WO2022065922A1 - 내후성 및 열방사 특성이 우수한 복합수지 조성물, 복합수지 코팅강판 및 이의 제조방법 - Google Patents
내후성 및 열방사 특성이 우수한 복합수지 조성물, 복합수지 코팅강판 및 이의 제조방법 Download PDFInfo
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- WO2022065922A1 WO2022065922A1 PCT/KR2021/013054 KR2021013054W WO2022065922A1 WO 2022065922 A1 WO2022065922 A1 WO 2022065922A1 KR 2021013054 W KR2021013054 W KR 2021013054W WO 2022065922 A1 WO2022065922 A1 WO 2022065922A1
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- steel sheet
- composite resin
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- 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
- C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
- C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
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- C09D123/06—Polyethene
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- 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
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
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- 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
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
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- 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
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- C09D191/00—Coating compositions based on oils, fats or waxes; Coating compositions based on derivatives thereof
- C09D191/06—Waxes
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Definitions
- the present invention relates to a composite resin composition having excellent weather resistance and heat radiation properties, a composite resin coated steel sheet, and a manufacturing method thereof.
- a solar cell using sunlight has been in the spotlight as an eco-friendly energy that can overcome environmental problems such as CO 2 generation problem and fine dust generation due to excessive use of fossil fuels.
- a solar cell is a technology that converts light energy into electrical energy by the photoelectric effect.
- the most used solar cell in solar technology is a silicon-based solar cell, which is divided into a crystalline type and an amorphous type.
- CIGS CuInGaSe
- the solar-integrated module manufacturing technology for application to the roof or wall of a building using a CIGS thin-film solar cell has been greatly developed.
- Crystalline silicon photovoltaic module consists of upper tempered glass, encapsulant, photovoltaic cell, encapsulant, and lower backsheet in order, so the solar module is not only heavy in weight but also insufficient in environmental safety. For this reason, there is a disadvantage in that the installation cost increases because an additional strong structure is installed in the building and a module is installed thereon.
- the second is the thermal issue. Since the solar cell generates electricity using the properties of a semiconductor, it is highly dependent on the amount of sunlight and has a problem in that power generation efficiency is greatly reduced when the temperature in summer increases. Roughly, when the surface temperature of the module is 45°C or higher, the power generation efficiency is rapidly reduced to -0.45%/°C. In the summer when the atmospheric temperature is the highest, the surface temperature of the solar module is at a high temperature of about 60 ⁇ 80°C. If maintained, the average solar power generation efficiency will drop from 20% to 12%.
- a method of attaching a heat dissipation sheet, a heat dissipation fin, or installing an additional cooling device such as a heat dissipation fan is applied, but is not preferable in terms of efficiency or cost.
- the weather resistance of the back sheet is required so that it can be used stably in an environment of 20 years or more.
- Patent Document 1 Korean Patent Publication No. 10-1487962
- One aspect of the present invention provides a composite resin composition having excellent weather resistance and heat radiation properties, and a composite resin coated steel sheet obtained therefrom, and a method for manufacturing the same, in providing a material suitable for a photovoltaic cell due to excellent weather resistance and heat radiation properties would like to
- the subject of the present invention is not limited to the above.
- the subject of the present invention will be understood from the overall content of the present specification, and those of ordinary skill in the art to which the present invention pertains will have no difficulty in understanding the additional subject of the present invention.
- a composite resin composition having excellent weather resistance and heat radiation properties.
- Another aspect of the present invention is a plated steel sheet; a heat dissipation film layer on the first surface of the plated steel sheet; and a weathering coating layer on the second surface of the plated steel sheet, wherein the heat dissipating coating layer is formed by the above-described composition to form a wrinkle pattern or a concave-convex structure on the surface, and the weathering coating layer is a part of the catalyst in the above-described composition And it provides a composite resin coated steel sheet formed by a composition excluding the wax component.
- Another aspect of the present invention comprises the steps of: a) preparing a plated steel sheet; b) applying the above-described composition to the first side of the plated steel sheet and applying a composition excluding some catalysts and wax components from the above-mentioned composition to the second side; and c) drying the composition applied to the first and second surfaces at 180 to 260° C. based on Peak Metal Temperature (PMT), wherein the second surface is a composite resin coating that is a surface bonding to the solar module
- PMT Peak Metal Temperature
- the composite resin-coated steel sheet obtained by using the composite resin composition according to the present invention has excellent weather resistance and heat radiation properties, and is suitable as a roof material for solar cells, etc., thereby improving the power generation efficiency of solar cells. .
- FIG. 1 is a side sectional view showing a composite resin coated steel sheet according to an embodiment of the present invention.
- FIG. 2 shows the results of observation under a microscope of the coating layer (heat dissipation coating layer) of the invention steel 10 (a) and the comparative steel 1 (b) according to an embodiment of the present invention.
- FIG. 4 is a view showing a heat dissipation temperature measuring device according to an embodiment of the present invention.
- the inventors of the present invention have studied deeply in order to solve the problems of the existing solar integrated module manufacturing technology.
- the present inventors utilize a plated steel sheet known to have excellent corrosion resistance, etc., but by coating a composition having excellent weather resistance and heat radiation characteristics. It was confirmed that a coated steel sheet suitable for a material could be provided, and the present invention was completed.
- the composite resin composition according to the present invention may be composed of a main resin, a curing agent, a pigment, a catalyst, and a residual solvent, and is characterized in that it is composed of a composition further including a wax component and a composition excluding some catalyst and wax components. .
- the composite resin composition further comprising the wax component may be expressed as Composition 1
- another composite resin composition may be expressed as Composition 2.
- composition 1 and composition 2 of the present invention may form respective coating layers on the surface of the substrate to which the composition can be applied, and the coating layers may have a feature that the surface shape is distinguished from each other. there is.
- the composition 1 and the composition 2 may be respectively applied to different surfaces of the substrate to form a dry coating film.
- the substrate may be a metal material, for example, a plated steel sheet.
- Composition 1 is (a) a main resin composed of a modified polyester resin, (b) a curing agent, (c) a pigment composed of a rust preventive pigment and a thermally conductive pigment, (d) a catalyst composed of an acid catalyst and an amine catalyst, ( e) wax.
- Such composition 1 may form a predetermined pattern such as a wrinkle pattern or a concave-convex structure on the surface of the dry coating film.
- each component is based on 100 parts by weight in total.
- the main resin made of the (a) modified polyester resin may be included in an amount of 20 to 60 parts by weight based on 100 parts by weight of the total.
- a polyester resin is a main component for forming a coating film (coating layer), and in the present invention, a modified polyester resin having an average molecular weight (Mw) of 5,000 to 50,000 may be used. If the molecular weight is less than 5,000, the chemical resistance and processability of the coating film are insufficient, whereas if it exceeds 50,000, there is a problem in that the storage stability and workability of the solution are inferior. More advantageously the average molecular weight may be between 10,000 and 40,000.
- Such a modified polyester resin may have a hydroxyl group (OH group, hydroxyl group).
- the resin may have a hydroxyl number of 20 to 60, and more advantageously may have a hydroxyl number of 30 to 50. If the hydroxyl value is less than 20, the cross-linking property of the coating film is lowered, whereas when it exceeds 60, there is a fear that the chemical resistance of the coating film is reduced.
- the modified polyester resin may have an acid value of 1 to 20 mgKOH/g, preferably 5 to 15 mgKOH/g.
- the acid value exceeds 20 mgKOH/g, the chemical resistance of the coating film is deteriorated, whereas when the acid value is less than 1 mgKOH/g, there is a problem in that the crosslinking property of the coating film is reduced.
- the content of the above-described modified polyester resin in the composition provided by the present invention is less than 20 parts by weight or exceeds 60 parts by weight, there is a fear that the drying property during curing of the coating film is lowered, crosslinking properties or chemical resistance may be lowered.
- the modified polyester resin is a bind resin that forms a fine pattern, for example, a wrinkle pattern or an uneven structure on the surface of the coating film upon curing, and has excellent processability and weather resistance.
- the (b) curing agent may be included in an amount of 3 to 20 parts by weight based on 100 parts by weight of the total, and more advantageously in an amount of 5 to 15 parts by weight.
- the curing agent may be added to form a dense cured film in terms of physical properties of the coating film, and the curing agent is preferably an amine-based curing agent.
- the amine-based curing agent may be a melamine-based curing agent.
- the melamine-based curing agent is hexa(N-butoxy)methylmelamine, hexa(Iso-butoxy)methylmelamine, hexa(N-propyl)methylmelamine, hexa(Iso-propyl)methylmelamine, hexa It may be at least one selected from ethoxymethylmelamine and hexamethoxymethylmelamine. That is, the melamine-based curing agent may be used alone or as a mixture of two or more compounds.
- the content of the amine-based curing agent in the composition provided by the present invention is less than 3 parts by weight or exceeds 20 parts by weight, it may be disadvantageous to form a dense cured film.
- a pigment may be included in the composition to improve corrosion resistance of the coating film.
- the pigment (c) may include a mixture of a rust preventive pigment and a heat conductive pigment, and may include 1 to 20 parts by weight of each pigment with respect to 100 parts by weight of the total, more advantageously 5 to It may be included in 15 parts by weight.
- the rust-preventing pigment is preferably a silicate compound, and as an example, may be at least one of lithium polysilicate, sodium polysilicate, potassium polysilicate, and colloidal silica.
- the present invention is not limited thereto.
- the thermally conductive pigment is preferably a component capable of realizing black when forming a coating film, and in the present invention, it is preferably an organic-inorganic thermally conductive pigment.
- the organic-inorganic thermal conductive pigment may be one or more of carbon black, carbon nanotubes, graphite, and graphene, but is not limited thereto.
- the content of the anticorrosive pigment in the composition provided by the present invention is less than 1 part by weight, the corrosion resistance effect is insufficient, and when it exceeds 20 parts by weight, the corrosion resistance is improved, while the roughness of the coating film is increased to deteriorate the workability.
- the content of the thermally conductive pigment in the composition is less than 1 part by weight, the hiding rate and heat radiation characteristics of the material by forming a coating film may be lowered, whereas if the content exceeds 20 parts by weight, the viscosity of the applied solution increases and workability This decreases and it is difficult to obtain a beautiful surface appearance.
- the average particle diameter is preferably 10 to 100 nm, more advantageously, 10 to 30 nm in consideration of dispersibility.
- the average particle diameter is 3 to 30 ⁇ m, more advantageously 5 to 20 ⁇ m.
- the graphite may have various shapes, such as granular, plate-like, bulky, flake-like, and there is no problem in applying any of these shapes. However, in order to provide excellent thermal conductivity of the coating film to be produced, it is preferably in the form of flakes.
- the average particle diameter of the pigment particles satisfy the range of 20 ⁇ 5 ⁇ m based on the dry film thickness of the composition.
- a catalyst may be included as an accelerator of the curing reaction.
- the (d) catalyst may include a mixture of an acid catalyst and an amine-based catalyst, and may be included in an amount of 0.05 to 3.0 parts by weight and 0.05 to 5.0 parts by weight, respectively, based on 100 parts by weight of the total.
- the acid catalyst may be a material blocked with organic chains that can be dissociated by heat, and sulfonic acid may be preferably used, but is not limited thereto.
- the sulfonic acid may be p -toluenesulfonic acid, dodecylbenzenedisulfonic acid, dinonyltoluenedisulfonic acid, dinonylnaphthalenesulfonic acid, or a mixture thereof. In the case of the mixture, two or more compounds may be mixed.
- an epoxy resin-based compound or an amine-based compound may be used as a material for the blocking.
- dinonylsulfonic acid (a material having a dissociation temperature of 160° C. or higher and an activity of 30% from King Co., USA) shielded with an epoxy resin may be used.
- the amine-based catalyst may be divided into primary amines (NH 2 -R 1 ), secondary amines (NH-R 1 ,-R 2 ), and tertiary amines (NR 1 ,-R 2 ,-R 3 ). , wherein the substituted hydrocarbon (R 1 ,R 2 ,R 3 ) may be an aliphatic or aromatic chain.
- the amine-based catalyst is not limited thereto, but diethylamine, diisopropylamine, diisopropanolamine, di-n-propylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine , diallylamine, diamylamine, N-ethyl-1,2-dimethylpropylamine, N-methylhexylamine, di-n-octylamine, piperidine, 2-pipeline, 3-piecholine, 4 - may be piecholine, morpholine, or a mixture thereof.
- a predetermined pattern can be formed on the surface of the coating film by the composition provided in the present invention, and in this case, the amine-based catalyst plays a main role.
- a predetermined pattern may be formed on the surface due to the difference in curing rate between the inside of the coating film and the surface during the curing reaction at a high temperature after the composition is applied. It is preferable to select and use a material with high volatility.
- the content of the acid catalyst in the composition provided in the present invention is less than 0.05 parts by weight or the content of the amine-based catalyst is less than 0.05 parts by weight, the curing temperature of the coating film becomes excessively high and the physical properties of the coating film cannot be maintained.
- the amount of the acid catalyst exceeds 3.0 parts by weight or the content of the amine-based catalyst exceeds 5.0 parts by weight, curing occurs rapidly or the stability of the solution over time is deteriorated.
- wax when wax is included in the paint, it is used for the purpose of improving the friction properties of the paint film, but in the present invention, it is meaningful to use it for the purpose of forming a predetermined pattern when the paint film is cured after the solution is applied. there is.
- the wax (e) may be included in an amount of 0.05 to 5.0 parts by weight, more advantageously, 0.1 to 3.0 parts by weight based on 100 parts by weight of the total.
- insoluble wax that does not dissolve well in an organic solvent.
- Insoluble wax exists in a solid state at room temperature and low temperature and is evenly distributed in the paint.
- a difference in local surface tension occurs depending on the presence or absence of a wax component on the surface of the coating film, and wax molecules It can be a starting point at which a pattern such as a wrinkle is formed.
- the insoluble wax is not limited thereto, but may be one or more of polyethylene, polypropylene, polyvinyl acetate, polystyrene, polystyrene-acrylonitrile, acrylic polymer, and polytetrafluoroethylene wax.
- the content of the wax in the composition provided by the present invention is less than 0.05 parts by weight, wrinkles or irregularities are widely formed and it is difficult to form a certain pattern, whereas when the content exceeds 5.0 parts by weight, the patterns such as wrinkles or irregularities are too narrow It becomes impossible to obtain a homogeneous texture.
- a solvent may be included in the balance other than the above-combined components for ease of operation and control of viscosity.
- the solvent toluene, xylene, isopropanol, solvent naphtha, cellosolve, cellosolve acetate, butyl cellosolve, etc. may be used, and these solvents may be used alone or as a mixture of two or more thereof.
- the viscosity of the composition is controlled according to the content of the solvent, the amount of the solvent is not particularly limited, and the content may be adjusted according to a technique commonly used in the art.
- the content of the solvent can be adjusted in consideration of the coating amount (application amount) control and adhesion of the composition, for example, to be adjusted to a viscosity that takes 20 to 200 seconds to be discharged from the DIN cup (DIN, 53211). It is advantageous in terms of productivity.
- the present invention provides a composite resin composition (composition 1) containing all of the above-mentioned components and a composite resin composition (composition 2) excluding some catalysts and wax components from the components.
- the composition 2 may include (a) a main resin composed of a modified polyester resin, (b) a curing agent, (c) a pigment composed of a rust preventive pigment and a thermally conductive pigment, and (d) a catalyst composed of an acid catalyst.
- Composition 2 excludes amine-based catalysts and wax components that affect the surface shape of a dry coating film obtained after application and curing of the composition, and the dry coating film formed by Composition 2 does not have a predetermined pattern, that is, It may have a flat surface shape.
- each of the components is the same as described above, a detailed description thereof will be omitted.
- the content of each component is also the same as described above, and it is revealed that the content of the excluded component compared to the composition 1 can be replaced with the remaining component.
- the remainder other than the above-described components may include a solvent, and the solvent is the same as described above.
- each of Composition 1 and Composition 2 is applied to a specific substrate to form a dry coating film, for the purpose of further improving the physical properties of the substrate, an additive may be further added as necessary.
- an additive may be further added as necessary.
- any composition may further contain at least one of a pigment aggregation inhibitor, an antifoaming agent, and a leveling agent.
- additives are components generally known in the art of the present invention, and their blending ratio is not particularly limited, and those skilled in the art will be able to appropriately mix these additives as needed.
- a composite resin coated steel sheet formed with a predetermined coating layer (coating layer) by applying the above composite resin composition according to another aspect of the present invention will be described in detail.
- the plated steel sheet can be applied as a substrate on which each of the above-described composite resin compositions can be applied to different surfaces.
- each composite resin composition may be applied to both surfaces of the plated steel sheet, and thus a heat dissipation film layer on one side (first side) and a weather resistance layer on the other side (second side) may be included. .
- the heat dissipation coating layer formed on the first surface of the plated steel sheet may be formed from Composition 1 including a wax component among the composite resin compositions, and the weathering coating layer formed on the second surface is the wax component. and composition 2 excluding some catalyst components.
- the composite resin coated steel sheet provided in the present invention can be applied to a structure such as a roof or wall of a solar cell.
- the second surface of the weathering coating layer can be bonded to the solar module (Solar Module).
- the first surface corresponds to the lower surface
- the second surface corresponds to the upper surface
- the second surface may be naturally exposed to the external environment.
- the heat of the solar cell is effectively radiated to lower the surface temperature.
- the weather resistance is excellent, and there is an advantage that it can be used in an external environment for a long period of time.
- the heat dissipation coating layer and the weathering coating layer may each have a thickness of 3 to 40 ⁇ m based on a dry coating thickness, and more advantageously, a thickness of 5 to 30 ⁇ m.
- each coating layer is less than 3 ⁇ m, the color, hiding power, processability and solvent resistance of the coating film formed by the composite resin composition are low. On the other hand, if the thickness exceeds 40 ⁇ m, the manufacturing cost increases and workability is low There is a problem with losing.
- the plated steel sheet may be a galvanized steel sheet.
- the galvanized steel sheet include, but are not limited to, hot-dip galvanized steel sheet (GI), alloyed hot-dip galvanized steel sheet (GA), electro-galvanized steel sheet (EG), alloyed aluminum-coated steel sheet (Al-Zn, Al- Zn-Si) and an alloyed hot-dip galvanized steel sheet (Zn-Al-Mg) may be used.
- the alloyed aluminum plated steel sheet may have a plating layer composed of Al-55%Zn, Al-8%Zn-0.3%Si, and the alloyed hot-dip galvanized steel sheet is a ternary (Zn-xAl- yMg) As a plated steel sheet, it may have a plating layer composed of Zn-(1.0 ⁇ 3.0%)Al-(1.0 ⁇ 5.0%)Mg.
- the present invention is not limited thereto.
- a plated steel sheet may be prepared first.
- the plated steel sheet may be a galvanized steel sheet, and the type thereof is the same as described above, and thus is omitted here.
- the composite resin composition may be applied to both surfaces of the plated steel sheet prepared according to the above, and at this time, the composition 1 containing the wax component is applied to the lower surface corresponding to the first surface of the plated steel sheet, while the plating Composition 2 excluding wax components and some catalysts is preferably applied to the second surface of the steel sheet, that is, the upper surface.
- the second surface of the plated steel sheet is a surface to be bonded to a practical object to be applied in the present invention, that is, a solar module.
- any method well known as a composition application method may be applied.
- a bar-coater, a roll coater, a slot-die coater, and a curtain coater may be applied.
- the final composite resin coated steel sheet can be manufactured by baking and drying the plated steel sheet coated with the composite resin composition of the present invention on each side according to the above.
- the drying temperature may be performed in a temperature range of 180 to 260° C. based on the Peak Metal Temperature (PMT) of the plated steel sheet. If the baking temperature during drying is less than 180°C based on PMT, the reaction between the inorganic material and the resin in the composition is not sufficient and the coating layer is not robust. There is a problem that the performance is inferior.
- PMT Peak Metal Temperature
- any method generally known in the art may be used. However, although not limited thereto, for example, it may be performed by a hot air heating method, an infrared heating method, or an induction heating method.
- the coated composition may be dried by hot air treatment at 200 to 340° C. for 10 to 50 seconds at an ambient temperature.
- the method is an induction heating method, it can be dried for 5 to 20 seconds with a frequency range of 5 to 50 MHz and power of 3 to 15 KW.
- the composite resin coated steel sheet of the present invention may be additionally coated in consideration of the workability and corrosion resistance of the plated steel sheet corresponding to the substrate, and an additional coating film may be formed thereon.
- the pretreatment layer and the undercoat layer may be sequentially formed on one or both surfaces of the plated steel sheet, and in this case, only the undercoat layer may be formed except for the pretreatment layer.
- the composite resin composition of the present invention is applied on the pretreatment layer and/or the undercoat layer to form a composite resin coating layer (preferably a heat dissipation coating layer, a weathering coating layer) intended in the present invention.
- a composite resin coating layer preferably a heat dissipation coating layer, a weathering coating layer
- Such a coated steel sheet may have an effect of further improved workability.
- the pretreatment layer and/or the undercoat layer may be located between the plated steel sheet and the composite resin coating layer to be ultimately formed in the present invention.
- the composite resin coating layer may be referred to as a top coating layer.
- FIG. 1 is a cross-sectional side view of a composite resin coated steel sheet formed using the composite resin composition provided in the present invention, and the coating layer made of the composition may have a black color.
- the pretreatment layer and/or the undercoat layer additionally formed on the upper (upper) and lower (lower) surfaces of the plated steel sheet in which the zinc-based plating layer is formed on both sides is a steel sheet and a composite resin. It is possible to increase the adhesion with the coating layer by the composition, and to provide physical properties required for the steel sheet, such as workability and corrosion resistance of the steel sheet.
- the composition for forming the pretreatment layer and the undercoat layer is not particularly limited, and any coating film known to be applicable between the steel sheet and the composite resin coating layer in the art may be used.
- Fig. 1 (b) shows a side cross-sectional view when one surface of the composite resin coated steel sheet is bonded to the solar module.
- the surface bonded to the solar module is a weathering coating layer with a flat surface
- the opposite surface is a heat dissipation coating layer having a predetermined pattern such as a wrinkle pattern or a concave-convex structure.
- the composite resin composition was prepared as follows.
- a urethane-modified polyester resin (average molecular weight: 10000 to 30000, hydroxyl value 30, acid value 10 mgKOH/g) is prepared in an amount of 30 to 50 parts by weight based on 100 parts by weight of the total composition, and here, a melamine curing type (Hexamethoxymethyl Melamine, HMMM) is prepared.
- Organic solvents (ketone and ester-based petrochemical solvents) were used as solvents for each composition.
- a composite resin-coated steel sheet on which a coating layer was formed by using each of the solutions prepared as described above was prepared as follows.
- each of the plated steel sheets shown in Table 2 (single-sided plating amount 60 g/m 2 ) was prepared, and then a pretreatment layer and an undercoat layer were sequentially formed on both sides of the plated steel sheet.
- the pretreatment solution was roll-coated so that the dry film adhesion amount was 100 ⁇ 50 mg/m 2 , and hot air dried at 100° C. to form a pretreatment layer, and the primer solution was roll-coated to a dry film thickness of 5 ⁇ 2 ⁇ m.
- PMT After baking and drying at 210°C, it was cooled to form a base coat layer.
- amine A composition solution excluding the catalyst and wax component was applied, and a composition solution capable of forming a heat dissipation film layer was applied to the lower surface.
- the thickness of the coating layer formed by using the above-described composition solution was measured with a non-destructive portable coating film thickness gauge.
- the pencil hardness was evaluated by using a Mitsubishi pencil (HB-4H), and after drawing a 10cm line at a 45° angle with a load of 1000 ⁇ 10g, the occurrence of scratches was evaluated.
- Corrosion resistance was evaluated by the complex salt spray method (Cyclic Corrosion Test, CCT). At this time, after performing salt spray (concentration 5%, spray pressure condition of 1 kg/cm 2 at 35°C) for 5 hours at 95% relative humidity, drying at 30% relative humidity and 70°C for 2 hours, and then The process of treatment for 3 hours at 95% humidity and 50 ° C. was set to 1 cycle, and after 100 cycles were repeated, the area of occurrence of red rust on the surface of the coated steel sheet was evaluated.
- CCT Complex Salt spray method
- Evaluation criteria are 0% of the corrosion area: ⁇ , 5% or less of the corrosion area: ⁇ , more than 5% of the corrosion area ⁇ 30%: ⁇ , more than 30% of the corrosion area: ⁇ .
- the workability evaluation was carried out by OT-bending, in which the coated steel sheet was placed in a vise and bent 180° with a pressure of 1 kgf as bending workability, and then tightened until it became flat. Then, after attaching a scotch tape to the bent surface of the coating film, when the coating film was peeled off, the occurrence of cracks on the peeled surface of the tape and the presence or absence of peeling of the coating film were evaluated.
- Evaluation criteria are: No cracks and peeling of the sub-coating film: ⁇ , No microcracks and no peeling in the coating film: ⁇ , severe cracking and no peeling: ⁇ , severe cracking and peeling of the coating film: ⁇ .
- the surface roughness was measured using a three-dimensional roughness meter (Leica, DCM8).
- the evaluation criteria can be evaluated as 10 ⁇ m or more: ⁇ , 7 ⁇ m or more to less than 10 ⁇ m: ⁇ , 5 ⁇ m or more to less than 7 ⁇ m: ⁇ , and less than 5 ⁇ m: ⁇ according to the measured roughness value.
- a 5% hydrochloric acid solution was applied to the coating film, the surface was covered, and the periphery was shielded with Vaseline, and then left at 25° C. for 24 hours, and then the state of the coating film was evaluated.
- the state with no trace at all was set at 5, and the state where the entire surface was peeled off was set as 1, and 1, 2, 3, 4, and 5 were evaluated according to the degree of peeling.
- 5% sodium hydroxide solution was applied to the coating film, the surface was covered, and the periphery was shielded with Vaseline, and then the state of the coating film was evaluated after leaving it at 25° C. for 24 hours.
- the state with no trace at all was set at 5, and the state where the entire surface was peeled off was set as 1, and 1, 2, 3, 4, and 5 were evaluated according to the degree of peeling.
- the evaluation criteria are maintained at 90% or more of gloss compared to initial gloss: ⁇ , 85% or more and less than 90%: ⁇ , 80% or more and less than 85%: ⁇ , less than 80%: ⁇ indicated.
- Thermal diffusivity and thermal conductivity were measured according to the KS L 1604:2017 test method using the laser flash method (LFA 457 of NETZSCH).
- the thermal emissivity was measured according to the KS L 2514:2011 test method using an FT-IR spectrometer (DIMAC M4500).
- heat dissipation evaluation was measured by manufacturing a test device simulating a solar module.
- the test apparatus was made of Styrofoam (a, insulation) having a thickness of 26 mm and a size of 340 ⁇ 265 ⁇ 195 mm, and the inside was coated with aluminum foil (b).
- an infrared lamp (c) was installed in the center of the bottom of the test apparatus, and a thermometer (d) was installed in the middle between the infrared lamp and the upper end of the test apparatus.
- the specimen (e) of the coated steel sheet was prepared by cutting it into a size of 150 cm in width ⁇ 150 cm in length, and it was attached to the upper surface opened to be 50 mm ( ⁇ ) in the infrared lamp of the measuring device and sealed.
- the alloy-coated steel sheet for contrast with the coated steel sheet corresponds to the 'contrast steel material' in Tables 2 and 3, and is a Zn-1.5%Al-1.5%Mg coated steel sheet, which is only pre-treated on the plating layer, and the undercoat layer and It is an alloyed hot-dip galvanized steel sheet without forming a composite resin coating layer.
- the weather resistance is the measurement result for the heat dissipation film layer
- the heat resistance characteristic shows the measurement result for the material itself on which the heat dissipation film layer and the weather resistance film layer are formed.
- the composite resin coated steel sheet (invention steel 1 to 28) in which a heat dissipation film layer and a weather resistance film layer are formed on one surface of the plated steel sheet using the composite resin composition provided in the present invention (invention steel 1 to 28) It can be seen that the weather resistance as well as the heat radiation characteristics were excellently displayed.
- the surface on which the weathering coating layer is formed is bonded to the solar module, while the heat dissipation coating layer is formed on the opposite surface to effectively radiate the heat of the module surface to lower the surface temperature, It has the effect of being suitably applicable as a building-integrated roofing material or wall with excellent weather resistance.
- the coated steel sheets (comparative steels 1 to 4) manufactured using a composition that was not in the composition of the present invention showed a significantly lower heat dissipation temperature compared to the invention steel due to poor heat emissivity.
- FIG. 2 is a photograph of the surface and cross-section of the coating layer of Inventive Steel 10 and Comparative Steel 1, particularly of the heat dissipation coating layer, measured with a microscope (optical microscope, scanning electron microscope (SEM)).
- the 'left arrow' indicates the primer coating layer
- the 'middle and right arrows' indicate the heat dissipation coating layer (heat dissipation coating layer).
- Comparative Steel 1 is very low compared to Inventive Steel 10.
- FIG. 5 is a graph showing the temperature change according to the measurement time in evaluating heat dissipation.
- the Invention Steel 10, Comparative Steel 1, and Comparative Steel were compared with a reference material corresponding to an untreated specimen (a pure plated steel sheet that was not treated with a pre-treatment or undercoat at all).
- the contrast steel material in which the coating film layer by the composition according to the present invention is not formed at all has a very insignificant heat dissipation effect even over time.
- Comparative Steel 1 although the heat dissipation effect can be confirmed, it can be seen that the effect does not reach about Inventive Example 10 corresponding to the present invention.
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Abstract
Description
Claims (19)
- 전체 100 중량부에 대해서,(a) 변성 폴리에스테르 수지로 이루어진 주제수지 20~60중량부,(b) 경화제 3~20중량부,(c) 안료: 방청 안료 1~20중량부, 열전도성 안료 1~20중량부,(d) 촉매제: 산 촉매 0.05~3.0중량부, 아민계 촉매 0.05~5.0중량부,(e) 왁스 0.05~5.0중량부 및(d) 잔부 용매를 포함하며,건조 도막 표면에 주름 무늬 또는 요철 구조를 형성하는 내후성 및 열방사 특성이 우수한 복합수지 조성물.
- 제 1항에 있어서,상기 아민계 촉매 및 왁스를 제외하여 포함하고,건조 도막 표면에 주름 무늬 또는 요철 구조가 미형성된 내후성 및 열방사 특성이 우수한 복합수지 조성물.
- 제 1항에 있어서,상기 변성 폴리에스테르 수지는 평균 분자량(Mw)이 5000~50000인 내후성 및 열방사 특성이 우수한 복합수지 조성물.
- 제 1항에 있어서,상기 변성 폴리에스테르 수지는 20~60의 수산(OH)기를 가지며, 1~20mgKOH/g의 산가를 가지는 내후성 및 열방사 특성이 우수한 복합수지 조성물.
- 제 1항에 있어서,상기 경화제는,헥사(N-부톡시)메틸멜라민, 헥사(Iso-부톡시)메틸멜라민, 헥사(N-프로필)메틸멜라민, 헥사(Iso-프로필)메틸멜라민, 헥사에톡시메틸멜라민 및 헥사메톡시메틸멜라민 중 선택된 1종 이상의 멜라민계 경화제인 내후성 및 열방사 특성이 우수한 복합수지 조성물.
- 제 1항에 있어서,상기 방청 안료는 실리케이트 화합물로서, 리튬 폴리실리케이트, 소디움 폴리실리케이트, 포타슘 폴리실리케이트 및 콜로이달 실리카 중 1종 이상이며,상기 열전도성 안료는 흑색의 유-무기 안료로서, 카본블랙, 카본나노튜브, 그래파이트(graphite) 및 그래핀(graphene) 중 1종 이상인 내후성 및 열방사 특성이 우수한 복합수지 조성물.
- 제 1항에 있어서,상기 산 촉매는 유기 사슬로 블록(block)화된 술폰산으로, p-톨루엔술폰산, 도데실벤젠다이술폰산, 디노닐톨루엔디술폰산, 디노닐나프탈렌술폰산 또는 이들의 혼합물인 내후성 및 열방사 특성이 우수한 복합수지 조성물.
- 제 7항에 있어서,상기 블록(block)화는 에폭시 수지계 또는 아민계 화합물을 이용하는 것인 내후성 및 열방사 특성이 우수한 복합수지 조성물.
- 제 1항에 있어서,상기 아민계 촉매는 1차 아민(NH2-R1), 2차 아민(NH-R1,-R2), 3차 아민(N-R1,-R2,-R3)으로 구분되고, 치환된 탄화수소(R1,R2,R3)는 지방족 혹은 방향족 사슬인 내후성 및 열방사 특성이 우수한 복합수지 조성물.
- 제 9항에 있어서,상기 아민계 촉매는 디에틸아민, 디이소프로필아민, 디이소프로판올아민, 디-n-프로필아민, 디-n-부틸아민, 디이소부틸아민, 디-2차-부틸아민, 디알릴아민, 디아밀아민, N-에틸-1,2-디메틸프로필아민, N-메틸헥실아민, 디-n-옥틸아민, 피페리딘, 2-피페콜린, 3-피에콜린, 4-피에콜린, 몰폴린 또는 이들의 혼합물인 내후성 및 열방사 특성이 우수한 복합수지 조성물.
- 제 1항에 있어서,상기 왁스는 불용성 왁스로서,폴리에틸렌, 폴리프로필렌, 폴리비닐아세테이트, 폴리스티렌, 폴리스티렌-아크릴로니트릴, 아크릴고분자 및 폴리테트라플로로에틸렌 왁스 중 하나 이상인 내후성 및 열방사 특성이 우수한 복합수지 조성물.
- 제 1항 또는 제 2항에 있어서,안료응집 방지제, 소포제 및 레벨링제 중 1종 이상을 추가로 포함하는 내후성 및 열방사 특성이 우수한 복합수지 조성물.
- 도금강판;상기 도금강판의 제1면에는 방열도막층; 및상기 도금강판의 제2면에는 내후도막층을 포함하며,상기 방열도막층은 제 1항의 조성물에 의해 형성되어 표면에 주름 무늬 또는 요철 구조가 형성되며, 상기 내후도막층은 제 2항의 조성물에 의해 형성되는 것인 복합수지 코팅강판.
- 제 13항에 있어서,상기 제2면의 내후도막층은 태양광 모듈과 접합하는 면인 복합수지 코팅강판.
- 제 13항에 있어서,상기 방열도막층과 내후도막층의 건조 도막 두께는 각각 3~40㎛인 복합수지 코팅강판.
- 제 13항에 있어서,상기 도금강판은 아연도금강판이며,상기 아연도금강판은 용융아연도금강판(GI), 합금화 용융아연도금강판(GA), 전기아연도금강판(EG), 합금화 알루미늄도금강판(Al-Zn, Al-Zn-Si), 합금화 용융아연도금강판(Zn-Al-Mg) 중 어느 하나인 복합수지 코팅강판.
- a) 도금강판을 준비하는 단계;b) 상기 도금강판의 제1면에 제 1항의 조성물을 도포하고, 제2면에 제 2항의 조성물을 도포하는 단계; 및c) 상기 제1면 및 제2면에 도포된 조성물을 PMT(Peak Metal Temperature) 기준 180~260℃에서 건조하는 단계를 포함하며,상기 제2면은 태양광 모듈과 접합하는 면인 복합수지 코팅강판의 제조방법.
- 제 17항에 있어서,상기 조성물을 도포하는 단계는, 바-코터, 롤 코터, 스롯 다이(Slot-Die) 코터, 및 커튼 코터 중 하나의 방법으로 행하는 것인 복합수지 코팅강판의 제조방법.
- 제 17항에 있어서,상기 조성물을 건조하는 단계는, 열풍가열방식, 적외선가열방식 또는 유도가열방식으로 행하는 것인 복합수지 코팅강판의 제조방법.
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CN202180066550.1A CN116249748A (zh) | 2020-09-28 | 2021-09-24 | 耐候性和热辐射特性优异的复合树脂组合物、复合树脂涂覆钢板及其制造方法 |
JP2023515739A JP2023542857A (ja) | 2020-09-28 | 2021-09-24 | 耐候性及び熱放射特性に優れた複合樹脂組成物、複合樹脂コーティング鋼板及びその製造方法 |
US18/025,779 US20230348712A1 (en) | 2020-09-28 | 2021-09-24 | Composition resin composition having excellent weather resistance and heat-radiation characteristics, composite-resin-coated steel sheet and method for manufacturing same |
EP21872950.7A EP4219636A4 (en) | 2020-09-28 | 2021-09-24 | COMPOSITE RESIN COMPOSITION HAVING EXCELLENT WEATHER RESISTANCE AND HEAT RADIATION CHARACTERISTICS, COMPOSITE RESIN COATED STEEL SHEET AND MANUFACTURING METHOD THEREFOR |
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- 2021-09-24 JP JP2023515739A patent/JP2023542857A/ja active Pending
- 2021-09-24 CN CN202180066550.1A patent/CN116249748A/zh active Pending
- 2021-09-24 EP EP21872950.7A patent/EP4219636A4/en active Pending
- 2021-09-24 US US18/025,779 patent/US20230348712A1/en active Pending
- 2021-09-24 WO PCT/KR2021/013054 patent/WO2022065922A1/ko active Application Filing
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2023
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EP4219636A4 (en) | 2024-02-21 |
EP4219636A1 (en) | 2023-08-02 |
KR20220043962A (ko) | 2022-04-06 |
KR20230158436A (ko) | 2023-11-20 |
CN116249748A (zh) | 2023-06-09 |
JP2023542857A (ja) | 2023-10-12 |
US20230348712A1 (en) | 2023-11-02 |
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