JP2017109483A - Heat shielding material, and heat shielding composition and heat shielding structure prepared therewith - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an improved heat shielding material that satisfies the requests of excellent solar reflectance and heat resistance.SOLUTION: The present invention provides a heat shielding material. The heat shielding material comprises a sheet material, and a pigment layer that covers the sheet material. The pigment layer comprises a crosslinked structure formed from a siloxane functional group, and a pigment dispersed in the crosslinked structure. There are also provided a heat shielding composition and a heat shielding structure prepared therewith.SELECTED DRAWING: Figure 1

Description

CROSS REFERENCE TO RELATED APPLICATIONS The entire disclosures of which are incorporated herein by reference.

  The present invention relates to a heat shielding material, a heat shielding composition using the same, and a heat shielding structure.

  The global climate is changing greatly due to global warming. Energy savings and carbon dioxide reduction are the most effective response strategies. At present, thermal barrier materials are important green energy products mainly used for building roofs, exterior walls and windows.

  About 40% of sunlight enters the room through the roof or outer wall. The white roof is an ideal cool roof because of its high solar reflectance. In practice, however, dark roofs are used more in consideration of the appearance and light pollution. Dark heat insulating materials depend on imports from overseas, so they are expensive and have few options. Also, the solar reflectance and heat resistance provided by the existing dark thermal barrier coating are insufficient.

US Pat. No. 8,361,597 US Pat. No. 8,394,498 US Pat. No. 8491985 US Pat. No. 8,679,617 U.S. Pat. No. 8,034,432

  One object of the present invention is to provide an improved thermal barrier material that meets the requirements of good solar reflectance and heat resistance.

  In order to achieve the above and other objects, embodiments of the present invention provide a thermal barrier material comprising a sheet material and a pigment layer covering the sheet material. The pigment layer includes a crosslinked structure formed from siloxane functional groups and a pigment dispersed in the crosslinked structure.

  Another embodiment of the present invention provides a thermal barrier composition comprising 1 part by weight of the thermal barrier material and 0.1 to 300 parts by weight of a solvent.

  Yet another embodiment of the present invention provides a thermal barrier structure including a substrate and a thermal barrier layer disposed on the substrate. The heat shield layer includes the heat shield material regularly arranged in the resin. The thermal barrier materials are parallel to each other and substantially parallel to the surface of the substrate. The weight ratio between the heat shielding material and the resin is 0.02 to 10.

  According to the present invention, the total solar reflectance (TSR) and the heat shielding property of the heat shielding material are improved. Furthermore, according to the invention, the shielding material also has a low L-value.

  The following embodiments will be described in detail with reference to the accompanying drawings.

The invention can be more fully understood by reading the following detailed description and examples with reference to the accompanying drawings.
2 is a cross-sectional view of a thermal barrier material according to an exemplary embodiment. FIG. FIG. 2 is a schematic view of a heat shield material during a reaction process according to an exemplary embodiment. 2 is a cross-sectional view of a thermal barrier structure according to an exemplary embodiment. FIG.

  In the following disclosure, numerous embodiments or examples are described to implement different features of the described subject matter. In the following, specific components and example arrangements are described to simplify the invention. These are, of course, merely examples and are not intended to be limiting. For example, in the following description, an embodiment in which the first feature and the second feature are formed in direct contact with each other to form the first feature above or above the second feature, and Embodiments can be included in which additional features can be formed between the first and second features such that the one and second features cannot be in direct contact. Further, in this disclosure, reference numbers and / or letters may be repeated in various examples. This repetition is made for the sake of brevity and clarity, and does not itself identify the relationship between the various embodiments and / or configurations described.

  The quality of the thermal barrier coating mainly depends on the solar reflectance (eg TSR) of the thermal barrier coating. The TSR of the white coating is about 90%, and the coating film formed using it can reflect most infrared (IR). In contrast, the TSR of the black coating is less than 10%, and the coating film formed using it has a poor ability to reflect infrared (IR).

  According to an embodiment of the present invention, the present invention provides a heat shielding material, a heat shielding composition using the same, and a heat shielding structure. The heat shielding material of the present invention is a sheet material formed by being covered with a pigment layer. The heat-shielding material can improve the total solar reflectance (TSR) of the obtained heat-shielding composition and the heat-shielding structure and reduce the L-value, and is widely applied to buildings, walls, roofs or automobiles. It can be done.

  FIG. 1 is a cross-sectional view of a thermal barrier material 100 according to an exemplary embodiment of the present invention. As shown in FIG. 1, an embodiment of the present invention provides a thermal barrier material 100 that includes a sheet material 102 and a pigment layer 104. The pigment layer 104 covers the sheet material 102. According to some embodiments, the sheet material 102 used in the present invention includes mica, synthetic mica, hygrophilite, kaolin clay, montmorillonite, silicon dioxide, sheet metal oxides, Slate flakes, aluminum silicate salt, or combinations thereof may be included. According to some embodiments, the average particle size of the sheet material 102 of the present invention can be 0.1-300 μm, such as 5-80 μm. According to some embodiments, the average aspect ratio (length / thickness value) of the sheet material 102 used in the present invention may be 10-100, such as 20-80. If the average aspect ratio of the sheet material 102 of the present invention is too high (that is, greater than 100), the dispersibility is deteriorated and the surface of the coating film becomes rough. If the average aspect ratio of the sheet material 102 of the present invention is too low (that is, smaller than 10), the shielding performance is deteriorated and the effect is insufficient.

In the embodiment of the present invention, the pigment layer 104 covering the sheet material 102 includes a crosslinked structure formed of siloxane functional groups and a pigment dispersed in the crosslinked structure. According to some embodiments, the siloxane functionality used in the present invention may comprise the chemical formula Si (OR) ₄ . In the formula, each R may independently be H or an alkyl group, and the alkyl group may be, for example, a C ₁ -C ₈ alkyl group.

  The siloxane functional group may include tetraethoxysilane (TEOS), methyltriethoxysilane (MTES), n-octyltriethoxysilane, or combinations thereof. After being hydrolyzed, the siloxane functional group can comprise OH groups. According to some embodiments, the pigments used in the present invention may include black pigments, red pigments, blue pigments, green pigments, yellow pigments, or combinations thereof. Each of these colored pigments can be used alone or in combination. In one Embodiment, the compounding ratio (weight ratio) of a black pigment and another coloring pigment can be 0.1-5. Examples of the black pigment used in the present invention include aniline black, carbon black, sungite, lamp black, vine black, bone black, graphite, mars black, iron titanium. Brown Spinel (Iron Titanium Brown Spinel), Cobalt Black (Cobalt Black), Manganese Black (Manganese Black), Chrome Green Black Hematite (Chromium Green Black Hematite), Zinc Sulfide, Mineral Black (Mineral Black) , Tin Antimony Gray (Tin Antimon Gray), titanium vanadium antimony gray (Titanium Vanadium Antimony Gray), cobalt nickel gray (Cobalt Nickel Gray), manganese ferrite black (Manganese Ferrite Black), iron cobalt chromite black (Iron Cobrate Chrome black) ), Iron cobalt black (Iron Cobalt Black), chrome iron nickel black (Chrome Iron Nickel Black), paliogen black (Paligen Black), perylene black (Perylene Black), iron manganese oxide (Iron M) nganese Oxide), molybdenum disulfide (Molybdenum Disulfide), titanium dioxide black (Titanium Dioxide Black), or may include a combination thereof.

  Red pigments used in the present invention include Toluidine Red, Permanent Red R, Naphthol Red DK, Permanent Red Y, Naphthol Crimson Red AS-TR, Permanent Red F4R, Naphthol AS Red, Permanent Bordeaux TRR, Toluidine Maroon, Permanent Bordeaux FGR, Permanent Maroon Medium Red, Permanent Maroon Medium Red, Permanent Maroon Medium Red (Permanent Maroon Medium Red) ), Gmentent Red 21, Naphthol Red Bright, Naphthol Red Dark, Naphthol Red Extra Dark, Pigment Red 32, Pyrazolone Red, Ariculium Sul , Pigment Red 47, Permanent Red BB, Permanent Red BB [FIAT], Irgalite Red 2BY, Permanent Red 2B, Lithol Red LN, Barium Lithol Red, Calcium Risol Red, Calcium Redol Red Pigmenture 52.1, Pigment Red 52.2, Lake Red C, Pigment Lake Red C, Sodium Lithol Rubin, Risol Rubin, Pigment Red 57: 2, Pigment Red 58: 4, Permanent Rose 9, Pigment Scarlet, Lake Carmine L, Pigment Carmine 3B, Pigment Red 63, Lithol Bordeaux G, Lithor Bordeaux G, Lithor Bordeaux G Rhodamine) 6G, rhodamine 6G [FIAT], rhodamine YS, loader Min YS PTMA, Alizarin Crimson, Alizarin Lake, Indo Red, Thioindigo Violet, Vermilionette, Geranium Red, Gerani A Red D, Mercadium red, Mercadium Lithopone Red, Pigment Red 114, Naphthol Red FG, Naphthol Red MEG-DR, Quinacridone Red, Perylene Scarlet (Perylene) Condensed Red (Azo Condensation Red), Permanent Carmine, Perylene Red BX, Pigment Red 150, Naphthol Carbamide, Anthraquinone Scarlet, Anthraquinquinone Red Benzimidazolone Bordeaux, D & C Red No. 3 Aluminum Lake, Rhodamine Red, Pigment Red 174, Benzimidazolone Red HFT, Benzimidazolone Carmine, Anthraquinone Red, Perylene Maroon, Pigment Red 4BS, Pyrrole Red, Pyraz Pyrrole Scarlet, Organic Nickel Violet, Shimura Fast Red, Pyrrole Red Rubin, or combinations thereof may be included.

  Blue pigments used in the present invention include Victoria Blue, Victoria Blue SMA, Pigment Blue 9, Phthalocyanine Blue, Phthalocyanine Alpha Blue, Heliogen Blue, and Heliogen Blue. Blue L7560, Phthalocyanine Cyan, Pigment Blue 25, Prussian Blue, Cobalt Blue, Ultramarine Blue, Copper Carbon, E Blue Blue, E (Smalt), Manganese Blue, Copper sulfide, Cerulean Blue, Cobalt Chromite, Zinc Cobalt Chrom Aluminum Spin, Reflex Blue (Reflex Blue) A5L-G, Fastogen Blue (Fastogen Blue) 5007, Zirconium Vanadium Blue, Cobalt Zinc Aluminate Blue (Cobalt Zinc Aluminate Blue), Cobalt Silicate Blue (Cobalt Blue) irate Blue), Chromofine Blue 5000P, Fastogen Blue 10GN, Aluminum Chloro-phthalocyanine, Hosta Palm Blue Cobalt RinR Blue T Blue Spinel), or a combination thereof.

  Examples of the green pigment used in the present invention include Pigment Green 1, Fast Green Lake, 3606 Fast Green Lake, Phthalocyanine Green BS, Nitroso Green, and Nickel-Azo. Yellow (Nickel Azo Yellow), phthalochrome green (Pthalochrome Green), cadmium green (Cadmium Green), chrome green (Chrome Green), zinc green (Zinc Green), chrome oxide green (Chrome Oxide Green) black Chromium Green B ack Hematite, Viridian, Cobalt Green, Verdigris, Emerald Green, Copper Arsenite, Green Earth, Green, Ultramarine Cobalt Chromite Green, Phthalocyanine Green YS, Copper Carbonate Hydroxide, Copper Ferrocyanide, Chromocyanin green, Chromocyanin green Victoria Green Garnet, Nickel Green Olivene, or combinations thereof may be included.

  Examples of yellow pigments used in the present invention include Hansa Yellow G, Monolite Yellow G, Hansa Yellow GR, Hansa Yellow 10G, Allide Yellow 13G, Hansa Yellow 5G, Hansa Yellow. 3G, Azo Yellow 2GX, Hansa Yellow R, Benzidine Yellow G, Benzidine Yellow GR, Diarylide Yellow AAOT, Permanent Yellow NCG, Diary Lily Yellow ) 17, C.I. I. Pigment Yellow 21, Flavorthrone Yellow, Lead Oxychloride, Barium Chromate, Strontium Chromate, Calcium Chromate, Lead Chromate (Lead Chrom sulfate) Lead chromate with lead sulfate, cadmium yellow (cadmium yellow), cadmium lithopone yellow, zinc yellow (Zinc Yellow), basic zinc yellow (Basic cell Zinc yellow) Deep (C dmium-Barium Yellow Deep), Tin Sulfide, Opiment, Realgar, Aureolin, Naples Yellow, Yellow Iron Oxide, Natural Iron Oxide Natural Yellow Iron Oxide, Basic cadmium chromate, Iron Chromate, Massicot Lithium, Lead Titanate, Nickel lead, Cyanamide lead Titanium Yellow Rutile (Nic el Antimony Titanium Yellow Rutile), Diarylide Yellow AAPT, Pigment Yellow 61, Pigment Yellow 62, Pigment Yellow 62: 1, Suimei Yellow 3G, Hansa Yellow 65, Allied Yellow GX, Allied Yellow 5GX, Allied Yellow, Disazo Condensed Yellow (Disazo Condensation Yellow), Diarylide Yellow H10G, Diarylide Yellow HR, Diarylide Yellow 1285, Disazo Yellow 3G, Chromophthal Yellow (Chromophthal Yellow) 6G, Disazo Yellow GR, Diarylide Yellow FGL, Diarylide Yellow, Tartrazine Lake (Tartrazine Lake), Lumogen Yellow, FD & C Yellow 6, D & C Yellow No. 10 rakes, Anthrapyrimidine Yellow, Isoindole Yellow, Isoindolinone Yellow, Hansa Brilliant Yellow, Flannel Yellow, Flavtron Yellow Yellow 10, Helio Fast Yellow ER, Paliotol Yellow, Chrome Titanium Yellow, Zinc Iron Yellow, PV Fast Yellow (Fa) t Yellow) H2G, Diarylide Yellow DGR, Benzidine Yellow GRL, DCC Diarylide Yellow, Azo Condensation Yellow, Irgazin Yellow, Pigment Yellow 130, Pigment Yellow 133, Pigment Yellow 134, Pigment Yellow 136, Isoindoline Yellow, Quinophthalone Yellow, Pigment Yellow 147, Filamid Yellow 4G, Nickel Azo Yellow, Benzimidazolone Yellow low) H4G, Diarylide Yellow 152, Nickel Dioxime Yellow, Benzimidazolone Yellow 154, Benzimidazolone Yellow 155, Benzimidazolone Yellow 156, Dipyroxide Yellow, Suzuvanadium Yellow (Tin Vanadium Yellow), Zirconium Prasodymium Silicate Yellow, Zirconium Vanadium Yellow, Nickel Niobium Titanium Yellow (Nickel Niobium Titanium Yellow) Tungsten Titanium Buff, Chromium Tungsten Titanium Buff, Manganese Antimony Titanium Buff Rutile, Yellow Titanium Buff Rutile, Manganese Antimony Titanium Buff Rutile Yellow (Chromofine Yellow), Seikafast Yellow A-3, Azo Yellow 168, Lionol Yellow (Lionol Yellow) K-2R, Pigment Yellow FRN, Lionol Yellow NBK, Irgalite Yellow LBT, Benzimidazolone Yellow H6G, Diaryl Yellow (Diaryl Yellow), Pigment Yellow 179, Benzimidazolone Yellow, Benzimidazo Golden, Sandolin Yellow (Sandorin Yellow), Pariotole Yellow K227, bismuth yellow vanadate Yellow), Irgalite Yellow, Nickel Titanate, Paliitol Yellow K1570, Pigment Brilliant Yellow HGR, Chromophthal Yellow, Sandofil Yellow, Anthraquinone Yellow, Novo Palm Yellow (N voperm Yellow) F2G, San Glow Yellow (Sunglow Yellow), Pigment Yellow 204, Neolor Yellow, Solaplex Yellow, titanium zinc antimony stannate (Titanium Zinc Antimony Stannate), or may include a combination thereof.

  In one embodiment of the present invention, the pigment layer 104 and the sheet material 102 form chemical bonds, such as Si—O—Si bonds, with siloxane functional groups. Further, since the intermolecular force is between the pigment 106 and the crosslinked structure, the pigment 106 adheres to the crosslinked structure by this intermolecular force and is dispersed in the crosslinked structure. Therefore, due to the above-described chemical bonds and intermolecular forces, the pigment 106 and the pigment layer 104 formed of a crosslinked structure can cover the sheet material 102 more completely and stably, and the resulting shielding. It can contribute to improvement of TSR% of the thermal composition and the thermal barrier structure.

  The heat shielding material 100 provided by the present invention can be formed by using a sol-gel method. For example, the siloxane functional group, the acid, the sheet material, and the pigment are first mixed, and then the mixture is subjected to heat treatment, whereby the above-described heat shielding material 100 of the present invention can be formed. In the following, specific examples are described for illustrative purposes, but are not intended to limit the present invention.

  In one embodiment of the present invention, tetraethoxysilane (TEOS), acid, sheet material 102, and pigment 106 are mixed, and then the heat treatment is performed on the mixture to form the heat shielding material 100. In the reaction process, TEOS first reacts with an acid, and four OR groups bonded to Si are hydrolyzed into four OH groups. At this time, one of the OH groups reacts with the OH group on the surface of the sheet material 102 to form a hydrogen bond. An intermolecular force is formed between the other three OH groups and the pigment 106, which causes the pigment 106 to adhere to the OH group as shown in FIG. Next, heat treatment is performed. The Si—OH condensation reaction of the siloxane functional group produces a Si—O—Si bond, thereby forming a crosslinked structure. The pigment 106 attached to the OH group is trapped and dispersed in a cross-linked structure formed with siloxane functional groups. At this time, the cross-linked structure and the pigment 106 dispersed therein form the pigment layer 104. The pigment layer 104 covers the sheet material 102. Furthermore, Si—O—Si bonds are also formed between the surface of the sheet material 102 and the siloxane functional group during the sol-gel reaction. Therefore, the pigment layer 104 can cover the sheet material 102 more completely and stably by this chemical bond, and can contribute to improvement of TSR% of the obtained heat shielding composition and the heat shielding structure.

The siloxane functional group used in the present invention in the sol-gel reaction is not limited to tetraethoxysilane (TEOS) and may be other suitable siloxane functional groups. In one embodiment, the siloxane functional group may comprise the chemical formula Si (OR) ₄ . In the formula, each R may independently be H or an alkyl group.

  In one embodiment, the siloxane functional group used in the present invention may be methyltriethoxysilane (MTES), n-octyltriethoxysilane, or a combination thereof. According to some embodiments, the acid used in the sol-gel reaction can include hydrochloric acid, nitric acid, acetic acid, sulfuric acid, or combinations thereof. According to some embodiments, the sheet material 102 includes mica, synthetic mica, hygrophilite, kaolin clay, montmorillonite, silicon dioxide, sheet metal oxides, plate flakes (slate flakes). ), Aluminum silicate salt, or a combination thereof. However, the sheet material 102 of the present invention is not limited to these, and any sheet material having an average aspect ratio of 10 to 100 can be applied to the present invention. According to some embodiments, the pigment 106 includes black pigments such as aniline black, carbon black, sungite, lamp black, vine black, bone black, graphite, Mars Black, Iron Titanium Brown Spinel (Iron Titanium Brown Spinel), Cobalt Black (Cobalt Black), Manganese Black (Manganese Black), Chrome Green Black Hematite (Chromium Green Black Hematite, Zinc Sulfide) Black), Slate Black, antimony tin Gray (Tin Antimony Gray), Titanium Vanadium Antimony Gray (Titanium Vanadium Antimony Gray), Cobalt Nickel Gray (Cobalt Nickel Gray), Manganese Ferrite Black, Iron Cobalt Chromium Black (Copper Chromite Black), Iron Cobalt Black (Iron Cobalt Black), Chrome Iron Nickel Black (Chrome Iron Nickel Black), Paliogen Black (Palylene Black), Perylene Black (Perylene Black), Manganese oxide (Iron Manganese Oxide), molybdenum disulfide (Molybdenum Disulfide), titanium dioxide black (Titanium Dioxide Black), or may include a combination thereof. It should be noted that these examples are merely illustrative and that the scope of the invention is not limited thereto.

  In the present invention, the number of OH groups is increased by adding siloxane functional groups and acids to the reaction, causing the pigment to react with more OH groups. It has been found that when the sheet material, siloxane functional group, and pigment are mixed directly without adding an acid, hydrolysis does not occur easily, and thus no sol-gel reaction occurs. Intermolecular force is formed between the pigment and the OH group on the surface of the sheet material, but steric hindrance is caused by the siloxane functional group, so that the number of pigments adhering to the sheet material surface is not large. Conversely, when the sheet material, siloxane functionality, and pigment are mixed with the acid, hydrolysis is accelerated. In such a case, the sol-gel reaction occurs. Before the Si-O-Si bond is formed, the steric hindrance caused by the hydrolyzed siloxane functional group is small, so intermolecular forces are easily formed between the pigment and the OH group on the sheet material surface. Therefore, the pigment adheres to the sheet material. Furthermore, as described above, the hydrolyzed siloxane functional group not only forms a hydrogen bond with the OH group on the sheet material, but the remaining OH group of the hydrolyzed siloxane functional group also exerts intermolecular forces with the material. And the material can be attached to the sheet material. Thus, the addition of an acid allows the pigment to react with more OH groups and more fully covers the sheet material.

  Another embodiment of the present invention provides a thermal barrier composition. In the present invention, the ratio of each reactive substance in the thermal barrier composition can be adjusted according to the desired characteristics of the thermal barrier composition. For example, 1 part by weight of the heat shielding material 100 and 0.1 to 300 parts by weight of the solvent can be used to form the heat shielding composition. Alternatively, 1 part by weight of the aforementioned heat shielding material 100 and 1 to 1000 parts by weight of the solvent can be used to form the heat shielding composition. According to some embodiments, the solvents used in the present invention include methanol, ethanol, isopropanol, n-butanol, methyl ethyl ketone, acetone, cyclohexane, methyl tertiary butyl ketone, diethyl ether, ethylene glycol dimethyl ether, glycol ether, Ethylene glycol monoethyl ether, tetrahydrofuran (THF), propylene glycol monomethyl ether acetate (PGMEA), ethyl-2-ethoxyethanol acetate, 3-ethoxypropionate, isoamyl acetate, ethyl acetate, butyl acetate, chloroform, pentane, n- Hexane, cyclohexane, heptane, benzene, toluene, xylene, or combinations thereof can be included.

  The heat shielding composition may further contain a resin. The amount of the resin can be adjusted according to the characteristics of the desired heat shielding composition and the thickness of the coating layer formed from the heat shielding composition. For example, the amount of resin may be 0.1 to 60 parts by weight or 1 to 45 parts by weight. The resin used in the present invention includes polyester resin, polyimide resin, acrylic resin, epoxy resin, silicone resin, phenoxy resin, urethane resin, urea resin, acrylonitrile butadiene styrene resin (ABS resin), polyvinyl butyral resin (PVB resin), A polyether resin, a fluorine-containing resin, a polycarbonate resin, a polystyrene resin, a polyamide resin, starch, cellulose, a copolymer thereof, or a mixture thereof may be included. Further, 0.1 to 3 parts by weight, for example, 0.5 to 2 parts by weight, of a dispersant can be optionally added to the heat shielding composition to improve the TSR% of the resulting heat shielding composition. The dispersant may be a polymer type dispersant, such as ethylene vinyl acetate copolymer, ethylene vinyl acetate copolymer mixture, ethylene acrylic acid copolymer, polyamide / polyethylene oxide copolymer mixture, polyethylene copolymer, Or it may be a combination thereof.

  It should be noted that even without the addition of a dispersant, the thermal barrier composition of the present invention already has a much superior TSR% compared to commercially available dark thermal barrier materials. However, TSR% of the thermal barrier composition of the present invention can be further improved by adding a dispersant. These results appear to be obtained because the thermal barrier material tends to produce a unidirectional alignment in the presence of the dispersant.

  FIG. 3 is a cross-sectional view of a thermal barrier structure 200 according to an exemplary embodiment of the present invention. As shown in FIG. 3, one embodiment of the present invention provides a thermal barrier structure 200 that includes a substrate 202 and a thermal barrier layer 204 disposed on the substrate 202. The thermal barrier layer 204 includes the thermal barrier material 100 regularly arranged in the resin 206. The weight ratio between the heat shielding material 100 and the resin 206 is 0.02 to 10. The thermal barrier materials 100 are parallel to each other and substantially parallel to the surface of the substrate 202. It should be noted that the angle between the planar direction of the heat shielding material 100 and the surface of the substrate 202 is not larger than 10 degrees when the above-described heat shielding material 100 is substantially parallel to the surface of the substrate 202. The condition can be included.

  According to some embodiments, the substrate 202 of the present invention may be any solid substrate, for example, metal, iron plate, steel plate, galvanized steel, aluminum alloy, magnesium alloy, lithium alloy, semiconductor, glass, ceramics. Rigid substrate such as cement, roof tile, silicon substrate, or PES (polyether sulfone), PEN (polyethylene naphthalate), PE (polyethylene), PI (polyimide), PVC (polyvinyl chloride), PET A flexible substrate such as a plastic substrate such as (polyethylene terephthalate), a resin, or a combination thereof can be used. The resin 206 used in the present invention includes polyester resin, polyimide resin, acrylic resin, epoxy resin, silicone resin, phenoxy resin, urethane resin, urea resin, acrylonitrile butadiene styrene resin (ABS resin), and polyvinyl butyral resin (PVB resin). , Polyether resin, fluorine-containing resin, polycarbonate resin, polystyrene resin, polyamide resin, starch, cellulose, copolymers thereof, or mixtures thereof.

  In the present invention, the thickness of the heat shield layer 204 can be adjusted according to various applications, and thereby a heat shield structure having desired characteristics can be obtained. For example, the thickness of the thermal barrier layer 204 can be 50 to 1000 nm or 200 to 600 nm. Furthermore, a dispersant can be optionally added to the heat shield layer 204 to improve the TSR% of the resulting heat shield layer 204. The dispersant may be a polymer type dispersant, such as ethylene vinyl acetate copolymer, ethylene vinyl acetate copolymer mixture, ethylene acrylic acid copolymer, polyamide / polyethylene oxide copolymer mixture, polyethylene copolymer, Or it may be a combination thereof. The weight ratio between the heat shielding material 100 and the dispersant can be 0.3 to 10, for example, 0.5 to 5.

  The thermal barrier material 100 of the present invention has a two-dimensional structure, and a thermal barrier layer 204 is coated on the substrate 202 using a specific coating process, and the thermal barrier material 100 is regularly formed on the substrate 202. Can be arranged. For example, regular coating application processes include blade coating, bar coating, wire bar coating, brush coating, roller coating, spray coating, flow coating, and other applicable regular arrays. Application processes, or a combination thereof. In one embodiment of the present invention, the L-value of the resulting thermal barrier structure 200 may be less than 30, such as less than 25 or less than 20. In one embodiment of the present invention, the TSR% of the resulting thermal barrier structure 200 is greater than 20%, such as greater than 30%, greater than 35%, greater than 40%, or greater than 45%. It can be.

  Since the heat shielding material provided by the present invention is formed by advancing the sol-gel reaction with siloxane functional group, acid, sheet material and pigment in one step, the process is easier. The step of applying the coating material containing the pigment on the inner material and the subsequent curing step are not necessary. In addition, the pigment layer covers the sheet material more completely and stably by the heat shielding material formed in the present invention. Furthermore, the resulting thermal barrier structure comprises a high TSR% (> 20%), a high thermal barrier and a low L-value (L <30). Therefore, the present invention provides a heat shielding material having sufficient TSR% and heat shielding properties.

  Hereinafter, examples and comparative examples will be described in detail so that those skilled in the art can easily understand.

  Example 1

  1 g of tetraethoxysilane (TEOS), 1 g of mica (Mica M) (average particle size 5.72 μm, average aspect ratio 23.83), and 1 g of black pigment (BASF Palogen S0084) are sufficiently added to 100 mL of isopropanol (IPA). Mixed. Then 0.5 mL of 0.1N hydrochloric acid was added to the mixture. Next, the sol-gel reaction was allowed to proceed at room temperature (25 ° C.) for 3 hours, and then the temperature was raised to 80 ° C. and the reaction was further continued for 3 hours to produce a heat shielding material.

  Example 2

  1 g of tetraethoxysilane (TEOS), 1 g of mica (Mica M) (average particle size 5.72 μm, average aspect ratio 23.83), 0.05 g of black pigment (BASF Palogen S0084), and red pigment (Pigment red 224) 0. 05 g was added to 100 mL of isopropanol (IPA) and mixed well. Then 0.5 mL of 0.1N hydrochloric acid was added to the mixture. Next, the sol-gel reaction was allowed to proceed at room temperature (25 ° C.) for 3 hours, and then the temperature was raised to 80 ° C. and the reaction was further continued for 6 hours to produce a heat shielding material.

  Comparative Example 1

The same steps as in Example 1 were repeated except that mica (Mica M) was replaced with spherical titanium dioxide (TiO ₂ ) fine particles (average particle size 0.45 μm).

  Comparative Example 2

  In Comparative Example 2, commercially available thermal barrier nanoparticles (spherical particles, Shepherd 10C909A) were used.

  According to ISO 9050 (measurement of building glass-light transmittance, direct solar radiation transmittance, total solar energy transmittance, ultraviolet transmittance, and related glazing coefficient) and heat shielding materials of Example 1 and Comparative Example 1 and Comparative Example The TSR% of 2 commercially available thermal barrier nanoparticles was measured. Moreover, the haze of the heat-shielding material of Example 1 and Comparative Example 1 and the commercially available heat-shielding nanoparticles of Comparative Example 2 was measured by ASTM D1003. The L-value was then calculated. The L-value is a value used to represent the brightness of the color from 1 to 100 (brightness of color). The higher the L-value, the brighter the color, and the lower the L-value, the darker the color. The measurement results and L-values of TSR% are shown in Table 1.

Table 1: Comparison of different thermal barrier materials

As shown in Table 1, when mica (Mica M) was used as the sheet material, the obtained thermal barrier material had the highest TSR% and the lowest L-value. TiO ₂ particulates and mica (Mica M) are similar in particle size and color (white). Although the TSR% of the thermal barrier material formed of TiO ₂ fine particles and the thermal barrier material formed of mica (Mica M) are close, the L-value of the thermal barrier material formed of mica (Mica M) is remarkably small. It was. Compared to commercially available thermal barrier nanoparticles, the thermal barrier material formed of mica (Mica M) had a significantly higher TSR%.

  Example 3

  The same steps as in Example 1 were repeated except that mica (Mica M) was replaced with synthetic mica.

  Example 4

  The same steps as in Example 1 were repeated except that mica (Mica M) was replaced with hygrophilite.

Table 2: Comparison of thermal barrier materials made of sheet materials with different average aspect ratios

  As shown in Table 2, the TSR% of the heat shielding material formed of the sheet material having an average aspect ratio of 23.83, 70.55, and 74.12 is greater than 40% and greater than 45%. There was also a thing. In addition, the L-values of these heat shielding materials were all less than 30 and some were less than 25.

  Hereinafter, the heat shielding materials of Example 5 and Example 6 were produced using different siloxane functional groups. TSR% of the obtained heat shield material was measured by ISO 9050, and L-value of the obtained heat shield material was calculated by ASTM D1003. The results of comparing Example 1 and Examples 5 and 6 are shown in Table 3.

  Example 5

  The same steps as in Example 1 were repeated except that TEOS was replaced with MTES (Momentive; A162).

  Example 6

  The same steps as in Example 1 were repeated except that TEOS was replaced with n-octyltriethoxysilane (Momentive; A137).

Table 3: Comparison of thermal barrier materials formed with different siloxane functional groups

  As shown in Table 3, the TSR% of the thermal barrier materials formed with different siloxane functional groups were all greater than 20%, and the TSR% of the thermal barrier materials formed with TEOS and MTES was greater than 40%. . Moreover, all of the L-values of these heat shielding materials formed with different siloxane functional groups were less than 30 and some were less than 25.

  Example 7

  1 g of the heat shielding material of Example 1 and 5 g of acrylic resin (Eternal Materials Co., Ltd., ETERAC 7132-2-M-20) were mixed thoroughly. The mixture was coated on a metal substrate by a blade coating process and then dried at 100 ° C. for 10 minutes to form a heat shield structure. TSR% of the obtained heat shield structure was measured by ISO 9050, and L-value of the obtained heat shield structure was calculated by ASTM D1003.

  Example 8

  After thoroughly mixing 1 g of the heat shielding material of Example 1 and 1 g of the dispersant (DISPARLON, 4200-10), 5 g of acrylic resin (Eternal Materials Co., Ltd., ETERAC 7132-2-M-20) was added. In addition, it was thoroughly mixed. The mixture was applied onto galvanized steel by a blade application process and then dried at 100 ° C. for 10 minutes to form a heat shield structure. TSR% of the obtained heat shield structure was measured by ISO 9050, and L-value of the obtained heat shield structure was calculated by ASTM D1003.

  Comparative Example 3

  1 g of commercially available carbon black (Cabot ML) and 5 g of an acrylic resin (Eternal Materials Co., Ltd., ETERAC 7132-2-M-20) were mixed well. The mixture was applied onto galvanized steel by a blade application process and then dried at 100 ° C. for 10 minutes to form a heat shield structure. TSR% of the obtained heat shield structure was measured by ISO 9050, and L-value of the obtained heat shield structure was calculated by ASTM D1003.

  Table 4 shows the TSR% measurement results and L-values of Example 7, Example 8, and Comparative Example 3. The thicknesses of the heat shield layers of the heat shield structures of Example 7, Example 8, and Comparative Example 3 are the same.

  As shown in Table 4, irrespective of the presence or absence of addition of a dispersant, the TSR% of the heat shield structure formed of the heat shield material of Example 1 is higher than that of a heat shield structure formed of commercially available carbon black. It was big. Further, the L-values of these heat shielding structures were all less than 30. When the heat-shielding structure is formed of the heat-shielding material of Example 1 that does not contain a dispersant, the TSR% is 35.1%. As a result, the TSR% was improved to 42.6%. That is, TSR% of the heat shield structure was improved by about 7.5% compared to the case where no dispersant was included.

  The accelerated weathering (QUV) test was conducted on the heat shield structures of Example 7 and Example 8. As a result, it was found that TSR% of the heat shielding structure can be maintained even after 1000 hours of QUV irradiation. According to the standard of ASTM G154, the service life of the heat shield structure has reached 5 years.

  The thermal barrier material provided by the present invention includes a pigment layer that completely and stably covers the sheet material, which contributes to improvement of TSR%. In addition, the thermal barrier structure made from this thermal barrier material has improved total solar reflectance (TSR%> 40%), low L-value (L <30), and improved weather resistance. Therefore, it can be widely applied to buildings, walls, roofs, and automobiles.

  It will be apparent to those skilled in the art that various modifications and variations can be made to the disclosed methods and materials. It is intended that the specification and examples be considered as exemplary only, with a true scope of the invention being indicated by the following claims and their equivalents.

DESCRIPTION OF SYMBOLS 100 ... Thermal insulation material 102 ... Sheet material 104 ... Pigment layer 106 ... Pigment particle 200 ... Thermal insulation structure 202 ... Substrate 204 ... Thermal insulation layer 206 ... Resin

Claims (17)

A pigment layer that covers the sheet material, and includes a crosslinked structure composed of a siloxane functional group, and a pigment dispersed in the crosslinked structure;
Insulation material including.   The heat shielding material according to claim 1, wherein the pigment layer and the sheet material form a chemical bond by the siloxane functional group.   The heat shielding material according to claim 1 or 2, wherein there is an intermolecular force between the pigment and the crosslinked structure.   The heat-shielding material according to any one of claims 1 to 3, wherein an average aspect ratio of the sheet material is 10 to 100.   Examples of the sheet material include mica, synthetic mica, hygrophilite, kaolin clay, montmorillonite, silicon dioxide, sheet metal oxides, plate flakes, and aluminum silicate. The heat-insulating material according to any one of claims 1 to 4, wherein a salt) or a combination thereof is included. The heat-shielding material according to any one of claims 1 to 5, wherein the siloxane functional group is selected from compounds having the chemical formula Si (OR) ₄ (wherein each R is independently H or an alkyl group). .   The thermal barrier material according to claim 6, wherein the siloxane functional group is selected from tetraethoxysilane (TEOS), methyltriethoxysilane (MTES), n-octyltriethoxysilane, or a combination thereof.   The heat shielding material according to claim 1, wherein the pigment includes a black pigment, a red pigment, a blue pigment, a green pigment, a yellow pigment, or a combination thereof. 1 part by weight of the heat shielding material according to any one of claims 1 to 8,
0.1 to 300 parts by weight of solvent;
A heat shielding composition comprising:   Examples of the solvent include methanol, ethanol, isopropanol, n-butanol, methyl ethyl ketone, acetone, cyclohexane, methyl tertiary butyl ketone, diethyl ether, ethylene glycol dimethyl ether, glycol ether, ethylene glycol monoethyl ether, tetrahydrofuran (THF), propylene glycol. Monomethyl ether acetate (PGMEA), ethyl-2-ethoxyethanol acetate, 3-ethoxypropionate, isoamyl acetate, ethyl acetate, butyl acetate, chloroform, pentane, n-hexane, cyclohexane, heptane, benzene, toluene, xylene, or The heat-shielding composition according to claim 9, wherein a combination thereof is included.   The resin further includes 0.1 to 60 parts by weight, and the resin includes polyester resin, polyimide resin, acrylic resin, epoxy resin, silicone resin, phenoxy resin, urethane resin, urea resin, acrylonitrile butadiene styrene resin (ABS resin), The heat-shielding composition according to claim 9 or 10, comprising polyvinyl butyral resin (PVB resin), polyether resin, fluorine-containing resin, polycarbonate resin, polystyrene resin, polyamide resin, starch, cellulose, or a combination thereof.   It further includes 0.1 to 3 parts by weight of a dispersant, and the dispersant includes a polymer type dispersant, and the polymer type dispersant includes an ethylene vinyl acetate copolymer and an ethylene vinyl acetate copolymer mixture. The heat-shielding composition according to any one of claims 9 to 11, wherein an ethylene acrylic acid copolymer, a polyamide / polyethylene oxide copolymer mixture, a polyethylene copolymer, or a combination thereof is included. A substrate,
The heat shielding layer disposed on the substrate, which is regularly arranged in the resin, is parallel to each other and substantially parallel to the surface of the substrate. A thermal barrier layer comprising the thermal barrier material according to claim,
Including
The heat insulation structure whose weight ratio of the said heat insulation material and the said resin is 0.02-10.   The thermal barrier structure according to claim 13, wherein the substrate includes a rigid substrate or a flexible substrate.   The resin includes polyester resin, polyimide resin, acrylic resin, epoxy resin, silicone resin, phenoxy resin, urethane resin, urea resin, acrylonitrile butadiene styrene resin (ABS resin), polyvinyl butyral resin (PVB resin), polyether resin, The heat-insulating structure according to claim 13 or 14, comprising a fluorine-containing resin, a polycarbonate resin, a polystyrene resin, a polyamide resin, starch, cellulose, or a combination thereof.   The dispersant further includes a weight ratio of the heat-shielding material and the dispersant of 0.3 to 10, and the dispersant includes a polymer-type dispersant, and the polymer-type dispersant includes 16. An ethylene vinyl acetate copolymer, an ethylene vinyl acetate copolymer mixture, an ethylene acrylic acid copolymer, a polyamide / polyethylene oxide copolymer mixture, a polyethylene copolymer, or combinations thereof are included. The heat shield structure according to any one of the above items.   The thermal barrier structure according to any one of claims 13 to 16, wherein the L-value is <30, and the total solar reflectance (TSR) is> 20%.

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