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WO2018012883A1 - Verre à faible émissivité - Google Patents

Verre à faible émissivité Download PDF

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Publication number
WO2018012883A1
WO2018012883A1 PCT/KR2017/007476 KR2017007476W WO2018012883A1 WO 2018012883 A1 WO2018012883 A1 WO 2018012883A1 KR 2017007476 W KR2017007476 W KR 2017007476W WO 2018012883 A1 WO2018012883 A1 WO 2018012883A1
Authority
WO
WIPO (PCT)
Prior art keywords
glass
dielectric layer
low
reflective metal
layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/KR2017/007476
Other languages
English (en)
Korean (ko)
Inventor
강현민
오영훈
윤윤희
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
KCC Corp
Original Assignee
KCC Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by KCC Corp filed Critical KCC Corp
Publication of WO2018012883A1 publication Critical patent/WO2018012883A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
    • C03C17/3657—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating having optical properties
    • C03C17/366—Low-emissivity or solar control coatings
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
    • C03C17/3626—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer one layer at least containing a nitride, oxynitride, boronitride or carbonitride
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
    • C03C17/3636—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer one layer at least containing silicon, hydrogenated silicon or a silicide
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
    • C03C17/3642—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating containing a metal layer
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
    • C03C17/3649—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer made of metals other than silver
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
    • C03C17/3652—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the coating stack containing at least one sacrificial layer to protect the metal from oxidation

Definitions

  • the present invention relates to low-emissivity glass.
  • Low-emissivity glass can be classified into two types according to the manufacturing method, soft low-E glass by the sputtering process and hard Roy by atmospheric pressure chemical vapor deposition (Atmospheric Pressure Chemical Vapor Deposition).
  • Hard Low-E There is glass.
  • Hard Roy has the advantage that post coating is possible because it is an oxide film produced at high temperature, and it is free to handle.However, due to the low electrical conductivity of the coating film, it has a decisive disadvantage that insulation and shielding performance is lower than that of soft Roy. There is a limit to large-scale dissemination.
  • the coating film is relatively excellent in insulation and shielding performance, and is composed of a multilayer film including various auxiliary films. It has the advantage of being able to supply products of various characteristics.
  • low-emission glass is favored by Neutral-based colors, which have little color rather than outstanding colors.
  • low-emission glass used in construction is important for outdoor color, that is, the color of glass. It is becoming.
  • the present invention includes a dual functional reflective metal layer having a specific thickness ratio, thereby providing a low-emissivity glass having an emissivity of 0.01 to 0.03 and a visible light transmittance of 40% or more and implementing a neutral color.
  • the low radiation glass of the present invention is a glass coated with a first dielectric layer, a first functional reflective metal layer, a second dielectric layer, a second functional reflective metal layer, and a third dielectric layer sequentially on a glass substrate, and reflects infrared rays or solar rays.
  • the sum of the thicknesses of the first and second functional reflective metal layers is 20 to 35 nm, and the ratio of the thickness of the first functional reflective metal layer to the total thickness of the first and second functional reflective metal layers is 55% to 65%.
  • the low-emission glass of the present invention while implementing a neutral color, it is possible to secure a high thermal performance of the emissivity of 0.01 to 0.03 and the visible light transmittance of 40% or more.
  • FIG. 1 shows a schematic view of the low-emissive glass of the present invention.
  • Figure 2 shows a schematic view of the low-emissive glass prepared in the embodiment of the present invention.
  • 3 is a graph showing color change according to the ratio of the first functional reflective metal layer (Ag layer).
  • the low radiation glass of the present invention is a glass coated with a first dielectric layer, a first functional reflective metal layer, a second dielectric layer, a second functional reflective metal layer, and a third dielectric layer sequentially on a glass substrate, and reflects infrared rays or solar rays.
  • the sum of the thicknesses of the first and second functional reflective metal layers is 20 to 35 nm, and the ratio of the thickness of the first functional reflective metal layer to the total thickness of the first and second functional reflective metal layers is 55% to 65%.
  • the low-emissive glass of the present invention includes the first and second functional reflective metal layers, and the thickness of the functional reflective metal layer has a specific ratio, thereby having excellent thermal performance and optical properties.
  • the low-emissive glass of the present invention may include other coating layers in addition to the functional absorbing metal protective layer and the dielectric layer, and is not limited to the description of the present invention.
  • the low-emissivity glass of the present invention is a multilayer comprising a plurality of coating layers on the glass substrate, ie, main dielectric layer, sub-dielectric layer, functional absorbing metal protective layer, functional reflective metal layer and top protective layer as shown in FIG.
  • a plurality of coating layers may be formed.
  • the glass substrate used for the low-emissivity glass of the present invention conventional glass such as soda-lime glass used for building or automobiles can be used.
  • the glass having a thickness of 2 to 12 mm may be used depending on the purpose of use, but is not limited thereto.
  • the first, second and third dielectric layers each contain Si-based nitride containing at least one element selected from Zr, Sn, Nb, Al, Sb, Mo, Cr, Ti and Ni.
  • At least one sub-dielectric layer comprising a main dielectric layer comprising and a Zn-based oxide containing at least one element selected from Sn, Nb, Al, Sb, Mo, Cr, Ti, and Ni, wherein the main dielectric layer is thicker than the sub dielectric layer. May be thick.
  • the main dielectric layer of each of the first to third main dielectric layers blocks Na + diffused from the lower soda lime glass during heat treatment for reinforcement and bending, and blocks oxygen or ions transferred to the metal layer. .
  • the main dielectric layer may contain at least one Si-based nitride selected from Zr, Sn, Nb, Al, Sb, Mo, Cr, Ti, and Ni, such as Si-based nitride containing Al.
  • the main dielectric layers of the first dielectric layer and the third dielectric layer are positioned on the low emission glass of the present invention, and the thickness of the main dielectric layers of the first and third dielectric layers may be 10 to 30 nm.
  • the main dielectric layer thickness of the second dielectric layer positioned between the first dielectric layer and the main dielectric layer of the third dielectric layer may be 70 to 90 nm. If the thickness of the main dielectric layer of the second dielectric layer is out of the above range, it is out of the thickness ratio of the first and second functional reflective metal layers described above, so that it is difficult to realize neutral colors, and the color change depending on the viewing angle is severe.
  • the low-emissive glass of the present invention includes first and second functional reflective metal layers coated between the dielectric layers, respectively, and reflecting infrared rays or solar rays.
  • the material of the functional reflective metal layer can be any one selected from Ag, Au, Cu, Al, Pt and combinations thereof, for example Ag. Ag best matches high transmittance and good durability in the visible region.
  • the functional reflective metal layer serves to selectively transmit or reflect the solar ray (IR) region.
  • the sum of the thicknesses of the first and second functional reflective metal layers may be 20 to 35 nm, and the thickness ratio of the first functional reflective metal layer close to the glass substrate is 55% to 65 relative to the total thickness of the first and second functional reflective metal layers. Can be%. If the sum of the thickness of the functional reflective metal layer is out of the above range, it may be difficult to implement the emissivity 0.01 ⁇ 0.03 required in the present invention, and if the thickness ratio is out of the above range, it may be difficult to implement the neutral color.
  • the low-emissive glass of the present invention is located on each of the top and bottom surfaces of the first and second functional reflective metal layers and includes Ni alloy or Ni alloy nitride containing one or more elements selected from Cr, Ti, Cu, Nb and Zr. It may include a first to fourth functional absorbing metal protective layer.
  • the functional absorbing metal protective layer serves as a barrier that prevents the movement of O 2 in the air during heat treatment for reinforcement and bending, and helps the reflective metal layer to have stable behavior even under high heat treatment conditions.
  • first and second functional absorbing metal protective layers are disposed on the lower and upper surfaces of the first functional reflective metal layer, and third and fourth functional absorbing metal protective layers are disposed on the lower and upper surfaces of the second functional reflective metal layer. This can be located.
  • the thickness of each functional absorbing metal protective layer may be 0.5 to 5 nm. If it is out of the thickness range, it may be difficult to implement a visible light transmittance of 40%.
  • the low-emissivity glass of the present invention is located on the upper surface of the first main dielectric, the upper surface and the lower surface of the second main dielectric, and the lower surface of the third main dielectric, and includes Sn, Nb, Al, Sb, Mo, Cr, Ti, and Ni. It may include a sub-dielectric layer comprising a Zn-based oxide containing one or more elements selected from, for example, Zn-based oxide containing Al.
  • the sub-dielectric layer is deposited on and under the reflective metal layer to induce crystallization of the reflective metal layer well. Also, when the reflective metal layer is heat-treated, it prevents the diffusion of oxygen gas into the upper and lower dielectric layers, and optically such as agglomeration. It serves to suppress the occurrence of defects.
  • a first sub dielectric layer is positioned on an upper surface of the first main dielectric
  • a second sub dielectric layer and a third sub dielectric layer are disposed on a lower surface and an upper surface of the second main dielectric layer, and a lower surface of the third main dielectric layer.
  • the fourth sub dielectric layer may be located at.
  • the thickness of each of the sub dielectric layers may be 5 to 20 nm. If the thickness is out of the above range, the crystallization of the reflective metal layer may not be performed well.
  • the low emissive glass of the present invention may comprise a top protective layer located on the top surface of the third main dielectric and containing an oxide, nitride or nitride oxide containing at least one element selected from Ti, Zr and Si, for example TiOxNy.
  • y / x ⁇ 1 for example, x: y may be 100 mol%: 0 mol% to 75 mol%: 25 mol% based on 100 mol% of the sum of x and y.
  • the top protective layer serves to reduce surface roughness, increase scratch resistance, and increase mechanical and chemical durability of the coating film.
  • the thickness of the uppermost protective layer is 2 to 15 nm, for example 2 to 9 nm. If the thickness is less than 2 nm, the durability may be lowered. If the thickness is more than 15 nm, the transmittance may be reduced or cause blurring.
  • the low-emissive glass of the present invention may have a * and b * values of the glass surface reflection color at ⁇ 7 to 1, an emissivity of 0.01 to 0.03, and a visible light transmittance of 40% or more at an observation angle of 0 ° to 55 °. .
  • CIE L * a * b * is an indicator that expresses the amount of color based on the value measured by the spectrophotometer. It is used to express the brightness and chromaticity of the color. L * indicates the brightness of the color by the metering amount, and a * means red, minus green, b * yellow, and minus blue.
  • the first main dielectric layer was first coated on 6 mm thick transparent glass at a thickness of 15 nm under nitrogen / argon atmosphere.
  • the first sub-dielectric layer was then coated at 10 nm under argon / oxygen atmosphere.
  • the first functional absorbing metal protective layer was coated to a thickness of 1 nm, and the first functional reflective metal layer Ag was coated to 15 nm under an argon atmosphere.
  • a second functional absorbing metal protective layer was coated with a thickness of 1 nm on the first functional reflective metal layer, and then the second sub dielectric layer and the second main dielectric layer were coated with 10 nm and 80 nm, respectively.
  • the third sub dielectric layer was coated at 10 nm under an argon / oxygen atmosphere on the upper surface of the second main dielectric layer, and the third functional absorbing metal protective layer was coated at a thickness of 1 nm. Thereafter, the second functional reflective metal layer was coated with 9 nm, and the fourth functional absorbing metal protective layer was coated with 1 nm. The fourth sub-dielectric layer was coated with 10 nm and the third main dielectric layer with 15 nm. Finally, the upper protective layer was coated with a thickness of 7 nm under an argon nitrogen atmosphere to prepare the low-emissive glass of Example 1.
  • Example 2 After fixing the total thickness of the first functional reflective metal layer and the second functional reflective metal layer to 31 nm, the same ratio as in Example 1 was applied except that the ratio of the first and second functional reflective metal layers was changed as shown in Table 1 below.
  • the low-emissivity glasses of Examples 2 and 3 were prepared by the method.
  • first, second and third main dielectric layers Si-based nitride including Al
  • first, second, third and fourth sub-dielectric layers Zn-based oxides including Al
  • Top protection layer TiOxNy containing TiOx ceramic material
  • the glass sample of the prepared example was heat-treated in the following manner.
  • a general tempered furnace used for producing tempered glass the glass bottom was maintained at a temperature of about 600 to 700 ° C., the glass sample was passed through, heated for about 5 minutes, and then heat treated under quenching conditions.
  • visible light transmittance and reflectance color were measured according to D65 standard light source 10 degrees KS L 2514 standard, and emissivity was measured by FT-IR.
  • Emissivity is a value measured by Ag which is a solar-ray reflective metal layer, and shows one evaluation property which can measure the performance as a low emission glass after heat processing.
  • the low-emissivity glass of the embodiment according to the present invention is excellent in thermal performance, suitable for use in architectural glass, etc., and also shows a neutral (Neutral) glass surface color in front and side observation.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Surface Treatment Of Glass (AREA)

Abstract

La présente invention concerne un verre à faible émissivité dans lequel une première couche diélectrique, une première couche métallique réfléchissante fonctionnelle, une deuxième couche diélectrique, une deuxième couche métallique réfléchissante fonctionnelle et une troisième couche diélectrique sont appliquées de manière séquentielle sur un substrat en verre, et qui comprend des double couches métalliques réfléchissantes fonctionnelles possédant un rapport d'épaisseur spécifique, possédant ainsi une émissivité de 0,01 à 0,03 et une transmissivité de la lumière visible de 40 % ou plus et présentant une couleur neutre.
PCT/KR2017/007476 2016-07-13 2017-07-12 Verre à faible émissivité Ceased WO2018012883A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020160088392A KR101975637B1 (ko) 2016-07-13 2016-07-13 저방사 유리
KR10-2016-0088392 2016-07-13

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WO2018012883A1 true WO2018012883A1 (fr) 2018-01-18

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PCT/KR2017/007476 Ceased WO2018012883A1 (fr) 2016-07-13 2017-07-12 Verre à faible émissivité

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WO (1) WO2018012883A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102433169B1 (ko) * 2018-09-12 2022-08-16 (주)엘엑스하우시스 창호용 기능성 건축 자재 및 복층 유리
KR102531278B1 (ko) * 2018-11-27 2023-05-11 (주)엘엑스하우시스 창호용 기능성 건축 자재 및 복층 유리
KR102485862B1 (ko) * 2020-08-21 2023-01-09 한국유리공업 주식회사 다층 박막 코팅이 구비된 투명 기재
KR102474951B1 (ko) * 2020-09-28 2022-12-07 한국유리공업 주식회사 다층 박막 코팅이 구비된 투명 기재

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5557462A (en) * 1995-01-17 1996-09-17 Guardian Industries Corp. Dual silver layer Low-E glass coating system and insulating glass units made therefrom
KR20100098199A (ko) * 2009-02-27 2010-09-06 주식회사 케이씨씨 열처리후 흐림 현상이 감소된 열처리 가능한 저방사 유리 및 그 제조방법
KR20130051521A (ko) * 2011-11-09 2013-05-21 주식회사 케이씨씨 열처리 가능한 저방사 유리 및 그 제조방법
KR20150065740A (ko) * 2012-10-04 2015-06-15 가디언 인더스트리즈 코퍼레이션. 낮은 가시광 투과율을 갖는 저-e 코팅 제품
KR20160043991A (ko) * 2013-08-16 2016-04-22 가디언 인더스트리즈 코퍼레이션. 낮은 가시투과율을 갖는 저-e 코팅을 포함하는 코팅 제품

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7901781B2 (en) 2007-11-23 2011-03-08 Agc Flat Glass North America, Inc. Low emissivity coating with low solar heat gain coefficient, enhanced chemical and mechanical properties and method of making the same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5557462A (en) * 1995-01-17 1996-09-17 Guardian Industries Corp. Dual silver layer Low-E glass coating system and insulating glass units made therefrom
KR20100098199A (ko) * 2009-02-27 2010-09-06 주식회사 케이씨씨 열처리후 흐림 현상이 감소된 열처리 가능한 저방사 유리 및 그 제조방법
KR20130051521A (ko) * 2011-11-09 2013-05-21 주식회사 케이씨씨 열처리 가능한 저방사 유리 및 그 제조방법
KR20150065740A (ko) * 2012-10-04 2015-06-15 가디언 인더스트리즈 코퍼레이션. 낮은 가시광 투과율을 갖는 저-e 코팅 제품
KR20160043991A (ko) * 2013-08-16 2016-04-22 가디언 인더스트리즈 코퍼레이션. 낮은 가시투과율을 갖는 저-e 코팅을 포함하는 코팅 제품

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KR20180007424A (ko) 2018-01-23

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