WO2024136047A1 - Color film for solar cell module - Google Patents

Color film for solar cell module Download PDF

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Publication number
WO2024136047A1
WO2024136047A1 PCT/KR2023/015482 KR2023015482W WO2024136047A1 WO 2024136047 A1 WO2024136047 A1 WO 2024136047A1 KR 2023015482 W KR2023015482 W KR 2023015482W WO 2024136047 A1 WO2024136047 A1 WO 2024136047A1
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Prior art keywords
layer
base film
color
solar cell
coating layer
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PCT/KR2023/015482
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French (fr)
Korean (ko)
Inventor
박예림
이종혁
김진호
Original Assignee
주식회사 상보
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Publication of WO2024136047A1 publication Critical patent/WO2024136047A1/en

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    • H—ELECTRICITY
    • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02S—GENERATION OF ELECTRIC POWER BY CONVERSION OF INFRARED RADIATION, VISIBLE LIGHT OR ULTRAVIOLET LIGHT, e.g. USING PHOTOVOLTAIC [PV] MODULES
    • H02S40/00—Components or accessories in combination with PV modules, not provided for in groups H02S10/00 - H02S30/00
    • H02S40/20—Optical components
    • 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
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • 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
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0091—Complexes with metal-heteroatom-bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B47/00—Porphines; Azaporphines
    • C09B47/04—Phthalocyanines abbreviation: Pc
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/048—Encapsulation of modules
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/054—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means
    • H01L31/055—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means where light is absorbed and re-emitted at a different wavelength by the optical element directly associated or integrated with the PV cell, e.g. by using luminescent material, fluorescent concentrators or up-conversion arrangements
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/20—Inorganic coating
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/28—Multiple coating on one surface

Definitions

  • the present invention relates to a color film for solar cell modules, and more specifically, to a first base film layer as a base substrate, a second base film layer disposed on one side of the first base film layer, and the first base film layer. and an adhesive layer formed between the second base film layer, a top coating layer formed on one side of the second base film layer, and a barrier coating layer formed on one side of the first base film layer, wherein one side of the adhesive layer is covered with the barrier coating layer. It is in contact with and contains 1 to 2 parts by weight of color pigment based on 100 parts by weight of the adhesive layer, and the other side is in contact with the second base film layer, wherein the barrier coating layer is formed by mixing metal alkoxide, water and an acid catalyst, and using the sol-gel method.
  • the barrier coating layer is inserted between the base layers to prevent the partial discharge voltage decrease that occurs when one side of the barrier coating layer is directly exposed to the outside, and at the same time, even over time. This is about a color film for solar cell modules, which is characterized by minimal color change in the color film.
  • Solar cells have been developed as a next-generation eco-friendly energy source and are rapidly being distributed for residential and industrial purposes.
  • Solar cells are made up of multiple solar cells that are modularized.
  • a plurality of solar cells are packed and fixed in an encapsulation layer, and a back sheet as a sealing member is attached to the lower surface of the encapsulation layer to form a module.
  • Figure 1 is a diagram showing the configuration of a general solar cell module.
  • the solar cell module generally includes a transparent glass layer 83 through which fixed light is incident through a frame, an upper encapsulation layer 82a, and a plurality of solar cells ( C), it has a structure in which the lower encapsulation layer 82b and the back sheet 81 are sequentially stacked.
  • a plurality of solar cells (C) are packed and fixed to the encapsulation layers (82a, 82b).
  • BIPV is short for Building-Integrated Photovoltaic, and refers to a solar power generation system that not only produces electricity from solar energy and supplies it to consumers, but also uses building-integrated photovoltaic modules as building exterior materials. Unlike existing solar power generation systems installed on large flat areas or roofs, building-integrated solar power generation systems are installed on the exterior walls of buildings, windows, etc., and solar cells are used as a building material, and the electric energy produced by solar cells is used directly. It can be supplied and used inside the building.
  • Partial discharge can be a problem when using film to achieve color and reduce weight.
  • Partial discharge refers to a partial discharge caused by a high electric field on the surface of an insulating material or an internal discharge that occurs in a gap or bubble inside the insulating material. In the area where the partial discharge occurs, the deterioration of the insulating material progresses due to high voltage stress. Therefore, the backsheet that comes into contact with the solar cell module must have a high partial discharge voltage.
  • Vdc Partial Discharge Voltage
  • Partial discharge voltage of the installed solar module is excessively high, insulation breakdown occurs due to overload of all cells connected in series. Partial discharge voltage is measured according to the partial discharge voltage test according to KS C IEC 60664-1, and the industry requires insulation breakdown resistance even at partial discharge voltages of 1,000 VDC or more.
  • the present invention was devised to solve the above problems,
  • the object of the present invention is a first base film layer as a base substrate, a second base film layer disposed on one side of the first base film layer, an adhesive layer formed between the first base film layer and the second base film layer, A solar cell module comprising a top coating layer formed on one side of the second base film layer, and the adhesive layer including a color pigment to secure sufficient partial discharge voltage and minimize color change within the adhesive layer by stacking base layers.
  • the goal is to provide color film.
  • An object of the present invention further includes a barrier coating layer formed on one side of the first base film layer, wherein the adhesive layer has one side in contact with the first base film layer or barrier coating layer and the other side in contact with the second base film layer.
  • the aim is to provide a color film for solar cell modules with excellent moisture permeability resistance.
  • the purpose of the present invention is to arrange the barrier coating layer between the base layers so that one side of the adhesive layer is in contact with the barrier coating layer and the other side is in contact with the second base film layer, so that one side of the barrier coating layer is directly exposed to the outside.
  • the goal is to provide a color film for solar cell modules that prevents partial discharge voltage reduction and color change caused by deterioration of the quality of the barrier coating layer.
  • the purpose of the present invention is to provide a color film for solar cell modules in which the adhesive layer contains 1 to 2 parts by weight of a color pigment based on 100 parts by weight of the adhesive layer, allowing color development even with a small amount of color pigment.
  • the object of the present invention is to provide a solar cell in which the color pigment includes at least one of an organic pigment having an azo group as a chromophore or a polycyclic organic pigment such as phthalocyanine, anthraquinone, and quinacridone, and the color pigment is smoothly dispersed in an organic solvent forming an adhesive layer.
  • the goal is to provide color film for modules.
  • the object of the present invention is that the color pigment includes a phosphor that converts a wavelength absorbed from light into a wavelength higher than the absorbed wavelength, and the phosphor absorbs ultraviolet rays and converts them into a wavelength higher than the ultraviolet wavelength to increase photoelectric conversion efficiency.
  • the goal is to provide colored films for solar cell modules.
  • the object of the present invention is to have a base layer of sufficient thickness to secure a partial discharge voltage, wherein the first base film layer and the second base film layer have a thickness of 50 to 200 ⁇ m, and the adhesive layer has a thickness of 5 to 20 ⁇ m.
  • the goal is to provide color films for battery modules.
  • the object of the present invention is to provide a solar cell in which the first base film layer and the second base film layer include at least one selected from polyester-based resin, polycarbonate-based resin, polyvinyl-based resin, polyimide-based resin, and polyurethane-based resin.
  • the goal is to provide color film for modules.
  • the object of the present invention is that the barrier coating layer is a metal oxide coated on a first base film layer, the metal oxide is a metal oxide sol, and the metal oxide includes alumina, titania, magnesia, zirconia, or a combination thereof.
  • the goal is to provide color films for battery modules.
  • the purpose of the present invention is to form a solar cell module in which the barrier coating layer is formed by dissolving a metal alkoxide in water under an acid catalyst, hydrolyzing and condensing it, coating it on one side of the first base film layer, and then curing it, allowing a quick process using the sol-gel method.
  • the goal is to provide color film for use.
  • the purpose of the present invention is to provide a color film for solar cell modules in which the barrier coating layer includes a metal oxide and a phosphorus-containing compound combined with graphene.
  • the purpose of the present invention is to provide a color film for solar cell modules, wherein the top coating layer includes one or more selected from the group consisting of fluorine-based silicone resin, acrylic resin, polyvinyl-based resin, and polyurethane-based resin.
  • the purpose of the present invention is to provide a color film for solar cell modules in which the top coating layer has a thickness of 3 to 5 ⁇ m and the barrier coating layer has a thickness of 1 ⁇ m or less.
  • the present invention is implemented by an embodiment having the following configuration.
  • the color film for a solar cell module includes a first base film layer as a base substrate, a second base film layer disposed on one side of the first base film layer, and the first base film layer. It includes an adhesive layer formed between a base film layer and a second base film layer, and a top coating layer formed on one side of the second base film layer, and the adhesive layer includes a color pigment.
  • it further includes a barrier coating layer formed on one side of the first base film layer, wherein one side of the adhesive layer is in contact with the first base film layer or the barrier coating layer, and the other side is in contact with the second base film. It is characterized by being in contact with the layer.
  • the adhesive layer is characterized in that one side is in contact with the barrier coating layer and the other side is in contact with the second base film layer.
  • the adhesive layer is characterized in that it contains 1 to 2 parts by weight of a color pigment based on 100 parts by weight of the adhesive layer.
  • the color pigment is characterized in that it contains at least one of an organic pigment having an azo group as a chromophore or a polycyclic organic pigment such as phthalocyanine, anthraquinone, and quinacridone.
  • the color pigment includes a phosphor that converts a wavelength absorbed from light into a wavelength higher than the absorbed wavelength, and the phosphor absorbs ultraviolet rays and converts them into a wavelength higher than the ultraviolet wavelength. It is characterized by
  • the first base film layer and the second base film layer have a thickness of 50 to 200 ⁇ m, and the adhesive layer has a thickness of 5 to 20 ⁇ m.
  • the first base film layer and the second base film layer include at least one selected from polyester-based resin, polycarbonate-based resin, polyvinyl-based resin, polyimide-based resin, and polyurethane-based resin. It is characterized by including.
  • the barrier coating layer is a metal oxide coated on the first base film layer, and the metal oxide is a metal oxide sol and includes alumina, titania, magnesia, zirconia, or a combination thereof. It is characterized by
  • the barrier coating layer is formed by dissolving a metal alkoxide in water under an acid catalyst, hydrolyzing condensation, coating it on one side of the first base film layer, and then curing it.
  • the barrier coating layer includes a metal oxide and a phosphorus-containing compound to which graphene is bonded.
  • the top coating layer is characterized in that it includes one or more selected from the group consisting of a fluorine-based silicone resin, an acrylic resin, a polyvinyl-based resin, and a polyurethane-based resin.
  • the top coating layer has a thickness of 3 to 5 ⁇ m, and the barrier coating layer has a thickness of 1 ⁇ m or less.
  • the present invention can achieve the following effects by combining the above-mentioned embodiment with the configuration, combination, and use relationship described below.
  • the present invention relates to a first base film layer as a base substrate, a second base film layer disposed on one side of the first base film layer, an adhesive layer formed between the first base film layer and the second base film layer, It includes a top coating layer formed on one side of the second base film layer, and the adhesive layer includes a color pigment and laminates the base layer to ensure sufficient partial discharge voltage and at the same time minimize color change in the adhesive layer.
  • the present invention further includes a barrier coating layer formed on one side of the first base film layer, wherein one side of the adhesive layer is in contact with the first base film layer or barrier coating layer and the other side is in contact with the second base film layer. It has excellent moisture permeability resistance.
  • the adhesive layer has one side in contact with the barrier coating layer and the other side in contact with the second base film layer, so that the barrier coating layer is disposed between the base layers, so that when one side of the barrier coating layer is directly exposed to the outside, the barrier This has the effect of preventing partial discharge voltage drop and color change caused by the quality deterioration of the coating layer.
  • the adhesive layer contains 1 to 2 parts by weight of color pigment based on 100 parts by weight of the adhesive layer, allowing color development even with a small amount of color pigment.
  • the color pigment includes at least one of an organic pigment having an azo group as a chromophore or a polycyclic organic pigment such as phthalocyanine, anthraquinone, and quinacridone, and has the effect of smoothly dispersing the color pigment in an organic solvent forming an adhesive layer. .
  • the color pigment includes a phosphor that converts a wavelength absorbed from light into a wavelength higher than the absorbed wavelength, and the phosphor absorbs ultraviolet rays and converts them into a wavelength higher than the ultraviolet wavelength, thereby increasing photoelectric conversion efficiency. It gives effect.
  • the first base film layer and the second base film layer have a thickness of 50 to 200 ⁇ m, and the adhesive layer has a thickness of 5 to 20 ⁇ m, so that the solar cell has a base layer of sufficient thickness to secure a partial discharge voltage.
  • the effect of providing color film for modules is derived.
  • the first base film layer and the second base film layer are solar cell modules comprising at least one selected from polyester-based resin, polycarbonate-based resin, polyvinyl-based resin, polyimide-based resin, and polyurethane-based resin. Provides color film for use.
  • the barrier coating layer is a solar cell in which a metal oxide is coated on a first base film layer, the metal oxide is a metal oxide sol, and the metal oxide includes alumina, titania, magnesia, zirconia, or a combination thereof. It has the effect of providing color film for modules.
  • the barrier coating layer is formed by dissolving a metal alkoxide in water under an acid catalyst, hydrolyzing condensation, coating it on one side of the first base film layer, and then curing it, enabling a quick process using the sol-gel method.
  • the present invention can provide a color film for solar cell modules in which the barrier coating layer includes a metal oxide and a phosphorus-containing compound combined with graphene.
  • the present invention has the effect of providing a color film for solar cell modules, wherein the top coating layer includes one or more selected from the group consisting of fluorine-based silicone resin, acrylic resin, polyvinyl-based resin, and polyurethane-based resin.
  • the present invention has the effect of providing a color film for solar cell modules in which the top coating layer has a thickness of 3 to 5 ⁇ m and the barrier coating layer has a thickness of 1 ⁇ m or less.
  • FIG. 1 is a cross-sectional configuration diagram of a solar cell module and back sheet according to the prior art.
  • Figure 2 is a cross-sectional view of a color film for solar cell modules according to a preferred embodiment of the present invention.
  • Figure 3 is a cross-sectional view of a color film for a solar cell module according to another embodiment of the present invention.
  • Figure 4 is a diagram showing the transmittance (%) according to the wavelength of Example 20 and Examples 22 to 28.
  • Figure 5 is a view showing the color, total light transmittance, haze, and photoelectric conversion efficiency of Examples 1, 21, and 22 visible to the naked eye on a black PV sheet.
  • substituted or “substituted” means that one or more hydrogen atoms in the functional groups of the present invention are halogen atoms (F, Br, Cl or I), hydroxy groups, nitro groups, cyano groups, amino groups, Amidino group, hydrazine group, hydrazone group, carboxyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkynyl group, substituted or unsubstituted alicyclic organic group, substituted or unsubstituted means substituted with one or more substituents selected from the group consisting of an aryl group and a substituted or unsubstituted heterocyclic group.
  • the color film 10 for solar cell modules is attached to one side of the solar cell module and protects the internal solar cells and/or solar cell modules from external environments such as moisture, shock, ultraviolet rays, and dirt. It can be attached to the side opposite to the incident surface.
  • the color film 10 for solar cell modules according to an embodiment of the present invention is light in color and has a partial discharge voltage in accordance with KS C IEC 60664-1 in order to solve the partial discharge problem that may occur in a structure in which films are stacked. Depending on the test, insulation breakdown resistance can be achieved even at partial discharge voltages of 1000 VDC or higher.
  • the color film 10 for solar cell modules includes a first base film layer 11, a barrier coating layer 12, a second base film layer 13, an adhesive layer 14, and a top coating layer 15.
  • the color film 10 for solar cell modules can be used on one side of the solar cell module by replacing the glass layer of the solar cell module.
  • the color film 10 for a solar cell module can be attached to the other side of the solar cell module and used as a backsheet in a double-sided solar cell.
  • the color film 10 for a solar cell module changes color over time. was designed to be minimized.
  • the solar cell module When colored glass is formed by sputtering colored pearls on a 15cm It weighs 21.5 to 22.5 g, so the solar cell module can be used in a lighter form.
  • the first base film layer 11 is a film layer as a base base material, and the first base film layer 11 may have a thickness of 50 to 200 ⁇ m. In a preferred embodiment, the first base film layer 11 may have a thickness of 188 ⁇ m. In one embodiment, a barrier coating layer 12 may be formed on one surface of the first base film layer 11.
  • the first base film layer 11 may be formed by casting or otherwise coating an aqueous dispersion or solution mixture onto a peelable carrier web or liner.
  • the first base film layer 11 may be a film layer containing one or more selected from polyester-based resin, polycarbonate-based resin, polyvinyl-based resin, polyimide-based resin, and polyurethane-based resin. In one embodiment, at least two or more layers containing one or more selected from polyester-based resin, polycarbonate-based resin, polyvinyl-based resin, polyimide-based resin, and polyurethane-based resin may be formed by laminating them.
  • the first base film layer 11 may be composed of a transparent polyethylene terephthalate (PET) film.
  • PET polyethylene terephthalate
  • the first base film layer 11 may face a lower encapsulation layer surrounding the solar cell.
  • the barrier coating layer 12 is a coating layer formed on one side of the first base film layer 11, and has excellent performance in blocking moisture and gas.
  • the barrier coating layer 12 may have a thickness of 1 ⁇ m or less, and preferably may have a thickness of 700nm to 1 ⁇ m.
  • the barrier coating layer 12 may be a metal oxide coated on the first base film layer.
  • the metal oxide may include alumina, titania, magnesia, zirconia, or a combination thereof.
  • the shape of the metal oxide is not particularly limited, and may have a spherical shape, a cubic shape, a spindle shape, an indeterminate shape, a fibrous shape, or a needle shape.
  • the metal oxides may all have the same shape or may be a combination of different shapes.
  • the metal oxide may have an average particle diameter of 1 nm to 150 nm.
  • the moisture barrier properties of the barrier film can be further improved.
  • the average particle size of the metal oxide can be confirmed by analyzing the particle size using a particle size analyzer (DLS). Considering the controllability of the shape and size of the metal oxide obtained, it may be preferable to produce the metal oxide by a liquid phase synthesis method.
  • the metal oxide may be a metal oxide sol.
  • the metal oxide When the metal oxide is present in the barrier coating layer in a sol form, it can react more easily with the phosphorus-containing compound than when it is present in a non-sol form, and further, dispersion stability can be greatly improved. It is preferable that the metal oxide does not contain phosphorus atoms.
  • the barrier coating layer 12 may include a phosphorus-containing compound along with a metal oxide sol.
  • the phosphorus-containing compound can induce gelation of the metal oxide by inducing the bonding of the metal oxide.
  • the phosphorus-containing compound contains a site capable of reacting with the metal oxide (a halogen atom or an oxygen atom directly bonded to a phosphorus atom, etc.), and may include, for example, phosphoric acid, polyphosphoric acid, phosphorous acid, phosphonic acid, or derivatives thereof. there is.
  • the halogen atom or oxygen atom directly bonded to the phosphorus atom in the phosphorus-containing compound undergoes a hydrolysis condensation reaction with a functional group (such as a hydroxyl group) present on the surface of the metal oxide, and the metal atom of the metal oxide and the phosphorus atom undergo a hydrolysis condensation reaction.
  • the phosphorus atom of the containing compound may be bonded using an oxygen atom as a mediator.
  • the barrier coating layer 12 may include a metal oxide and a phosphorus-containing compound to which graphene is bonded. It can also be manufactured by combining graphene with a metal oxide and then reacting it with a phosphorus-containing compound.
  • Phosphorus-containing compounds can induce the bonding of metal oxides to which graphene is bonded, thereby inducing gelation of the metal oxides to which graphene is bonded.
  • the metal oxide to which the graphene is bonded is bonded to a phosphorus-containing compound, the metal atom of the metal oxide and the phosphorus atom of the phosphorus-containing compound are bonded using an oxygen atom as a medium.
  • the barrier coating layer according to an embodiment of the present invention may be formed by the following composition.
  • the composition can be prepared by dissolving the metal alkoxide in water to prepare an aqueous solution.
  • the aqueous solution is prepared by mixing the metal alkoxide, water and an acid catalyst, and hydrolyzing and condensing the metal alkoxide by a sol-gel method.
  • the acid catalyst may include hydrochloric acid, sulfuric acid, nitric acid, p-toluenesulfonic acid, benzoic acid, acetic acid, lactic acid, butyric acid, carbonic acid, oxalic acid, maleic acid, or a combination thereof.
  • the prepared aqueous solution may have a pH value of about 3 to 5.
  • the pH value of the aqueous solution must be about 3 to 5 to improve the dispersibility of the metal alkoxide in water.
  • the metal alkoxide may be metal isopropoxide or metal butoxide.
  • the metal alkoxide may be metal isopropoxide, metal triisopropoxide, or metal tri-s-butoxide.
  • the metal may be aluminum, titanium, magnesium, or zirconia.
  • graphene oxide is added to the aqueous solution and reacted at a temperature of 70°C to 80°C for 10 to 14 hours to obtain a graphene-bound metal oxide and a graphene-bound alumina sol.
  • acid is added to the aqueous solution containing the graphene-bound alumina sol and heated.
  • the added acid may include nitric acid, hydrochloric acid, perchloric acid, formic acid, acetic acid, propionic acid, or a combination thereof.
  • the acid and heating When adding the acid and heating, it can be heated at a temperature of 40°C to 200°C.
  • a temperature of 40°C to 200°C By heating in the above temperature range, it is possible to control the particle size of the alumina sol combined with graphene, and at the same time, increase the viscosity stability.
  • the heating time takes too long and is uneconomical, and when heated at a temperature above 200°C, the heating time is shortened, but a separate high-pressure vessel is required, which is also uneconomical.
  • the concentration of the alumina sol to which graphene is bound can be controlled by diluting it by adding a solvent or concentrating it by heating.
  • heat concentration when heat concentration is carried out, it is preferably carried out under reduced pressure and at 60°C or lower, but is not necessarily limited to this.
  • a phosphorus-containing compound is further added to prepare a barrier coating layer composition.
  • the phosphorus-containing compound can be added in the form of a solution, for example, by dissolving the phosphorus-containing compound in water.
  • the temperatures of both solutions can be controlled to 50°C or lower, for example, 30°C or lower. In this case, aggregation between metal oxides can be prevented.
  • the graphene-bound metal oxide e.g., graphene-bound alumina sol
  • the phosphorus-containing compound can be uniformly mixed, thereby improving the moisture barrier properties of the barrier film produced. can be greatly improved.
  • stirring may be continued for an additional 30 minutes after mixing is completed.
  • the heat treatment can be performed at a temperature of 130°C to 140°C. After coating the barrier coating layer composition on the first base film layer, heat treatment is usually performed at a high temperature of 200 °C or higher. However, in order to improve flexibility by coating the barrier coating layer composition according to one embodiment on the plastic substrate, 130 Heat treatment can be performed at a low temperature of °C to 140°C. Additionally, the coating may be continuous wet coating (roll to roll coating), such as micro gravure coating or slot die coating.
  • the barrier coating layer 12 is coated on the first base film layer 11 and then heat-treated, so that the color film 10 for solar cell modules can have weather resistance and moisture permeability resistance.
  • the barrier film layer 12 according to a preferred embodiment is formed on the first base film layer 11, so that moisture permeability according to the ASTM F1249 evaluation standard can preferably be achieved up to 0.05 g/m 2 /day or less. .
  • the barrier coating layer 12 according to an embodiment of the present invention is superior to barrier layers containing polyolefin, PVF, etc.
  • a polyolefin film layer after laminating a PET layer on the backsheet or the front of a solar cell, there is a problem of discoloration because the polyolefin film is a non-fluorine type, and the production process requires a high process temperature and a long time.
  • polyolefin films have a higher melting point than EVA, so there is a limitation in that process optimization for additional lamination is necessary.
  • the water permeability rate (WVTR) is relatively high, which causes moisture to penetrate through the backsheet or the front part of the solar cell, and the moisture penetrated at high temperatures corrodes the EVA, causing further degradation of solar cell module performance. If moisture penetrates, delamination may occur at the encapsulant (EVA) and the interface between the encapsulant and the film, and delamination allows a greater amount of moisture to infiltrate, ultimately causing a decrease in output.
  • the barrier coating layer 12 was made by gelling a metal oxide sol and coating it on the first base film layer 11 to maintain transparency and obtain higher resistance to moisture.
  • the metal oxide sol of the barrier coating layer 12 composition may be selected from SnO x , SiN x , TiO 2 , and Al 2 O 3 .
  • the metal oxide sol may be Al 2 O 3 .
  • the barrier coating layer 12 can use Al 2 O 3 as a metal oxide sol. It has excellent moisture prevention properties, but when directly exposed to a high temperature and humidity environment, it hydrolyzes into crystalline boehmite. There is a problem that the phase transition causes the volume to expand and moisture can penetrate through the grain boundaries within the crystal. Therefore, in a preferred embodiment of the present invention, durability is increased by arranging the barrier coating layer 12 between the first base film layer 11 and the second base film layer 13.
  • the second base film layer 13 may be attached to the surface of the first base film layer 11 after applying an adhesive as an adhesive layer. At this time, since the barrier coating layer 12 can be coated on one side of the first base film layer 11 and then heat treated, the second base film layer 13 will be attached to the other side of the first base film layer 11. You can. That is, the barrier coating layer 12, the first base film layer 11, the adhesive layer 14, and the second base film layer 13 may be laminated in that order.
  • the adhesive layer 14 is formed between the first base film layer 11 and the second base film layer 13 and forms the second base film layer 13 and the first base film layer 11 or the barrier coating layer 12. It is a composition that strengthens the attachment.
  • the adhesive layer 14 is applied or coated on the first base film layer 11 or the barrier coating layer 12 coated and heat-treated on one side of the first base film layer 11 to attach the second base film layer 13. You can do it.
  • the adhesive used in the adhesive layer is not particularly limited, and for example, one or more adhesives selected from acrylic-based, urethane-based, Brookfield-based and epoxy-based resins can be used.
  • the thickness of the adhesive layer 14 may be 5 to 20 ⁇ m, preferably 9 to 11 ⁇ m.
  • the adhesive layer 14 may contain 40 to 50 parts by weight of an acrylic binder based on 100 parts by weight of the adhesive layer, 0.05 to 1 part by weight of an epoxy-based hardener based on 100 parts by weight of the adhesive layer, and a color pigment may be included in an amount of 0.05 to 1 part by weight based on 100 parts by weight of the adhesive layer. It may contain 1 to 5 parts by weight.
  • the color pigment may be an organic pigment that exhibits color.
  • the color pigment may include at least one of an organic pigment having an azo group as a chromophore or a polycyclic organic pigment such as phthalocyanine, anthraquinone, or quinacridone.
  • the organic pigments are not denatured at the adhesive layer composition temperature of 100 to 140°C, and the organic pigments are absorbed by sunlight due to the outermost top coating layer 15. Denaturation can be minimized, and since the adhesive layer 14 is formed between the first base film layer 11, the barrier coating layer 12, and the second base film layer 13, it can be prevented from being damaged by foreign substances or moisture flowing in from the outside. Color change can be prevented as much as possible.
  • the color pigment dispersed in the adhesive layer 14 may include a phosphor.
  • the phosphor is a substance that converts the wavelength absorbed from light into a wavelength higher than the absorbed wavelength.
  • the phosphor can absorb ultraviolet rays and emit the absorbed ultraviolet rays as visible light with a higher wavelength than the ultraviolet rays.
  • the phosphor can absorb ultraviolet rays with a wavelength of 400 nm or less and emit visible light with a wavelength of 400 to 550 nm.
  • the top coating layer 15 may be applied on one side of the second base film layer 13 to protect the first base film layer 11 and the second base film layer 13 as a base layer, and may be provided to protect the first base film layer 11 and the second base film layer 13 as a base layer. Protects the base layer from external contaminants such as dirt and dust.
  • the top coating layer 15 is preferably made of a transparent material with weather resistance.
  • the top coating layer 15 may include one or more selected from the group consisting of fluorine-based silicone resin, acrylic resin, polyvinyl-based resin, and polyurethane-based resin. In a preferred embodiment, the top coating layer 15 may be formed by coating a fluorine-based silicone resin.
  • the top coating layer 15 preferably has a thickness of 3 to 5 ⁇ m. The top coating layer 15 faces the outside of the solar cell module and may face the outside or the junction box.
  • a solution of 10% by weight of aluminum isopropoxide dispersed in 30% by weight of 98% purity ethanol in 49% by weight of distilled water at 70°C was added dropwise over 1 hour, and 5% by weight of graphene oxide was added while stirring.
  • a hydrolysis condensation reaction was performed by gradually raising the temperature to 95°C and discharging isopropanol. Afterwards, 3% by weight of an aqueous nitric acid solution was added and stirred at 95°C for 10 hours, and then 3% by weight of an aqueous phosphoric acid solution was added. When adding the phosphoric acid aqueous solution, the temperature of both solutions was controlled to 20°C.
  • PET film (ASTROLL, Kolon Industries) with a thickness of 188 ⁇ m was used as the first base film layer 11 and the second base film layer 13.
  • the barrier coating layer composition according to Preparation Example 1 was coated on the first base film layer 11, cured in an environment of 120°C for 5 min, and then cured again in an environment of 140°C for 1 min to form a 1 ⁇ m layer. It was made to be thick.
  • the adhesive layer 14 contains 35 parts by weight of an acrylic binder (AT-377, Samwon) based on 100 parts by weight of the adhesive layer, 1 part by weight of an epoxy-based hardener (CAT-EX, Samwon) based on 100 parts by weight of the adhesive layer, and MEK solvent to the adhesive layer.
  • a composition mixed at 64 parts by weight based on 100 parts by weight was cured for 2 minutes in an environment at 120°C to obtain a thickness of 10 ⁇ m.
  • the adhesive layer 14 was formed on one side of the barrier coating layer 12, and the second base film layer 13 was attached thereon.
  • a dispersion (FAS 001, DCT material) dispersed in 65 parts by weight of MEK based on 100 parts by weight of the top coating layer to include 35 parts by weight of fluorine-based silicon based on 100 parts by weight of the top coating layer is applied to the second base film layer.
  • the solvent was removed for 1 minute in a ventilated oven at 80°C.
  • the coating was cured at 500mJ/cm 2 using a UV curing machine to have a thickness of 5 ⁇ m.
  • first base film layer (11) barrier coating layer (12) - adhesive layer (14) - second base film layer (13) - top coating layer (15).
  • An adhesive layer 14 was formed on the first base film layer 11 of Example 1, and the second base film layer 13 of Example 1 was attached thereon to form the first base film layer 11-adhesive layer 14. ) - A film was formed laminated in the order of the second base film layer 13.
  • the adhesive layer 14 is formed on the other side of the first base film layer 11, so that the stacking order is barrier coating layer 12 - first base film layer 11 - adhesive layer 14.
  • a film consisting of -second base film layer (13) and top coating layer (15) was formed.
  • the barrier coating layer 12 of Example 1 was omitted to form a film laminated in the following order: first base film layer 11 - adhesive layer 14 - second base film layer 13 - top coating layer 15.
  • the top coating layer 15 of Example 2 was omitted to form a film laminated in the following order: barrier coating layer - first base film layer 11 - adhesive layer 14 - second base film layer 13.
  • the top coating layer 15 of Example 1 was omitted to form a film laminated in the following order: first base film layer 11 - barrier coating layer - adhesive layer 14 - second base film layer 13.
  • the top coating layer 15 of Example 1 was coated on the first base film layer 11 of Example 1 to form a film laminated in the order of first base film layer 11 - top coating layer 15.
  • the barrier coating layer 12 of Example 1 was coated on the first base film layer 11 of Example 1 to form a film laminated in the order of barrier coating layer 12 - first base film layer 11.
  • a film was formed in which the thickness of the adhesive layer 14 of Example 2 was 5 ⁇ m.
  • a film was formed in which the thickness of the adhesive layer 14 of Example 2 was 20 ⁇ m.
  • a film was formed in which the thickness of the adhesive layer 14 of Example 2 was 30 ⁇ m.
  • the composition of the top coating layer 15 was an acrylic coating.
  • the acrylic coating is formed to a thickness of 5 ⁇ m through micro gravure coating by mixing 30 parts by weight of urethane acrylate, 5 parts by weight of epoxy isocyanate, 18 parts by weight of toluene, and 47 parts by weight of methyl ethyl ketone (MEK) with respect to 100 parts by weight of the top coating layer. did.
  • Example 1 In the film of Example 1, a film was formed in which the composition of the top coating layer 15 was replaced with the acrylic coating of Example 12.
  • a film was formed using a single layer of PET film (ASTROLL, Kolon Industries) with a thickness of 50 ⁇ m.
  • a film was formed using a single layer of PET film (ASTROLL, Kolon Industries) with a thickness of 100 ⁇ m.
  • a film was formed using a single layer of PET film (ASTROLL, Kolon Industries) with a thickness of 125 ⁇ m.
  • a film was formed using a single layer of PET film (ASTROLL, Kolon Industries) with a thickness of 188 ⁇ m.
  • a film was formed using a single layer of PET film (ASTROLL, Kolon Industries) with a thickness of 250 ⁇ m.
  • a film was formed using two layers of PET film (ASTROLL, Kolon Industries) with a thickness of 50 ⁇ m, and the adhesive layer of Example 1 formed between them to a thickness of 10 ⁇ m.
  • a film was formed using three layers of PET film (ASTROLL, Kolon Industries) with a thickness of 50 ⁇ m, and the adhesive layer of Example 1 formed between them to a thickness of 10 ⁇ m.
  • a PVF film layer (Tedlar, Dupont) with a thickness of 30 ⁇ m is used, and the first base film layer 11 and the second base film layer 13 are PET with a thickness of 188 ⁇ m. Film (ASTROLL, Kolon Industries) was used. The top coating layer coated on one side of the second base film layer 13 was the same as the top coating layer in Example 1.
  • a film was formed by lamination in the following order: PVF film layer - first base film layer (11) - adhesive layer (14) - second base film layer (13) - top coating layer (15).
  • Visible light transmission ratio was performed on the films formed by Examples 1 to 13 and the film formed by Comparative Example 4. At this time, the transmittance is the amount of visible light measured on the back side of the film compared to the visible light irradiated on the first base film layer 11 side of the film. This was measured with a spectrometer, Jasco V-770.
  • a partial discharge voltage test was performed on the films formed in Examples 1 to 13 and Comparative Examples 1 to 7.
  • the partial discharge voltage test was measured and calculated according to the partial discharge voltage test according to KS C IEC 60664-1.
  • Example 1 1,206 91.69 1.05
  • Example 2 1,170 83.58 3.75
  • Example 3 930 91.27 2.18
  • Example 4 1,340 89.81 2.07
  • Example 5 990 84.40 3.66
  • Example 6 1,190 84.37 3.60 Comparative example 4 830 91.13 1.71
  • the partial discharge voltage test results for the comparative examples in Table 2 it can be seen that the partial discharge voltage increases as the thickness of the PET layer as the base layer increases, Examples 1 and 2, and Examples 9 to 9. According to the test results in Fig. 11, it can be confirmed that the thickness of the adhesive layer 14 between the first base film layer 11 and the second base film layer 13 does not significantly affect the partial discharge voltage. Accordingly, securing a base layer of a predetermined thickness is advantageous in terms of partial discharge voltage. However, considering that direct contact of the barrier coating layer 12 with the encapsulation layer or encapsulant reduces the partial discharge voltage, it is better to stack the base layer in multiple layers and place the barrier coating layer 12 between the base layers. You can see that it is advantageous.
  • Example 1 1,206 91.69 1.05
  • Example 7 870 94.42 1.14
  • Example 8 830 91.91 1.62
  • Example 12 860 90.55 2.61
  • Example 13 1,216 91.10 1.68
  • Example 1 and Example 13 in Table 3 there is no significant difference in the composition of the top coating layer 15 in the partial discharge voltage test, but in terms of visible light transmittance and haze, the top coating layer 15 is coated with fluorine-based silicon. It can be seen that it is advantageous to use . Even when comparing Example 7 and Example 12, coating fluorine-based silicone as the top coating layer 15 on the PET film is advantageous in terms of haze compared to acrylic-based coating. In addition, in cases where the PET film is not laminated, that is, in Examples 7, 8, and 12 in which a sufficient thickness of the base layer is not secured, partial discharge of 1,000 VDC occurs even if the barrier coating layer 12 or the top coating layer 15 is formed. You can confirm that the voltage is not reached.
  • Example 1 For the films of Example 1, Example 3, and Comparative Example 8, the water vapor transmission rate (WVTR) was measured under conditions of 38°C and 100% RH according to the ASTM F1249 test method.
  • WVTR water vapor transmission rate
  • a water permeability rate (WVTR) of 1.3 g/m 2 /day was measured, and in Examples 1 and 3, a water permeability rate (WVTR) of 0.05 g/m 2 /day was measured. Therefore, it is preferable to use the barrier coating layer 12 according to an embodiment of the present invention as a barrier layer to prevent moisture penetration of the color film for solar cell modules.
  • the adhesive layer 14 contained 35 parts by weight of an acrylic binder (AT-377, Samwon) based on 100 parts by weight of the adhesive layer, and 1 part by weight of an epoxy-based hardener (CAT-EX, Samwon) based on 100 parts by weight of the adhesive layer.
  • a composition in which 1 part by weight of a red pigment (Irgalite Red K 4170, BASF) containing Quinacridone is mixed in an amount of 1 part by weight based on 100 parts by weight of the adhesive layer and 63 parts by weight of MEK solvent based on 100 parts by weight of the adhesive layer is mixed in an environment at 120°C. It was cured for 2 min to achieve a thickness of 10 ⁇ m.
  • the adhesive layer 14 was formed on one side of the barrier coating layer 12, and a film was formed by laminating the second base film layer 13 thereon.
  • the adhesive layer 14 was formed by including 1 part by weight of a blue pigment (Irgalite Blue GBP, BASF) containing Cu-phthalocyanine instead of the red pigment, based on 100 parts by weight of the adhesive layer.
  • a blue pigment Irgalite Blue GBP, BASF
  • the adhesive layer 14 was formed by including 1 part by weight of a green pigment (Irgalite Green GFNP, BASF) containing Cu-phthalocyanine instead of the red pigment, based on 100 parts by weight of the adhesive layer.
  • a green pigment Irgalite Green GFNP, BASF
  • Cu-phthalocyanine instead of the red pigment
  • the adhesive layer 14 contained 35 parts by weight of an acrylic binder (AT-377, Samwon) based on 100 parts by weight of the adhesive layer, and 1 part by weight of an epoxy-based hardener (CAT-EX, Samwon) based on 100 parts by weight of the adhesive layer.
  • a composition in which 1 part by weight of a red pigment (Irgalite Red K 4170, BASF) containing Quinacridone is mixed in an amount of 1 part by weight based on 100 parts by weight of the adhesive layer and 63 parts by weight of MEK solvent based on 100 parts by weight of the adhesive layer is mixed in an environment at 120°C. It was cured for 2 min to achieve a thickness of 10 ⁇ m.
  • the adhesive layer 14 was formed on one side of the barrier coating layer 12, and a film was formed by laminating the second base film layer 13 thereon.
  • the adhesive layer 14 was formed by including 1 part by weight of a blue pigment (Irgalite Blue GBP, BASF) containing Cu-phthalocyanine instead of the red pigment, based on 100 parts by weight of the adhesive layer.
  • a blue pigment Irgalite Blue GBP, BASF
  • the adhesive layer 14 was formed by including 1 part by weight of a green pigment (Irgalite Green GFNP, BASF) containing Cu-phthalocyanine instead of the red pigment, based on 100 parts by weight of the adhesive layer.
  • a green pigment Irgalite Green GFNP, BASF
  • Cu-phthalocyanine instead of the red pigment
  • ASTM G155 Cycle No. 1 Experiment was conducted. Through the above experiment, the weathering effect that occurs when the films of Examples 14 to 19 of the present invention are exposed to sunlight was measured.
  • the filter value was set to Daylight, and the illuminance was 0.35 W/m2 using a Xe arc lamp at 340 nm.
  • the exposure cycle was performed with 102min Light only & 18min Light and spray at 63°C Black Panel Temperature.
  • the color change of the color film was investigated by measuring the Lab color difference over 1000 hours.
  • Color difference ( ⁇ E) is the standard CIE formula for expressing color differences between CIELab values, calculated by L (brightness), a (amount of change in opposite colors of red-green), and b (amount of change in opposite colors of blue-yellow). It can be. After measuring the L, a, and b values at the beginning of the test (0 hr), measuring the L, a, and b values at 500 hr and 1,000 hr and comparing the color difference, the smaller the color difference ( ⁇ E), the more the color of the color film was maintained. can be judged.
  • the color difference ( ⁇ E) is 5 or more, the discoloration is felt to be too severe to be recognized by the naked eye, so the test should be discontinued.
  • the color difference ( ⁇ E) measured at 500 hr and 1,000 hr was lower for Examples 14 to 16 than for Examples 17 to 19. You can see that it is mostly 20% or more smaller than that.
  • the top coating layer (15) of the present invention prevents surface changes (cracks, yellowing) in a solar exposure environment to maintain the color of the color film, and the barrier coating layer (12) prevents moisture penetration to maintain the color. It can be confirmed that discoloration of the adhesive layer containing pigment is prevented.
  • Examples 14 to 16 have a higher photoelectric conversion efficiency than the films of Examples 17 to 19, at 18% or more. This can be seen to be due to the fact that the film of Example 1 has a higher visible light transmittance than the film of Example 2.
  • the adhesive layer 14 was formed by including 1 part by weight of a pigment (SX-217, SINLOIHI) containing a pink phosphor instead of a red pigment, based on 100 parts by weight of the adhesive layer.
  • a pigment SX-217, SINLOIHI
  • a pigment (SX-217, SINLOIHI) containing a pink phosphor of the adhesive layer 14 was incorporated in an amount of 3 parts by weight based on 100 parts by weight of the adhesive layer, and an amount of MEK decreased by the increment of the pigment was added. The mixture was mixed to form a film.
  • Example 20 5 parts by weight of a pigment (SX-217, SINLOIHI) containing a pink phosphor of the adhesive layer 14 was incorporated based on 100 parts by weight of the adhesive layer, and an amount of MEK decreased by the increment of the pigment was added. The mixture was mixed to form a film.
  • a pigment SX-217, SINLOIHI
  • the adhesive layer 14 was formed by including 1 part by weight of a pigment (FM-103, SINLOIHI) containing a red phosphor instead of a red pigment, based on 100 parts by weight of the adhesive layer.
  • a pigment FM-103, SINLOIHI
  • Example 23 3 parts by weight of a pigment (FM-103, SINLOIHI) containing a red phosphor of the adhesive layer 14 was incorporated based on 100 parts by weight of the adhesive layer, and an amount of MEK decreased by the increment of the pigment was added. The mixture was mixed to form a film.
  • a pigment FM-103, SINLOIHI
  • Example 23 5 parts by weight of a pigment (FM-103, SINLOIHI) containing a red phosphor of the adhesive layer 14 was incorporated based on 100 parts by weight of the adhesive layer, and an amount of MEK decreased by the increment of the pigment was added. The mixture was mixed to form a film.
  • a pigment FM-103, SINLOIHI
  • the adhesive layer 14 was formed by including 1 part by weight of a pigment (FM-105, SINLOIHI) containing a yellow phosphor instead of a red pigment, based on 100 parts by weight of the adhesive layer.
  • a pigment FM-105, SINLOIHI
  • Example 26 a pigment (FM-105, SINLOIHI) containing a yellow phosphor of the adhesive layer 14 was incorporated in an amount of 3 parts by weight based on 100 parts by weight of the adhesive layer, and an amount of MEK decreased by the increment of the pigment was added. The mixture was mixed to form a film.
  • a pigment FM-105, SINLOIHI
  • Example 26 a pigment (FM-105, SINLOIHI) containing a yellow phosphor of the adhesive layer 14 was incorporated in an amount of 5 parts by weight based on 100 parts by weight of the adhesive layer, and an amount of MEK decreased by the increment of the pigment was added. The mixture was mixed to form a film.
  • a pigment FM-105, SINLOIHI
  • Figure 4 is a diagram showing the transmittance (%) according to the wavelength of Example 20 and Examples 22 to 28.
  • a pigment containing a phosphor is incorporated into the adhesive layer 14
  • the transmittance of visible light with a wavelength of 400 to 550 nm, which has high conversion efficiency in the solar cell module, is high. Therefore, when the phosphor is distributed within the adhesive layer 14, visible light with a wavelength of 400 to 550 nm can be set to the target wavelength range of the solar cell module, resulting in excellent photoelectric conversion efficiency.
  • Figure 5 is a diagram showing the visible color, total light transmittance, haze, and photoelectric conversion efficiency of Examples 1, 21, and 22 on a black PV sheet.
  • the total light transmittance TT (%) decreases, confirming that color reproduction is high.
  • Haze (%) tends to increase, but the phosphor particles can supply light again through the photovoltaic effect.
  • the photoelectric conversion efficiency is 17.8%, which is superior to the color film showing the same color rendition and haze.

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Abstract

The present invention relates to a color film for a solar cell module and, more specifically, to a color film for a solar cell module, which comprises: a first substrate film layer as a base substrate; a second substrate film layer disposed at one side surface of the first substrate film layer; an adhesive layer formed between the first substrate film layer and the second substrate film layer; a top coating layer formed on one side of the second substrate film layer; and a barrier coating layer formed on one surface of the first substrate film layer, wherein: the adhesive layer has one surface contacting with the barrier coating layer and containing 1 to 2 parts by weight of a color pigment relative to 100 parts by weight of the adhesive layer and the other surface contacting with the second base film layer; the barrier coating layer is formed by mixing a metal alkoxide, water, and an acid catalyst and subjecting the metal alkoxide to hydrolysis condensation by a sol-gel method; and the barrier coating layer is inserted between the substrate layers to prevent a decrease in partial discharge voltage occurring when one surface of the barrier coating layer is directly exposed to the outside and to minimize the color change of the color film even over time.

Description

태양전지 모듈용 컬러필름Color film for solar cell modules
본 발명은 태양전지 모듈용 컬러필름에 관한 것으로, 더욱 상세하게는 베이스 기재로서의 제1기재필름층, 상기 제1기재필름층의 일측면에 배치되는 제2기재필름층, 상기 제1기재필름층과 제2기재필름층 사이에 형성되는 접착층, 상기 제2기재필름층의 일측에 형성되는 탑코팅층, 상기 제1기재필름층의 일면에 형성되는 배리어코팅층을 포함하고, 접착층은 일면이 상기 배리어코팅층과 접하며 색상안료를 접착층 100 중량부 기준 1 내지 2 중량부 포함하고, 타면이 제2기재필름층과 접하도록 하되, 상기 배리어코팅층은 금속 알콕사이드, 물 및 산 촉매를 혼합하고, 졸-겔법으로 상기 금속 알콕사이드를 가수 분해 축합시켜 형성하고, 상기 배리어코팅층을 기재층 사이에 삽입하여 배리어코팅층의 일면이 외부에 직접적으로 외부로 노출되는 경우 발생하는 부분방전전압 저하 현상을 방지함과 동시에 시간이 지나더라도 컬러필름의 색상 변화가 최소화되는 것을 특징으로 하는 태양전지 모듈용 컬러필름에 대한 것이다.The present invention relates to a color film for solar cell modules, and more specifically, to a first base film layer as a base substrate, a second base film layer disposed on one side of the first base film layer, and the first base film layer. and an adhesive layer formed between the second base film layer, a top coating layer formed on one side of the second base film layer, and a barrier coating layer formed on one side of the first base film layer, wherein one side of the adhesive layer is covered with the barrier coating layer. It is in contact with and contains 1 to 2 parts by weight of color pigment based on 100 parts by weight of the adhesive layer, and the other side is in contact with the second base film layer, wherein the barrier coating layer is formed by mixing metal alkoxide, water and an acid catalyst, and using the sol-gel method. It is formed by hydrolytic condensation of metal alkoxide, and the barrier coating layer is inserted between the base layers to prevent the partial discharge voltage decrease that occurs when one side of the barrier coating layer is directly exposed to the outside, and at the same time, even over time. This is about a color film for solar cell modules, which is characterized by minimal color change in the color film.
차세대 친환경 에너지원으로서 태양전지가 개발되어 주택용, 공업용 등으로 급속하게 보급되고 있다. 태양전지는 다수의 태양전지 셀(cell)이 모듈화되어 구성된다. 복수의 태양전지 셀은 봉지층에 패킹(packing), 고정되며, 상기 봉지층의 하부 면에는 밀봉 부재로서의 백시트(back sheet)가 접착되어 모듈화된다. 도 1은 일반적인 태양전지 모듈의 구성을 도시한 도면으로, 태양전지 모듈은 일반적으로 프레임을 통해 고정된 광이 입사되는 투명한 유리층(83), 상부 봉지층(82a), 다수의 태양전지 셀(C), 하부 봉지층(82b) 및 백시트(81)가 순차적으로 적층된 구조를 갖는다. 다수의 태양전지 셀(C)은 봉지층(82a, 82b)에 패킹 및 고정된다. Solar cells have been developed as a next-generation eco-friendly energy source and are rapidly being distributed for residential and industrial purposes. Solar cells are made up of multiple solar cells that are modularized. A plurality of solar cells are packed and fixed in an encapsulation layer, and a back sheet as a sealing member is attached to the lower surface of the encapsulation layer to form a module. Figure 1 is a diagram showing the configuration of a general solar cell module. The solar cell module generally includes a transparent glass layer 83 through which fixed light is incident through a frame, an upper encapsulation layer 82a, and a plurality of solar cells ( C), it has a structure in which the lower encapsulation layer 82b and the back sheet 81 are sequentially stacked. A plurality of solar cells (C) are packed and fixed to the encapsulation layers (82a, 82b).
BIPV는 Building-Integrated Photovoltaic의 줄임말로, 태양광 에너지로 전기를 생산하여 소비자에게 공급하는 것 외에 건물 일체형 태양광 모듈을 건축물 외장재로 사용하는 태양광 발전 시스템을 지칭한다. 건물일체형 태양발전 시스템은 기존에 넓은 평지나 지붕에 태양발전 시스템을 설치하는 것과 달리 건물의 외벽, 창호 등에 설치하게 되고, 태양전지가 하나의 건축자재로 활용되며 태양전지에서 생산된 전기에너지를 바로 건물 내부로 공급하여 사용할 수 있다. BIPV is short for Building-Integrated Photovoltaic, and refers to a solar power generation system that not only produces electricity from solar energy and supplies it to consumers, but also uses building-integrated photovoltaic modules as building exterior materials. Unlike existing solar power generation systems installed on large flat areas or roofs, building-integrated solar power generation systems are installed on the exterior walls of buildings, windows, etc., and solar cells are used as a building material, and the electric energy produced by solar cells is used directly. It can be supplied and used inside the building.
현재 BIPV에 심미성을 부여하기 위해 사용되는 복층구조의 태양광 유리는 공정이 어려우며 무게가 무거운 문제가 있다. 따라서 유리 대비 무게가 가벼우며 심미성을 가지고 태양전지의 출력저하가 적은 컬러필름이 요구되고 있다.Currently, the multi-layer solar glass used to give BIPV aesthetics is difficult to process and is heavy. Therefore, there is a demand for color films that are lighter in weight compared to glass, have aesthetics, and reduce solar cell output.
색상 구현과 경량화를 위하여 필름을 사용하는 경우 부분방전이 문제될 수 있다. 부분방전이란 절연물의 표면에서 고전계에 의한 부분적인 방전 또는 절연물 내부에 존재하는 틈이나 기포에 생기는 내부방전 등을 의미하며, 부분방전이 발생하는 구역에서 고전압 스트레스에 의해 절연물의 열화가 진전된다. 따라서 태양전지 모듈과 접촉하게 되는 백시트는 부분방전전압이 높아야 한다. 백시트는 설치된 태양광 모듈의 부분 방전전압(Vdc; Partial Discharge Voltage)이 과도하게 높을 경우 직렬로 연결된 셀 전체의 과부하에 의하여 절연파괴 현상이 발생하게 된다. 부분방전전압은 KS C IEC 60664-1에 따른 부분방전전압시험에 따라 측정되며, 업계에서는 1,000VDC 이상의 부분방전전압에서도 절연파괴 내성을 가질 것을 요구하고 있다.Partial discharge can be a problem when using film to achieve color and reduce weight. Partial discharge refers to a partial discharge caused by a high electric field on the surface of an insulating material or an internal discharge that occurs in a gap or bubble inside the insulating material. In the area where the partial discharge occurs, the deterioration of the insulating material progresses due to high voltage stress. Therefore, the backsheet that comes into contact with the solar cell module must have a high partial discharge voltage. When the partial discharge voltage (Vdc; Partial Discharge Voltage) of the installed solar module is excessively high, insulation breakdown occurs due to overload of all cells connected in series. Partial discharge voltage is measured according to the partial discharge voltage test according to KS C IEC 60664-1, and the industry requires insulation breakdown resistance even at partial discharge voltages of 1,000 VDC or more.
본 발명은 상기와 같은 문제점을 해결하기 위해 출안된 것으로,The present invention was devised to solve the above problems,
본 발명의 목적은 베이스 기재로서의 제1기재필름층, 상기 제1기재필름층의 일측면에 배치되는 제2기재필름층, 상기 제1기재필름층과 제2기재필름층 사이에 형성되는 접착층, 상기 제2기재필름층의 일측에 형성되는 탑코팅층을 포함하고, 상기 접착층은 색상안료를 포함하여 기재층을 적층하여 충분한 부분방전전압을 확보함과 동시에 접착층 내 색상 변화를 최소화하는 태양전지 모듈용 컬러필름을 제공하는 데 있다.The object of the present invention is a first base film layer as a base substrate, a second base film layer disposed on one side of the first base film layer, an adhesive layer formed between the first base film layer and the second base film layer, A solar cell module comprising a top coating layer formed on one side of the second base film layer, and the adhesive layer including a color pigment to secure sufficient partial discharge voltage and minimize color change within the adhesive layer by stacking base layers. The goal is to provide color film.
본 발명의 목적은 상기 제1기재필름층의 일면에 형성되는 배리어코팅층을 더 포함하고, 상기 접착층은 일면이 상기 제1기재필름층 또는 배리어코팅층과 접하고, 타면이 제2기재필름층과 접하도록 하여 내투습성이 우수한 태양전지 모듈용 컬러필름을 제공하는 데 있다.An object of the present invention further includes a barrier coating layer formed on one side of the first base film layer, wherein the adhesive layer has one side in contact with the first base film layer or barrier coating layer and the other side in contact with the second base film layer. The aim is to provide a color film for solar cell modules with excellent moisture permeability resistance.
본 발명의 목적은 상기 접착층은 일면이 상기 배리어코팅층과 접하고, 타면이 제2기재필름층과 접하도록 하여 배리어코팅층을 기재층 사이에 배치하여 배리어코팅층의 일면이 외부에 직접적으로 외부로 노출되는 경우 배리어코팅층의 품질저하로 인해 발생하는 부분방전전압 저하 현상과 색상 변화를 방지하는 태양전지 모듈용 컬러필름을 제공하는 데 있다.The purpose of the present invention is to arrange the barrier coating layer between the base layers so that one side of the adhesive layer is in contact with the barrier coating layer and the other side is in contact with the second base film layer, so that one side of the barrier coating layer is directly exposed to the outside. The goal is to provide a color film for solar cell modules that prevents partial discharge voltage reduction and color change caused by deterioration of the quality of the barrier coating layer.
본 발명의 목적은 상기 접착층은 색상안료를 접착층 100 중량부 기준 1 내지 2 중량부 포함하여 적은 양의 색상안료로도 발색이 가능한 태양전지 모듈용 컬러필름을 제공하는 데 있다.The purpose of the present invention is to provide a color film for solar cell modules in which the adhesive layer contains 1 to 2 parts by weight of a color pigment based on 100 parts by weight of the adhesive layer, allowing color development even with a small amount of color pigment.
본 발명의 목적은 상기 색상안료는 발색단으로 아조기를 가지는 유기안료 또는 Phthalocyanine, Anthraquinone, Quinacridone의 다환기 유기안료 중 적어도 하나 이상을 포함하여 색상안료가 접착층을 형성하는 유기용매 내에 원활하게 분산되는 태양전지 모듈용 컬러필름을 제공하는 데 있다.The object of the present invention is to provide a solar cell in which the color pigment includes at least one of an organic pigment having an azo group as a chromophore or a polycyclic organic pigment such as phthalocyanine, anthraquinone, and quinacridone, and the color pigment is smoothly dispersed in an organic solvent forming an adhesive layer. The goal is to provide color film for modules.
본 발명의 목적은 상기 색상안료는 광으로부터 흡수된 파장을 상기 흡수된 파장보다 높은 파장으로 변환시키는 형광체를 포함하며, 상기 형광체는 자외선을 흡수하여 자외선 파장보다 높은 파장으로 변환시켜 광전 변환효율을 증대시킨 태양전지 모듈용 컬러필름을 제공하는 데 있다.The object of the present invention is that the color pigment includes a phosphor that converts a wavelength absorbed from light into a wavelength higher than the absorbed wavelength, and the phosphor absorbs ultraviolet rays and converts them into a wavelength higher than the ultraviolet wavelength to increase photoelectric conversion efficiency. The goal is to provide colored films for solar cell modules.
본 발명의 목적은 상기 제1기재필름층 및 제2기재필름층은 50 내지 200㎛의 두께, 상기 접착층은 5 내지 20 ㎛의 두께를 가져 부분방전전압 확보를 위해 충분한 두께의 기재층을 가지는 태양전지 모듈용 컬러필름을 제공하는 데 있다.The object of the present invention is to have a base layer of sufficient thickness to secure a partial discharge voltage, wherein the first base film layer and the second base film layer have a thickness of 50 to 200 ㎛, and the adhesive layer has a thickness of 5 to 20 ㎛. The goal is to provide color films for battery modules.
본 발명의 목적은 상기 제1기재필름층 및 제2기재필름층은 폴리에스테르계 수지, 폴리카보네이트계 수지, 폴리비닐계 수지, 폴리이미드계 수지, 폴리우레탄계 수지 중 선택된 하나 이상을 포함하는 태양전지 모듈용 컬러필름을 제공하는 데 있다.The object of the present invention is to provide a solar cell in which the first base film layer and the second base film layer include at least one selected from polyester-based resin, polycarbonate-based resin, polyvinyl-based resin, polyimide-based resin, and polyurethane-based resin. The goal is to provide color film for modules.
본 발명의 목적은 상기 배리어코팅층은 금속산화물이 제1기재필름층 상에 코팅된 것으로, 상기 금속산화물은 금속산화물 졸이며, 상기 금속산화물은 알루미나, 티타니아, 마그네시아, 지르코니아 또는 이들의 조합을 포함하는 태양전지 모듈용 컬러필름을 제공하는 데 있다.The object of the present invention is that the barrier coating layer is a metal oxide coated on a first base film layer, the metal oxide is a metal oxide sol, and the metal oxide includes alumina, titania, magnesia, zirconia, or a combination thereof. The goal is to provide color films for battery modules.
본 발명의 목적은 상기 배리어코팅층은 산 촉매 하에서 금속 알콕사이드를 물에 용해시켜 가수 분해 축합시키고 상기 제1기재필름층의 일면에 코팅한 후 경화시켜 형성하여 졸-겔법으로 빠른 공정이 가능한 태양전지 모듈용 컬러필름을 제공하는 데 있다.The purpose of the present invention is to form a solar cell module in which the barrier coating layer is formed by dissolving a metal alkoxide in water under an acid catalyst, hydrolyzing and condensing it, coating it on one side of the first base film layer, and then curing it, allowing a quick process using the sol-gel method. The goal is to provide color film for use.
본 발명의 목적은 상기 배리어코팅층은 그래핀이 결합된 금속 산화물 및 인 함유 화합물을 포함하는 태양전지 모듈용 컬러필름을 제공하는 데 있다.The purpose of the present invention is to provide a color film for solar cell modules in which the barrier coating layer includes a metal oxide and a phosphorus-containing compound combined with graphene.
본 발명의 목적은 상기 탑코팅층은 불소계 실리콘 수지, 아크릴계 수지,폴리비닐계 수지, 폴리우레탄계 수지 중 선택된 하나 이상을 포함하는 태양전지 모듈용 컬러필름을 제공하는 데 있다.The purpose of the present invention is to provide a color film for solar cell modules, wherein the top coating layer includes one or more selected from the group consisting of fluorine-based silicone resin, acrylic resin, polyvinyl-based resin, and polyurethane-based resin.
본 발명의 목적은 상기 탑코팅층은 3 내지 5㎛의 두께, 상기 배리어코팅층은 1㎛ 이하의 두께를 가지는 태양전지 모듈용 컬러필름을 제공하는 데 있다.The purpose of the present invention is to provide a color film for solar cell modules in which the top coating layer has a thickness of 3 to 5 ㎛ and the barrier coating layer has a thickness of 1 ㎛ or less.
본 발명은 앞서 본 목적을 달성하기 위해서 다음과 같은 구성을 가진 실시예에 의해서 구현된다.In order to achieve the above-described object, the present invention is implemented by an embodiment having the following configuration.
본 발명의 일 실시예에 따르면, 본 발명에 따른 태양전지 모듈용 컬러필름은 베이스 기재로서의 제1기재필름층, 상기 제1기재필름층의 일측면에 배치되는 제2기재필름층, 상기 제1기재필름층과 제2기재필름층 사이에 형성되는 접착층, 상기 제2기재필름층의 일측에 형성되는 탑코팅층을 포함하고, 상기 접착층은 색상안료를 포함하는 것을 특징으로 한다.According to one embodiment of the present invention, the color film for a solar cell module according to the present invention includes a first base film layer as a base substrate, a second base film layer disposed on one side of the first base film layer, and the first base film layer. It includes an adhesive layer formed between a base film layer and a second base film layer, and a top coating layer formed on one side of the second base film layer, and the adhesive layer includes a color pigment.
본 발명의 일 실시예에 따르면, 상기 제1기재필름층의 일면에 형성되는 배리어코팅층을 더 포함하고, 상기 접착층은 일면이 상기 제1기재필름층 또는 배리어코팅층과 접하고, 타면이 제2기재필름층과 접하는 것을 특징으로 한다.According to one embodiment of the present invention, it further includes a barrier coating layer formed on one side of the first base film layer, wherein one side of the adhesive layer is in contact with the first base film layer or the barrier coating layer, and the other side is in contact with the second base film. It is characterized by being in contact with the layer.
본 발명의 일 실시예에 따르면, 상기 접착층은 일면이 상기 배리어코팅층과 접하고, 타면이 제2기재필름층과 접하는 것을 특징으로 한다.According to one embodiment of the present invention, the adhesive layer is characterized in that one side is in contact with the barrier coating layer and the other side is in contact with the second base film layer.
본 발명의 일 실시예에 따르면, 상기 접착층은 색상안료를 접착층 100 중량부 기준 1 내지 2 중량부 포함하는 것을 특징으로 한다.According to one embodiment of the present invention, the adhesive layer is characterized in that it contains 1 to 2 parts by weight of a color pigment based on 100 parts by weight of the adhesive layer.
본 발명의 일 실시예에 따르면, 상기 색상안료는 발색단으로 아조기를 가지는 유기안료 또는 Phthalocyanine, Anthraquinone, Quinacridone의 다환기 유기안료 중 적어도 하나 이상을 포함하는 것을 특징으로 한다.According to one embodiment of the present invention, the color pigment is characterized in that it contains at least one of an organic pigment having an azo group as a chromophore or a polycyclic organic pigment such as phthalocyanine, anthraquinone, and quinacridone.
본 발명의 일 실시예에 따르면, 상기 색상안료는 광으로부터 흡수된 파장을 상기 흡수된 파장보다 높은 파장으로 변환시키는 형광체를 포함하며, 상기 형광체는 자외선을 흡수하여 자외선 파장보다 높은 파장으로 변환시키는 것을 특징으로 한다.According to one embodiment of the present invention, the color pigment includes a phosphor that converts a wavelength absorbed from light into a wavelength higher than the absorbed wavelength, and the phosphor absorbs ultraviolet rays and converts them into a wavelength higher than the ultraviolet wavelength. It is characterized by
본 발명의 일 실시예에 따르면, 상기 제1기재필름층 및 제2기재필름층은 50 내지 200㎛의 두께, 상기 접착층은 5 내지 20 ㎛의 두께를 가지는 것을 특징으로 한다.According to one embodiment of the present invention, the first base film layer and the second base film layer have a thickness of 50 to 200 ㎛, and the adhesive layer has a thickness of 5 to 20 ㎛.
본 발명의 일 실시예에 따르면, 상기 제1기재필름층 및 제2기재필름층은 폴리에스테르계 수지, 폴리카보네이트계 수지, 폴리비닐계 수지, 폴리이미드계 수지, 폴리우레탄계 수지 중 선택된 하나 이상을 포함하는 것을 특징으로 한다.According to one embodiment of the present invention, the first base film layer and the second base film layer include at least one selected from polyester-based resin, polycarbonate-based resin, polyvinyl-based resin, polyimide-based resin, and polyurethane-based resin. It is characterized by including.
본 발명의 일 실시예에 따르면, 상기 배리어코팅층은 금속산화물이 제1기재필름층 상에 코팅된 것으로, 상기 금속산화물은 금속산화물 졸이며, 알루미나, 티타니아, 마그네시아, 지르코니아 또는 이들의 조합을 포함하는 것을 특징으로 한다.According to one embodiment of the present invention, the barrier coating layer is a metal oxide coated on the first base film layer, and the metal oxide is a metal oxide sol and includes alumina, titania, magnesia, zirconia, or a combination thereof. It is characterized by
본 발명의 일 실시예에 따르면, 상기 배리어코팅층은 산 촉매 하에서 금속 알콕사이드를 물에 용해시켜 가수 분해 축합시키고 상기 제1기재필름층의 일면에 코팅한 후 경화시켜 형성된 것을 특징으로 한다.According to one embodiment of the present invention, the barrier coating layer is formed by dissolving a metal alkoxide in water under an acid catalyst, hydrolyzing condensation, coating it on one side of the first base film layer, and then curing it.
본 발명의 일 실시예에 따르면, 상기 배리어코팅층은 그래핀이 결합된 금속 산화물 및 인 함유 화합물을 포함하는 것을 특징으로 한다.According to one embodiment of the present invention, the barrier coating layer includes a metal oxide and a phosphorus-containing compound to which graphene is bonded.
본 발명의 일 실시예에 따르면, 상기 탑코팅층은 불소계 실리콘 수지, 아크릴계 수지, 폴리비닐계 수지, 폴리우레탄계 수지 중 선택된 하나 이상을 포함하는 것을 특징으로 한다.According to one embodiment of the present invention, the top coating layer is characterized in that it includes one or more selected from the group consisting of a fluorine-based silicone resin, an acrylic resin, a polyvinyl-based resin, and a polyurethane-based resin.
본 발명의 일 실시예에 따르면, 상기 탑코팅층은 3 내지 5㎛의 두께, 상기 배리어코팅층은 1㎛ 이하의 두께를 가지는 것을 특징으로 한다.According to one embodiment of the present invention, the top coating layer has a thickness of 3 to 5㎛, and the barrier coating layer has a thickness of 1㎛ or less.
본 발명은 앞서 본 실시예와 하기에 설명할 구성과 결합, 사용관계에 의해 다음과 같은 효과를 얻을 수 있다.The present invention can achieve the following effects by combining the above-mentioned embodiment with the configuration, combination, and use relationship described below.
본 발명은, 베이스 기재로서의 제1기재필름층, 상기 제1기재필름층의 일측면에 배치되는 제2기재필름층, 상기 제1기재필름층과 제2기재필름층 사이에 형성되는 접착층, 상기 제2기재필름층의 일측에 형성되는 탑코팅층을 포함하고, 상기 접착층은 색상안료를 포함하여 기재층을 적층하여 충분한 부분방전전압을 확보함과 동시에 접착층 내 색상 변화를 최소화하는 효과를 준다.The present invention relates to a first base film layer as a base substrate, a second base film layer disposed on one side of the first base film layer, an adhesive layer formed between the first base film layer and the second base film layer, It includes a top coating layer formed on one side of the second base film layer, and the adhesive layer includes a color pigment and laminates the base layer to ensure sufficient partial discharge voltage and at the same time minimize color change in the adhesive layer.
본 발명은, 상기 제1기재필름층의 일면에 형성되는 배리어코팅층을 더 포함하고, 상기 접착층은 일면이 상기 제1기재필름층 또는 배리어코팅층과 접하고, 타면이 제2기재필름층과 접하도록 하여 내투습성이 우수한 효과가 있다.The present invention further includes a barrier coating layer formed on one side of the first base film layer, wherein one side of the adhesive layer is in contact with the first base film layer or barrier coating layer and the other side is in contact with the second base film layer. It has excellent moisture permeability resistance.
본 발명은, 상기 접착층은 일면이 상기 배리어코팅층과 접하고, 타면이 제2기재필름층과 접하도록 하여 배리어코팅층을 기재층 사이에 배치하여 배리어코팅층의 일면이 외부에 직접적으로 외부로 노출되는 경우 배리어코팅층의 품질저하로 인해 발생하는 부분방전전압 저하 현상과 색상 변화를 방지하는 효과를 얻는다.In the present invention, the adhesive layer has one side in contact with the barrier coating layer and the other side in contact with the second base film layer, so that the barrier coating layer is disposed between the base layers, so that when one side of the barrier coating layer is directly exposed to the outside, the barrier This has the effect of preventing partial discharge voltage drop and color change caused by the quality deterioration of the coating layer.
본 발명은, 상기 접착층은 색상안료를 접착층 100 중량부 기준 1 내지 2 중량부 포함하여 적은 양의 색상안료로도 발색이 가능하다.In the present invention, the adhesive layer contains 1 to 2 parts by weight of color pigment based on 100 parts by weight of the adhesive layer, allowing color development even with a small amount of color pigment.
본 발명은, 상기 색상안료는 발색단으로 아조기를 가지는 유기안료 또는 Phthalocyanine, Anthraquinone, Quinacridone의 다환기 유기안료 중 적어도 하나 이상을 포함하여 색상안료가 접착층을 형성하는 유기용매 내에 원활하게 분산되는 효과를 가진다.In the present invention, the color pigment includes at least one of an organic pigment having an azo group as a chromophore or a polycyclic organic pigment such as phthalocyanine, anthraquinone, and quinacridone, and has the effect of smoothly dispersing the color pigment in an organic solvent forming an adhesive layer. .
본 발명은, 상기 색상안료는 광으로부터 흡수된 파장을 상기 흡수된 파장보다 높은 파장으로 변환시키는 형광체를 포함하며, 상기 형광체는 자외선을 흡수하여 자외선 파장보다 높은 파장으로 변환시켜 광전 변환효율을 증대시킨 효과를 준다.In the present invention, the color pigment includes a phosphor that converts a wavelength absorbed from light into a wavelength higher than the absorbed wavelength, and the phosphor absorbs ultraviolet rays and converts them into a wavelength higher than the ultraviolet wavelength, thereby increasing photoelectric conversion efficiency. It gives effect.
본 발명은, 상기 제1기재필름층 및 제2기재필름층은 50 내지 200㎛의 두께, 상기 접착층은 5 내지 20 ㎛의 두께를 가져 부분방전전압 확보를 위해 충분한 두께의 기재층을 가지는 태양전지 모듈용 컬러필름을 제공하는 효과를 도출한다.In the present invention, the first base film layer and the second base film layer have a thickness of 50 to 200 ㎛, and the adhesive layer has a thickness of 5 to 20 ㎛, so that the solar cell has a base layer of sufficient thickness to secure a partial discharge voltage. The effect of providing color film for modules is derived.
본 발명은, 상기 제1기재필름층 및 제2기재필름층은 폴리에스테르계 수지, 폴리카보네이트계 수지, 폴리비닐계 수지, 폴리이미드계 수지, 폴리우레탄계 수지 중 선택된 하나 이상을 포함하는 태양전지 모듈용 컬러필름을 제공한다.In the present invention, the first base film layer and the second base film layer are solar cell modules comprising at least one selected from polyester-based resin, polycarbonate-based resin, polyvinyl-based resin, polyimide-based resin, and polyurethane-based resin. Provides color film for use.
본 발명은, 상기 배리어코팅층은 금속산화물이 제1기재필름층 상에 코팅된 것으로, 상기 금속산화물은 금속산화물 졸이며, 상기 금속산화물은 알루미나, 티타니아, 마그네시아, 지르코니아 또는 이들의 조합을 포함하는 태양전지 모듈용 컬러필름을 제공하는 효과를 가진다.In the present invention, the barrier coating layer is a solar cell in which a metal oxide is coated on a first base film layer, the metal oxide is a metal oxide sol, and the metal oxide includes alumina, titania, magnesia, zirconia, or a combination thereof. It has the effect of providing color film for modules.
본 발명은, 상기 배리어코팅층은 산 촉매 하에서 금속 알콕사이드를 물에 용해시켜 가수 분해 축합시키고 상기 제1기재필름층의 일면에 코팅한 후 경화시켜 형성하여 졸-겔법으로 빠른 공정이 가능한 효과가 있다.In the present invention, the barrier coating layer is formed by dissolving a metal alkoxide in water under an acid catalyst, hydrolyzing condensation, coating it on one side of the first base film layer, and then curing it, enabling a quick process using the sol-gel method.
본 발명은, 상기 배리어코팅층은 그래핀이 결합된 금속 산화물 및 인 함유 화합물을 포함하는 태양전지 모듈용 컬러필름을 제공할 수 있다.The present invention can provide a color film for solar cell modules in which the barrier coating layer includes a metal oxide and a phosphorus-containing compound combined with graphene.
본 발명은, 상기 탑코팅층은 불소계 실리콘 수지, 아크릴계 수지,폴리비닐계 수지, 폴리우레탄계 수지 중 선택된 하나 이상을 포함하는 태양전지 모듈용 컬러필름을 제공하는 효과를 가진다.The present invention has the effect of providing a color film for solar cell modules, wherein the top coating layer includes one or more selected from the group consisting of fluorine-based silicone resin, acrylic resin, polyvinyl-based resin, and polyurethane-based resin.
본 발명은, 상기 탑코팅층은 3 내지 5㎛의 두께, 상기 배리어코팅층은 1㎛ 이하의 두께를 가지는 태양전지 모듈용 컬러필름을 제공하는 효과가 있다.The present invention has the effect of providing a color film for solar cell modules in which the top coating layer has a thickness of 3 to 5 ㎛ and the barrier coating layer has a thickness of 1 ㎛ or less.
도 1은 종래 기술에 따른 태양전지 모듈과 백 시트의 단면 구성도1 is a cross-sectional configuration diagram of a solar cell module and back sheet according to the prior art.
도 2는 본 발명의 바람직한 일 실시예에 따른 태양전지 모듈용 컬러필름의 단면도Figure 2 is a cross-sectional view of a color film for solar cell modules according to a preferred embodiment of the present invention.
도 3은 본 발명의 다른 일 실시예에 따른 태양전지 모듈용 컬러필름의 단면도Figure 3 is a cross-sectional view of a color film for a solar cell module according to another embodiment of the present invention.
도 4는 실시예 20, 실시예 22 내지 28의 파장에 따른 투과율(%)을 도시한 도면Figure 4 is a diagram showing the transmittance (%) according to the wavelength of Example 20 and Examples 22 to 28.
도 5는 실시예 1, 실시예 21, 실시예 22가 검정색 PV sheet 상에서 육안으로 보이는 색상과 전광선 투과율, 헤이즈 및 광전변환효율을 나타낸 도면Figure 5 is a view showing the color, total light transmittance, haze, and photoelectric conversion efficiency of Examples 1, 21, and 22 visible to the naked eye on a black PV sheet.
이하에서는 본 발명에 따른 태양전지 모듈용 컬러필름을 첨부된 도면을 참조하여 상세히 설명한다. 또한 본 발명의 요지를 불필요하게 흐릴 수 있는 공지 기능 및 구성에 대한 상세한 설명은 생략한다. 특별한 정의가 없는 한 본 명세서의 모든 용어는 본 발명이 속하는 기술분야의 통상의 지식을 가진 기술자가 이해하는 당해 용어의 일반적 의미와 동일하고 만약 본 명세서에 사용된 용어의 의미와 충돌하는 경우에는 본 명세서에 사용된 정의에 따른다. Hereinafter, the color film for solar cell modules according to the present invention will be described in detail with reference to the attached drawings. Additionally, detailed descriptions of well-known functions and configurations that may unnecessarily obscure the gist of the present invention are omitted. Unless otherwise specified, all terms in this specification have the same general meaning as understood by a person skilled in the art to which the present invention pertains, and if there is a conflict with the meaning of the terms used in this specification, this specification Follow the definitions used in the specification.
본 명세서에서 특별한 언급이 없는 한, "치환" 내지 "치환된"이란, 본 발명의 작용기 중의 하나 이상의 수소 원자가 할로겐 원자(F, Br, Cl 또는 I), 히드록시기, 니트로기, 시아노기, 아미노기, 아미디노기, 하이드라진기, 하이드라존기, 카르복실기, 치환 또는 비치환된 알킬기, 치환 또는 비치환된 알케닐기, 치환 또는 비치환된 알키닐기, 치환 또는 비치환된 지환족 유기기, 치환 또는 비치환된 아릴기, 및 치환 또는 비치환된 헤테로고리기로 이루어진 군에서 선택되는 1종 이상의 치환기로 치환된 것을 의미한다.Unless otherwise specified herein, “substituted” or “substituted” means that one or more hydrogen atoms in the functional groups of the present invention are halogen atoms (F, Br, Cl or I), hydroxy groups, nitro groups, cyano groups, amino groups, Amidino group, hydrazine group, hydrazone group, carboxyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkynyl group, substituted or unsubstituted alicyclic organic group, substituted or unsubstituted means substituted with one or more substituents selected from the group consisting of an aryl group and a substituted or unsubstituted heterocyclic group.
본 명세서에서 특별한 언급이 없는 한, "조합"이란 혼합 또는 공중합을 의미한다.Unless otherwise specified herein, “combination” means mixing or copolymerization.
본 명세서 내 화학식에서 별도의 정의가 없는 한, 화학 결합이 그려져야 하는 위치에 화학결합이 그려져 있지 않은 경우는 상기 위치에 수소 원자가 결합되어 있음을 의미한다.Unless otherwise defined in the chemical formulas in this specification, if a chemical bond is not drawn at a position where a chemical bond should be drawn, it means that a hydrogen atom is bonded at that position.
또한, 본 명세서에서 별도의 정의가 없는 한, "*"는 동일하거나 상이한 원자 또는 화학식과 연결되는 부분을 의미한다.Additionally, unless otherwise defined herein, “*” means a portion connected to the same or different atom or chemical formula.
태양전지 모듈용 컬러필름(10)은 태양전지 모듈의 일면에 부착되어 수분, 충격, 자외선, 오물 등의 외부환경으로부터 내부의 태양전지 셀 및/또는 태양전지 모듈을 보호하는 구성으로, 태양광이 입사하는 면의 반대측에 부착될 수 있다. 본 발명의 일 실시예에 따른 태양전지 모듈용 컬러필름(10)은 색상 가벼우면서, 필름이 적층된 구조에서 발생할 수 있는 부분방전 문제를 해결하기 위하여, KS C IEC 60664-1에 따른 부분방전전압시험에 따라 1000VDC 이상의 부분방전전압에서도 절연파괴 내성을 가질 수 있다. The color film 10 for solar cell modules is attached to one side of the solar cell module and protects the internal solar cells and/or solar cell modules from external environments such as moisture, shock, ultraviolet rays, and dirt. It can be attached to the side opposite to the incident surface. The color film 10 for solar cell modules according to an embodiment of the present invention is light in color and has a partial discharge voltage in accordance with KS C IEC 60664-1 in order to solve the partial discharge problem that may occur in a structure in which films are stacked. Depending on the test, insulation breakdown resistance can be achieved even at partial discharge voltages of 1000 VDC or higher.
상기 태양전지 모듈용 컬러필름(10)은 제1기재필름층(11), 배리어코팅층(12), 제2기재필름층(13), 접착층(14), 탑코팅층(15)을 포함한다. 바람직한 일 실시예에서, 태양전지 모듈용 컬러필름(10)은 태양전지 모듈의 유리층을 대체하여 태양전지 모듈의 일면에 사용될 수 있다. 다른 일 실시예에서, 상기 태양전지 모듈용 컬러필름(10)은 양면형 태양전지에서는 태양전지 모듈의 다른 면에 부착되어 백시트로도 사용할 수 있다.The color film 10 for solar cell modules includes a first base film layer 11, a barrier coating layer 12, a second base film layer 13, an adhesive layer 14, and a top coating layer 15. In a preferred embodiment, the color film 10 for solar cell modules can be used on one side of the solar cell module by replacing the glass layer of the solar cell module. In another embodiment, the color film 10 for a solar cell module can be attached to the other side of the solar cell module and used as a backsheet in a double-sided solar cell.
또한 본 발명의 일 실시예에서는, 색상을 띄는 물질을 제1기재필름층(11) 및 제2기재필름층(13) 사이에 배치함으로써, 태양전지 모듈용 컬러필름(10)의 시간에 따른 변색을 최소화하도록 하였다.In addition, in one embodiment of the present invention, by disposing a colored material between the first base film layer 11 and the second base film layer 13, the color film 10 for a solar cell module changes color over time. was designed to be minimized.
15cm × 15cm의 유리판에 색상을 띄는 펄을 스퍼터링하여 색상유리를 형성하는 경우 약 500g의 무게를 가지게 되나, 본 발명에 따른 태양전지 모듈용 컬러필름(10)을 사용하는 경우 15cm × 15cm의 넓이 당 21.5 내지 22.5g의 무게를 가져 태양전지 모듈을 경량화하여 사용할 수 있다.When colored glass is formed by sputtering colored pearls on a 15cm It weighs 21.5 to 22.5 g, so the solar cell module can be used in a lighter form.
상기 제1기재필름층(11)은 베이스 기재로서의 필름층으로, 제1기재필름층(11)은 50 내지 200㎛의 두께를 가질 수 있다. 바람직한 일 실시예에서, 제1기재필름층(11)은 188㎛의 두께를 가질 수 있다. 일 실시예에서, 상기 제1기재필름층(11)의 일면에 배리어코팅층(12)이 형성될 수 있다. 예를 들면 수성 분산액 또는 용액 혼합물을 박리가능한 캐리어 웹 또는 라이너 상에 캐스팅하거나 달리 코팅하여 제1기재필름층(11)이 형성될 수 있다.The first base film layer 11 is a film layer as a base base material, and the first base film layer 11 may have a thickness of 50 to 200㎛. In a preferred embodiment, the first base film layer 11 may have a thickness of 188 μm. In one embodiment, a barrier coating layer 12 may be formed on one surface of the first base film layer 11. For example, the first base film layer 11 may be formed by casting or otherwise coating an aqueous dispersion or solution mixture onto a peelable carrier web or liner.
제1기재필름층(11)은 폴리에스테르계 수지, 폴리카보네이트계 수지, 폴리비닐계 수지, 폴리이미드계 수지, 폴리우레탄계 수지 중 선택된 하나 이상을 포함하는 필름층일 수 있다. 일 실시예에서, 폴리에스테르계 수지, 폴리카보네이트계 수지, 폴리비닐계 수지, 폴리이미드계 수지, 폴리우레탄계 수지 중 선택된 하나 이상을 포함하는 층이 적어도 둘 이상 적층형성될 수 있다. 바람직한 일 실시예에서, 상기 제1기재필름층(11)은 투명 폴리에틸렌테레프탈레이트(PET) 필름으로 구성될 수 있다. 바람직한 일 실시예에서, 상기 제1기재필름층(11)은 태양전지 셀을 둘러싸는 하부 봉지층과 면할 수 있다.The first base film layer 11 may be a film layer containing one or more selected from polyester-based resin, polycarbonate-based resin, polyvinyl-based resin, polyimide-based resin, and polyurethane-based resin. In one embodiment, at least two or more layers containing one or more selected from polyester-based resin, polycarbonate-based resin, polyvinyl-based resin, polyimide-based resin, and polyurethane-based resin may be formed by laminating them. In a preferred embodiment, the first base film layer 11 may be composed of a transparent polyethylene terephthalate (PET) film. In a preferred embodiment, the first base film layer 11 may face a lower encapsulation layer surrounding the solar cell.
상기 배리어코팅층(12)은 상기 제1기재필름층(11)의 일측면에 형성되는 코팅층으로, 수분 및 기체를 차단하는 성능이 우수하다. PET 필름으로 구성된 제1기재필름층(11)만을 사용하거나 복수 층의 PET 필름을 사용하는 경우 태양전지 모듈 백시트 및 전면부 필름에 요구되는 물성을 만족할 수 없으나, 본 발명의 일 실시예에 따른 배리어코팅층(12)을 제1기재필름층(11) 상에 코팅하는 경우 일반적으로 요구되는 물성보다 높게 수분투습을 방지할 수 있다. 상기 배리어코팅층(12)은 1㎛ 이하의 두께를 가질 수 있으며, 바람직하게는 700nm 내지 1㎛의 두께를 가질 수 있다.The barrier coating layer 12 is a coating layer formed on one side of the first base film layer 11, and has excellent performance in blocking moisture and gas. When using only the first base film layer 11 made of PET film or using multiple layers of PET film, the physical properties required for the solar cell module backsheet and front film cannot be satisfied, but according to an embodiment of the present invention When the barrier coating layer 12 is coated on the first base film layer 11, moisture permeation can be prevented by higher than the generally required physical properties. The barrier coating layer 12 may have a thickness of 1㎛ or less, and preferably may have a thickness of 700nm to 1㎛.
상기 배리어코팅층(12)은 금속산화물이 제1기재필름층 상에 코팅된 것일 수 있다. 상기 금속 산화물은 알루미나, 티타니아, 마그네시아, 지르코니아 또는 이들의 조합을 포함할 수 있다. 상기 금속 산화물의 형상은 특별히 한정되지 않으며, 구형상, 입방체상, 방추형상, 부정형상, 섬유상, 침상 등의 형상을 가질 수 있다. 예컨대, 상기 금속 산화물의 형상이 섬유상 또는 침상일 경우 수분 차단성이 보다 높아지는 효과가 있다. 예컨대, 상기 금속 산화물은 모두 동일한 형상을 가질 수도 있고, 서로 상이한 형상들의 조합일 수도 있다. 상기 금속 산화물은 1nm 내지 150nm의 평균 입경을 가질 수 있다. 상기 금속 산화물이 상기 범위의 평균 입경을 가짐으로써, 배리어 필름의 수분 차단성을 보다 높일 수 있다. 상기 금속 산화물의 평균 입경은 입도분석기(DLS)를 사용하여 입경을 분석하여 확인할 수 있다. 상기 금속 산화물은 수득되는 금속 산화물의 형상이나 크기의 제어성 등을 고려하면, 액상 합성법에 의해 제조하는 것이 바람직할 수 있다.The barrier coating layer 12 may be a metal oxide coated on the first base film layer. The metal oxide may include alumina, titania, magnesia, zirconia, or a combination thereof. The shape of the metal oxide is not particularly limited, and may have a spherical shape, a cubic shape, a spindle shape, an indeterminate shape, a fibrous shape, or a needle shape. For example, when the shape of the metal oxide is fibrous or needle-like, the moisture barrier property is improved. For example, the metal oxides may all have the same shape or may be a combination of different shapes. The metal oxide may have an average particle diameter of 1 nm to 150 nm. When the metal oxide has an average particle size within the above range, the moisture barrier properties of the barrier film can be further improved. The average particle size of the metal oxide can be confirmed by analyzing the particle size using a particle size analyzer (DLS). Considering the controllability of the shape and size of the metal oxide obtained, it may be preferable to produce the metal oxide by a liquid phase synthesis method.
상기 금속 산화물은 금속 산화물 졸(sol)일 수 있다. 상기 금속 산화물이 졸 형태로 배리어코팅층에 존재할 경우, 졸이 아닌 형태로 존재하는 경우에 비해, 상기 인 함유 화합물과 용이하게 반응할 수 있으며, 나아가 분산 안정성을 크게 향상시킬 수 있다. 상기 금속 산화물은 인 원자를 포함하지 않는 것이 바람직하다.The metal oxide may be a metal oxide sol. When the metal oxide is present in the barrier coating layer in a sol form, it can react more easily with the phosphorus-containing compound than when it is present in a non-sol form, and further, dispersion stability can be greatly improved. It is preferable that the metal oxide does not contain phosphorus atoms.
일 실시예에서, 상기 배리어코팅층(12)은 금속산화물 졸과 함께 인 함유 화합물을 포함할 수 있다.In one embodiment, the barrier coating layer 12 may include a phosphorus-containing compound along with a metal oxide sol.
상기 인 함유 화합물은 금속 산화물의 결합을 유도함으로써 금속 산화물의 겔(gel)화를 유도할 수 있다. 상기 인 함유 화합물은 상기 금속 산화물과 반응 가능한 사이트(인 원자와 직접 결합을 이루고 있는 할로겐 원자나 산소 원자 등)를 포함하며, 예컨대 인산, 폴리인산, 아인산, 포스폰산 또는 이들의 유도체를 포함할 수 있다. 상기 인 함유 화합물에서 인 원자와 직접 결합을 이루고 있는 할로겐 원자나 산소 원자는 상기 금속 산화물 표면에 존재하는 관능기(예컨대 수산기 등)와 가수 분해 축합 반응을 진행하게 되고, 상기 금속 산화물의 금속 원자와 인 함유 화합물의 인 원자가 산소 원자를 매개체로 하여 결합될 수 있다.The phosphorus-containing compound can induce gelation of the metal oxide by inducing the bonding of the metal oxide. The phosphorus-containing compound contains a site capable of reacting with the metal oxide (a halogen atom or an oxygen atom directly bonded to a phosphorus atom, etc.), and may include, for example, phosphoric acid, polyphosphoric acid, phosphorous acid, phosphonic acid, or derivatives thereof. there is. The halogen atom or oxygen atom directly bonded to the phosphorus atom in the phosphorus-containing compound undergoes a hydrolysis condensation reaction with a functional group (such as a hydroxyl group) present on the surface of the metal oxide, and the metal atom of the metal oxide and the phosphorus atom undergo a hydrolysis condensation reaction. The phosphorus atom of the containing compound may be bonded using an oxygen atom as a mediator.
일 실시예에서, 상기 배리어코팅층(12)은 그래핀이 결합된 금속 산화물 및 인 함유 화합물을 포함할 수 있다. 금속 산화물에 그래핀을 결합시킨 후 이를 인 함유 화합물과 반응시켜 제조할 수도 있다.In one embodiment, the barrier coating layer 12 may include a metal oxide and a phosphorus-containing compound to which graphene is bonded. It can also be manufactured by combining graphene with a metal oxide and then reacting it with a phosphorus-containing compound.
인 함유 화합물은 그래핀이 결합된 금속 산화물의 결합을 유도하여, 그래핀이 결합된 금속 산화물의 겔화를 유도할 수 있다. 상기 그래핀이 결합된 금속 산화물이 인 함유 화합물과 결합되면, 상기 금속 산화물의 금속 원자와 인 함유 화합물의 인 원자가 산소 원자를 매개체로 하여 결합되게 된다.Phosphorus-containing compounds can induce the bonding of metal oxides to which graphene is bonded, thereby inducing gelation of the metal oxides to which graphene is bonded. When the metal oxide to which the graphene is bonded is bonded to a phosphorus-containing compound, the metal atom of the metal oxide and the phosphorus atom of the phosphorus-containing compound are bonded using an oxygen atom as a medium.
본 발명의 일 실시예에 따른 배리어코팅층은 다음과 같은 조성물은에 의해 형성될 수 있다. 상기 조성물은 금속 알콕사이드를 물에 용해시켜 수용액을 제조할 수 있는데, 구체적으로 금속 알콕사이드, 물 및 산 촉매를 혼합하고, 졸-겔법으로 상기 금속 알콕사이드를 가수 분해 축합시켜, 수용액을 제조한다. 상기 산 촉매는 염산, 황산, 질산, p-톨루엔설폰산, 벤조산, 아세트산, 락트산, 부티르산, 탄산, 옥살산, 말레산 또는 이들의 조합을 포함할 수 있다. 상기 산 촉매를 사용하기 때문에, 제조된 수용액은 약 3 내지 5 정도의 pH값을 가질 수 있다. 상기 수용액의 pH값이 3 내지 5 정도여야 금속 알콕사이드의 물에 대한 분산성이 향상될 수 있다. 금속 알콕사이드는 금속 이소프로폭사이드 또는 금속 부톡사이드일 수 있다. 예컨대, 상기 금속 알콕사이드는 금속 이소프로폭사이드, 금속 트리이소프로폭사이드 또는 금속 트리-s-부톡사이드일 수 있다. 상술한 바와 같이 상기 금속은 알루미늄, 티타늄, 마그네슘 또는 지르코니아일 수 있다.The barrier coating layer according to an embodiment of the present invention may be formed by the following composition. The composition can be prepared by dissolving the metal alkoxide in water to prepare an aqueous solution. Specifically, the aqueous solution is prepared by mixing the metal alkoxide, water and an acid catalyst, and hydrolyzing and condensing the metal alkoxide by a sol-gel method. The acid catalyst may include hydrochloric acid, sulfuric acid, nitric acid, p-toluenesulfonic acid, benzoic acid, acetic acid, lactic acid, butyric acid, carbonic acid, oxalic acid, maleic acid, or a combination thereof. Because the acid catalyst is used, the prepared aqueous solution may have a pH value of about 3 to 5. The pH value of the aqueous solution must be about 3 to 5 to improve the dispersibility of the metal alkoxide in water. The metal alkoxide may be metal isopropoxide or metal butoxide. For example, the metal alkoxide may be metal isopropoxide, metal triisopropoxide, or metal tri-s-butoxide. As described above, the metal may be aluminum, titanium, magnesium, or zirconia.
그리고 상기 수용액에 그래핀 옥사이드를 첨가하고, 70℃내지 80℃의 온도에서 10시간 내지 14시간 동안 반응시켜, 그래핀이 결합된 금속 산화물, 그래핀이 결합된 알루미나 졸을 수득한다. 이후 그래핀이 결합된 알루미나 졸을 함유하는 수용액에 산을 첨가하고 가열한다. 이 때 상기 첨가되는 산은 질산, 염산, 과염소산, 포름산, 아세트산, 프로피온산 또는 이들의 조합을 포함할 수 있다. 상기 산을 첨가하고 가열함으로써, 보다 투명하고 점도 안정성이 우수한, 그래핀이 결합된 알루미나 졸을 수득할 수 있다.Then, graphene oxide is added to the aqueous solution and reacted at a temperature of 70°C to 80°C for 10 to 14 hours to obtain a graphene-bound metal oxide and a graphene-bound alumina sol. Afterwards, acid is added to the aqueous solution containing the graphene-bound alumina sol and heated. At this time, the added acid may include nitric acid, hydrochloric acid, perchloric acid, formic acid, acetic acid, propionic acid, or a combination thereof. By adding the acid and heating, a graphene-bound alumina sol that is more transparent and has excellent viscosity stability can be obtained.
상기 산을 첨가하고 가열 시, 40℃ 내지 200℃의 온도에서 가열할 수 있다. 상기 온도 범위에서 가열함으로써, 그래핀이 결합된 알루미나 졸의 입경 제어가 가능하며, 동시에 점도 안정성도 높일 수 있다. 예컨대, 상기 40℃ 미만의 온도에서 가열할 경우 가열 시간이 너무 오래걸려 비경제적이고, 상기 200℃ 초과의 온도에서 가열할 경우 가열 시간은 단축되는 반면, 고내압 용기 등이 따로 필요해 역시 비경제적이다.When adding the acid and heating, it can be heated at a temperature of 40°C to 200°C. By heating in the above temperature range, it is possible to control the particle size of the alumina sol combined with graphene, and at the same time, increase the viscosity stability. For example, when heated at a temperature below 40°C, the heating time takes too long and is uneconomical, and when heated at a temperature above 200°C, the heating time is shortened, but a separate high-pressure vessel is required, which is also uneconomical.
상기 산을 첨가하고 가열한 후, 인 함유 화합물을 첨가하기 전에, 용매를 추가하여 희석하거나 또는 가열하여 농축함으로써, 그래핀이 결합된 알루미나 졸의 농도를 제어할 수 있다. 단, 증점이나 겔화를 억제하기 위해, 가열 농축을 실시하는 경우에는, 감압 하에, 60℃이하에서 실시하는 것이 바람직하나, 반드시 이에 한정되는 것은 아니다.After adding and heating the acid and before adding the phosphorus-containing compound, the concentration of the alumina sol to which graphene is bound can be controlled by diluting it by adding a solvent or concentrating it by heating. However, in order to suppress thickening or gelation, when heat concentration is carried out, it is preferably carried out under reduced pressure and at 60°C or lower, but is not necessarily limited to this.
상기 산을 첨가하고 가열한 후, 인 함유 화합물을 더 첨가하여, 배리어코팅층 조성물을 제조한다. 상기 인 함유 화합물은 용액의 형태로 첨가, 예컨대, 상기 인 함유 화합물을 물에 용해시켜 첨가할 수 있다. 상기 물에 용해된 인 함유 화합물을 첨가할 때에는 천천히 첨가하여, 국소 반응을 억제하는 것이 바람직하며, 동 시에 강하게 교반을 실시하면서 혼합하는 것이 국소 반응 억제에 더욱 바람직할 수 있다. 상기 혼합 시 두 용액의 온도를 모두 50℃이하, 예컨대 30℃이하로 제어할 수 있다. 이 경우 금속 산화물 간 응집을 방지할 수 있다. 상기 혼합 시 두 용액의 온도가 상기 범위 내일 경우 그래핀이 결합된 금속 산화물(예컨대, 그래핀이 결합된 알루미나 졸)과 인 함유 화합물이 균일하게 혼합될 수 있어, 제조되는 배리어 필름의 수분 차단성을 크게 향상시킬 수 있다. 보존 안정성을 향상시키기 위해, 혼합 완료 후, 추가로 30분 정도 교반을 계속할 수 있다.After adding and heating the acid, a phosphorus-containing compound is further added to prepare a barrier coating layer composition. The phosphorus-containing compound can be added in the form of a solution, for example, by dissolving the phosphorus-containing compound in water. When adding the phosphorus-containing compound dissolved in the water, it is preferable to add it slowly to suppress local reaction, and it may be more preferable to mix while vigorously stirring to suppress local reaction. When mixing, the temperatures of both solutions can be controlled to 50°C or lower, for example, 30°C or lower. In this case, aggregation between metal oxides can be prevented. When the temperature of the two solutions is within the above range during mixing, the graphene-bound metal oxide (e.g., graphene-bound alumina sol) and the phosphorus-containing compound can be uniformly mixed, thereby improving the moisture barrier properties of the barrier film produced. can be greatly improved. To improve storage stability, stirring may be continued for an additional 30 minutes after mixing is completed.
상기 열처리는 130℃ 내지 140℃의 온도에서 실시할 수 있다. 제1기재필름층 상에 배리어코팅층 조성물을 코팅한 후, 200℃이상의 고온에서 열처리를 실시하는 게 보통이나, 일 구현예에 따른 배리어코팅층 조성물을 플라스틱 기재 상에 코팅하여 유연성을 향상시키기 위해서, 130℃내지 140℃의 저온에서 열처리를 실시할 수 있다. 또한, 상기 코팅은 연속성 습식코팅(roll to roll coating), 예컨대 마이크로 그라비아 코팅, 슬롯다이 코팅일 수 있다.The heat treatment can be performed at a temperature of 130°C to 140°C. After coating the barrier coating layer composition on the first base film layer, heat treatment is usually performed at a high temperature of 200 ℃ or higher. However, in order to improve flexibility by coating the barrier coating layer composition according to one embodiment on the plastic substrate, 130 Heat treatment can be performed at a low temperature of ℃ to 140℃. Additionally, the coating may be continuous wet coating (roll to roll coating), such as micro gravure coating or slot die coating.
상기 배리어코팅층(12)이 제1기재필름층(11) 상에 코팅 후 열처리됨으로써 태양전지 모듈용 컬러필름(10)이 내후성, 내투습성을 가질 수 있다. 바람직한 일 실시예에 따른 배리어필름층(12)이 제1기재필름층(11) 상에 형성되어 ASTM F1249 평가표준에 따른 수분투습도가 바람직하게는 0.05g/m2/day 이하까지 달성될 수 있다.The barrier coating layer 12 is coated on the first base film layer 11 and then heat-treated, so that the color film 10 for solar cell modules can have weather resistance and moisture permeability resistance. The barrier film layer 12 according to a preferred embodiment is formed on the first base film layer 11, so that moisture permeability according to the ASTM F1249 evaluation standard can preferably be achieved up to 0.05 g/m 2 /day or less. .
본 발명의 일 실시예에 따른 배리어코팅층(12)은 폴리올레핀, PVF 등을 포함하는 배리어층보다 우수하다는 것이 본 발명자들에 의해 발견되었다. 백시트 또는 태양전지 셀의 전면부에 PET층을 적층한 후 폴리올레핀 필름층을 사용하는 경우, 폴리올레핀 필름이 비불소계 타입이기 때문에 변색의 문제가 있고 생산공정에서 높은 공정온도와 긴 시간이 필요하다는 한계가 있다. 또한 폴리올레핀 필름의 경우 EVA에 비해 융점이 높아 추가적인 라미네이션을 위한 공정최적화가 필요하다는 한계가 있다. PVF 필름의 경우 수분투과율(WVTR)이 상대적으로 높아 백시트 또는 태양전지 셀의 전면부를 통한 수분 침투가 발생하고, 높은 온도에서 투과된 수분은 EVA를 부식시켜 추가적인 태양전지 모듈 성능 저하를 발생시킨다. 수분이 침투할 경우 봉지재(EVA)와 봉지재와 필름 사이의 계면에서 박리가 발생할 수 있고, 박리는 더 많은 양의 수분 침투를 허용하며, 결국 출력 저하를 유발하게 된다.The present inventors discovered that the barrier coating layer 12 according to an embodiment of the present invention is superior to barrier layers containing polyolefin, PVF, etc. When using a polyolefin film layer after laminating a PET layer on the backsheet or the front of a solar cell, there is a problem of discoloration because the polyolefin film is a non-fluorine type, and the production process requires a high process temperature and a long time. There is. In addition, polyolefin films have a higher melting point than EVA, so there is a limitation in that process optimization for additional lamination is necessary. In the case of PVF film, the water permeability rate (WVTR) is relatively high, which causes moisture to penetrate through the backsheet or the front part of the solar cell, and the moisture penetrated at high temperatures corrodes the EVA, causing further degradation of solar cell module performance. If moisture penetrates, delamination may occur at the encapsulant (EVA) and the interface between the encapsulant and the film, and delamination allows a greater amount of moisture to infiltrate, ultimately causing a decrease in output.
본 발명의 일 실시예에 따른 배리어코팅층(12)은 금속산화물 졸을 겔화시켜 제1기재필름층(11) 상에 코팅하여 투명성을 유지하면서 보다 높은 수분에 대한 저항성을 획득하였다. 상기 배리어코팅층(12) 조성물의 금속산화물 졸은 SnOx, SiNx, TiO2, Al2O3 중 선택된 것이 사용될 수 있다. 바람직한 일 실시예에서, 상기 금속산화물 졸은 Al2O3일 수 있다. The barrier coating layer 12 according to an embodiment of the present invention was made by gelling a metal oxide sol and coating it on the first base film layer 11 to maintain transparency and obtain higher resistance to moisture. The metal oxide sol of the barrier coating layer 12 composition may be selected from SnO x , SiN x , TiO 2 , and Al 2 O 3 . In a preferred embodiment, the metal oxide sol may be Al 2 O 3 .
상기 제2기재필름층(13)은 접착층(14)에 의해 제1기재필름층(11) 또는 배리어코팅층(12)의 일면상에 부착될 수 있다. 상기 제2기재필름층(13)은 필름의 기재층의 두께를 실질적으로 증가시킴으로써 백시트 또는 전면부 필름에 요구되는 부분방전전압의 물성을 만족시키도록 할 수 있으며, 나아가 우수한 내후성 및 내가수분해성을 가질 수 있다.The second base film layer 13 may be attached to one surface of the first base film layer 11 or the barrier coating layer 12 by an adhesive layer 14. The second base film layer 13 can satisfy the partial discharge voltage properties required for the backsheet or front film by substantially increasing the thickness of the base layer of the film, and further has excellent weather resistance and hydrolysis resistance. You can have
바람직한 일 실시예에서, 상기 제2기재필름층(13)은 제1기재필름층(11) 상에 코팅 후 열처리 과정을 통해 형성된 배리어코팅층(12)의 표면에 접착층(14)으로서의 접착제를 도포한 뒤 부착될 수 있다. 즉, 제1기재필름층(11), 배리어코팅층(12), 접착층(14), 제2기재필름층(13)의 순서로 적층될 수 있다. 본 발명의 일 실시예에 따른 태양전지 모듈용 컬러필름은, 2 layer 이상의 기재층 구조를 가지면서, 기재층으로서의 PET층 사이에 배리어코팅층(12)을 삽입하여 배리어코팅층(12)의 일면이 외부에 직접적으로 외부로 노출되는 경우 발생하는 부분방전전압 저하 현상을 방지할 수 있다. 본 발명의 일 실시예에 따른 배리어코팅층(12)은 금속산화물 졸로 Al2O3을 사용할 수 있는데, 우수한 투습방지특성을 지니고 있으나 고온다습한 환경에 직접적으로 노출되는 경우 가수분해를 통해 결정질 boehmite로 상전이하여 부피가 팽창하고, 결정 내 입계를 통해 수분이 침투할 수 있는 문제가 있다. 따라서 본 발명의 바람직한 일 실시예에서는 배리어코팅층(12)이 제1기재필름층(11)과 제2기재필름층(13) 사이에 배치되도록 함으로써 내구성을 증대시켰다.In a preferred embodiment, the second base film layer 13 is formed by applying an adhesive as an adhesive layer 14 to the surface of the barrier coating layer 12 formed through a heat treatment process after coating on the first base film layer 11. Can be attached to the back. That is, the first base film layer 11, the barrier coating layer 12, the adhesive layer 14, and the second base film layer 13 may be laminated in that order. The color film for solar cell modules according to an embodiment of the present invention has a base layer structure of two or more layers, and inserts a barrier coating layer 12 between the PET layers as the base layer, so that one side of the barrier coating layer 12 is exposed to the outside. It is possible to prevent the partial discharge voltage drop that occurs when exposed directly to the outside. The barrier coating layer 12 according to an embodiment of the present invention can use Al 2 O 3 as a metal oxide sol. It has excellent moisture prevention properties, but when directly exposed to a high temperature and humidity environment, it hydrolyzes into crystalline boehmite. There is a problem that the phase transition causes the volume to expand and moisture can penetrate through the grain boundaries within the crystal. Therefore, in a preferred embodiment of the present invention, durability is increased by arranging the barrier coating layer 12 between the first base film layer 11 and the second base film layer 13.
다른 일 실시예에서, 상기 제2기재필름층(13)은 제1기재필름층(11)의 표면에 접착층으로서의 접착제를 도포한 뒤 부착될 수 있다. 이때 제1기재필름층(11)의 일면 상에는 배리어코팅층(12)을 코팅한 후 열처리하여 형성할 수 있으므로, 제2기재필름층(13)은 제1기재필름층(11)의 타면에 부착될 수 있다. 즉, 배리어코팅층(12), 제1기재필름층(11), 접착층(14), 제2기재필름층(13)의 순서로 적층될 수도 있다.In another embodiment, the second base film layer 13 may be attached to the surface of the first base film layer 11 after applying an adhesive as an adhesive layer. At this time, since the barrier coating layer 12 can be coated on one side of the first base film layer 11 and then heat treated, the second base film layer 13 will be attached to the other side of the first base film layer 11. You can. That is, the barrier coating layer 12, the first base film layer 11, the adhesive layer 14, and the second base film layer 13 may be laminated in that order.
상기 제2기재필름층(13)은 제1기재필름층(11)과 같이 50 내지 200㎛의 두께를 가질 수 있다. 바람직한 일 실시예에서, 제2기재필름층(13)은 188㎛의 두께를 가질 수 있다.The second base film layer 13 may have a thickness of 50 to 200 μm, like the first base film layer 11. In a preferred embodiment, the second base film layer 13 may have a thickness of 188 μm.
제2기재필름층(13)은 폴리에스테르계 수지, 폴리카보네이트계 수지, 폴리비닐계 수지, 폴리이미드계 수지, 폴리우레탄계 수지 중 선택된 하나 이상을 포함하는 필름층일 수 있다. 일 실시예에서, 폴리에스테르계 수지, 폴리카보네이트계 수지, 폴리비닐계 수지, 폴리이미드계 수지, 폴리우레탄계 수지 중 선택된 하나 이상을 포함하는 층이 적어도 둘 이상 적층형성될 수 있다. 바람직한 일 실시예에서, 상기 제2기재필름층(13)은 폴리에틸렌테레프탈레이트(PET) 필름으로 구성될 수 있다.The second base film layer 13 may be a film layer containing one or more selected from polyester-based resin, polycarbonate-based resin, polyvinyl-based resin, polyimide-based resin, and polyurethane-based resin. In one embodiment, at least two or more layers containing one or more selected from polyester-based resin, polycarbonate-based resin, polyvinyl-based resin, polyimide-based resin, and polyurethane-based resin may be formed by laminating them. In a preferred embodiment, the second base film layer 13 may be made of polyethylene terephthalate (PET) film.
상기 접착층(14)은 제1기재필름층(11)과 제2기재필름층(13) 사이에 형성되어 제2기재필름층(13)과 제1기재필름층(11) 또는 배리어코팅층(12)의 부착을 견고하게 하는 구성이다. 접착층(14)은 제1기재필름층(11) 또는 제1기재필름층(11)의 일면에 코팅 및 열처리된 배리어코팅층(12) 상에 도포되거나 코팅되어 제2기재필름층(13)을 부착시킬 수 있다. 상기 접착층에 사용되는 접착제는 특별히 제한되지 않으며, 예컨대 아크릴계, 우레탄계, 브룩필드계 및 에폭시계 수지로부터 선택된 1종 이상의 접착제를 사용할 수 있다. 상기 접착층(14)의 두께는 5 내지 20 ㎛의 두께를 가질 수 있으며, 바람직하게는 9 내지 11 ㎛의 두께를 가질 수 있다.The adhesive layer 14 is formed between the first base film layer 11 and the second base film layer 13 and forms the second base film layer 13 and the first base film layer 11 or the barrier coating layer 12. It is a composition that strengthens the attachment. The adhesive layer 14 is applied or coated on the first base film layer 11 or the barrier coating layer 12 coated and heat-treated on one side of the first base film layer 11 to attach the second base film layer 13. You can do it. The adhesive used in the adhesive layer is not particularly limited, and for example, one or more adhesives selected from acrylic-based, urethane-based, Brookfield-based and epoxy-based resins can be used. The thickness of the adhesive layer 14 may be 5 to 20 ㎛, preferably 9 to 11 ㎛.
상기 접착층(14)은 아크릴계 바인더가 접착층의 100 중량부 기준 40 내지 50 중량부, 에폭시계 경화제가 접착층의 100 중량부 기준 0.05 내지 1 중량부 포함되도록 할 수 있으며, 색상안료가 접착층의 100 중량부 기준 1 내지 5 중량부 포함될 수 있다. 상기 색상안료는 색상을 띄는 유기안료일 수 있다. 상기 색상안료는 발색단으로 아조기를 가지는 유기안료 또는 Phthalocyanine, Anthraquinone, Quinacridone의 다환기 유기안료 중 적어도 하나 이상을 포함할 수 있다.The adhesive layer 14 may contain 40 to 50 parts by weight of an acrylic binder based on 100 parts by weight of the adhesive layer, 0.05 to 1 part by weight of an epoxy-based hardener based on 100 parts by weight of the adhesive layer, and a color pigment may be included in an amount of 0.05 to 1 part by weight based on 100 parts by weight of the adhesive layer. It may contain 1 to 5 parts by weight. The color pigment may be an organic pigment that exhibits color. The color pigment may include at least one of an organic pigment having an azo group as a chromophore or a polycyclic organic pigment such as phthalocyanine, anthraquinone, or quinacridone.
색상안료가 후술하는 탑코팅층(15)에 분산되는 경우 태양광이 입사하는 최외측에 안료가 위치하게 되어 직사광선으로부터 안료의 변색을 제어하는 것이 어렵다. 또한 기재필름층에 색상을 띄는 유기안료를 혼입시키는 경우, 기재층을 이루는 고분자의 용융온도(150 내지 250℃)를 버티지 못하고 발화 또는 산화되기 때문에 온전한 색상을 유지할 수 없는 단점이 있다. 나아가 배리어코팅층(12)에 안료를 분산시키는 경우, 본 발명의 일 실시예에 따른 배리어코팅층(12)의 졸-겔 공정에서 산을 사용하기 때문에 유기안료가 다른 입자와 반응하여 색상을 유지하기 어렵다. When the color pigment is dispersed in the top coating layer 15, which will be described later, the pigment is located on the outermost side where sunlight enters, making it difficult to control discoloration of the pigment from direct sunlight. In addition, when a colored organic pigment is incorporated into the base film layer, there is a disadvantage in that the intact color cannot be maintained because it cannot withstand the melting temperature (150 to 250°C) of the polymer forming the base film layer and is ignited or oxidized. Furthermore, when dispersing the pigment in the barrier coating layer 12, it is difficult to maintain the color because the organic pigment reacts with other particles because acid is used in the sol-gel process of the barrier coating layer 12 according to an embodiment of the present invention. .
이에 비해 본 발명에서와 같이 색상안료를 접착층(14)에 혼입시키는 경우 100 내지 140℃의 접착층 조성온도에서 유기안료가 변성되지 않으며, 최외측 탑코팅층(15)에 의해 유기안료가 태양광에 의해 변성되는 것을 최소화할 수 있으며, 접착층(14)이 제1기재필름층(11)과 배리어코팅층(12), 제2기재필름층(13) 사이에 형성되기 때문에 외부로부터 유입되는 이물질이나 수분으로 인한 색상 변화를 최대한 막을 수 있다.In contrast, when color pigments are incorporated into the adhesive layer 14 as in the present invention, the organic pigments are not denatured at the adhesive layer composition temperature of 100 to 140°C, and the organic pigments are absorbed by sunlight due to the outermost top coating layer 15. Denaturation can be minimized, and since the adhesive layer 14 is formed between the first base film layer 11, the barrier coating layer 12, and the second base film layer 13, it can be prevented from being damaged by foreign substances or moisture flowing in from the outside. Color change can be prevented as much as possible.
본 발명의 일 실시예에서, 상기 접착층(14)에 분산되는 색상안료는 형광체를 포함할 수 있다. 상기 형광체는 광선으로부터 흡수된 파장을 흡수된 파장보다 높은 파장으로 변환시키는 물질이다. 일 실시예에서 상기 형광체는 자외선을 흡수하고 흡수한 자외선을 자외선 파장보다 높은 파장의 가시광선으로 내보낼 수 있다. 상기 형광체는 400nm 이하의 자외선 파장을 흡수하여 400 내지 550nm의 파장을 가지는 가시광선을 방출할 수 있다. 상기 접착층(14)에서 자외선을 흡수하는 경우, 자외선의 투과에 따른 제1기재필름층(11)나 태양전지 셀의 열화가 방지될 수 있으며, 자외선을 가시광선으로 변환시키므로 광전 변환효율이 향상될 수 있다. 일 실시예에서 상기 형광체는 나프탈이미드(Naphtalimide)계 화합물, 금속-유기 복합물 및 페릴린(Perylene)계 화합물 등의 형광 물질로부터 선택된 하나 이상을 포함할 수 있다. 특히, 도 4에 도시되는 것과 같이 상기 형광체는 태양전지 모듈에서 광전 변환효율이 높은 400 내지 550nm 사이의 파장을 가지는 가시광선을 효과적으로 투과시켜 높은 광전 변환효율을 가지게 된다.In one embodiment of the present invention, the color pigment dispersed in the adhesive layer 14 may include a phosphor. The phosphor is a substance that converts the wavelength absorbed from light into a wavelength higher than the absorbed wavelength. In one embodiment, the phosphor can absorb ultraviolet rays and emit the absorbed ultraviolet rays as visible light with a higher wavelength than the ultraviolet rays. The phosphor can absorb ultraviolet rays with a wavelength of 400 nm or less and emit visible light with a wavelength of 400 to 550 nm. When the adhesive layer 14 absorbs ultraviolet rays, deterioration of the first base film layer 11 or solar cells due to the transmission of ultraviolet rays can be prevented, and photoelectric conversion efficiency can be improved by converting ultraviolet rays into visible light. You can. In one embodiment, the phosphor may include one or more selected from fluorescent materials such as naphtalimide-based compounds, metal-organic complexes, and perylene-based compounds. In particular, as shown in FIG. 4, the phosphor effectively transmits visible light with a wavelength between 400 and 550 nm, which has high photoelectric conversion efficiency in a solar cell module, thereby achieving high photoelectric conversion efficiency.
상기 탑코팅층(15)은 제2기재필름층(13)의 일면상에 도포되어 기재층으로서의 제1기재필름층(11) 및 제2기재필름층(13)을 보호하도록 구비될 수 있으며, 수분이나 먼지 등 외부 이물질로부터 기재층을 보호한다. 상기 탑코팅층(15)은 내후성을 가지는 투명한 소재로 형성됨이 바람직하다. 상기 탑코팅층(15)은 불소계 실리콘 수지, 아크릴계 수지, 폴리비닐계 수지, 폴리우레탄계 수지 중 선택된 하나 이상을 포함할 수 있다. 바람직한 일 실시예에서, 상기 탑코팅층(15)은 불소계 실리콘 수지가 코팅되어 형성된 것일 수 있다. 상기 탑코팅층(15)은 3 내지 5㎛의 두께를 가짐이 바람직하다. 탑코팅층(15)은 태양전지 모듈의 외측을 면하며, 외부 또는 정션 박스를 면할 수 있다.The top coating layer 15 may be applied on one side of the second base film layer 13 to protect the first base film layer 11 and the second base film layer 13 as a base layer, and may be provided to protect the first base film layer 11 and the second base film layer 13 as a base layer. Protects the base layer from external contaminants such as dirt and dust. The top coating layer 15 is preferably made of a transparent material with weather resistance. The top coating layer 15 may include one or more selected from the group consisting of fluorine-based silicone resin, acrylic resin, polyvinyl-based resin, and polyurethane-based resin. In a preferred embodiment, the top coating layer 15 may be formed by coating a fluorine-based silicone resin. The top coating layer 15 preferably has a thickness of 3 to 5㎛. The top coating layer 15 faces the outside of the solar cell module and may face the outside or the junction box.
상기 탑코팅층(15)은 불소계 실리콘을 탑코팅층의 100 중량부 기준 30 내지 40 중량부 포함되도록 헥산, 디이소프로필에테르, MEK 등의 용제에 분산시켜 형성할 수 있다.The top coating layer 15 can be formed by dispersing fluorine-based silicon in a solvent such as hexane, diisopropyl ether, or MEK to contain 30 to 40 parts by weight based on 100 parts by weight of the top coating layer.
배리어코팅층 조성물의 제조Preparation of barrier coating layer composition
제조예 1Manufacturing Example 1
70℃의 증류수 49 중량%에 알루미늄 이소프로폭사이드 10중량%를 98% 순도의 에탄올 30중량%에 분산시킨 용액을 1시간동안 적하시키고, 그래핀 옥사이드 5중량%를 교반하면서 첨가한다. 온도를 서서히 95℃까지 올려 이소프로판올을 유출시킴으로써, 가수 분해 축합 반응을 실시하였다. 이 후, 질산 수용액 3중량%을 첨가하고 95℃에서 10시간 동안 교반한 후, 인산 수용액 3중량%을 첨가하였다. 인산 수용액 첨가 시 두 용액의 온도는 모두 20℃로 제어하였다.A solution of 10% by weight of aluminum isopropoxide dispersed in 30% by weight of 98% purity ethanol in 49% by weight of distilled water at 70°C was added dropwise over 1 hour, and 5% by weight of graphene oxide was added while stirring. A hydrolysis condensation reaction was performed by gradually raising the temperature to 95°C and discharging isopropanol. Afterwards, 3% by weight of an aqueous nitric acid solution was added and stirred at 95°C for 10 hours, and then 3% by weight of an aqueous phosphoric acid solution was added. When adding the phosphoric acid aqueous solution, the temperature of both solutions was controlled to 20°C.
(실시예 1)(Example 1)
제1기재필름층(11) 및 제2기재필름층(13)으로 두께가 188㎛인 PET 필름(ASTROLL, 코오롱 인더스트리)을 사용하였다. PET film (ASTROLL, Kolon Industries) with a thickness of 188㎛ was used as the first base film layer 11 and the second base film layer 13.
배리어코팅층(12)으로는 제조예 1에 따른 배리어코팅층 조성물을 제1기재필름층(11)에 코팅하고, 120℃의 환경에서 5 min 경화 후 다시 140℃의 환경에서 1 min 경화하여 1㎛의 두께가 되도록 하였다.As the barrier coating layer 12, the barrier coating layer composition according to Preparation Example 1 was coated on the first base film layer 11, cured in an environment of 120°C for 5 min, and then cured again in an environment of 140°C for 1 min to form a 1㎛ layer. It was made to be thick.
접착층(14)은 아크릴계 바인더(AT-377, 삼원)를 접착층의 100 중량부 기준 35 중량부, 에폭시계 경화제(CAT-EX, 삼원)를 접착층의 100 중량부 기준 1 중량부, MEK 용매를 접착층의 100 중량부 기준 64 중량부가 되도록 혼합한 조성물을 120℃의 환경에서 2 min 경화하여 10㎛의 두께가 되도록 하였다. 상기 접착층(14)을 배리어코팅층(12)의 일면 상에 형성하고, 그 위에 제2기재필름층(13)을 부착하였다.The adhesive layer 14 contains 35 parts by weight of an acrylic binder (AT-377, Samwon) based on 100 parts by weight of the adhesive layer, 1 part by weight of an epoxy-based hardener (CAT-EX, Samwon) based on 100 parts by weight of the adhesive layer, and MEK solvent to the adhesive layer. A composition mixed at 64 parts by weight based on 100 parts by weight was cured for 2 minutes in an environment at 120°C to obtain a thickness of 10㎛. The adhesive layer 14 was formed on one side of the barrier coating layer 12, and the second base film layer 13 was attached thereon.
탑코팅층(15)으로는 불소계 실리콘이 탑코팅층의 100 중량부 기준 35 중량부 포함되도록 탑코팅층의 100 중량부 기준 65 중량부의 MEK에 분산된 분산액(FAS 001, DCT 머티리얼)을 제2기재필름층(13)의 일면 상에 코팅한 후, 80℃의 통풍오븐 내 환경에서 1분동안 용매를 제거하였다. 그 후 UV경화기를 사용하여 500mJ/cm2로 코팅을 경화하여 5㎛의 두께를 가지도록 하였다.As the top coating layer 15, a dispersion (FAS 001, DCT material) dispersed in 65 parts by weight of MEK based on 100 parts by weight of the top coating layer to include 35 parts by weight of fluorine-based silicon based on 100 parts by weight of the top coating layer is applied to the second base film layer. After coating on one side of (13), the solvent was removed for 1 minute in a ventilated oven at 80°C. Afterwards, the coating was cured at 500mJ/cm 2 using a UV curing machine to have a thickness of 5㎛.
이에 따라 제1기재필름층(11)-배리어코팅층(12)-접착층(14)-제2기재필름층(13)-탑코팅층(15)의 순서로 적층된 필름을 형성하였다.Accordingly, a film was formed laminated in the following order: first base film layer (11) - barrier coating layer (12) - adhesive layer (14) - second base film layer (13) - top coating layer (15).
(실시예 2)(Example 2)
실시예 1의 제1기재필름층(11) 상에 접착층(14)을 형성하고 그 위에 실시예 1의 제2기재필름층(13)을 부착하여 제1기재필름층(11)-접착층(14)-제2기재필름층(13)의 순서로 적층된 필름을 형성하였다.An adhesive layer 14 was formed on the first base film layer 11 of Example 1, and the second base film layer 13 of Example 1 was attached thereon to form the first base film layer 11-adhesive layer 14. ) - A film was formed laminated in the order of the second base film layer 13.
(실시예 3)(Example 3)
실시예 1과 동일한 구성을 가지되, 접착층(14)을 제1기재필름층(11)의 타면에 형성하여 적층순서가 배리어코팅층(12)-제1기재필름층(11)-접착층(14)-제2기재필름층(13)-탑코팅층(15)인 필름을 형성하였다.It has the same configuration as Example 1, but the adhesive layer 14 is formed on the other side of the first base film layer 11, so that the stacking order is barrier coating layer 12 - first base film layer 11 - adhesive layer 14. A film consisting of -second base film layer (13) and top coating layer (15) was formed.
(실시예 4)(Example 4)
실시예 1의 배리어코팅층(12)을 생략하여 제1기재필름층(11)-접착층(14)-제2기재필름층(13)-탑코팅층(15)의 순서로 적층된 필름을 형성하였다.The barrier coating layer 12 of Example 1 was omitted to form a film laminated in the following order: first base film layer 11 - adhesive layer 14 - second base film layer 13 - top coating layer 15.
(실시예 5)(Example 5)
실시예 2의 탑코팅층(15)을 생략하여 배리어코팅층-제1기재필름층(11)-접착층(14)-제2기재필름층(13)의 순서로 적층된 필름을 형성하였다.The top coating layer 15 of Example 2 was omitted to form a film laminated in the following order: barrier coating layer - first base film layer 11 - adhesive layer 14 - second base film layer 13.
(실시예 6)(Example 6)
실시예 1의 탑코팅층(15)을 생략하여 제1기재필름층(11)-배리어코팅층-접착층(14)-제2기재필름층(13)의 순서로 적층된 필름을 형성하였다.The top coating layer 15 of Example 1 was omitted to form a film laminated in the following order: first base film layer 11 - barrier coating layer - adhesive layer 14 - second base film layer 13.
(실시예 7)(Example 7)
실시예 1의 제1기재필름층(11) 상에 실시예 1의 탑코팅층(15)을 코팅하여 제1기재필름층(11)-탑코팅층(15)의 순서로 적층된 필름을 형성하였다.The top coating layer 15 of Example 1 was coated on the first base film layer 11 of Example 1 to form a film laminated in the order of first base film layer 11 - top coating layer 15.
(실시예 8)(Example 8)
실시예 1의 제1기재필름층(11) 상에 실시예 1의 배리어코팅층(12)을 코팅하여 배리어코팅층(12)-제1기재필름층(11)의 순서로 적층된 필름을 형성하였다.The barrier coating layer 12 of Example 1 was coated on the first base film layer 11 of Example 1 to form a film laminated in the order of barrier coating layer 12 - first base film layer 11.
(실시예 9)(Example 9)
실시예 2의 접착층(14)의 두께를 5㎛로 한 필름을 형성하였다.A film was formed in which the thickness of the adhesive layer 14 of Example 2 was 5 μm.
(실시예 10)(Example 10)
실시예 2의 접착층(14)의 두께를 20㎛로 한 필름을 형성하였다.A film was formed in which the thickness of the adhesive layer 14 of Example 2 was 20 μm.
(실시예 11)(Example 11)
실시예 2의 접착층(14)의 두께를 30㎛로 한 필름을 형성하였다.A film was formed in which the thickness of the adhesive layer 14 of Example 2 was 30 μm.
(실시예 12)(Example 12)
실시예 7의 필름에서, 탑코팅층(15)의 조성을 아크릴계 코팅으로 하였다.In the film of Example 7, the composition of the top coating layer 15 was an acrylic coating.
상기 아크릴계 코팅은 탑코팅층 100중량부에 대하여 우레탄 아크릴레이트 30중량부, 에폭시 이소시아네이트 5중량부, 톨루엔 18중량부, 메틸에틸케톤(MEK) 47 중량부를 혼합하여 마이크로 그라비아 코팅을 통해 5㎛ 두께로 형성하였다.The acrylic coating is formed to a thickness of 5㎛ through micro gravure coating by mixing 30 parts by weight of urethane acrylate, 5 parts by weight of epoxy isocyanate, 18 parts by weight of toluene, and 47 parts by weight of methyl ethyl ketone (MEK) with respect to 100 parts by weight of the top coating layer. did.
(실시예 13)(Example 13)
실시예 1의 필름에서, 탑코팅층(15)의 조성을 실시예 12의 아크릴계 코팅으로 대체한 필름을 형성하였다.In the film of Example 1, a film was formed in which the composition of the top coating layer 15 was replaced with the acrylic coating of Example 12.
(비교예1)(Comparative Example 1)
두께가 50㎛인 PET 필름(ASTROLL, 코오롱 인더스트리) 단층을 사용한 필름을 형성하였다.A film was formed using a single layer of PET film (ASTROLL, Kolon Industries) with a thickness of 50 μm.
(비교예2)(Comparative Example 2)
두께가 100㎛인 PET 필름(ASTROLL, 코오롱 인더스트리) 단층을 사용한 필름을 형성하였다.A film was formed using a single layer of PET film (ASTROLL, Kolon Industries) with a thickness of 100 μm.
(비교예3)(Comparative Example 3)
두께가 125㎛인 PET 필름(ASTROLL, 코오롱 인더스트리) 단층을 사용한 필름을 형성하였다.A film was formed using a single layer of PET film (ASTROLL, Kolon Industries) with a thickness of 125 μm.
(비교예4)(Comparative Example 4)
두께가 188㎛인 PET 필름(ASTROLL, 코오롱 인더스트리) 단층을 사용한 필름을 형성하였다.A film was formed using a single layer of PET film (ASTROLL, Kolon Industries) with a thickness of 188 μm.
(비교예5)(Comparative Example 5)
두께가 250㎛인 PET 필름(ASTROLL, 코오롱 인더스트리) 단층을 사용한 필름을 형성하였다.A film was formed using a single layer of PET film (ASTROLL, Kolon Industries) with a thickness of 250 μm.
(비교예6)(Comparative Example 6)
두께가 50㎛인 PET 필름(ASTROLL, 코오롱 인더스트리) 2개 층을 사용하고, 그 사이를 10㎛의 두께가 되도록 형성한 실시예 1의 접착층을 사용하여 필름을 형성하였다.A film was formed using two layers of PET film (ASTROLL, Kolon Industries) with a thickness of 50㎛, and the adhesive layer of Example 1 formed between them to a thickness of 10㎛.
(비교예7)(Comparative Example 7)
두께가 50㎛인 PET 필름(ASTROLL, 코오롱 인더스트리) 3개 층을 사용하고, 그 사이를 10㎛의 두께가 되도록 형성한 실시예 1의 접착층을 사용하여 필름을 형성하였다.A film was formed using three layers of PET film (ASTROLL, Kolon Industries) with a thickness of 50㎛, and the adhesive layer of Example 1 formed between them to a thickness of 10㎛.
(비교예 8)(Comparative Example 8)
실시예의 배리어코팅층(12) 대신 두께가 30㎛인 PVF 필름층(Tedlar, Dupont)을 사용하고, 제1기재필름층(11) 및 제2기재필름층(13)으로는 두께가 188㎛인 PET 필름(ASTROLL, 코오롱 인더스트리)을 사용하였다. 제2기재필름층(13)의 일면상에 코팅되는 탑코팅층은 실시예 1의 탑코팅층과 동일한 것을 사용하였다.Instead of the barrier coating layer 12 of the example, a PVF film layer (Tedlar, Dupont) with a thickness of 30㎛ is used, and the first base film layer 11 and the second base film layer 13 are PET with a thickness of 188㎛. Film (ASTROLL, Kolon Industries) was used. The top coating layer coated on one side of the second base film layer 13 was the same as the top coating layer in Example 1.
PVF 필름층-제1기재필름층(11)-접착층(14)-제2기재필름층(13)-탑코팅층(15)의 순서로 적층된 필름을 형성하였다.A film was formed by lamination in the following order: PVF film layer - first base film layer (11) - adhesive layer (14) - second base film layer (13) - top coating layer (15).
가시광에 대한 투과 시험Transmission test for visible light
실시예 1 내지 13에 의해 형성된 필름, 비교예 4에 의해 형성된 필름에 대해 가시광 투과 비율을 수행하였다. 이때 투과율은 필름의 제1기재필름층(11) 측에 조사된 가시광 대비 필름의 이면에서 측정 되는 가시광의 광량이다. 이를 분광계(Spectrometer) Jasco社 V-770으로 측정하였다. Visible light transmission ratio was performed on the films formed by Examples 1 to 13 and the film formed by Comparative Example 4. At this time, the transmittance is the amount of visible light measured on the back side of the film compared to the visible light irradiated on the first base film layer 11 side of the film. This was measured with a spectrometer, Jasco V-770.
부분방전전압 시험Partial discharge voltage test
실시예 1 내지 13 및 비교예 1 내지 7에 의해 형성된 필름에 대해 부분방전전압 시험을 하였다. 부분방전전압 시험은 KS C IEC 60664-1에 따른 부분방전전압시험에 따라 측정 및 계산되었다.A partial discharge voltage test was performed on the films formed in Examples 1 to 13 and Comparative Examples 1 to 7. The partial discharge voltage test was measured and calculated according to the partial discharge voltage test according to KS C IEC 60664-1.
실시예Example 부분방전전압(VDC)Partial discharge voltage (VDC) 가시광투과율(%)Visible light transmittance (%) 헤이즈(%)Haze (%)
실시예1Example 1 1,2061,206 91.6991.69 1.051.05
실시예2Example 2 1,1701,170 83.5883.58 3.753.75
실시예3Example 3 930930 91.2791.27 2.182.18
실시예4Example 4 1,3401,340 89.8189.81 2.072.07
실시예5Example 5 990990 84.4084.40 3.663.66
실시예6Example 6 1,1901,190 84.3784.37 3.603.60
비교예4Comparative example 4 830830 91.1391.13 1.711.71
표 1에 나타난 바와 같이, 두께 188㎛인 PET 필름 단층을 백시트 또는 전면부 필름으로 사용하는 것에 비해, PET 필름을 다층 적층하여 사용하는 것이 부분방전전압 측면에서 유리함이 관찰되었다. 이때 실시예 3 및 실시예 5의 경우 배리어코팅층(12)이 봉지재와 접하게 되어 부분방전전압의 저하가 발생한 것이 확인될 수 있다. 배리어코팅층(12)의 필름의 최외곽에 노출시키도록 적층하는 것에 비해, 제1기재필름층(11)과 제2기재필름층(13) 사이에 배치하는 것이 부분방전전압 측면에서 유리한 것을 확인할 수 있다.As shown in Table 1, compared to using a single layer of PET film with a thickness of 188㎛ as a backsheet or front film, it was observed that using a multilayer stack of PET films was advantageous in terms of partial discharge voltage. At this time, in the case of Examples 3 and 5, it can be confirmed that the barrier coating layer 12 came into contact with the encapsulant, resulting in a decrease in partial discharge voltage. It can be seen that placing the barrier coating layer 12 between the first base film layer 11 and the second base film layer 13 is advantageous in terms of partial discharge voltage, compared to lamination to expose the outermost layer of the film. there is.
탑코팅층(15)이 결여된 실시예 2, 실시예 5, 실시예 6은 가시광 투과율이 감소하고 헤이즈(Haze)가 증가하였다. 이를 통해 탑코팅층(15)을 필름의 외곽 측면에 코팅함으로써 내후성과 광 효율이 증가함을 확인할 수 있다.In Examples 2, 5, and 6 lacking the top coating layer 15, visible light transmittance decreased and haze increased. Through this, it can be confirmed that weather resistance and light efficiency are increased by coating the top coating layer 15 on the outer side of the film.
실시예/비교예Examples/Comparative Examples 부분방전전압(VDC)Partial discharge voltage (VDC) 실시예/비교예Examples/Comparative Examples 부분방전전압(VDC)Partial discharge voltage (VDC)
실시예1Example 1 1,2061,206 비교예2Comparative example 2 610610
실시예2Example 2 1,1701,170 비교예3Comparative Example 3 710710
실시예9Example 9 1,2201,220 비교예4Comparative example 4 830830
실시예10Example 10 1,1501,150 비교예5Comparative Example 5 950950
실시예11Example 11 1,2201,220 비교예6Comparative Example 6 560560
비교예1Comparative Example 1 470470 비교예7Comparative example 7 740740
표 2의 비교예들에 대한 부분방전전압 시험결과를 참고하면, 기재층으로서의 PET층의 두께가 두꺼워짐에 따라 부분방전전압이 상승함을 확인할 수 있으며, 실시예 1과 2, 실시예 9 내지 11의 시험결과에 따라 제1기재필름층(11)과 제2기재필름층(13) 사이 접착층(14)의 두께는 부분방전전압에 큰 영향을 미치지 않는 것을 확인할 수 있다. 이에 따라 소정 두께의 기재층을 확보하는 것이 부분방전전압 측면에서 유리하다. 다만 배리어코팅층(12)이 봉지층 또는 봉지재와 직접 닿는 것이 부분방전전압의 저하를 가져오는 것을 고려하면, 기재층을 복수 층으로 적층하고, 배리어코팅층(12)을 기재층 사이에 배치하는 것이 유리한 것을 확인할 수 있다.Referring to the partial discharge voltage test results for the comparative examples in Table 2, it can be seen that the partial discharge voltage increases as the thickness of the PET layer as the base layer increases, Examples 1 and 2, and Examples 9 to 9. According to the test results in Fig. 11, it can be confirmed that the thickness of the adhesive layer 14 between the first base film layer 11 and the second base film layer 13 does not significantly affect the partial discharge voltage. Accordingly, securing a base layer of a predetermined thickness is advantageous in terms of partial discharge voltage. However, considering that direct contact of the barrier coating layer 12 with the encapsulation layer or encapsulant reduces the partial discharge voltage, it is better to stack the base layer in multiple layers and place the barrier coating layer 12 between the base layers. You can see that it is advantageous.
실시예Example 부분방전전압(VDC)Partial discharge voltage (VDC) 가시광투과율(%)Visible light transmittance (%) 헤이즈(%)Haze (%)
실시예1Example 1 1,2061,206 91.6991.69 1.051.05
실시예7Example 7 870870 94.4294.42 1.141.14
실시예8Example 8 830830 91.9191.91 1.621.62
실시예12Example 12 860860 90.5590.55 2.612.61
실시예13Example 13 1,2161,216 91.1091.10 1.681.68
표 3의 실시예 1과 실시예 13의 시험결과를 참고하면, 부분방전 전압 시험에서는 탑코팅층(15)의 조성에 별다른 차이가 없으나, 가시광투과율 및 헤이즈 측면에서 탑코팅층(15)으로 불소계 실리콘 코팅을 사용하는 것이 유리한 것을 확인할 수 있다. 실시예 7과 실시예 12를 비교하는 경우에도, PET 필름 상에 탑코팅층(15)으로 불소계 실리콘을 코팅하는 것이 아크릴계 코팅보다 헤이즈 측면에서 유리하다. 또한 PET 필름이 적층되지 않는 경우, 즉 기재층의 충분한 두께가 확보되지 않은 실시예 7, 실시예 8, 실시예 12에서는 배리어코팅층(12)이나 탑코팅층(15)이 형성되더라도 1,000VDC의 부분방전전압에 미치지 못하는 것을 확인할 수 있다.Referring to the test results of Example 1 and Example 13 in Table 3, there is no significant difference in the composition of the top coating layer 15 in the partial discharge voltage test, but in terms of visible light transmittance and haze, the top coating layer 15 is coated with fluorine-based silicon. It can be seen that it is advantageous to use . Even when comparing Example 7 and Example 12, coating fluorine-based silicone as the top coating layer 15 on the PET film is advantageous in terms of haze compared to acrylic-based coating. In addition, in cases where the PET film is not laminated, that is, in Examples 7, 8, and 12 in which a sufficient thickness of the base layer is not secured, partial discharge of 1,000 VDC occurs even if the barrier coating layer 12 or the top coating layer 15 is formed. You can confirm that the voltage is not reached.
수분투과율 시험Moisture permeability test
실시예 1, 실시예 3 및 비교예 8의 필름에 대하여, ASTM F1249 시험방법에 따라 38℃, 100% RH 조건 하에서 수분투과율(WVTR)을 측정하였다.For the films of Example 1, Example 3, and Comparative Example 8, the water vapor transmission rate (WVTR) was measured under conditions of 38°C and 100% RH according to the ASTM F1249 test method.
비교예 8의 경우 1.3g/m2/day의 수분투과율(WVTR)이 측정되었으며, 실시예 1 및 실시예 3의 경우 0.05g/m2/day의 수분투과율(WVTR)이 측정되었다. 따라서 태양전지모듈용 컬러필름의 수분투과를 막기 위한 배리어층으로는 본 발명의 일 실시예에 따른 배리어코팅층(12)을 사용하는 것이 바람직하다.In Comparative Example 8, a water permeability rate (WVTR) of 1.3 g/m 2 /day was measured, and in Examples 1 and 3, a water permeability rate (WVTR) of 0.05 g/m 2 /day was measured. Therefore, it is preferable to use the barrier coating layer 12 according to an embodiment of the present invention as a barrier layer to prevent moisture penetration of the color film for solar cell modules.
(실시예 14)(Example 14)
실시예 1의 필름에서, 접착층(14)은 아크릴계 바인더(AT-377, 삼원)를 접착층의 100 중량부 기준 35 중량부, 에폭시계 경화제(CAT-EX, 삼원)를 접착층의 100 중량부 기준 1 중량부, Quinacridone을 포함하는 적색안료(Irgalite Red K 4170, BASF)를 접착층의 100중량부 기준 1 중량부, MEK 용매를 접착층의 100 중량부 기준 63 중량부가 되도록 혼합한 조성물을 120℃의 환경에서 2 min 경화하여 10㎛의 두께가 되도록 하였다. 상기 접착층(14)을 배리어코팅층(12)의 일면 상에 형성하고, 그 위에 제2기재필름층(13)을 합지한 필름을 형성하였다.In the film of Example 1, the adhesive layer 14 contained 35 parts by weight of an acrylic binder (AT-377, Samwon) based on 100 parts by weight of the adhesive layer, and 1 part by weight of an epoxy-based hardener (CAT-EX, Samwon) based on 100 parts by weight of the adhesive layer. A composition in which 1 part by weight of a red pigment (Irgalite Red K 4170, BASF) containing Quinacridone is mixed in an amount of 1 part by weight based on 100 parts by weight of the adhesive layer and 63 parts by weight of MEK solvent based on 100 parts by weight of the adhesive layer is mixed in an environment at 120°C. It was cured for 2 min to achieve a thickness of 10㎛. The adhesive layer 14 was formed on one side of the barrier coating layer 12, and a film was formed by laminating the second base film layer 13 thereon.
(실시예 15)(Example 15)
실시예 14의 필름에서, 접착층(14)이 적색안료 대신 Cu-phthalocyanine을 포함하는 청색안료(Irgalite Blue GBP, BASF)를 접착층의 100중량부 기준 1 중량부 포함하도록 하여 필름을 형성하였다.In the film of Example 14, the adhesive layer 14 was formed by including 1 part by weight of a blue pigment (Irgalite Blue GBP, BASF) containing Cu-phthalocyanine instead of the red pigment, based on 100 parts by weight of the adhesive layer.
(실시예 16)(Example 16)
실시예 14의 필름에서, 접착층(14)이 적색안료 대신 Cu-phthalocyanine을 포함하는 녹색안료(Irgalite Green GFNP, BASF)를 접착층의 100중량부 기준 1 중량부 포함하도록 하여 필름을 형성하였다.In the film of Example 14, the adhesive layer 14 was formed by including 1 part by weight of a green pigment (Irgalite Green GFNP, BASF) containing Cu-phthalocyanine instead of the red pigment, based on 100 parts by weight of the adhesive layer.
(실시예 17)(Example 17)
실시예 2의 필름에서, 접착층(14)은 아크릴계 바인더(AT-377, 삼원)를 접착층의 100 중량부 기준 35 중량부, 에폭시계 경화제(CAT-EX, 삼원)를 접착층의 100 중량부 기준 1 중량부, Quinacridone을 포함하는 적색안료(Irgalite Red K 4170, BASF)를 접착층의 100중량부 기준 1 중량부, MEK 용매를 접착층의 100 중량부 기준 63 중량부가 되도록 혼합한 조성물을 120℃의 환경에서 2 min 경화하여 10㎛의 두께가 되도록 하였다. 상기 접착층(14)을 배리어코팅층(12)의 일면 상에 형성하고, 그 위에 제2기재필름층(13)을 합지한 필름을 형성하였다.In the film of Example 2, the adhesive layer 14 contained 35 parts by weight of an acrylic binder (AT-377, Samwon) based on 100 parts by weight of the adhesive layer, and 1 part by weight of an epoxy-based hardener (CAT-EX, Samwon) based on 100 parts by weight of the adhesive layer. A composition in which 1 part by weight of a red pigment (Irgalite Red K 4170, BASF) containing Quinacridone is mixed in an amount of 1 part by weight based on 100 parts by weight of the adhesive layer and 63 parts by weight of MEK solvent based on 100 parts by weight of the adhesive layer is mixed in an environment at 120°C. It was cured for 2 min to achieve a thickness of 10㎛. The adhesive layer 14 was formed on one side of the barrier coating layer 12, and a film was formed by laminating the second base film layer 13 thereon.
(실시예 18)(Example 18)
실시예 17의 필름에서, 접착층(14)이 적색안료 대신 Cu-phthalocyanine을 포함하는 청색안료(Irgalite Blue GBP, BASF)를 접착층의 100중량부 기준 1 중량부 포함하도록 하여 필름을 형성하였다.In the film of Example 17, the adhesive layer 14 was formed by including 1 part by weight of a blue pigment (Irgalite Blue GBP, BASF) containing Cu-phthalocyanine instead of the red pigment, based on 100 parts by weight of the adhesive layer.
(실시예 19)(Example 19)
실시예 17의 필름에서, 접착층(14)이 적색안료 대신 Cu-phthalocyanine을 포함하는 녹색안료(Irgalite Green GFNP, BASF)를 접착층의 100중량부 기준 1 중량부 포함하도록 하여 필름을 형성하였다.In the film of Example 17, the adhesive layer 14 was formed by including 1 part by weight of a green pigment (Irgalite Green GFNP, BASF) containing Cu-phthalocyanine instead of the red pigment, based on 100 parts by weight of the adhesive layer.
색상 유지 시험Color retention test
탑코팅층(15) 및 배리어코팅층(12)의 유무에 따른 컬러필름의 색상유지 정도를 확인하기 위하여, Q-SUN(제조사: Q-LAB, Xe-3 XENON TEST CHAMBER)을 통하여 ASTM G155 Cycle No#1 실험을 진행하였다. 상기 실험을 통해 본 발명의 실시예 14 내지 19의 필름이 태양광에 노출될 때 발생하는 풍화 효과를 측정하였다. 필터값을 Daylight으로, 조도는 340nm에서 Xe arc lamp를 사용하여 0.35 W/㎡로 조사하였다. 노출 사이클은 102min Light only & 18min Light and spray at 63℃ Black Panel Temperature으로 수행하였다. 1000시간이 지나는 동안 Lab 색차를 측정하여 컬러필름의 색상 변화를 조사하였다. 색차(ΔE)는 CIELab 값들 사이의 색상 차이를 표현하기 위한 표준 CIE공식으로, L(밝음도), a(빨강-녹색 반대 색상의 변화량), b(파랑-노랑 반대 색상의 변화량)에 의해 산정될 수 있다. 시험 초기(0hr)의 L, a, b값을 측정한 후, 500hr 및 1,000hr 시점에서 L, a, b값을 측정하여 색차를 비교할 때 색차(ΔE)가 적을수록 컬러필름의 색상이 유지되었다고 판정할 수 있다.In order to check the degree of color retention of the color film depending on the presence or absence of the top coating layer 15 and the barrier coating layer 12, ASTM G155 Cycle No. 1 Experiment was conducted. Through the above experiment, the weathering effect that occurs when the films of Examples 14 to 19 of the present invention are exposed to sunlight was measured. The filter value was set to Daylight, and the illuminance was 0.35 W/㎡ using a Xe arc lamp at 340 nm. The exposure cycle was performed with 102min Light only & 18min Light and spray at 63℃ Black Panel Temperature. The color change of the color film was investigated by measuring the Lab color difference over 1000 hours. Color difference (ΔE) is the standard CIE formula for expressing color differences between CIELab values, calculated by L (brightness), a (amount of change in opposite colors of red-green), and b (amount of change in opposite colors of blue-yellow). It can be. After measuring the L, a, and b values at the beginning of the test (0 hr), measuring the L, a, and b values at 500 hr and 1,000 hr and comparing the color difference, the smaller the color difference (ΔE), the more the color of the color film was maintained. can be judged.
광전 변환효율
(Eff%)Photoelectric conversion efficiency
(Eff%) 		L*(0hr)L*(0hr) a*(0hr)a*(0hr) b*(0hr)b*(0hr) ΔE(500)hrΔE(500)hr ΔE(1000hr)ΔE(1000hr)
실시예14Example 14 18.7118.71 87.787.7 -6.97-6.97 -0.5-0.5 1.431.43 2.712.71
실시예15Example 15 18.318.3 89.1589.15 -3.76-3.76 -3.47-3.47 0.550.55 2.252.25
실시예16Example 16 1818 90.2990.29 -9.21-9.21 0.090.09 1.441.44 4.314.31
실시예17Example 17 15.2515.25 87.4687.46 6.376.37 -0.24-0.24 1.821.82 3.173.17
실시예18Example 18 15.4615.46 89.0989.09 -3.84-3.84 -3.19-3.19 1.371.37 2.232.23
실시예19Example 19 17.0517.05 89.4689.46 -10.7-10.7 -0.04-0.04 2.152.15 5 이상5 or more
색차(ΔE)가 5 이상인 경우 육안으로 인식하기에 변색이 심하다고 느껴져 시험을 중단하도록 한다. 실시예 14와 17, 실시예 15와 18, 실시예 16과 19를 각각 비교하면, 500hr과 1,000hr 시점에서 측정한 색차(ΔE)가 실시예 14 내지 16의 경우가 실시예 17 내지 19의 경우보다 대부분 20% 이상 작은 것을 확인할 수 있다. 이를 통해 본 발명의 탑코팅층(15)이 태양광 노출 환경에서 표면의 변화(크랙, 황변)를 방지하여 컬러필름의 색상을 유지할 수 있도록 하며, 배리어코팅층(12)이 수분의 투습을 방지하여 색상안료가 포함된 접착층의 변색을 방지하는 것을 확인할 수 있다.If the color difference (ΔE) is 5 or more, the discoloration is felt to be too severe to be recognized by the naked eye, so the test should be discontinued. When comparing Examples 14 and 17, Examples 15 and 18, and Examples 16 and 19, respectively, the color difference (ΔE) measured at 500 hr and 1,000 hr was lower for Examples 14 to 16 than for Examples 17 to 19. You can see that it is mostly 20% or more smaller than that. Through this, the top coating layer (15) of the present invention prevents surface changes (cracks, yellowing) in a solar exposure environment to maintain the color of the color film, and the barrier coating layer (12) prevents moisture penetration to maintain the color. It can be confirmed that discoloration of the adhesive layer containing pigment is prevented.
또한, 광전 변환효율(Eff, %) 측면에서도 실시예 14 내지 16의 경우 18% 이상으로 실시예 17 내지 19의 필름보다 높은 광전 변환효율을 가짐을 확인할 수 있다. 이는 실시예 1의 필름이 실시예 2의 필름보다 높은 가시광투과도를 가지는 것에서 기인하는 것으로 볼 수 있다. In addition, in terms of photoelectric conversion efficiency (Eff, %), it can be confirmed that Examples 14 to 16 have a higher photoelectric conversion efficiency than the films of Examples 17 to 19, at 18% or more. This can be seen to be due to the fact that the film of Example 1 has a higher visible light transmittance than the film of Example 2.
(실시예 20)(Example 20)
실시예 14의 필름에서, 접착층(14)이 적색안료 대신 핑크색을 띄는 형광체를 포함하는 안료(SX－217, SINLOIHI)를 접착층의 100중량부 기준 1 중량부 포함하도록 하여 필름을 형성하였다.In the film of Example 14, the adhesive layer 14 was formed by including 1 part by weight of a pigment (SX-217, SINLOIHI) containing a pink phosphor instead of a red pigment, based on 100 parts by weight of the adhesive layer.
(실시예 21)(Example 21)
실시예 20의 필름에서, 접착층(14)의 핑크색을 띄는 형광체를 포함하는 안료(SX－217, SINLOIHI)를 접착층의 100중량부 기준 3 중량부 혼입하고, 상기 안료의 증분만큼 감소한 양의 MEK를 혼합하여 필름을 형성하였다.In the film of Example 20, a pigment (SX-217, SINLOIHI) containing a pink phosphor of the adhesive layer 14 was incorporated in an amount of 3 parts by weight based on 100 parts by weight of the adhesive layer, and an amount of MEK decreased by the increment of the pigment was added. The mixture was mixed to form a film.
(실시예 22)(Example 22)
실시예 20의 필름에서, 접착층(14)의 핑크색을 띄는 형광체를 포함하는 안료(SX－217, SINLOIHI)를 접착층의 100중량부 기준 5 중량부 혼입하고, 상기 안료의 증분만큼 감소한 양의 MEK를 혼합하여 필름을 형성하였다.In the film of Example 20, 5 parts by weight of a pigment (SX-217, SINLOIHI) containing a pink phosphor of the adhesive layer 14 was incorporated based on 100 parts by weight of the adhesive layer, and an amount of MEK decreased by the increment of the pigment was added. The mixture was mixed to form a film.
(실시예 23)(Example 23)
실시예 14의 필름에서, 접착층(14)이 적색안료 대신 적색을 띄는 형광체를 포함하는 안료(FM－103, SINLOIHI)를 접착층의 100중량부 기준 1 중량부 포함하도록 하여 필름을 형성하였다.In the film of Example 14, the adhesive layer 14 was formed by including 1 part by weight of a pigment (FM-103, SINLOIHI) containing a red phosphor instead of a red pigment, based on 100 parts by weight of the adhesive layer.
(실시예 24)(Example 24)
실시예 23의 필름에서, 접착층(14)의 적색을 띄는 형광체를 포함하는 안료(FM－103, SINLOIHI)를 접착층의 100중량부 기준 3 중량부 혼입하고, 상기 안료의 증분만큼 감소한 양의 MEK를 혼합하여 필름을 형성하였다.In the film of Example 23, 3 parts by weight of a pigment (FM-103, SINLOIHI) containing a red phosphor of the adhesive layer 14 was incorporated based on 100 parts by weight of the adhesive layer, and an amount of MEK decreased by the increment of the pigment was added. The mixture was mixed to form a film.
(실시예 25)(Example 25)
실시예 23의 필름에서, 접착층(14)의 적색을 띄는 형광체를 포함하는 안료(FM－103, SINLOIHI)를 접착층의 100중량부 기준 5 중량부 혼입하고, 상기 안료의 증분만큼 감소한 양의 MEK를 혼합하여 필름을 형성하였다.In the film of Example 23, 5 parts by weight of a pigment (FM-103, SINLOIHI) containing a red phosphor of the adhesive layer 14 was incorporated based on 100 parts by weight of the adhesive layer, and an amount of MEK decreased by the increment of the pigment was added. The mixture was mixed to form a film.
(실시예 26)(Example 26)
실시예 14의 필름에서, 접착층(14)이 적색안료 대신 황색을 띄는 형광체를 포함하는 안료(FM－105, SINLOIHI)를 접착층의 100중량부 기준 1 중량부 포함하도록 하여 필름을 형성하였다.In the film of Example 14, the adhesive layer 14 was formed by including 1 part by weight of a pigment (FM-105, SINLOIHI) containing a yellow phosphor instead of a red pigment, based on 100 parts by weight of the adhesive layer.
(실시예 27)(Example 27)
실시예 26의 필름에서, 접착층(14)의 황색을 띄는 형광체를 포함하는 안료(FM－105, SINLOIHI)를 접착층의 100중량부 기준 3 중량부 혼입하고, 상기 안료의 증분만큼 감소한 양의 MEK를 혼합하여 필름을 형성하였다.In the film of Example 26, a pigment (FM-105, SINLOIHI) containing a yellow phosphor of the adhesive layer 14 was incorporated in an amount of 3 parts by weight based on 100 parts by weight of the adhesive layer, and an amount of MEK decreased by the increment of the pigment was added. The mixture was mixed to form a film.
(실시예 28)(Example 28)
실시예 26의 필름에서, 접착층(14)의 황색을 띄는 형광체를 포함하는 안료(FM－105, SINLOIHI)를 접착층의 100중량부 기준 5 중량부 혼입하고, 상기 안료의 증분만큼 감소한 양의 MEK를 혼합하여 필름을 형성하였다.In the film of Example 26, a pigment (FM-105, SINLOIHI) containing a yellow phosphor of the adhesive layer 14 was incorporated in an amount of 5 parts by weight based on 100 parts by weight of the adhesive layer, and an amount of MEK decreased by the increment of the pigment was added. The mixture was mixed to form a film.
도 4는 실시예 20, 실시예 22 내지 28의 파장에 따른 투과율(%)을 도시한 도면이다. 도 4를 참고하면, 형광체를 포함하는 안료를 접착층(14)에 혼입시키는 경우 태양전지 모듈에서 변환 효율이 높은 400 내지 550nm 파장의 가시광선에 대한 투과율이 높은 것을 확인할 수 있다. 따라서 형광체를 접착층(14) 내에 분포시키는 경우 400 내지 550nm 파장의 가시광선을 태양전지 모듈의 타겟 파장범위로 설정할 수 있어 우수한 광전 변환효율을 가질 수 있다.Figure 4 is a diagram showing the transmittance (%) according to the wavelength of Example 20 and Examples 22 to 28. Referring to FIG. 4, it can be seen that when a pigment containing a phosphor is incorporated into the adhesive layer 14, the transmittance of visible light with a wavelength of 400 to 550 nm, which has high conversion efficiency in the solar cell module, is high. Therefore, when the phosphor is distributed within the adhesive layer 14, visible light with a wavelength of 400 to 550 nm can be set to the target wavelength range of the solar cell module, resulting in excellent photoelectric conversion efficiency.
도 5는 실시예 1, 실시예 21, 실시예 22가 검정색 PV sheet 상에서 육안으로 보이는 색상과 전광선 투과율, 헤이즈 및 광전변환효율을 나타낸 도면이다. 형광체의 혼입량이 증가함에 따라 전광선 투과율 TT(%)가 낮아져 색상구현도가 높은 것을 확인할 수 있으며, Haze(%)가 높아지는 경향이 있지만 형광체가 입자가 광기전력 효과로 다시 빛을 공급할 수 있다. 특히 실시예 22의 경우 헤이즈가 약 30%까지 증가하더라도 광전 변환효율이 17.8%로, 동일한 색상구현도 및 헤이즈를 나타내는 컬러필름에 비해 우수한 광전 변환효율을 가지게 된다.Figure 5 is a diagram showing the visible color, total light transmittance, haze, and photoelectric conversion efficiency of Examples 1, 21, and 22 on a black PV sheet. As the amount of phosphor mixed increases, the total light transmittance TT (%) decreases, confirming that color reproduction is high. Haze (%) tends to increase, but the phosphor particles can supply light again through the photovoltaic effect. In particular, in the case of Example 22, even if the haze increases to about 30%, the photoelectric conversion efficiency is 17.8%, which is superior to the color film showing the same color rendition and haze.
이상의 상세한 설명은 본 발명을 예시하는 것이다. 또한 전술한 내용은 본 발명의 바람직한 실시 형태를 나타내어 설명하는 것이며, 본 발명은 다양한 다른 조합, 변경 및 환경에서 사용할 수 있다. 즉 본 명세서에 개시된 발명의 개념의 범위, 저술한 개시 내용과 균등한 범위 및/또는 당업계의 기술 또는 지식의 범위 내에서 변경 또는 수정이 가능하다. 전술한 실시예는 본 발명의 기술적 사상을 구현하기 위한 최선의 상태를 설명하는 것이며, 본 발명의 구체적인 적용 분야 및 용도에서 요구되는 다양한 변경도 가능하다. 따라서 이상의 발명의 상세한 설명은 개시된 실시 상태로 본 발명을 제한하려는 의도가 아니다. 또한 첨부된 청구범위는 다른 실시 상태도 포함하는 것으로 해석되어야 한다. The above detailed description is illustrative of the present invention. Additionally, the foregoing is intended to illustrate preferred embodiments of the present invention, and the present invention can be used in various other combinations, modifications, and environments. That is, changes or modifications can be made within the scope of the inventive concept disclosed in this specification, a scope equivalent to the written disclosure, and/or within the scope of technology or knowledge in the art. The above-described embodiments illustrate the best state for implementing the technical idea of the present invention, and various changes required for specific application fields and uses of the present invention are also possible. Accordingly, the above detailed description of the invention is not intended to limit the invention to the disclosed embodiments. Additionally, the appended claims should be construed to include other embodiments as well.

Claims (14)

  1. 베이스 기재로서의 제1기재필름층, 상기 제1기재필름층의 일측면에 배치되는 제2기재필름층, 상기 제1기재필름층과 제2기재필름층 사이에 형성되는 접착층, 상기 제2기재필름층의 일측에 형성되는 탑코팅층을 포함하고, A first base film layer as a base substrate, a second base film layer disposed on one side of the first base film layer, an adhesive layer formed between the first base film layer and the second base film layer, and the second base film. It includes a top coating layer formed on one side of the layer,
    상기 접착층은 색상안료를 포함하는 것을 특징으로 하는 태양전지 모듈용 컬러필름.The adhesive layer is a color film for a solar cell module, characterized in that it contains a color pigment.
  2. 제1항에 있어서, 상기 제1기재필름층의 일면에 형성되는 배리어코팅층을 더 포함하고, 상기 접착층은 일면이 상기 제1기재필름층 또는 배리어코팅층과 접하고, 타면이 제2기재필름층과 접하는 것을 특징으로 하는 태양전지 모듈용 컬러필름.The method of claim 1, further comprising a barrier coating layer formed on one side of the first base film layer, wherein one side of the adhesive layer is in contact with the first base film layer or barrier coating layer and the other side is in contact with the second base film layer. Color film for solar cell modules, characterized in that.
  3. 제2항에 있어서, 상기 접착층은 일면이 상기 배리어코팅층과 접하고, 타면이 제2기재필름층과 접하는 것을 특징으로 하는 태양전지 모듈용 컬러필름.The color film for a solar cell module according to claim 2, wherein one side of the adhesive layer is in contact with the barrier coating layer and the other side is in contact with the second base film layer.
  4. 제3항에 있어서, 상기 접착층은 색상안료를 접착층 100 중량부 기준 1 내지 2 중량부 포함하는 것을 특징으로 하는 태양전지 모듈용 컬러필름.The color film for a solar cell module according to claim 3, wherein the adhesive layer contains 1 to 2 parts by weight of a color pigment based on 100 parts by weight of the adhesive layer.
  5. 제4항에 있어서, 상기 색상안료는 발색단으로 아조기를 가지는 유기안료 또는 Phthalocyanine, Anthraquinone, Quinacridone의 다환기 유기안료 중 적어도 하나 이상을 포함하는 것을 특징으로 하는 태양전지 모듈용 컬러필름.The color film for a solar cell module according to claim 4, wherein the color pigment includes at least one of an organic pigment having an azo group as a chromophore or a polycyclic organic pigment such as phthalocyanine, anthraquinone, and quinacridone.
  6. 제4항에 있어서, 상기 색상안료는 광으로부터 흡수된 파장을 상기 흡수된 파장보다 높은 파장으로 변환시키는 형광체를 포함하는 것을 특징으로 하는 태양전지 모듈용 컬러필름.The color film for a solar cell module according to claim 4, wherein the color pigment includes a phosphor that converts a wavelength absorbed from light into a wavelength higher than the absorbed wavelength.
  7. 제6항에 있어서, 상기 형광체는 자외선을 흡수하여 자외선 파장보다 높은 파장으로 변환시키는 것을 특징으로 하는 태양전지 모듈용 컬러필름.The color film for solar cell modules according to claim 6, wherein the phosphor absorbs ultraviolet rays and converts them into a wavelength higher than the ultraviolet rays.
  8. 제5항에 있어서, 상기 제1기재필름층 및 제2기재필름층은 50 내지 200㎛의 두께, 상기 접착층은 5 내지 20 ㎛의 두께를 가지는 것을 특징으로 하는 태양전지 모듈용 컬러필름.The color film for a solar cell module according to claim 5, wherein the first base film layer and the second base film layer have a thickness of 50 to 200 ㎛, and the adhesive layer has a thickness of 5 to 20 ㎛.
  9. 제4항에 있어서, 상기 제1기재필름층 및 제2기재필름층은 폴리에스테르계 수지, 폴리카보네이트계 수지, 폴리비닐계 수지, 폴리이미드계 수지, 폴리우레탄계 수지 중 선택된 하나 이상을 포함하는 것을 특징으로 하는 태양전지 모듈용 컬러필름.The method of claim 4, wherein the first base film layer and the second base film layer include at least one selected from polyester-based resin, polycarbonate-based resin, polyvinyl-based resin, polyimide-based resin, and polyurethane-based resin. Characterized by color film for solar cell modules.
  10. 제1항 내지 제9항 중 어느 한 항에 있어서, 상기 배리어코팅층은 금속산화물이 제1기재필름층 상에 코팅된 것으로, The method of any one of claims 1 to 9, wherein the barrier coating layer is a metal oxide coated on the first base film layer,
    상기 금속산화물은 금속산화물 졸이며, 알루미나, 티타니아, 마그네시아, 지르코니아 또는 이들의 조합을 포함하는 것을 특징으로 하는 태양전지 모듈용 컬러필름.The metal oxide is a metal oxide sol, and a color film for a solar cell module, characterized in that it contains alumina, titania, magnesia, zirconia, or a combination thereof.
  11. 제10항에 있어서, 상기 배리어코팅층은 산 촉매 하에서 금속 알콕사이드를 물에 용해시켜 가수 분해 축합시키고 상기 제1기재필름층의 일면에 코팅한 후 경화시켜 형성된 것을 특징으로 하는 태양전지 모듈용 컬러필름.The color film for a solar cell module according to claim 10, wherein the barrier coating layer is formed by dissolving a metal alkoxide in water under an acid catalyst, hydrolyzing and condensing the metal alkoxide, coating it on one side of the first base film layer, and then curing it.
  12. 제11항에 있어서, 상기 배리어코팅층은 그래핀이 결합된 금속 산화물 및 인 함유 화합물을 포함하는 것을 특징으로 하는 태양전지 모듈용 컬러필름.The color film for a solar cell module according to claim 11, wherein the barrier coating layer includes a metal oxide bonded with graphene and a phosphorus-containing compound.
  13. 제10항에 있어서, 상기 탑코팅층은 불소계 실리콘 수지, 아크릴계 수지, 폴리비닐계 수지, 폴리우레탄계 수지 중 선택된 하나 이상을 포함하는 것을 특징으로 하는 태양전지 모듈용 컬러필름.The color film for a solar cell module according to claim 10, wherein the top coating layer includes one or more selected from the group consisting of a fluorine-based silicone resin, an acrylic resin, a polyvinyl-based resin, and a polyurethane-based resin.
  14. 제10항에 있어서, 상기 탑코팅층은 3 내지 5㎛의 두께, 상기 배리어코팅층은 1㎛ 이하의 두께를 가지는 것을 특징으로 하는 태양전지 모듈용 컬러필름.The color film for a solar cell module according to claim 10, wherein the top coating layer has a thickness of 3 to 5㎛, and the barrier coating layer has a thickness of 1㎛ or less.
PCT/KR2023/015482 2022-12-23 2023-10-10 Color film for solar cell module WO2024136047A1 (en)

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US20110203643A1 (en) * 2008-12-16 2011-08-25 Techno Polymer Co., Ltd. Solar cell backsheet and solar cell module provided with same
KR20120014161A (en) * 2009-05-19 2012-02-16 에보니크 룀 게엠베하 Transparent, weather-resistant barrier foil, production thereof by means of lamination, extrusion lamination or extrusion coating
JP2012197435A (en) * 2011-03-07 2012-10-18 Fujifilm Corp Easily adhesive sheet, protective sheet for solar cell, back sheet member for solar cell, back sheet for solar cell, and solar cell module
KR20170078436A (en) * 2015-12-29 2017-07-07 코오롱글로텍주식회사 Textile-based back sheet
KR20170079468A (en) * 2015-12-30 2017-07-10 주성엔지니어링(주) Structure using a solar cell

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US20110203643A1 (en) * 2008-12-16 2011-08-25 Techno Polymer Co., Ltd. Solar cell backsheet and solar cell module provided with same
KR20120014161A (en) * 2009-05-19 2012-02-16 에보니크 룀 게엠베하 Transparent, weather-resistant barrier foil, production thereof by means of lamination, extrusion lamination or extrusion coating
JP2012197435A (en) * 2011-03-07 2012-10-18 Fujifilm Corp Easily adhesive sheet, protective sheet for solar cell, back sheet member for solar cell, back sheet for solar cell, and solar cell module
KR20170078436A (en) * 2015-12-29 2017-07-07 코오롱글로텍주식회사 Textile-based back sheet
KR20170079468A (en) * 2015-12-30 2017-07-10 주성엔지니어링(주) Structure using a solar cell

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