서도 배리어 성능을 지속적으로 유지할 수 있게 된다. On the other hand, the barrier film according to the present invention was applied to the mixed composition of the thermoplastic resin and the thermosetting resin to form an overcoating layer, the overcoating layer has a good adhesive strength with the inorganic layer and the polymer resin layer under high temperature and high humidity conditions. In addition, by including an undercoat layer having excellent heat resistance, barrier performance can be continuously maintained even under high temperature and high humidity conditions.
한편, 본 발명에 있어서, 층이라 함은 단층 혹은 1층 이상의 다층 구조로 형성되는 것을 의미하는 것일 수 있다. Meanwhile, in the present invention, the layer may mean to be formed in a single layer or a multilayer structure of one or more layers.
이하, 본 발명을 상세히 살펴본다.Hereinafter, the present invention will be described in detail.
배리어필름Barrier film
기재materials
본 발명의 배리어필름에 있어서 기재는 화학적 내지 물리적 강도가 우수하고, 무기물층을 형성하는 조건에 견디며, 상기 형성되는 무기물층 등의 특성을 손상시키지 않고 양호하게 보존할 수 있는 것일 수 있고, 또한 투명성을 가지는 것일 수 있다.In the barrier film of the present invention, the base material is excellent in chemical and physical strength, can withstand the conditions for forming the inorganic layer, and can be satisfactorily preserved without impairing the properties of the inorganic layer, etc., which are formed, and also has transparency. It may be to have.
본 발명의 일실시예에서, 상기 기재는 환상 폴리올레핀계 수지; 폴리스티렌계 수지; 아크릴로니트릴-스티렌 공중합체(AS 수지); 아크릴로니트릴-부타디엔-스티렌 공중합체(ABS 수지); 폴리(메타)아크릴계 수지; 폴리카보네이트계 수지, 폴리에틸렌테레프탈레이트 및 폴리에틸렌나프탈레이트를 포함하는 폴리에스테르계 수지; 나일론을 포함하는 폴리아마이드계 수지; 폴리우레탄계 수지; 아세탈계 수지; 및 셀룰로오스계 수지;로 이루어지는 군에서 선택되는 1종 이상의 수지로 제조된 필름 또는 시트 형태일 수 있다. In one embodiment of the present invention, the substrate is a cyclic polyolefin-based resin; Polystyrene resin; Acrylonitrile-styrene copolymer (AS resin); Acrylonitrile-butadiene-styrene copolymer (ABS resin); Poly (meth) acrylic resins; Polyester-based resins including polycarbonate-based resins, polyethylene terephthalate and polyethylene naphthalate; Polyamide-based resins including nylon; Polyurethane-based resins; Acetal resins; And cellulose-based resin; may be in the form of a film or sheet made of one or more resins selected from the group consisting of.
한편, 기재는 상기 고분자 수지 1종 또는 그 이상을 이용하여 압출법, 캐스트 성형법, T다이법, 절삭법, 인플레이션법 등의 제막화법을 이용하여 상기 각종 수지를 단독으로 제막화하는 방법, 또는 2종 이상의 고분자 수지를 사용하여 다층 공압출 제막화하는 방법, 더 나아가 2종 이상의 수지를 사용하여 제막화하기 전에 혼합하여 제막화하는 방법 등에 의해 제조된 것일 수 있고, 또한 텐터(tenter) 방식 또는 튜블러(tubular) 방식 등을 이용하여 1축 혹은 2축 방향으로 연신하여 제조된 것일 수 있다.On the other hand, the base material is a method of forming a film of the various resins alone using a film forming method such as extrusion method, cast molding method, T-die method, cutting method, inflation method using one or more of the polymer resin, or 2 It may be prepared by a method of forming a multilayer coextrusion film using at least one polymer resin, or further, by mixing and forming a film before forming a film by using at least two resins, and also using a tenter method or a tube. It may be manufactured by stretching in the uniaxial or biaxial direction using a blur (tubular) method.
또한, 상기 기재는 필요에 따라 필름 제막 공정 및 제막 공정 이후에 표면 처리된 것일 수 있는데, 상기 표면 처리는 코로나 처리, 플라즈마 처리, 이온 빔 처리, 스퍼터링 처리 또는 코팅 처리일 수 있다. 코팅 수지로는 우레탄계, 아크릴계, 폴리에스테르계 중 기재의 양면에 선택적으로 적용할 수 있다. In addition, the substrate may be surface treated after the film forming process and the film forming process, if necessary, the surface treatment may be corona treatment, plasma treatment, ion beam treatment, sputtering treatment or coating treatment. As the coating resin, it can be selectively applied to both sides of the substrate among the urethane, acrylic, and polyester.
한편, 상기 기재의 두께는 예를 들어 25 내지 188 ㎛, 더욱 상세하게는 50 내지 125 ㎛ 일 수 있으며, 상기 범위 내에서 충분한 내열 성능, 기계적 물성 및 가스 차단성능을 확보하도록 조절 가능하다. On the other hand, the thickness of the substrate may be, for example, 25 to 188 ㎛, more specifically 50 to 125 ㎛, it can be adjusted to ensure sufficient heat resistance, mechanical properties and gas barrier performance within the above range.
한편, 본 발명의 일실시예에 따른 기재는 일면 혹은 양면에 매트코팅(Matt coating) 처리된 것일 수 있으며, 상세하게는 기재의 표면 중 언더코팅층과 접촉하는 면의 반대면에 매트코팅 처리된 것일 수 있다. On the other hand, the substrate according to an embodiment of the present invention may be one or both surfaces of the mat coating (Matt coating), in detail, the surface of the substrate is a mat coating on the opposite surface of the contact surface with the undercoat layer Can be.
상기 기재가 매트코팅 처리되면 다른 광학시트와 접촉 시 접촉 면적이 줄어들어 wet-out이 발생하는 것을 줄일 수 있으며, 매트코팅에 의해 부여되는 헤이즈(haze)로 인하여, 기재 자체 혹은 외부 요인에 의한 기재의 디펙트(defect)를 육안으로 보이지 않게 하는 효과를 부여할 수 있다. 또한, 상기 매트코팅은 빛의 확산을 높여줌으로써 위치별 광 효율을 균일하게 만들 수 있게 된다. When the substrate is matte-coated, the contact area is reduced when it is in contact with another optical sheet, thereby reducing the occurrence of wet-out, and due to the haze imparted by the matte coating, The effect of making a defect invisible to the naked eye can be given. In addition, the matte coating can make light efficiency of each position uniform by increasing light diffusion.
언더코팅층Undercoating layer
일반적으로 배리어필름에 있어서 언더코팅층은 평탄화층 역할을 수행하여 기재의 조도를 낮춤으로써 무기물층 성막 시, 치밀한 구조로서 defect가 없는 무기물층을 형성할 수 있도록 한다. In general, the undercoat in the barrier film serves as a planarization layer to lower the roughness of the substrate to form an inorganic layer without a defect as a dense structure when forming the inorganic layer.
본 발명에서 상기 언더코팅층은 평탄화 기능 이외에도 유리전이온도(Tg) 조절을 통해 고온·고습 조건 하에서 열팽창 또는 열수축으로 인한 무기물층 하단의 유동 및 이로 인하여 발생되는 무기물층의 크랙(crack) 발생을 방지하는 역할 또한 수행한다. 이를 통하여 본 발명의 배리어필름은 고온·고습 조건 하에서도 배리어 성능을 균일하게 유지하며, 광학시트의 휘도 감소가 효과적으로 방지된다. In the present invention, in addition to the flattening function, the undercoating layer prevents the occurrence of cracking of the inorganic layer caused by flow and lowering of the inorganic layer due to thermal expansion or thermal contraction under high temperature and high humidity conditions by controlling the glass transition temperature (T g ). It also plays a role. Through this, the barrier film of the present invention maintains barrier performance uniformly even under high temperature and high humidity conditions, and effectively reduces the brightness of the optical sheet.
특히 본 발명에 있어서 상기 언더코팅층을 형성하는 언더코팅 조성물에 포함되는 고분자 수지는 기재를 구성하는 고분자 수지 대비 상대적으로 높은 유리전이 온도(Tg)를 가지는 것을 특징으로 한다. 예를 들어 PET 기재를 사용하는 경우, 언더코팅층 조성물에 포함되는 고분자 수지는 80 내지 250℃의 유리전이 온도, 더욱 상세하게는 80 내지 200℃의 유리전이 온도를 가지는 것일 수 있다. In particular, the polymer resin included in the undercoat composition forming the undercoat layer in the present invention is characterized by having a relatively high glass transition temperature (T g ) compared to the polymer resin constituting the substrate. For example, when using a PET substrate, the polymer resin included in the undercoat layer composition may have a glass transition temperature of 80 to 250 ℃, more specifically, a glass transition temperature of 80 to 200 ℃.
언더코팅층에 포함되는 고분자 수지가 상기와 같이 기재를 구성하는 고분자 수지 대비 상대적으로 높은 유리전이 온도를 가짐으로써 고온에서 무기물층 성막 시 언더코팅층의 수축을 방지하여 무기물층에 크랙이 발생하는 것을 최소화할 수 있고, 이에 따라 배리어 성능이 감소하는 것을 방지할 수 있으며, 또한 고온 신뢰성 평가 시 내열성을 확보해 무기물층에 크랙이 발생하는 것을 방지할 수 있게 된다. The polymer resin included in the undercoat layer has a relatively higher glass transition temperature than the polymer resin constituting the substrate as described above to prevent the undercoat layer from shrinking when the inorganic layer is formed at a high temperature to minimize the occurrence of cracks in the inorganic layer. Accordingly, the barrier performance may be prevented from being reduced, and heat resistance may be ensured at the high temperature reliability evaluation to prevent cracks in the inorganic layer.
본 발명의 일실시예에서, 상기 언더코팅층은 비스페놀 A계 아크릴레이트, 나프탈렌계 아크릴레이트, 아이소보닐계 아크릴레이트 및 아마만틸계 아크릴레이트를 포함하는 우레탄 아크릴레이트; 비스페놀 A, 비스페놀 F, 메틸렌 비스(4-하이드록시페닐) 등의 비스페놀계열, 레조르시놀, 디히드록시 나프탈렌, 디히드록시 바이페닐, 디히드록시 페닐 에탄올, 디히드록시 피리딘, 디히드록시퀴노살린, 디히드록시 테트라히드로나프탈렌 및 디히드록시피리미딘를 포함하는 방향족 폴리올 화합물; 및 1,3-프로페인 다이올, 1,4-부테인 다이올, 1,5-펜테인 다이올, 1,6-헥세인 다이올, 3-메틸-1,5-펜테인 다이올, 1,8-옥테인 다이올, 2-메틸-1,8-옥테인 다이올, 1,9-노네인 다이올 및 1,10-데케인 다이올을 포함하는 지방족 폴리올 화합물;로 이루어지는 군에서 선택되는 1종 이상의 고분자 수지 또는 이들의 조합을 포함할 수 있다. In one embodiment of the present invention, the undercoat layer is a urethane acrylate including bisphenol A-based acrylate, naphthalene-based acrylate, isobornyl-based acrylate and ammanthyl-based acrylate; Bisphenols such as bisphenol A, bisphenol F, methylene bis (4-hydroxyphenyl), resorcinol, dihydroxy naphthalene, dihydroxy biphenyl, dihydroxy phenyl ethanol, dihydroxy pyridine, dihydroxyquino Aromatic polyol compounds including saline, dihydroxy tetrahydronaphthalene and dihydroxypyrimidine; And 1,3-propane diol, 1,4-butane diol, 1,5-pentane diol, 1,6-hexane diol, 3-methyl-1,5-pentane diol, Aliphatic polyol compounds comprising 1,8-octane diol, 2-methyl-1,8-octane diol, 1,9-nonane diol and 1,10-decane diol; It may include one or more polymer resins selected or a combination thereof.
또한, 상기 언더코팅층은 우레탄 아크릴레이트 올리고머, 디펜타에리스리톨펜타아크릴레이트 및 트리히드록시에틸 이소시아누레이트 트리아크릴레이트로 이루어지는 군에서 선택되는 1종 이상의 고분자 수지 또는 이들의 조합을 포함할 수 있다.In addition, the undercoat layer may include at least one polymer resin selected from the group consisting of urethane acrylate oligomer, dipentaerythritol pentaacrylate and trihydroxyethyl isocyanurate triacrylate or a combination thereof.
한편, 상기 형성되는 언더코팅층의 두께는 0.01 내지 100㎛범위를 가질 수 있고, 더욱 상세하게는 0.1 내지 10 ㎛ 범위를 가질 수 있다. 상기 언더코팅층의 두께가 상기 범위 이내로 형성되는 경우, 평탄화 기능 및 내열성을 동시에 확보 할 수 있게 된다. On the other hand, the thickness of the formed undercoat layer may have a range of 0.01 to 100㎛, more specifically may have a range of 0.1 to 10㎛. When the thickness of the undercoat layer is formed within the above range, it is possible to ensure a flattening function and heat resistance at the same time.
무기물층Mineral layer
본 발명의 배리어필름에 있어서 무기물층은 수분 및 산소 차폐성이 있는 것이어야 한다. 본 발명의 광학시트에 포함되는 양자점은 수분 및 산소에 취약하여 수분 및 산소에 노출 시 표면이 산화하여 광학시트의 수명을 단축시키고 휘도가 감소하는 문제점이 있으므로, 상기 무기물층은 수분 및 산소를 차단하여 양자점이 산화되는 것을 방지한다.In the barrier film of the present invention, the inorganic layer should have moisture and oxygen shielding properties. Since the quantum dots included in the optical sheet of the present invention are vulnerable to moisture and oxygen, the surface is oxidized when exposed to moisture and oxygen, which shortens the lifespan of the optical sheet and decreases the brightness. Thus, the inorganic layer blocks moisture and oxygen. This prevents the quantum dots from oxidizing.
본 발명의 일실시예에서, 상기 무기물층에 포함되는 무기물은 규소(Si), 알루미늄(Al), 인듐(In), 주석(Sn), 아연(Zn), 지르코늄(Zr), 티타늄(Ti), 구리(Cu), 세륨(Ce), 이트륨(Yt), 란탄(La), 바륨(Ba), 마그네슘(Mg), 플루오르(F2), 안티몬(Sb), 스트론튬(Sr) 및 탄탈륨(Ta)으로 이루어지는 군에서 선택되는 1종 이상의 금속을 포함하는 산화물, 질화물, 탄화물, 산화질화물, 산화탄화물, 질화탄화물, 또는 산화질화탄화물일 수 있다. In one embodiment of the present invention, the inorganic material included in the inorganic layer is silicon (Si), aluminum (Al), indium (In), tin (Sn), zinc (Zn), zirconium (Zr), titanium (Ti) , Copper (Cu), cerium (Ce), yttrium (Yt), lanthanum (La), barium (Ba), magnesium (Mg), fluorine (F 2 ), antimony (Sb), strontium (Sr) and tantalum (Ta) It may be an oxide, nitride, carbide, oxynitride, oxidized carbide, nitride carbide, or oxynitride carbide containing at least one metal selected from the group consisting of.
한편, 상기 형성되는 무기물층의 두께는 예를 들어 10 내지 1000㎚일 수 있으며, 상기 설명한 바와 같이 언더코팅층으로 인하여 무기물층의 두께가 종래의 배리어필름 대비 상대적으로 얇을 수 있다. 또한, 상기 무기물층은 1층 이상의 다층 구조일 수 있으며, 다층 구조로 형성 시 접착력 향상을 위하여 Tie-layer 또는 투과도 향상을 위한 층이 더 포함될 수 있다. On the other hand, the thickness of the inorganic layer formed may be, for example, 10 to 1000nm, the thickness of the inorganic layer may be relatively thin compared to the conventional barrier film due to the undercoat as described above. In addition, the inorganic layer may have a multilayer structure of one or more layers, and may further include a layer for improving tie or layer or permeability to improve adhesion when formed into a multilayer structure.
오버코팅층Overcoat Layer
본 발명에 있어서, 오버코팅층은 무기물층을 스크래치 등으로부터 보호하는 동시에, 상기 오버코팅층의 하단과 접촉하는 무기물층 및 상기 오버코팅층의 상단과 접촉하는 양자점을 포함하는 고분자 수지층과의 충분한 접착력을 확보하기 위한 것이다. 또한, 무기물층에 존재하는 미세한 핀홀을 막아 배리어 성능을 향상시킨다. In the present invention, the overcoat layer protects the inorganic layer from scratches and at the same time secures sufficient adhesion to the polymer resin layer including an inorganic layer in contact with the bottom of the overcoating layer and a quantum dot in contact with the top of the overcoating layer. It is to. In addition, the barrier performance is improved by preventing fine pinholes present in the inorganic layer.
특히, 본 발명의 일실시예에서, 상기와 같은 과제를 달성하기 위하여 오버코팅층에는 열가소성 수지와 열경화성 수지를 함께 포함한다.In particular, in one embodiment of the present invention, in order to achieve the above problems, the overcoat layer includes a thermoplastic resin and a thermosetting resin together.
본 발명의 일실시예에서, 상기 열가소성 수지는 폴리에테르계 수지, 폴리우레탄계 수지, 폴리에스테르계 수지, 폴리비닐부티랄계 수지 및 폴리비닐알콜계 수지로 이루어지는 군에서 선택되는 1종 이상의 고분자 수지일 수 있다. 상기 열가소성 수지는 양자점이 분산된 고분자 수지층과의 접착력 확보를 위하여 적용된다. In one embodiment of the present invention, the thermoplastic resin may be at least one polymer resin selected from the group consisting of polyether resin, polyurethane resin, polyester resin, polyvinyl butyral resin and polyvinyl alcohol resin. have. The thermoplastic resin is applied to secure adhesion to the polymer resin layer in which the quantum dots are dispersed.
한편, 본 발명의 일실시예에서, 상기 열경화성 수지는 에폭시 수지, 불포화 폴리에스테르 수지, 폴리우레탄 수지, 폴리카보네이트 폴리우레탄, 폴리에스테르 폴리우레탄, 페놀 수지, 멜라민 수지, 요소 수지 및 규소 수지로 이루어지는 군에서 선택되는 1종 이상의 고분자 수지일 수 있다. 상기 열경화성 수지는 고온·고습 조건 하에서 장기 신뢰성 확보를 위하여 적용된다.On the other hand, in one embodiment of the present invention, the thermosetting resin is a group consisting of epoxy resin, unsaturated polyester resin, polyurethane resin, polycarbonate polyurethane, polyester polyurethane, phenol resin, melamine resin, urea resin and silicon resin It may be at least one polymer resin selected from. The thermosetting resin is applied to ensure long-term reliability under high temperature and high humidity conditions.
한편, 상기 오버코팅층 내에 포함되는 열가소성 수지 대 열경화성 수지의 고형분 중량비는 2 : 8 내지 8 : 2의 범위를 가질 수 있다. 보다 상세하게 설명하면, 열가소성 수지가 상기 범위를 초과하여 포함되는 경우 양자점이 분산된 고분자 수지층과의 접착력은 향상되나 고온·고습 조건 하에서 접착력 및 장기 신뢰성 확보가 어려워지며, 열경화성 수지가 상기 범위를 초과하여 포함되는 경우 고온·고습 조건 하에서 장기 신뢰성 확보는 용이하나, 양자점이 분산된 고분자 수지와의 접착력이 떨어질 수 있어 문제된다.On the other hand, the solid content weight ratio of the thermoplastic resin to the thermosetting resin included in the overcoating layer may have a range of 2: 8 to 8: 2. In more detail, when the thermoplastic resin is included in the above range, adhesion to the polymer resin layer in which the quantum dots are dispersed is improved, but it is difficult to secure adhesion and long-term reliability under high temperature and high humidity conditions. When included in excess, it is easy to secure long-term reliability under high temperature and high humidity conditions, but there is a problem in that adhesion to the polymer resin in which the quantum dots are dispersed may be degraded.
한편, 상기 오버코팅층의 형성 방법은 특별히 제한되지 않으나, 바 코터, 롤 코터 또는 다이 코터와 같은 코터를 이용하여 무기물층 상에 오버코팅 조성물을 적용하여 형성하는 것일 수 있으며, 선택적으로 무기물층에 플라즈마 처리, 코로나 처리, 산처리 등과 같이 전처리한 후 오버코팅 조성물을 적용한 것일 수 있다. 상기 오버코팅 조성물은 열가소성 수지 및 열경화성 수지를 용매에 넣고 교반하여 형성한 것일 수 있고, 필요에 따라 반응촉진제, 대전 방지제, 광선 차단제, 자외선 흡수제, 가소제, 활제, 필러, 착색제, 안정제, 윤활제, 가교제, 블로킹 방지제, 산화 방지제, 접착증진제 등과 같은 첨가제를 추가로 넣어 제조한 것일 수 있다. On the other hand, the method of forming the overcoating layer is not particularly limited, but may be formed by applying the overcoating composition on the inorganic layer using a coater such as a bar coater, a roll coater or a die coater, optionally the plasma on the inorganic layer After treatment, such as treatment, corona treatment, acid treatment, etc. may be applied to the overcoating composition. The overcoating composition may be formed by stirring a thermoplastic resin and a thermosetting resin in a solvent, and as necessary, a reaction accelerator, an antistatic agent, a sunscreen agent, an ultraviolet absorber, a plasticizer, a lubricant, a filler, a colorant, a stabilizer, a lubricant, a crosslinking agent. It may be prepared by additionally adding an additive, such as an antiblocking agent, an antioxidant, an adhesion promoter, and the like.
한편, 본 발명의 일실시예에서 상기 오버코팅층은 투과도, 헤이즈 조절 등과 같은 추가적인 기능을 구현하기 위하여 패턴화된 것일 수도 있으며 1층 이상의 다층으로 구성될 수도 있다. 예를 들어 오버코팅층은 무기물층 상에 격자 형태로 도포되어 형성되거나, 라인 형태 혹은 다양한 형상으로 패턴화된 것일 수 있으며, 상기 패턴화의 경우 경제성과 오버코팅층의 투과도 및 헤이즈 조절을 고려하여 필요에 따라 다양한 형태로 형성될 수 있다.Meanwhile, in one embodiment of the present invention, the overcoating layer may be patterned to implement additional functions such as transmittance, haze control, or the like, and may be formed of one or more layers. For example, the overcoating layer may be formed in a lattice form on the inorganic layer, or may be patterned in a line shape or various shapes. In the case of the patterning, the overcoating layer may be adjusted in consideration of economical efficiency and transmittance and haze of the overcoating layer. According to the present invention.
한편, 본 발명의 일실시예에서, 상기 오버코팅 조성물에는 커플링제 및 가수분해 방지제 및 접착증진제 중 선택되는 1종 이상의 첨가제를 더 포함할 수 있다. Meanwhile, in one embodiment of the present invention, the overcoating composition may further include at least one additive selected from a coupling agent and a hydrolysis inhibitor and an adhesion promoter.
상기 커플링제는 오버코팅층과 무기물층 간의 접착력을 추가적으로 향상시키는 역할을 수행하며, 보다 상세하게는 무기물층의 표면에 존재하는 하이드록시 그룹과 반응하여 표면을 개질함으로써 오버코팅층과 무기물층 간의 접착력을 향상시키게 된다. The coupling agent serves to further improve the adhesion between the overcoating layer and the inorganic layer, and more specifically, by modifying the surface by reacting with hydroxy groups present on the surface of the inorganic layer to improve the adhesion between the overcoating layer and the inorganic layer. Let's go.
본 발명의 일실시예에서 상기 커플링제는 메톡시(Methoxy), 에톡시(Ethoxy), 아미노(Amino), 에폭시(Epoxy), 아크릴(Acryl), 머캅토(Mercapto), 비닐(Vinyl) 및 메타크릴(Methacryl)계 실란 커플링제로 이루어지는 군에서 선택되는 1종 이상의 물질 또는 이들의 조합일 수 있다.In one embodiment of the present invention, the coupling agent is methoxy, ethoxy, amino, epoxy, acryl, mercapto, vinyl and meta. It may be one or more materials selected from the group consisting of Methacryl-based silane coupling agents or a combination thereof.
한편, 상기 가수분해 방지제는 폴리머의 안정한 상태 화합물을 생성하여 고온·고습 접착력 신뢰성을 개선하는 역할을 하며, 보다 상세하게는 가수분해 방지제가 수분과 반응하여, 우레아(urea)구조를 만들게 되므로, 수분에 의한 노화를 방지해서 접착력과 내구성이 보다 우수해진다.On the other hand, the hydrolysis inhibitor serves to improve the high-temperature and high-humidity adhesion reliability by generating a stable state compound of the polymer, and more specifically, the hydrolysis inhibitor reacts with water to form a urea structure, It prevents the aging caused by the adhesion and the durability is excellent.
본 발명의 일실시예에서, 상기 가수분해 방지제는 방향족 카르보디이미드(aromatic carbodiimide) 계열로 이루어지는 군에서 선택되는 1종 이상의 물질 또는 이들의 조합일 수 있다. In one embodiment of the present invention, the hydrolysis inhibitor may be one or more substances selected from the group consisting of aromatic carbodiimide series or a combination thereof.
한편, 상기 접착증진제는 고분자 수지층과의 접착력 확보 혹은 무기물층과의 접착력 확보에 도움을 줄 수 있는 것이라면 특별히 제한되지 않으며, 당해 분야에서 일반적으로 사용되는 것일 수 있다. On the other hand, the adhesion promoter is not particularly limited as long as it can help to secure the adhesive force with the polymer resin layer or the adhesive force with the inorganic material layer, it may be generally used in the art.
한편, 상기 오버코팅층의 두께는 예를 들어 0.1 내지 10㎛, 더욱 상세하게는 0.5 내지 2㎛일 수 있다. 오버코팅층의 두께가 0.1㎛ 미만인 경우 고분자 수지층과의 접착력에 문제가 있을 수 있으며, 10㎛를 초과하면 수분 및 가스가 사이드로 침투하여 배리어 성능이 나빠지는 문제가 있을 수 있다.On the other hand, the thickness of the overcoat layer may be, for example, 0.1 to 10㎛, more specifically 0.5 to 2㎛. If the thickness of the overcoating layer is less than 0.1㎛ may have a problem with the adhesive strength with the polymer resin layer, if it exceeds 10㎛ there may be a problem that the barrier performance deteriorates due to the penetration of water and gas to the side.
상기 설명한 바와 같이 본 발명의 배리어필름은, 고온·고습 조건 하에서 안정성이 뛰어난 오버코팅층을 포함함으로써 고온·고습 조건 하에서 무기물층 및 고분자 수지층과의 충분한 접착력을 유지하게 되며, 또한 언더코팅층을 포함함으로써 고온·고습 조건 하에서 무기물층에 크랙(crack)이 발생하는 것을 방지하여 배리어 성능을 지속적으로 유지하고, 나아가 광학시트의 휘도 저하를 방지한다. As described above, the barrier film of the present invention includes an overcoating layer having excellent stability under high temperature and high humidity conditions, thereby maintaining sufficient adhesion to the inorganic material layer and the polymer resin layer under high temperature and high humidity conditions, and further including an undercoating layer. By preventing cracks in the inorganic layer under high temperature and high humidity conditions, barrier performance is continuously maintained, and further, brightness degradation of the optical sheet is prevented.
광학시트Optical sheet
한편, 상기와 같은 배리어필름을 포함하는 광학시트는 오버코팅층이 무기물층 및 고분자 수지층과 충분한 접착력을 확보하고, 언더코팅층이 고온·고습 조건 하에서 배리어 성능을 유지해 고온·고습 조건에서 신뢰성이 향상되며, 또한 추가적인 배리어성능을 기대할 수 있어 광학시트의 광학성능 유지 및 신뢰특성이 향상되는 효과가 있다. On the other hand, in the optical sheet including the barrier film as described above, the overcoating layer secures sufficient adhesion with the inorganic material layer and the polymer resin layer, and the undercoating layer maintains barrier performance under high temperature and high humidity conditions, thereby improving reliability under high temperature and high humidity conditions. In addition, it is possible to expect additional barrier performance, thereby improving the optical performance and reliability of the optical sheet.
본 발명의 일실시예에 따른 광학시트는, 서로 대향하는 상기 2장의 배리어필름; 및 상기 2장의 배리어필름의 오버코팅층(40) 사이에 형성되는 양자점이 분산된 고분자 수지층(50);을 포함한다(도 2 참조). Optical sheet according to an embodiment of the present invention, the two barrier film facing each other; And a polymer resin layer 50 in which quantum dots formed between the overcoating layers 40 of the two barrier films are dispersed (see FIG. 2).
먼저 기재를 준비하고, 상기 기재 상에 언더코팅 조성물을 도포하여 언더코팅층을 형성한다(단계 a).First, a substrate is prepared, and an undercoat composition is applied on the substrate to form an undercoat layer (step a).
상기 기재는 앞서 설명한 바와 같으며, 언더코팅층의 형성 방법은 특별히 제한되지 않으나, 롤 코터와 같은 코터를 이용하여 기재 상에 언더코팅 조성물을 적용하여 형성하는 것일 수 있으며, 상기 언더코팅 조성물은 고분자 수지 및 중합개시제를 용매에 넣고 교반하여 형성한 것일 수 있다. The substrate is as described above, the method of forming the undercoat layer is not particularly limited, but may be formed by applying the undercoat composition on the substrate using a coater such as a roll coater, the undercoat composition is a polymer resin And it may be formed by putting a polymerization initiator in a solvent and stirred.
상기 언더코팅 조성물에 포함되는 고분자 수지는 앞서 설명한 바와 같이 언더코팅층에 포함되는 고분자 수지에 해당하며, 필요에 따라 중합개시제와 같은 첨가제를 더 포함할 수 있다.The polymer resin included in the undercoat composition corresponds to the polymer resin included in the undercoat layer as described above, and may further include an additive such as a polymerization initiator as necessary.
다음으로, 상기 언더코팅층 상에 무기물층을 형성한다(단계 b).Next, to form an inorganic layer on the undercoat layer (step b).
상기 무기물층을 형성하는 방법은 증착법, 코팅법 등 다양한 방법을 사용할 수 있으나, 가스 배리어성을 충분히 확보하고 균일한 박막을 얻기 위해서는 증착법을 사용할 수 있다. 상기 증착법은 진공 증착, 이온 플레이팅, 스퍼터링 등의 물리적 기상 증착법(PVD), 화학적 기상 증착법(CVD) 등의 방법을 모두 포함할 수 있다. 한편, 스퍼터링 방법으로서 진공 챔버 내에 타깃을 설치하고, 고전압을 가하여 이온화한 희가스 원소(통상 아르곤)를 타깃에 충돌시켜 타깃 표면의 원자를 떨어뜨리고, 기재에 부착시키는 방법이다. 이때, 챔버 내에 질소 가스 또는 산소 가스를 흘림으로써 아르곤 가스에 의해 타깃으로부터 떨어진 원소와 질소 또는 산소를 반응시켜 가스 배리어성층을 형성하는 반응성 스퍼터링 방법을 사용할 수도 있다. The inorganic layer may be formed by various methods such as a deposition method and a coating method. However, the deposition method may be used to sufficiently secure a gas barrier property and obtain a uniform thin film. The deposition method may include all methods such as physical vapor deposition (PVD), chemical vapor deposition (CVD), and the like, such as vacuum deposition, ion plating, and sputtering. On the other hand, as a sputtering method, a target is provided in a vacuum chamber, and a rare gas element (normally argon) ionized by applying a high voltage is collided with the target to drop atoms on the target surface and adhere to the substrate. At this time, a reactive sputtering method may be used in which a gas barrier layer is formed by reacting nitrogen or oxygen with an element separated from the target by argon gas by flowing nitrogen gas or oxygen gas into the chamber.
한편, 상기 무기물층 형성 후에는 전처리 과정을 추가적으로 거칠 수 있는데, 상기 전처리 과정은 플라즈마 처리, 코로나 처리 혹은 산처리 등일 수 있고, 흡착된 각종 불순물을 제거하는 과정으로서, 상기 과정을 통하여 무기물층과 오버코팅층 간의 접착력을 더욱 향상시킬 수 있다. 특히, 플라즈마 처리 또는 코로나 처리는 무기물층 상에 존재하는 저분자량 불순물을 효과적으로 제거할 수 있다. Meanwhile, after the inorganic layer is formed, a pretreatment may be additionally performed. The pretreatment may be plasma treatment, corona treatment, or acid treatment, and removes various adsorbed impurities. The adhesion between the coating layers can be further improved. In particular, the plasma treatment or the corona treatment can effectively remove the low molecular weight impurities present on the inorganic layer.
다음으로, 열가소성 수지 및 열경화성 수지를 포함하는 오버코팅 조성물을 상기 무기물층 상에 도포하여 오버코팅층을 형성하고, 열경화하면 배리어필름이 제조된다(단계 c). Next, an overcoating composition comprising a thermoplastic resin and a thermosetting resin is applied on the inorganic layer to form an overcoating layer and thermally cured to produce a barrier film (step c).
한편, 상기 배리어필름 제조 직후에 필요에 따라 후경화 공정을 추가로 거칠 수도 있다. On the other hand, the post-curing step may be further roughened as needed immediately after the barrier film is manufactured.
상기 오버코팅 조성물에는 앞서 설명한 바와 같이, 열가소성 수지 및 열경화성 수지 이외에 커플링제, 가수분해 방지제 및 접착증진제로 이루어지는 군에서 선택되는 1종 이상의 첨가제를 더 포함할 수 있다. As described above, the overcoating composition may further include at least one additive selected from the group consisting of a coupling agent, a hydrolysis inhibitor, and an adhesion promoter in addition to the thermoplastic resin and the thermosetting resin.
한편, 본 발명의 또 다른 실시예에서는 상기 오버코팅 조성물 내에 반응촉진제, 대전 방지제, 광선 차단제, 자외선 흡수제, 가소제, 활제, 필러, 착색제, 안정제, 윤활제, 가교제, 블로킹 방지제, 산화 방지제 또는 접착증진제 등과 같은 첨가제를 추가로 넣어 제조한 것일 수 있다. On the other hand, in another embodiment of the present invention, in the overcoating composition, the reaction accelerator, the antistatic agent, the sunscreen, the ultraviolet absorber, the plasticizer, the lubricant, the filler, the colorant, the stabilizer, the lubricant, the crosslinking agent, the antiblocking agent, the antioxidant or the adhesion promoter, etc. It may be prepared by adding the same additives.
한편, 상기 오버코팅 조성물에 포함되는 열가소성 수지 대 열경화성 수지의 고형분 중량비는 2 : 8 내지 8 : 2일 수 있다.Meanwhile, the solids weight ratio of the thermoplastic resin to the thermosetting resin included in the overcoating composition may be 2: 8 to 8: 2.
한편, 상기 커플링제는 조성물 전체 중량을 기준으로 1 내지 20wt%로 포함될 수 있고, 더욱 상세하게는 1 내지 10wt%로 포함될 수 있다. On the other hand, the coupling agent may be included in 1 to 20wt% based on the total weight of the composition, more specifically may be included in 1 to 10wt%.
한편, 상기 가수분해 방지제는 조성물 전체 중량을 기준으로 1 내지 20wt%로 포함될 수 있고, 더욱 상세하게는 1 내지 5wt%로 포함될 수 있다. On the other hand, the hydrolysis inhibitor may be included in 1 to 20wt% based on the total weight of the composition, more specifically may be included in 1 to 5wt%.
한편, 상기 접착증진제는 조성물 전체 중량을 기준으로 1 내지 20wt%로 포함될 수 있고, 더욱 상세하게는 1 내지 5wt%로 포함될 수 있다. On the other hand, the adhesion promoter may be included in 1 to 20wt% based on the total weight of the composition, more specifically may be included in 1 to 5wt%.
한편, 상기 오버코팅층 형성 전 혹은 오버코팅층 형성 시 무기물층 표면의 불순물을 제거하기 위한 화학적 처리를 추가적으로 할 수 있으며, 상기 화학 처리는 소듐 하이드록사이드(sodium hydroxide) 및 포타슘 하이드록사이드(potassium hydrdoxide)를 포함하는 커스틱(caustics); 소듐 메타 실리케이트(sodium meta silicate)를 포함하는 실리케이트(silicate); 트리에탄올아민(triethanolamine) 및 모노에탄올아민아민(monoethanolamine)를 포함하는 아민(amine); 트리소듐 포스페이트(trisodium phophate), 테트라 포타슘 파이로 포스페이트(tetra potaasium pyro phosphate)를 포함하는 포스페이트(phosphate); 포스포릭(phosphoric), 하이드로플루오릭(hydrofluoric), 시트릭(citric)을 포함하는 산(acids); 및 EDTA를 포함하는 킬레이트(chelates);를 포함하는 군에서 선택되는 1종 이상의 화학적 클리너(chemical cleaner)를 사용하여 이루어지는 것일 수 있다. Meanwhile, before the overcoating layer is formed or when the overcoating layer is formed, a chemical treatment for removing impurities on the surface of the inorganic layer may be additionally performed, and the chemical treatment is sodium hydroxide and potassium hydrdoxide. Caustics including; Silicates, including sodium meta silicate; Amines including triethanolamine and monoethanolamine; Phosphates including trisodium phophate, tetra potaasium pyro phosphate; Acids, including phosphoric, hydrofluoric, and citric; And chelates including EDTA; and one or more chemical cleaners selected from the group including chelates.
한편, 상기 열경화 과정은 오버코팅 조성물 내의 열가소성 및 열경화성 수지를 열을 가하여 경화시키는 과정이며, 열경화를 위한 구체적인 조건은 80 내지 150 ℃의 온도 조건에서 30초 내지 5분 동안 용매(Solvent)를 건조 및 경화시킨 후, 30 내지 60 ℃의 온도 조건에서 1일 내지 3일 동안 후경화가 수행되는 것일 수 있다. 더욱 상세하게는 100 내지 120℃의 온도 조건에서 30초 내지 60초 동안 용매(Solvent)를 건조 및 경화시킨 후, 40 내지 60 ℃의 온도 조건에서 24 내지 72 시간 동안 후경화가 수행되는 것일 수 있다. On the other hand, the thermosetting process is a process of curing the thermoplastic and the thermosetting resin in the overcoating composition by applying heat, specific conditions for the thermosetting is a solvent (Solvent) for 30 seconds to 5 minutes at a temperature of 80 to 150 ℃ After drying and curing, the post-curing may be performed for 1 to 3 days at a temperature condition of 30 to 60 ℃. More specifically, after drying and curing the solvent (Solvent) for 30 seconds to 60 seconds at a temperature of 100 to 120 ℃, after curing may be performed for 24 to 72 hours at a temperature of 40 to 60 ℃. .
상기의 방법으로 제조한 2장의 배리어필름을 준비하고, 상기 배리어필름의 오버코팅층을 서로 마주보게 배치한 다음, 상기 2장의 배리어필름 사이에 양자점이 분산된 고분자 조성물을 도포하여 UV 경화하면 광학시트가 제조된다(단계 d).When the two barrier films prepared by the above method were prepared, the overcoating layers of the barrier film were disposed to face each other, and then the optical sheet was applied by UV curing by applying a polymer composition having quantum dots dispersed between the two barrier films. Prepared (step d).
상기 양자점이 분산된 고분자 조성물에 포함되는 고분자 수지는 양자점을 포함하는 매트릭스 역할을 하는 것으로서, 1층 이상의 층구조를 가지는 것일 수 있으며, 낮은 산소 및 수분투과성을 가지는 것이 바람직하고, 또한 높은 광 안정성 및 화학적 안정성을 가지는 것이 바람직하다. The polymer resin included in the polymer composition in which the quantum dots are dispersed may serve as a matrix including quantum dots, and may have a layer structure of one or more layers, and preferably have low oxygen and moisture permeability, and also have high light stability and It is desirable to have chemical stability.
본 발명의 일실시예에서, 상기 고분자 수지는 예를 들어, 에폭시, 에폭시 아크릴레이트, 라우릴 아크릴레이트, 노르보렌, 폴리에틸렌, 폴리스타이렌, 에틸렌-스타이렌 공중합체, 비스페놀 A 및 비스페놀 A유도체가 포함된 아크릴레이트, 플루오렌 유도체가 포함된 아크릴레이트, 이소보닐아크릴레이트, 폴리페닐알킬실록산, 폴리디페닐실록산, 폴리디알킬실록산, 실세스퀴옥산, 플루오르화 실리콘, 비닐 및 수소화물 치환 실리콘으로 이루어지는 군에서 선택되는 1종 이상의 고분자 수지일 수 있다. In one embodiment of the present invention, the polymer resin, for example, epoxy, epoxy acrylate, lauryl acrylate, norborene, polyethylene, polystyrene, ethylene-styrene copolymer, bisphenol A and bisphenol A derivatives are included Acrylate, acrylate containing fluorene derivative, isobornyl acrylate, polyphenylalkylsiloxane, polydiphenylsiloxane, polydialkylsiloxane, silsesquioxane, fluorinated silicone, vinyl and hydride substituted silicone It may be at least one polymer resin selected from.
한편, 상기 양자점은 실질적으로 단결정질인 나노구조들을 지칭하는 것으로서, 상기 양자점은 광원으로부터 방출된 1차 광을 흡수한 다음, 2차 광을 방출할 수 있으며, 상기 양자점의 크기에 따라 파장이 다른 광을 방출할 수 있다. 한편, 상기 양자점의 전형적인 크기는 1 내지 10 ㎚일 수 있는데, 상기 양자점의 크기가 4 내지 5㎚ 인 경우 광원으로부터 1차 광을 흡수한 후 적색을 가지는 2차 광을 방출할 수 있고, 2 내지 3㎚ 인 경우 광원으로부터 1차 광을 흡수한 후 녹색을 가지는 2차 광을 방출할 수 있다. Meanwhile, the quantum dots refer to nanostructures that are substantially monocrystalline, and the quantum dots absorb primary light emitted from a light source and then emit secondary light, and have different wavelengths depending on the size of the quantum dot. It can emit light. On the other hand, the typical size of the quantum dot may be 1 to 10 nm, when the size of the quantum dot is 4 to 5 nm may absorb the secondary light from the light source and then emit a secondary light having a red, 2 to In the case of 3 nm, the secondary light having green color may be emitted after absorbing the primary light from the light source.
한편, 상기 양자점은 고분자 매트릭스 내에 균일하게 분산될 수 있으며, 상기 고분자 레진층이 다층 구조인 경우, 층층마다 다른 크기의 양자점이 배치될 수도 있으며, 단일 층 내에 서로 다른 크기의 양자점이 혼재되어 분산된 형태를 가질 수도 있다. On the other hand, the quantum dots may be uniformly dispersed in the polymer matrix, when the polymer resin layer is a multi-layer structure, quantum dots of different sizes may be arranged for each layer layer, quantum dots of different sizes are mixed and dispersed in a single layer It may have a form.
한편, 본 발명의 일실시예에 따른 양자점은 비카드뮴계 양자점일 수도 있으며, 본 발명에 사용하기 위한 양자점들은 임의의 적합한 무기 재료를 포함할 수 있다. On the other hand, the quantum dot according to an embodiment of the present invention may be a non-cadmium-based quantum dot, the quantum dots for use in the present invention may include any suitable inorganic material.
본 발명의 일실시예에서, 상기 비카드뮴계 양자점은 II-VI 족, III-V족, IV-VI 족 및 IV 족 반도체로 이루어지는 군에서 선택되는 무기 재료를 포함할 수 있다. In one embodiment of the present invention, the non-cadmium-based quantum dots may include an inorganic material selected from the group consisting of Group II-VI, III-V, IV-VI and Group IV semiconductors.
본 발명의 일실시예에서, 상기 비카드뮴계 양자점은 Si, Ge, Sn, Se, Te, B, C, P, BN, BP, BAs, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, ZnO, ZnS, ZnSe, ZnTe, HgS, HgSe, HgTe, BeS, BeSe, BeTe, MgS, MgSe, GeS, GeSe, GeTe, SnS, SnSe, SnTe, PbO, PbS, PbSe, PbTe, CuF, CuCl, CuBr, CuI, Si3N4, Ge3N4 및 이들의 조합으로 이루어지는 군에서 선택되는 1종 이상의 무기 재료를 포함할 수 있다.In one embodiment of the present invention, the non-cadmium-based quantum dot is Si, Ge, Sn, Se, Te, B, C, P, BN, BP, BAs, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, ZnO, ZnS, ZnSe, ZnTe, HgS, HgSe, HgTe, BeS, BeSe, BeTe, MgS, MgSe, At least one selected from the group consisting of GeS, GeSe, GeTe, SnS, SnSe, SnTe, PbO, PbS, PbSe, PbTe, CuF, CuCl, CuBr, CuI, Si 3 N 4 , Ge 3 N 4, and combinations thereof Inorganic materials.
상기와 같은 고분자 조성물을 배리어필름 사이에 도포하고 UV 경화하는 단계를 거치면 광학시트를 제조할 수 있다. 한편, 상기 UV 경화 단계는 100 내지 5000mJ/cm2의 노광 조건에서 수행되는 것일 수 있다. UV 경화 시 상기 범위 이외의 노광 조건에서는 UV 경화가 효과적으로 이루어지지 않아 배리어필름과 고분자 수지층 간에 피착파괴될 정도의 접착력을 가지지 못할 수 있다. The optical sheet may be prepared by applying the polymer composition as described above between the barrier films and undergoing UV curing. On the other hand, the UV curing step may be performed under exposure conditions of 100 to 5000mJ / cm 2 . In the case of UV curing, UV curing may not be performed effectively under exposure conditions other than the above range, and thus may not have adhesive strength enough to be deposited between the barrier film and the polymer resin layer.
또한 IR　Peak (Acrylate, 810 or 1635cm- 1)에서 UV 노광에너지에 따른 data를 보면 경화도(노광되지 않을 상태를 100% 로 볼 때 Peak 가 감소되는 비율)가 60 내지 80%가 되는 것이 바람직할 수 있다.In addition, when looking at the data according to the UV exposure energy at IR Peak (Acrylate, 810 or 1635cm - 1 ), it is desirable that the degree of hardening (the rate at which the peak decreases when the state is not exposed to 100%) is 60 to 80%. Can be.
한편, 상기 고분자 조성물을 배리어필름 사이에 도포하는 과정은 특별히 제한되지 않으며, 예를 들어 롤투롤(Roll-to-roll) 공정으로 수행되는 것일 수 있다. On the other hand, the process of applying the polymer composition between the barrier film is not particularly limited, for example, may be performed by a roll-to-roll process.
상기 일련의 과정을 거쳐 제조되는 광학시트는 접착력 평가 시 피착재가 파괴되며, 이는 종래의 기술에 따라 제조된 광학시트 대비 배리어필름과 고분자 수지층 간의 접착력이 현저히 향상된 것이다. In the optical sheet manufactured through the series of processes, the adherend is destroyed when the adhesive force is evaluated. This is a remarkable improvement in the adhesive force between the barrier film and the polymer resin layer compared to the optical sheet manufactured according to the prior art.
한편, 본 발명에 따라 제조된 광학시트는 60℃의 고온, 상대습도 90%의 고습 조건 하에서 장시간 방치하여도 동일한 접착력을 유지하는 바, 신뢰성 측면에서도 종래 기술에 따라 제조된 광학시트 대비 현저한 개선효과가 있다.On the other hand, the optical sheet manufactured according to the present invention maintains the same adhesive strength even if left for a long time under high temperature conditions of 60 ℃ high temperature, 90% relative humidity, a significant improvement effect compared to the optical sheet manufactured according to the prior art in terms of reliability There is.
이하에서 실시예 등을 통해 본 발명을 더욱 상세히 설명하고자 하며, 다만 이하에 실시예 등에 의해 본 발명의 범위와 내용이 축소되거나 제한되어 해석될 수 없다. 또한, 이하의 실시예를 포함한 본 발명의 개시 내용에 기초한다면, 구체적으로 실험 결과가 제시되지 않은 본 발명을 통상의 기술자가 용이하게 실시할 수 있음은 명백한 것이며, 이러한 변형 및 수정이 첨부된 특허청구범위에 속하는 것도 당연하다.Hereinafter, the present invention will be described in more detail with reference to examples and the like, but the scope and contents of the present invention are not limited or interpreted by the following examples. In addition, if it is based on the disclosure of the present invention including the following examples, it will be apparent that those skilled in the art can easily carry out the present invention, the results of which are not specifically presented experimental results, these modifications and modifications are attached to the patent It goes without saying that it belongs to the claims.
실시예Example
실시예 1Example 1
언더코팅 조성물의 제조Preparation of Undercoat Composition
아크릴레이트 수지(Aica Kogyo사, Z-711 grade)를 메틸에틸케톤(Methyl Ethyl Ketone) 용제로 희석한 후 광개시제(Igacure 184)를 아크릴레이트 수지 고형분의 3파트 추가해 충분히 용해시켜 고형분 20wt%의 언더코팅 조성물을 제조하였다.After diluting the acrylate resin (Z-711 grade, Aica Kogyo Co., Ltd.) with methyl ethyl ketone solvent, add 3 parts of photoinitiator (Igacure 184) to the acrylate resin solid to dissolve it sufficiently to undercoat 20wt% solids. The composition was prepared.
오버코팅 조성물의 제조Preparation of Overcoating Composition
오버코팅 조성물의 전체 고형분 중량을 기준으로 열가소성 폴리우레탄(Polyurethane, Ellas/KOLON)을 50wt%, 열경화성 폴리우레탄(Polyurethane, PCB3200/필텍)을 45wt%, 경화제(isocyanate, P300/필텍)를 5 wt%로 하여 용매인 메틸에틸케톤(Methyl Ethyl Ketone)에 섞은 후, 교반하여 고형분 20wt%의 오버코팅 조성물을 제조하였다. 50 wt% of thermoplastic polyurethane (Ellas / KOLON), 45 wt% of thermosetting polyurethane (Polyurethane, PCB3200 / Piltec) and 5 wt% of hardener (isocyanate, P300 / Piltec) based on the total solids weight of the overcoating composition The mixture was mixed with methyl ethyl ketone (Methyl Ethyl Ketone) as a solvent, followed by stirring to prepare an overcoating composition having a solid content of 20wt%.
배리어필름의 제조Manufacture of barrier film
두께 125㎛인 폴리에틸렌 테레프탈레이트(Polyethylene terephthalate, KOLON사 U43R grade)의 일면에 상기 언더코팅 조성물을 도포하고, 80℃ 오븐에서 3분 동안 건조한 다음, 자외선 조사장치(Fusion 社)에 type-D bulb를 장착하여 언더코팅 조성물을 도포한 방향에서 500mJ/㎝2의 노광량으로 조사하여 기재 상에 언더코팅층을 형성하였다. 이때 언더코팅층의 두께는 5㎛로 제조하였다. The undercoating composition was coated on one surface of a polyethylene terephthalate (KOLON U43R grade) having a thickness of 125 μm, dried in an oven at 80 ° C. for 3 minutes, and a type-D bulb was applied to an ultraviolet irradiation device (Fusion). It mounted and irradiated with the exposure amount of 500mJ / cm <2> in the direction which apply | coated the undercoat composition, and the undercoat layer was formed on the base material. At this time, the thickness of the undercoat layer was prepared in 5㎛.
다음으로 상기 언더코팅층 상에 롤투롤 스퍼터(Roll to Roll Sputter)를 이용해 플라즈마 전처리를 한 후 SiNx 10㎚/SiOx 70㎚ 총 80㎚두께로 드라이코팅(Dry Coating)하여 무기물층을 형성하고, 상기 무기물층 상단에 코로나 처리를 실시하였다. Next, after plasma pretreatment using a roll to roll sputter on the undercoat layer, dry coating is performed to a total thickness of 80 nm in SiN x 10 nm / SiO x 70 nm, thereby forming an inorganic layer. Corona treatment was performed on the inorganic layer top.
상기 오버코팅 조성물을 무기물층이 형성된 기재 위에 마이크로 그라비아를 이용하여 형성하였다. 다음으로 120℃에서 1분 동안 건조 및 경화시켜 1㎛ 두께로 오버코팅층을 형성하였다. 이 후 40℃에서 3일 동안 후경화시켜 최종 배리어필름을 제조하였다. The overcoating composition was formed on the substrate on which the inorganic layer was formed using microgravure. Next, dried and cured at 120 ° C. for 1 minute to form an overcoat layer having a thickness of 1 μm. Thereafter, after curing for 3 days at 40 ℃ to produce a final barrier film.
광학시트의 제조Manufacture of optical sheet
다음으로, 상기 제조된 2장의 배리어필름 사이에 비카드뮴계 양자점이 분산된 우레탄 아크릴 수지 고분자 조액을 100㎛ 두께로 도포하고 1000mJ/㎝2 노광 조건에서 UV 경화시켜 광학시트를 제작하였다.Next, the urethane acrylic resin polymer crude liquid in which a cadmium-based quantum dot was dispersed between the two barrier films prepared above was applied to a thickness of 100 μm, and UV cured under 1000 mJ / cm 2 exposure conditions to prepare an optical sheet.
실시예 2Example 2
상기 실시예 1과 동일한 조건으로 광학시트를 제조하되, 오버코팅 조성물의 전체 고형분 중량을 기준으로 열가소성 폴리우레탄(Polyurethane, Ellas/KOLON)을 80wt%, 열경화성 폴리우레탄(Polyurethane, PCB3200/필텍)을 18wt%, 경화제(isocyanate, P300/필텍)를 2 wt%로 하여 용매인 메틸에틸케톤(Methyl Ethyl Ketone)에 섞은 후, 교반하여 제조한 고형분 20wt%의 오버코팅 조성물을 적용한 것만 달리하였다.An optical sheet was manufactured under the same conditions as in Example 1, but 80 wt% of thermoplastic polyurethane (Ellas / KOLON) and 18 wt% of thermosetting polyurethane (Polyurethane, PCB3200 / Piltec) based on the total solid weight of the overcoating composition. %, The curing agent (isocyanate, P300 / filtec) 2 wt% was mixed with a solvent methyl ethyl ketone (Methyl Ethyl Ketone), and then stirred only to apply the overcoating composition of 20wt% of the solid content prepared by stirring.
실시예 3Example 3
상기 실시예 1과 동일한 조건으로 광학시트를 제조하되, 오버코팅 조성물의 전체 고형분 중량을 기준으로 열가소성 폴리우레탄(Polyurethane, Ellas/KOLON)을 20wt%, 열경화성 폴리우레탄(Polyurethane, PCB3200/필텍)을 72wt%, 경화제(isocyanate, P300/필텍)를 8 wt%로 하여 용매인 메틸에틸케톤(Methyl Ethyl Ketone)에 섞은 후, 교반하여 제조한 고형분 20wt%의 오버코팅 조성물을 적용한 것만 달리하였다. An optical sheet was manufactured under the same conditions as in Example 1, but 20 wt% of thermoplastic polyurethane (Ellas / KOLON) and 72 wt% of thermosetting polyurethane (Polyurethane, PCB3200 / Piltec) based on the total solid weight of the overcoating composition %, 8 wt% of a curing agent (isocyanate, P300 / filtec) was mixed with a solvent, methyl ethyl ketone (Methyl Ethyl Ketone), and then applied only to the overcoating composition of 20wt% of the solid content prepared by stirring.
실시예 4Example 4
상기 실시예 1과 동일한 조건으로 광학시트를 제조하되, 오버코팅 조성물의 전체 고형분 중량을 기준으로 열가소성 폴리우레탄(Polyurethane, Ellas/KOLON)을 45wt%, 열경화성 폴리우레탄(Polyurethane, PCB3200/필텍)을 41wt%, 경화제(isocyanate, P300/필텍)를 4 wt%, 실란 커플링제(silan coupling agent, OFS6020/DOW)를 10wt%로 하여 용매인 메틸에틸케톤(Methyl Ethyl Ketone)에 섞은 후, 교반하여 제조한 고형분 20wt%의 오버코팅 조성물을 적용한 것만 달리하였다.Prepare an optical sheet under the same conditions as in Example 1, 45wt% of thermoplastic polyurethane (Polyurethane, Ellas / KOLON) based on the total solid weight of the overcoating composition, 41wt of thermosetting polyurethane (Polyurethane, PCB3200 / piltech) %, 4 wt% of isocyanate (P300 / Piltec) and 10 wt% of silane coupling agent (OFS6020 / DOW) were mixed in a solvent of methyl ethyl ketone (Methyl Ethyl Ketone), followed by stirring Only the application of the overcoating composition of 20 wt% solids was different.
실시예 5Example 5
상기 실시예 1과 동일한 조건으로 광학시트를 제조하되, 오버코팅 조성물의 전체 고형분 중량을 기준으로 열가소성 폴리우레탄(Polyurethane, Ellas/KOLON)을 49wt%, 열경화성 폴리우레탄(Polyurethane, PCB3200/필텍)을 45wt%, 경화제(isocyanate, P300/필텍)를 5wt%, 접착증진제(Lubrizol 2061, /Lubrizol)를 1wt%로 하여 용매인 메틸에틸케톤(Methyl Ethyl Ketone)에 섞은 후, 교반하여 제조한 고형분 20wt%의 오버코팅 조성물을 적용한 것만 달리하였다.An optical sheet was manufactured under the same conditions as in Example 1, but 49 wt% of thermoplastic polyurethane (Ellas / KOLON) and 45 wt% of thermosetting polyurethane (Polyurethane, PCB3200 / Piltec) based on the total solid weight of the overcoating composition. %, 5 wt% of hardener (isocyanate, P300 / filtec) and 1 wt% of adhesion promoter (Lubrizol 2061, / Lubrizol) were mixed in a solvent of methyl ethyl ketone, and then stirred to a solid content of 20 wt%. Only the application of the overcoating composition was different.
실시예 6Example 6
상기 실시예 1과 동일한 조건으로 광학시트를 제조하되, 오버코팅 조성물의 전체 고형분 중량을 기준으로 열가소성 폴리우레탄(Polyurethane, Ellas/KOLON)을 39wt%, 열경화성 폴리우레탄(Polyurethane, PCB3200/필텍)을 54.6wt%, 경화제(isocyanate, P300/필텍)를 4.4 wt%, 가수분해 방지제(Altfona5151/Green Chem)를 2 wt%로 하여 용매인 메틸에틸케톤(Methyl Ethyl Ketone)에 섞은 후, 교반하여 제조한 고형분 20wt%의 오버코팅 조성물을 적용한 것만 달리하였다.An optical sheet was manufactured under the same conditions as in Example 1, except that 39 wt% of thermoplastic polyurethane (Ellas / KOLON) based on the total solid weight of the overcoating composition and 54.6 of thermosetting polyurethane (Polyurethane, PCB3200 / Piltec) were used. wt%, 4.4 wt% of a curing agent (isocyanate, P300 / filtec) and 2 wt% of an anti-hydrolysis agent (Altfona5151 / Green Chem) were mixed in a solvent, methyl ethyl ketone, and then stirred to a solid content. Only the application of 20 wt% of the overcoating composition was different.
실시예Example 7 7
상기 실시예 1과 동일한 조건으로 광학시트를 제조하되, 오버코팅 조성물의 전체 고형분 중량을 기준으로 열가소성 폴리우레탄(Polyurethane, Ellas/KOLON)을 47wt%, 열경화성 폴리우레탄(Polyurethane, PCB3200/필텍)을 36wt%, 경화제(isocyanate, P300/필텍)를 4wt%, 실란 커플링제(Silan coupling gent, OFS6020/DOW)를 10wt%, 가수분해 방지제(Altfona5151/Green Chem)를 1wt%, 접착증진제(Lubrizol 2061, /Lubrizol)를 2 wt%로 하여 용매인 메틸에틸케톤(Methyl Ethyl Ketone)에 섞은 후, 교반하여 제조한 오버코팅 조성물을 적용한 것만 달리하였다.Prepare an optical sheet under the same conditions as in Example 1, 47wt% of thermoplastic polyurethane (Polyurethane, Ellas / KOLON) based on the total solid weight of the overcoating composition, 36wt of thermosetting polyurethane (Polyurethane, PCB3200 / piltech) %, 4 wt% of hardener (isocyanate, P300 / filtec), 10 wt% of silane coupling agent (Silan coupling gent, OFS6020 / DOW), 1 wt% of hydrolysis inhibitor (Altfona5151 / Green Chem), adhesion promoter (Lubrizol 2061, / Lubrizol) was mixed with 2 wt% of methyl ethyl ketone (Methyl Ethyl Ketone) as a solvent, and only the application of the overcoating composition prepared by stirring was different.
실시예 8Example 8
상기 실시예 1과 동일한 조건으로 광학시트를 제조하되, 언더코팅층 상에 롤투롤 스퍼터(Roll to Roll Sputter)를 이용해 플라즈마 전처리를 한 후 SiNx 10㎚/SiOx 30㎚ 총 40㎚ 두께로 드라이코팅(Dry Coating)하여 무기물층을 형성한 것만 달리하였다. The optical sheet was manufactured under the same conditions as in Example 1, but after plasma pretreatment using a roll to roll sputter on the undercoat layer, dry coating was performed on a total thickness of 40 nm in SiN x 10 nm / SiO x 30 nm. Only the inorganic layer was formed by (Dry Coating).
실시예 9Example 9
상기 실시예 1과 동일한 조건으로 광학시트를 제조하되, 언더코팅층 조성물을 달리하였다. 언더코팅층 조성물은 Negami사 UN9000grade 아크릴레이트와 아크릴레이트 수지(Aica Kogyo사, Z-711 grade)를 고형분비 5 : 5로 혼합한 후 메틸에틸케톤(Methyl Ethyl Ketone) 용제로 희석한 후, 광개시제(Igacure 184)를 아크릴레이트 수지 고형분의 3파트 추가해 충분히 용해시켜 제조한 고형분 20wt% 언더코팅 조성물이었다.An optical sheet was manufactured under the same conditions as in Example 1, but the undercoating layer composition was changed. The undercoat composition was mixed with Negami's UN9000grade acrylate and an acrylate resin (Aica Kogyo, Z-711 grade) at a solid ratio of 5: 5, diluted with methyl ethyl ketone solvent, and then a photoinitiator (Igacure). 184) was added to 3 parts of acrylate resin solids to fully dissolve a 20 wt% undercoating composition.
비교예 1Comparative Example 1
상기 실시예 1과 동일한 조건으로 광학시트를 제조하되, 오버코팅 조성물의 전체 고형분 중량을 기준으로 열가소성 폴리우레탄(Polyurethane, Ellas/KOLON)을 100wt%, 열경화성 폴리우레탄(Polyurethane, PCB3200/필텍)을 0wt%로 하여 용매인 메틸에틸케톤(Methyl Ethyl Ketone)에 섞은 후, 교반하여 제조한 오버코팅 조성물을 적용한 것만 달리하였다. The optical sheet is manufactured under the same conditions as in Example 1, but 100 wt% of thermoplastic polyurethane (Elur / KOLON) and 0 wt% of thermosetting polyurethane (Polyurethane, PCB3200 / Piltec) based on the total solid weight of the overcoating composition. % Was mixed with the solvent methyl ethyl ketone (Methyl Ethyl Ketone), and then applied only to the overcoating composition prepared by stirring.
비교예Comparative example 2 2
상기 실시예 1과 동일한 조건으로 광학시트를 제조하되, 오버코팅 조성물의 전체 고형분 중량을 기준으로 열가소성 폴리우레탄(Polyurethane, Ellas/KOLON)을 95wt%, 열경화성 폴리우레탄(Polyurethane, PCB3200/필텍)을 4.5wt%, 경화제(isocyanate, P300/필텍)를 0.5wt%로 하여 용매인 메틸에틸케톤(Methyl Ethyl Ketone)에 섞은 후, 교반하여 제조한 오버코팅 조성물을 적용한 것만 달리하였다. An optical sheet was manufactured under the same conditions as in Example 1, but based on the total solids weight of the overcoating composition, 95 wt% of thermoplastic polyurethane (Polyurethane, Ellas / KOLON) and 4.5 of thermosetting polyurethane (Polyurethane, PCB3200 / Piltec) were used. Wt%, the curing agent (isocyanate, P300 / filtec) was 0.5 wt%, and mixed with a solvent, methyl ethyl ketone (Methyl Ethyl Ketone), followed by applying only the overcoating composition prepared by stirring.
비교예 3Comparative Example 3
상기 실시예 1과 동일한 조건으로 광학시트를 제조하되, 오버코팅 조성물의 전체 고형분 중량을 기준으로 열가소성 폴리우레탄(Polyurethane, Ellas/KOLON)을 5wt%, 열경화성 폴리우레탄(Polyurethane, PCB3200/필텍)을 85.5wt%, 경화제(isocyanate, P300/필텍)를 9.5wt%로 하여 용매인 메틸에틸케톤(Methyl Ethyl Ketone)에 섞은 후, 교반하여 제조한 오버코팅 조성물을 적용한 것만 달리하였다. An optical sheet was manufactured under the same conditions as in Example 1, but based on the total solids weight of the overcoating composition, 5wt% of thermoplastic polyurethane (Ellas / KOLON) and 85.5 of thermosetting polyurethane (Polyurethane, PCB3200 / Piltec) were used. Wt%, the curing agent (isocyanate, P300 / filtec) to 9.5wt% mixed in a solvent methyl ethyl ketone (Methyl Ethyl Ketone), and then the only difference was applied to the overcoating composition prepared by stirring.
비교예 4Comparative Example 4
언더코팅층이 없는 것을 제외하고는 상기 실시예 1과 동일한 조건으로 광학시트를 제조하였다. An optical sheet was manufactured under the same conditions as in Example 1 except that there was no undercoat layer.
비교예 5Comparative Example 5
상기 실시예 1과 동일한 조건으로 광학시트를 제조하되, 언더코팅층 조성물을 달리하였다. 언더코팅층 조성물은 Negami사 KY-11grade 아크릴레이트에 광개시제(Igacure 184)를 아크릴레이트 수지 고형분의 3파트 추가해 충분히 용해시켜 제조한 고형분 20wt% 의 언더코팅 조성물이었다.An optical sheet was manufactured under the same conditions as in Example 1, but the undercoating layer composition was changed. The undercoating layer composition was an undercoating composition of 20 wt% of solids prepared by adding 3 parts of photoinitiator (Igacure 184) to Negami KY-11grade acrylate and sufficiently dissolving it.
비교예 6Comparative Example 6
상기 실시예 1과 동일한 조건으로 광학시트를 제조하되, 언더코팅층이 없고, 무기물층을 롤투롤 스퍼터(Roll to Roll Sputter)를 이용해 플라즈마 전처리를 한 후 SiNx 10㎚/SiOx 30㎚ 총 40㎚ 두께로 드라이코팅(Dry Coating)하여 무기물층을 형성하였다. The optical sheet was manufactured under the same conditions as in Example 1, but there was no undercoating layer, and the inorganic layer was subjected to plasma pretreatment using a roll to roll sputter, followed by SiN x 10 nm / SiO x 30 nm in total 40 nm. Dry coating to a thickness (Dry Coating) to form an inorganic layer.
실험Experiment
상기 실시예 및 비교예에서 제조된 광학시트를 아래의 평가방법을 통해 평가하고 그 결과를 표 1에 나타내었다.The optical sheets prepared in Examples and Comparative Examples were evaluated through the following evaluation method, and the results are shown in Table 1 below.
1. 초기 접착력 평가 1. Initial Adhesion Evaluation
광학시트 제조 후 폭 25㎜ 길이 200㎜의 시편을 5개 제조 후 UTM(INSTRON)을 이용해 분당 300㎜의 속도로 T-peel 테스트 실시한다.After the preparation of the optical sheet, five specimens having a width of 25 mm and a length of 200 mm were prepared and subjected to T-peel test at a speed of 300 mm per minute using UTM (INSTRON).
양호 : 5개 시편중 4개이상의 시편에서 기재필름이 찢어짐.(피착재 파괴)Good: The base film is torn in four or more specimens out of five specimens.
불량 : 피착재 파괴 시편이 4개 미만Poor: Less than 4 substrate fracture specimens
2. 배리어성 측정2. Barrierity Measurement
WVTR 값을 측정하기 위해 MOCON Permatran-W700 장비를 이용하여 온도 37.8℃, 습도 100% 조건에서 측정한다.To measure the WVTR value, use a MOCON Permatran-W700 instrument at 37.8 ° C and 100% humidity.
양호 : WVTR 값이 0.1g/m2/day 보다 우수하면 양호Good: Good if WVTR value is better than 0.1g / m 2 / day
불량 : WVTR 값이 0.1g/m2/day 보다 나쁘면 불량Poor: Poor if WVTR value is worse than 0.1g / m 2 / day
3. 고온 고습 접착 신뢰성 3. High temperature and high humidity adhesion reliability
광학 시트를 고온 고습 챔버(60℃, 90%)에 넣어둔 후 24시간 마다 꺼내어 위의 접착력 평가를 진행한다. The optical sheet is placed in a high temperature and high humidity chamber (60 ° C., 90%), and then taken out every 24 hours to evaluate the above adhesive strength.
양호 : 500시간 이상 피착재 파괴 유지Good: Maintain destruction of adherend over 500 hours
불량 : 500시간 미만 피착재 파괴 유지Defective: Destroys adherend less than 500 hours
4. 언더코팅층의 유리전이온도 측정 4. Glass transition temperature measurement of undercoat
PET이형코팅필름 원단에 언더코팅층 조성을 두께 100㎛으로 제작한다. 제작된 샘플에서 PET이형필름을 제거하고 언더코팅층만을 샘플로 취해 유리전이온도를 측정하였다. 측정은 TA사 AR G2 rheometer 장비를 활용해 Tanδ값이 최대값을 나타내는 온도를 유리전이온도로 하였다. The undercoating layer composition is produced with a thickness of 100 μm on a PET release coating film fabric. The PET release film was removed from the produced sample, and only the undercoating layer was taken as a sample to measure the glass transition temperature. The glass transition temperature was measured by using TA AR AR G2 rheometer.
5. 고온방치 후 배리어성 평가5. Evaluation of barrier property after high temperature
85℃ 오븐에 배리어필름을 500시간 동안 보관된 샘플을 상온(25℃)에서 1시간 동안 방치한다. 고온방치 전 샘플의 배리어성과 고온방치 후 배리어성은 MOCON Permatran-W700 장비를 이용하여 WVTR 값을 온도 37.8℃, 습도 100% 조건에서 측정한다.The sample kept for 500 hours in a barrier film in an 85 ℃ oven is left at room temperature (25 ℃) for 1 hour. The barrier properties of the samples before high temperature and after high temperature were measured using a MOCON Permatran-W700 instrument to measure the WVTR value at 37.8 ° C and 100% humidity.
양호 : 고온방치 후 WVTR값 ≥고온방치 전 WVTR값×2를 만족하고, 고온 방치 후 WVTR값이 0.1g/m2/day 이하의 값을 가짐.Good: WVTR value after high temperature standing ≥WVTR value x2 before high temperature standing is satisfied, and WVTR value having a value of 0.1g / m 2 / day or less after high temperature standing.
불량 : 고온방치 후 WVTR값 < 고온방치 전 WVTR값×2Poor: WVTR value after high temperature left <WVTR value before high temperature left x 2
6. 적용성 평가6. Applicability Evaluation
위의 평가 항목 중 초기 접착력, 고온 고습 접착 신뢰성, 배리어성, 고온 방치 후 배리어성 총 4개 항목을 모두 만족하면 적용 가능, 4개 항목 중 한 개 항목이라도 만족하지 못하면 적용 불가Applicable if all four items in the above evaluation items are satisfied with the initial adhesive strength, high temperature and high humidity adhesive reliability, barrier property, and barrier property after high temperature leaving, and if none of the four items are satisfied
구분division 실시예1Example 1 실시예2Example 2 실시예3Example 3 실시예4Example 4 실시예5Example 5 실시예6Example 6 실시예7Example 7 실시예8Example 8 실시예9Example 9 비교예1Comparative Example 1 비교예2Comparative Example 2 비교예3Comparative Example 3 비교예4Comparative Example 4 비교예5Comparative Example 5 비교예6Comparative Example 6
언더코팅유무Under coating 있음has exist 있음has exist 있음has exist 있음has exist 있음has exist 있음has exist 있음has exist 있음has exist 있음has exist 있음has exist 있음has exist 있음has exist 없음none 있음has exist 없음none
언더코팅 유리전이온도Undercoat Glass Transition Temperature 200℃200 ℃ 200℃200 ℃ 200℃200 ℃ 200℃200 ℃ 200℃200 ℃ 200℃200 ℃ 200℃200 ℃ 200℃200 ℃ 100℃100 ℃ 200℃200 ℃ 200℃200 ℃ 200℃200 ℃ -- 60℃60 ℃ --
무기막 두께Inorganic film thickness 80nm80 nm 80nm80 nm 80nm80 nm 80nm80 nm 80nm80 nm 80nm80 nm 80nm80 nm 40nm40 nm 80nm80 nm 80nm80 nm 80nm80 nm 80nm80 nm 80nm80 nm 80nm80 nm 40nm40 nm
WVTR(g/m2/day)WVTR (g / m 2 / day) 0.050.05 0.060.06 0.060.06 0.050.05 0.050.05 0.050.05 0.060.06 0.080.08 0.050.05 0.060.06 0.070.07 0.050.05 0.070.07 0.060.06 0.10.1
고온방치후WVTR(g/m2/day)After high temperature standing WVTR (g / m 2 / day) 0.060.06 0.070.07 0.060.06 0.050.05 0.060.06 0.050.05 0.070.07 0.10.1 0.080.08 0.080.08 0.070.07 0.060.06 0.150.15 0.130.13 0.180.18
초기 접착력Initial adhesion 양호Good 양호Good 양호Good 양호Good 양호Good 양호Good 양호Good 양호Good 양호Good 불량Bad 불량Bad 불량Bad 양호Good 양호Good 불량Bad
고온/고습 접착 신뢰성High temperature / high humidity adhesion reliability 양호Good 양호Good 양호Good 양호Good 양호Good 양호Good 양호Good 양호Good 양호Good 불량Bad 불량Bad 불량Bad 양호Good 양호Good 불량Bad
배리어성Barrier 양호Good 양호Good 양호Good 양호Good 양호Good 양호Good 양호Good 양호Good 양호Good 양호Good 양호Good 양호Good 양호Good 양호Good 불량Bad
고온방치후 배리어성Barrier after high temperature 양호Good 양호Good 양호Good 양호Good 양호Good 양호Good 양호Good 양호Good 양호Good 양호Good 양호Good 양호Good 불량Bad 불량Bad 불량Bad
적용성Applicability 적용가능Applicable 적용가능Applicable 적용가능Applicable 적용가능Applicable 적용가능Applicable 적용가능Applicable 적용가능Applicable 적용가능Applicable 적용가능Applicable 적용불가Not applicable 적용불가Not applicable 적용불가Not applicable 적용불가Not applicable 적용불가Not applicable 적용불가Not applicable
상기 표 1의 결과를 참조하면, 본 발명의 실시예에 따라 제조된 광학시트의 경우 고온·고습 조건 하에서 500h 이상 피착파괴 수준을 나타내며, 고온에서 500시간 방치 후에도 안정적인 배리어 성능을 발현한다. Referring to the results of Table 1, the optical sheet manufactured according to the embodiment of the present invention exhibits a deposition failure level of 500 h or more under high temperature and high humidity conditions, and exhibits stable barrier performance even after being left for 500 hours at a high temperature.
반면, 비교예에 따라 제조된 광학시트의 경우 500h 이하에서 접착력 문제가 발생하거나, 배리어 성능이 나빠지는 것을 확인하였다. On the other hand, in the case of the optical sheet manufactured according to the comparative example it was confirmed that the adhesion problem occurs at 500h or less, or the barrier performance deteriorated.
즉, 실시예의 경우, 초기 및 고온 고습 접착 신뢰성 확보를 위해서는 열가소성 수지 : 열경화성(경화제포함) 수지의 고형분 중량비가 2 : 8 내지 8 : 2 의 범위에 포함되어야 하며, 고온 방치 후에도 배리어 성능을 안정적으로 유지하기 위해서는 기재인 PET 필름의 일반적인 유리전이온도인 76℃ 이상의 유리전이온도를 가지는 언더코팅층을 가져야 함을 확인할 수 있었다. That is, in the case of the embodiment, in order to secure the initial and high temperature and high humidity adhesion reliability, the solid weight ratio of the thermoplastic resin: the thermosetting resin (curing agent) resin should be included in the range of 2: 8 to 8: 2, and the barrier performance is stably maintained even after high temperature standing. In order to maintain it, it was confirmed that the undercoat layer having a glass transition temperature of 76 ° C. or more, which is a general glass transition temperature of the PET film as the base material, was confirmed.
본 발명은 배리어필름 및 그 제조방법에 이용가능하다.The present invention can be used for the barrier film and its manufacturing method.
10: 기재10: description
20: 언더코팅층20: undercoating layer
30: 무기물층30: inorganic layer
40: 오버코팅층40: overcoating layer
50: 양자점이 분산된 고분자 수지층50: polymer resin layer in which quantum dots are dispersed

Claims (16)

  1. 기재; 상기 기재 상에 형성된 언더코팅층; 상기 언더코팅층 상에 형성된 무기물층; 및 상기 무기물층 상에 형성되며 열가소성 수지 및 열경화성 수지를 함께 포함하는 오버코팅층;을 포함하는 배리어필름.materials; An undercoat layer formed on the substrate; An inorganic layer formed on the undercoat layer; And an overcoat layer formed on the inorganic layer and including both a thermoplastic resin and a thermosetting resin.
  2. 제 1 항에 있어서,The method of claim 1,
    상기 기재는 환상 폴리올레핀계 수지; 폴리스티렌계 수지; 아크릴로니트릴-스티렌 공중합체(AS 수지); 아크릴로니트릴-부타디엔-스티렌 공중합체(ABS 수지); 폴리(메타)아크릴계 수지; 폴리카보네이트계 수지, 폴리에틸렌테레프탈레이트 및 폴리에틸렌나프탈레이트를 포함하는 폴리에스테르계 수지; 나일론을 포함하는 폴리아마이드계 수지; 폴리우레탄계 수지; 아세탈계 수지; 및 셀룰로오스계 수지;로 이루어지는 군에서 선택되는 1종 이상의 수지로 제조된 필름 또는 시트인 배리어필름.The base material is a cyclic polyolefin resin; Polystyrene resin; Acrylonitrile-styrene copolymer (AS resin); Acrylonitrile-butadiene-styrene copolymer (ABS resin); Poly (meth) acrylic resins; Polyester-based resins including polycarbonate-based resins, polyethylene terephthalate and polyethylene naphthalate; Polyamide-based resins including nylon; Polyurethane-based resins; Acetal resins; And a cellulose resin; a barrier film which is a film or sheet made of at least one resin selected from the group consisting of cellulose-based resins.
  3. 제 1 항에 있어서,The method of claim 1,
    상기 기재는 매트코팅(Matt coating) 처리된 것인 배리어필름.The substrate is a matte coating (Matt coating) barrier film.
  4. 제 1 항에 있어서,The method of claim 1,
    상기 언더코팅층은 비스페놀 A계 아크릴레이트, 나프탈렌계 아크릴레이트, 아이소보닐계 아크릴레이트 및 아마만틸계 아크릴레이트를 포함하는 우레탄 아크릴레이트; 비스페놀 A, 비스페놀 F, 메틸렌 비스(4-하이드록시페닐) 등의 비스페놀계열, 레조르시놀, 디히드록시 나프탈렌, 디히드록시 바이페닐, 디히드록시 페닐 에탄올, 디히드록시 피리딘, 디히드록시퀴노살린, 디히드록시 테트라히드로나프탈렌 및 디히드록시피리미딘를 포함하는 방향족 폴리올 화합물; 및 1,3-프로페인 다이올, 1,4-부테인 다이올, 1,5-펜테인 다이올, 1,6-헥세인 다이올, 3-메틸-1,5-펜테인 다이올, 1,8-옥테인 다이올, 2-메틸-1,8-옥테인 다이올, 1,9-노네인 다이올 및 1,10-데케인 다이올을 포함하는 지방족 폴리올 화합물;로 이루어지는 군에서 선택되는 1종 이상의 고분자 수지 또는 이들의 조합을 포함하는 배리어필름.The undercoat layer is a urethane acrylate including bisphenol A acrylate, naphthalene acrylate, isobornyl acrylate and ammanthyl acrylate; Bisphenols such as bisphenol A, bisphenol F, methylene bis (4-hydroxyphenyl), resorcinol, dihydroxy naphthalene, dihydroxy biphenyl, dihydroxy phenyl ethanol, dihydroxy pyridine, dihydroxyquino Aromatic polyol compounds including saline, dihydroxy tetrahydronaphthalene and dihydroxypyrimidine; And 1,3-propane diol, 1,4-butane diol, 1,5-pentane diol, 1,6-hexane diol, 3-methyl-1,5-pentane diol, Aliphatic polyol compounds comprising 1,8-octane diol, 2-methyl-1,8-octane diol, 1,9-nonane diol and 1,10-decane diol; Barrier film containing at least one polymer resin selected or a combination thereof.
  5. 제 1 항에 있어서,The method of claim 1,
    상기 언더코팅층은 우레탄 아크릴레이트 올리고머, 디펜타에리스리톨펜타아크릴레이트 및 트리히드록시에틸 이소시아누레이트 트리아크릴레이트로 이루어지는 군에서 선택되는 1종 이상의 고분자 수지 또는 이들의 조합을 포함하는 배리어필름.The undercoat layer comprises at least one polymer resin selected from the group consisting of urethane acrylate oligomer, dipentaerythritol pentaacrylate, and trihydroxyethyl isocyanurate triacrylate, or a combination thereof.
  6. 제 1 항에 있어서,The method of claim 1,
    상기 언더코팅층에 포함되는 고분자 수지는 기재를 구성하는 고분자 수지 대비 상대적으로 높은 유리전이 온도(Tg)를 가지는 배리어필름.The polymer resin included in the undercoat layer has a relatively high glass transition temperature (T g ) than the polymer resin constituting the substrate.
  7. 제 6 항에 있어서,The method of claim 6,
    상기 언더코팅층에 포함되는 고분자 수지의 유리전이 온도(Tg)는 80 내지 250℃ 의 온도 범위를 가지는 배리어필름.The glass transition temperature (T g ) of the polymer resin included in the undercoat layer has a temperature range of 80 to 250 ℃.
  8. 제 1 항에 있어서,The method of claim 1,
    상기 무기물층은 규소(Si), 알루미늄(Al), 인듐(In), 주석(Sn), 아연(Zn), 지르코늄(Zr), 티타늄(Ti), 구리(Cu), 세륨(Ce), 이트륨(Yt), 란탄(La), 바륨(Ba), 마그네슘(Mg), 플루오르(F2), 안티몬(Sb), 스트론튬(Sr) 및 탄탈륨(Ta)으로 이루어지는 군에서 선택되는 1종 이상의 금속을 포함하는 산화물, 질화물, 탄화물, 산화질화물, 산화탄화물, 질화탄화물, 또는 산화질화탄화물로 이루어지는 군에서 선택되는 1종 이상의 무기물을 포함하는 배리어필름. The inorganic layer is silicon (Si), aluminum (Al), indium (In), tin (Sn), zinc (Zn), zirconium (Zr), titanium (Ti), copper (Cu), cerium (Ce), yttrium At least one metal selected from the group consisting of (Yt), lanthanum (La), barium (Ba), magnesium (Mg), fluorine (F 2 ), antimony (Sb), strontium (Sr), and tantalum (Ta) A barrier film comprising at least one inorganic material selected from the group consisting of oxides, nitrides, carbides, oxynitrides, oxidized carbides, nitrides, or oxynitride carbides.
  9. 제 1 항에 있어서,The method of claim 1,
    상기 열가소성 수지는 폴리에테르계 수지, 폴리우레탄계 수지, 폴리에스테르계 수지, 폴리비닐부티랄계 수지 및 폴리비닐알콜계 수지로 이루어지는 군에서 선택되는 1종 이상의 고분자 수지인 배리어필름.The thermoplastic resin is at least one polymer resin selected from the group consisting of polyether resins, polyurethane resins, polyester resins, polyvinyl butyral resins and polyvinyl alcohol resins.
  10. 제 1 항에 있어서,The method of claim 1,
    상기 열경화성 수지는 에폭시 수지, 불포화 폴리에스테르 수지, 폴리우레탄 수지, 폴리카보네이트 폴리우레탄, 폴리에스테르 폴리우레탄, 페놀 수지, 멜라민 수지, 요소 수지 및 규소 수지로 이루어지는 군에서 선택되는 1종 이상의 고분자 수지인 배리어필름.The thermosetting resin is a barrier that is at least one polymer resin selected from the group consisting of epoxy resins, unsaturated polyester resins, polyurethane resins, polycarbonate polyurethanes, polyester polyurethanes, phenol resins, melamine resins, urea resins and silicon resins. film.
  11. 제 1 항에 있어서,The method of claim 1,
    상기 오버코팅층 내에 포함되는 열가소성 수지 대 열경화성 수지의 고형분 중량비는 2 : 8 내지 8 : 2의 범위를 가지는 배리어필름. The solid film weight ratio of the thermoplastic resin and the thermosetting resin included in the overcoating layer has a range of 2: 8 to 8: 2.
  12. 서로 대향하는 제 1 항에 따른 2장의 배리어필름; 및 상기 2장의 배리어필름의 오버코팅층 사이에 형성되는 양자점이 분산된 고분자 수지층;을 포함하는 광학시트.Two barrier films according to claim 1 facing each other; And a polymer resin layer in which a quantum dot is formed between the overcoating layers of the two barrier films.
  13. a) 준비된 기재 상에 언더코팅 조성물을 도포하여 언더코팅층을 형성하는 단계;a) applying an undercoat composition on the prepared substrate to form an undercoat layer;
    b) 상기 언더코팅층 상에 무기물층을 형성하는 단계; b) forming an inorganic layer on the undercoat layer;
    c) 열가소성 수지 및 열경화성 수지를 포함하는 오버코팅 조성물을 상기 무기물층 상에 도포하여 오버코팅층을 형성하고, 열경화하여 배리어필름을 제조하는 단계; 및c) applying an overcoating composition comprising a thermoplastic resin and a thermosetting resin on the inorganic layer to form an overcoating layer, and thermosetting to prepare a barrier film; And
    d) 상기 2장의 배리어필름 사이에 양자점이 분산된 고분자 조성물을 도포하고 UV 경화하는 단계;를 더 포함하는 광학시트 제조방법. d) coating a polymer composition having a quantum dot dispersed between the two barrier films and UV curing.
  14. 제 13 항에 있어서, The method of claim 13,
    상기 c) 단계의 오버코팅 조성물에는 커플링제, 가수분해 방지제 및 접착증진제로 이루어지는 군에서 선택되는 1종 이상의 첨가제가 더 포함되는 광학시트 제조방법.The overcoating composition of step c) further comprises at least one additive selected from the group consisting of a coupling agent, a hydrolysis inhibitor and an adhesion promoter.
  15. 제 13 항에 있어서,The method of claim 13,
    상기 c) 단계의 열경화는 80 내지 150℃의 온도에서 30초 내지 5분 동안 용매를 건조 및 경화시킨 후, 30 내지 60℃ 온도 조건에서 1일 내지 3일 동안 후경화가 수행되는 것인 광학시트 제조방법.The thermal curing step c) is an optical and drying after curing the solvent for 30 seconds to 5 minutes at a temperature of 80 to 150 ℃, the post-cure is carried out for 1 to 3 days at 30 to 60 ℃ temperature conditions Sheet manufacturing method.
  16. 제 13 항에 있어서,The method of claim 13,
    상기 d) 단계의 UV 경화는 100 내지 5000mJ/cm2 의 노광 조건에서 수행되는 광학시트 제조방법.UV curing step d) is carried out under the exposure conditions of 100 to 5000mJ / cm 2 optical sheet manufacturing method.
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