HK1176961B - Near-infrared shielding coating agent curable at ordinary temperatures, near-infrared shielding film using same, and manufacturing method therefor - Google Patents
Near-infrared shielding coating agent curable at ordinary temperatures, near-infrared shielding film using same, and manufacturing method therefor Download PDFInfo
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- HK1176961B HK1176961B HK13103605.6A HK13103605A HK1176961B HK 1176961 B HK1176961 B HK 1176961B HK 13103605 A HK13103605 A HK 13103605A HK 1176961 B HK1176961 B HK 1176961B
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Description
Technical Field
The present invention relates to a coating agent for shielding near-infrared rays, which is curable at normal temperature. In addition, the present invention relates to a near-infrared shielding coating layer obtained using the near-infrared shielding coating agent, and a method for producing the near-infrared shielding coating layer. In addition, the present invention relates to an article in which the above near-infrared shielding coating layer is formed on a substrate, an article in which a photocatalytic coating layer is formed on the near-infrared shielding coating layer and an article in which a photocatalytic coating layer is formed on a surface different from the surface on which the near-infrared shielding coating layer is formed, and a method for producing the article.
Background
Windows, showcases, sunroofs, roofs, walls, and the like of buildings, and windows and vehicle bodies of automobiles, trains, and the like are exposed to sunlight, and therefore, particularly in summer, the interior temperature increases and the comfort level deteriorates. Therefore, a measure is proposed in which a material for shielding sunlight, particularly near infrared rays, is applied to an element such as a window of a building to shield near infrared rays, thereby suppressing an increase in the interior temperature and improving comfort. In order to apply the near-infrared shielding material to an element such as a window of a building, when glass, ceramic, or plastic is produced or molded, a coating agent containing the near-infrared shielding material is applied to the surface of the glass, ceramic, or plastic, which is a raw material of the element. In addition, a coating agent containing a near-infrared shielding material is applied to the surface of an element using it on a window or the like.
As such a near-infrared shielding material, oxide materials such as tin oxide, antimony-doped tin oxide, indium oxide, tin-doped indium oxide, zinc oxide, aluminum-doped zinc oxide, lanthanum boride, cerium oxide, ruthenium oxide, and tungsten oxide are known. In addition, metallic materials such as silver, copper and aluminum are also known.
As a binder component to be mixed into a coating agent, for example, patent document 1 describes a coating agent composed of Si (OR)mRnThe alkoxy silanes represented (wherein m + n is 4, m is 1 to 4, n is 0 to 3, and R is C1-C4Alkyl) or a polymer or partial hydrolysate thereof, and the preparation of a heat reflective coating by applying a coating agent and then heating it is described. In addition, patent document 2 describes a composition represented by the average composition formula (CH)3)mSi(OR)4-mA mixture of the alkoxysilanes represented, wherein R is methyl or ethyl, and m is 0.2 to 0.95, a hydrolysate of the above mixture and a polycondensate of the above mixture, and application of the composition to a surface of a glass substrate, semi-curing the composition at a temperature of 200 ℃ or less, additionally applying a composition comprising a polysilazane compound thereto, and then performing heat treatment at a temperature of 400 ℃ or more and 750 ℃ or less to produce a glass having an infrared shielding coating.
In addition, patent document 3 describes a polymer substance obtained by reacting a silane containing an amino group with a boron compound, and also describes that an alkoxysilane such as tetramethoxysilane or tetraethoxysilane or a polycondensate thereof is additionally added. In addition, patent document 4 describes that when a substance obtained by mixing and reacting a glycidoxypropyl group-containing alkoxysilane and an aminopropyl group-containing alkoxysilane is used, curing is possible at normal temperature.
Reference list
Patent document
Patent document 1: JP 5-70178A
Patent document 2: JP 2005-194169A
Patent document 3: JP 2008-111048A
Patent document 4: JP 2001 + 262064A
Summary of The Invention
Technical problem
The above patent documents 1 and 2 describe using a tetrafunctional silicon compound of tetraalkoxysilane, a trifunctional silicon compound of alkyltrialkoxysilane, a mixture thereof or a hydrolysate thereof or a polycondensate thereof as a binder. Although the coating hardness is high, curing is difficult at normal temperature, and thus heating is required. In addition, there is a problem that when heat curing is performed, shrinkage increases, and thus the coating surface is cracked.
In addition, in patent document 3, a polymer substance obtained by reacting an amino group-containing silane compound with a boron compound is used as a binder. When these compounds are mixed, a thick liquid is obtained in several minutes to several tens of minutes, and then solidified. Since a thick liquid is obtained, it is suitable to be processed into a coating or the like. However, there is a problem in that the thick liquid is not suitable for application, and the application is limited to application by a roll or the like. In addition, in patent document 4, a substance obtained by reacting a glycidoxypropyl group-containing alkoxysilane and an aminopropyl group-containing alkoxysilane is used as a binder. In order to make curing at normal temperature feasible, it is necessary to use a curing catalyst for mixing and reaction and to age the base material. In addition, there is a problem that a long time is required for aging.
Accordingly, the present invention provides a coating agent in which the preparation of a base material is easy, heating at a temperature of 200 ℃ or more is not required, the base material can be cured at a normal temperature of about 5 to 40 ℃, and thus a near infrared shielding coating layer can be formed at a normal temperature. In addition, the present invention provides a near infrared shielding coating that can be prepared at normal temperature, and in addition has high coating hardness and is less likely to crack, and a method of preparing the near infrared shielding coating.
In addition, the present invention provides an article in which the above near-infrared shielding coating layer is formed on a substrate, an article in which a photocatalytic coating layer is formed on the near-infrared shielding coating layer, and an article in which a photocatalytic coating layer is formed on a surface different from the surface on which the near-infrared shielding coating layer is formed, and a method for producing these articles.
Means for solving the problems
The present inventors have studied various coating agents that can form a near-infrared shielding coating at normal temperature, and as a result, have found that when three tetrafunctional silicon-based compounds, trifunctional silicon-based compounds, and silane-based coupling agents are used, a desired near-infrared shielding coating having high coating hardness and less possibility of cracking can be formed, and have completed the present invention.
Specifically, the present invention is a near-infrared shielding coating agent curable at normal temperature, which comprises (1) an inorganic near-infrared absorber; (2) selected from the group consisting of Si (OR1)4At least one of tetrafunctional silicon compounds represented by (i) wherein R1 are the same or different and are an alkyl group having 1 to 10 carbon atoms, hydrolysates thereof and polycondensates thereof; (3) selected from the general formula R2Si (OR3)3At least one of a trifunctional silicon compound represented by the formula (I) wherein R2 and R3 are each the same or different and an alkyl group having 1 to 10 carbon atoms; (4) selected from the general formula Si (X)3-Y or R4Si (X)2At least one of a silane coupling agent represented by-Y, a hydrolyzate thereof, and a polycondensate thereof, wherein X is the same or different and represents an alkoxy group, an acetoxy group, or a chlorine atomR4 is an alkyl group having 1 to 10 carbon atoms, and Y represents an organic group other than an alkyl group, an alkoxy group and an acetoxy group; and (5) a solvent. In addition, the present invention is a near-infrared shielding coating layer formed by applying a near-infrared shielding coating agent curable at normal temperature to at least one surface of a substrate.
In addition, the present invention is an article comprising a near-infrared shielding coating layer formed by applying a near-infrared shielding coating agent to at least one surface of a substrate, and an article in which a photocatalytic coating layer is formed on at least a part of the near-infrared shielding coating layer, and an article in which a near-infrared shielding coating agent is applied to one surface of a substrate to form a near-infrared shielding coating layer, and a photocatalytic coating layer is formed on the other surface of the substrate.
In addition, the present invention is a method for producing a near-infrared shielding coating or an article, which comprises applying a near-infrared shielding coating agent onto at least one surface of a substrate and drying the near-infrared shielding coating agent at ordinary temperature, and a method for producing an article, which comprises applying a near-infrared shielding coating agent onto at least one surface of a substrate, then applying a coating agent containing a photocatalyst onto it, and drying the near-infrared shielding coating agent and the coating agent, and a method for producing an article, which comprises applying a near-infrared shielding coating agent onto one surface of a substrate, applying a coating agent containing a photocatalyst onto the other surface of the substrate, and drying the near-infrared shielding coating agent and the coating agent, and the like.
Advantageous effects of the invention
The near-infrared shielding coating agent can be used for preparing a near-infrared shielding coating at the normal temperature of about 5-40 ℃, and can also be applied to substrates which are easy to heat, such as plastics. Therefore, the near infrared shielding property can be provided to the surface of all the substrates.
The near-infrared shielding coating layer prepared using the above near-infrared shielding coating agent has high near-infrared shielding performance, and further has high coating hardness and is less likely to crack. In addition, the binder itself has high visible light transmittance, and thus a near infrared shielding coating having high transparency is obtained by selecting an inorganic near infrared absorbent having high transparency. In addition to transparent materials such as glass and plastic, such transparent near-infrared shielding coatings can also provide near-infrared shielding properties to opaque materials such as steel and ceramics, colored materials, and patterned materials.
In addition, the near infrared shielding coating layer can be produced by a relatively simple method, for example, applying the above near infrared shielding coating agent to a substrate, and then forming the coating layer at a temperature of 5 to 40 ℃. Therefore, it is possible to directly provide near infrared shielding performance to places where heating operation is difficult, such as windows of buildings, showcases, sunroofs, roofs, walls, and the like, and windows and bodies of automobiles, trains, and the like.
In addition, the above near-infrared shielding coating can be combined with a photocatalytic coating, and in addition to near-infrared shielding performance, hydrophilicity, antifogging performance and anti-pollution performance can be provided to a substrate through photocatalytic performance, and malodorous materials, harmful materials and the like can be decomposed.
Description of the embodiments
The near-infrared shielding coating agent capable of being cured at normal temperature comprises (1) an inorganic near-infrared absorbent; (2) selected from the group consisting of Si (OR1)4At least one of tetrafunctional silicon compounds represented by (i) wherein R1 are the same or different and are an alkyl group having 1 to 10 carbon atoms, hydrolysates thereof and polycondensates thereof; (3) selected from the general formula R2Si (OR3)3At least one of a trifunctional silicon compound represented by the formula (I) wherein R2 and R3 are each the same or different and an alkyl group having 1 to 10 carbon atoms; (4) general formula Si (X)3-Y or R4Si (X)2At least one of a silane coupling agent represented by Y, a hydrolysate thereof, and a polycondensate thereof, wherein X is the same or different and represents an alkoxy group, an acetoxy group, or a chlorine atom, R4 is an alkyl group having 1 to 10 carbon atoms, and Y represents an organic group other than the alkyl group, the alkoxy group, and the acetoxy group; and (5) a solvent.
For the above inorganic near-infrared absorber (1), well-known ones can be used. Specifically, oxide materials such as tin oxide, antimony-doped tin oxide, indium oxide, tin-doped indium oxide, zinc oxide, aluminum-doped zinc oxide, lanthanum boride, cerium oxide, ruthenium oxide, and tungsten oxide, and metal materials such as silver, copper, and aluminum can be used. The near infrared absorber is preferably one that provides high visible light transmittance when the coating layer is formed. Such a near-infrared absorbent is preferably fine particles containing at least one selected from tin oxide, indium oxide, zinc oxide, and lanthanum boride as a main component, and more preferably antimony-doped tin oxide fine particles having higher transmittance. The particle diameter of the fine particles is preferably about 0.01 to 0.1. mu.m, more preferably 0.01 to 0.03. mu.m. If the particle diameter of the fine particles is larger than 0.1 μm, the transmittance may decrease. The content of the inorganic near-infrared absorbent is preferably 40 to 90% by weight, more preferably 60 to 80% by weight, and still more preferably 70 to 80% by weight, relative to the total solid content of the coating agent. If the content is less than 40% by weight, the near infrared shielding property is lowered, which is not preferable. If the content is more than 90% by weight, the hardness of the coating tends to decrease, which is not preferable.
The above component (2) is selected from the group consisting of Si (OR1)4At least one of the tetrafunctional silicon compounds represented, the hydrolysis products thereof and polycondensates thereof (hereinafter sometimes referred to as tetrafunctional silicon-based compounds). In the above formula, R1 is an alkyl group having 1 to 10 carbon atoms, and four R1 may be the same or different. R1 is preferably one having 1 to 5 carbon atoms in which hydrolysis and polycondensation are likely to occur. Monomers of the tetrafunctional silicon compound are preferred, but hydrolysis and polycondensation may be carried out during storage of the coating agent. In addition, the above component (2) may be a product obtained by hydrolyzing a monomer of the tetrafunctional silicon compound in advance, such as a partial hydrolysate. Further, the above component (2) may be a product obtained by hydrolyzing and polycondensing in advance a monomer of the tetrafunctional silicon compound, for example, an oligomer having a polymerization degree of about 2 to 20, preferably an oligomer having a polymerization degree of about 2 to 10. Specific examples of such compounds include monomers such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane,and hydrolysis products and hydrolysis and polycondensation products thereof.
The above component (3) is selected from the group consisting of general formula R2Si (OR3)3At least one of the trifunctional silicon compound represented, a hydrolysate thereof, and a polycondensate thereof (hereinafter sometimes referred to as a trifunctional silicon-based compound). In the above formula, R2 is an alkyl group having 1 to 10 carbon atoms, R3 is an alkyl group having 1 to 10 carbon atoms, and three R3 may be the same or different and may be the same or different as R2. R3 is preferably one having 1 to 5 carbon atoms, in which hydrolysis and polycondensation can occur. Monomers of the trifunctional silicon compound are preferred, but hydrolysis and polycondensation may be carried out during storage of the coating agent. In addition, the above component (3) may be a product obtained by hydrolyzing a monomer of the trifunctional silicon compound in advance, such as a partial hydrolysate. Further, the above component (3) may be a product obtained by hydrolyzing and polycondensing in advance a monomer of the trifunctional silicon compound, for example, an oligomer having a polymerization degree of about 2 to 20, preferably an oligomer having a polymerization degree of about 2 to 10. Specific examples of such compounds include monomers such as methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, and ethyltributoxysilane, and hydrolysis products and hydrolysis and polycondensation products thereof. The weight ratio of the respective components of the above tetrafunctional silicon based compound (2) to the above trifunctional silicon based compound (3) is preferably 1:1 to 1: 10. Within this range, a coating having a high coating hardness and less likely to crack may be formed.
The above component (4) is selected from the group consisting of the general formula Si (X)3-Y or R4Si (X)2At least one of a silane coupling agent represented by-Y, a hydrolyzate thereof, and a polycondensate thereof (hereinafter sometimes referred to as silane-based coupling agent). In the general formula Si (X)3-Y wherein X is an alkoxy group, an acetoxy group or a chlorine atom, three X's may be the same or different, and Y is an organic group other than an alkyl group, an alkoxy group and an acetoxy group. In addition, in the general formula R4Si (X)2-Y wherein R4 is an alkyl group having 1 to 10 carbon atoms, X is an alkoxy group, an acetoxy group or a chlorine atom, and both X's may be the same or different, andy is an organic group other than alkyl, alkoxy, and acetoxy. The above alkoxy group for X is preferably an alkoxy group having 1 to 10 carbon atoms. Examples thereof include methoxy, ethoxy, butoxy and methoxyethoxy. In addition, examples of the organic group Y include those having a vinyl group, an epoxy group, an amino group, a ureido group, a methacryloyl group, an acryloyl group, a sulfide group, a mercapto group, a ketimino group, an isocyanate group, a chloropropyl group, a styryl group, and the like. Organic groups having an epoxy group, an amino group, or a urea group are more preferable because a coating layer having high coating hardness and less likely to crack can be formed. The monomer of the silane coupling agent is preferable, but hydrolysis and polycondensation may be performed during storage of the coating agent. In addition, the above component (4) may be a product obtained by hydrolyzing a monomer of the silane coupling agent in advance, such as a partial hydrolysate. In addition, the above component (4) may be a product obtained by hydrolyzing and polycondensing a monomer of the silane coupling agent, for example, an oligomer having a polymerization degree of about 2 to 20, preferably an oligomer having a polymerization degree of about 2 to 10.
Silane coupling agents having vinyl groups include vinyltrimethoxysilane (KBM-1003 produced by Shin-Etsu CHEMICAL CO., LTD., and Z-6300 produced by TOKYO CHEMICALINDUSTRY CO., LTD., LTBE-1003 produced by Shin-Etsu CHEMICAL CO., LTD., and Z-6519 produced by TOKYO CHEMICALINDUSTRY CO., LTD., vinyltriisopropoxysilane (Z-6550 produced by TOKYO CHEMICAL INDUSTRY CO., LTD., allyltrimethoxysilane (Z-6825 produced by TOKYO CHEMICAL INDUSTRY CO., LTD., vinyltriacetoxysilane (Z-6075 produced by TOKYO CHEMICALINDUSTRY., LTD.), and vinyltris (2-methoxyethoxy) silane (MICROBEL-6172 produced by TOKYO CHEMICAL CO., LTD.).
Silane coupling agents having epoxy groups include 3-glycidoxypropyltrimethoxysilane (KBM-403 produced by Shin-Etsu Chemical CO., LTD., and Z-6040 produced by TOKYOCHEMICAL INDUSTRY CO., LTD., 3-glycidoxypropyltriethoxysilane (KBE-403 produced by Shin-Etsu Chemical CO., LTD., and Z-6041 produced by TOKYO CHEMICAL INDUSTRY CO., LTD., 3-glycidoxypropylmethyldiethoxysilane (KBE-402 produced by Shin-Etsu Chemical CO., LTD., and Z-6042 produced by TOKYO CHEMICAL INDUSTRY CO., LTD., 3-glycidoxypropylmethyldimethoxysilane (Z-3- (cyclohexyl) trimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane (KBE-402 produced by TOKYO CHEMICAL CO., LTD., and Z-2- (3-epoxycyclohexyltrimethoxysilane), LTD. manufactured Z-6043).
Specific examples of the silane coupling agent having an amino group include 3-aminopropyltrimethoxysilane (KBM-903 manufactured by Shin-Etsu Chemical CO., LTD., and Z-6610 manufactured by TOKYOCHEMICAL INDUSTRY CO., LTD., 3-aminopropyltriethoxysilane (KBE-903 manufactured by Shin-Etsu Chemical CO., LTD., and Z-6011), N-2- (aminoethyl) -3-aminopropyltrimethoxysilane (KBM-603 manufactured by Shin-Etsu Chemical CO., LTD., and Z-6020 manufactured by TOKYO CHEMICAL INDUSTRY CO., LTD., N-2- (aminoethyl) -3-aminopropyltriethoxysilane (KBM-603 manufactured by Shin-Etsu Chemical CO., LTD., N-2- (aminoethyl) -3-aminopropyltriethoxysilane (KBM-603 manufactured by Shin-Etsu Chemical CO., LTD., N-2- (aminoethyl) -3-aminopropyl-2- (aminopropyl-2- (aminopropyl-2-aminopropyl-2-amino-ethyl) -trimethoxysilane (KBM-603 manufactured by Shin-Etsu Chemical CO., LTD -KBM-602 manufactured by Etsu Chemical co, ltd; and Z-6023 produced by tokyococcus INDUSTRY co., ltd.; ) And N-phenyl-3-aminopropyltrimethoxysilane (KBM-573 manufactured by Shin-Etsu Chemical co., ltd.; and Z-6883 produced by TOKYO CHEMICAL INDUSTRY co., ltd.).
Silane coupling agents having an ureido group include 3-ureidopropyltriethoxysilane (KBE-585, manufactured by Shin-Etsu chemical CO., LTD.; and Z-6675 and Z-6676, manufactured by TOKYO CHEMICALINDUSTRY CO., LTD.).
Polymethacryloyl silane coupling agents include 3-methacryloxypropyl methyldimethoxysilane (KBE-502 manufactured by Shin-Etsu Chemical CO., LTD., and Z-6033 manufactured by TOKYOCHEMICAL INDUSTRY CO., LTD.), 3-methacryloxypropyltrimethoxysilane (KBM-503 manufactured by Shin-Etsu Chemical CO., LTD., and Z-6030 manufactured by TOKYO CHEMICAL INDUSTRY CO., LTD.), and 3-methacryloxypropyltriethoxysilane (Z-6036 manufactured by TOKYO CHEMICAL INDURYCO., LTD.).
Silane coupling agents having an acryloyl group include 3-acryloxypropyltrimethoxysilane (KBM-5103 manufactured by Shin-Etsu Chemical CO., LTD., and Z-6530 manufactured by TOKYOCHEMICAL INDUSTRY CO., LTD.).
The content of the above silane-based coupling agent (4) is preferably 1 to 30% by weight relative to the total amount of the above tetrafunctional silicon-based compound (2) and the above trifunctional silicon-based compound (3). Within this range, curing at an ordinary temperature of about 5 to 40 ℃ is performed, and furthermore, a coating having a high coating hardness and less likely to crack can be formed. If the content is less than 1% by weight, curing at an ordinary temperature of about 5 to 40 ℃ is less likely to be performed. If the content is more than 30% by weight, the hardness of the coating tends to decrease, which is not preferable.
The above solvent (5) can be appropriately selected. For example, polar solvents such as water, alcohols, nitriles, amides, ketones, sulfoxides and the like are preferred. Those having a low boiling point are preferable because drying at low temperature is easy. At least one selected from water and alcohol is more preferable. Examples of alcohols include methanol, ethanol, propanol, and butanol. The amount of the solvent is not particularly limited and is appropriately set in consideration of application conditions, application environment, and the like.
A catalyst for hydrolyzing or polycondensing the above tetrafunctional silicon-based compound (2), the above trifunctional silicon-based compound (3) or the above silane-based coupling agent (4), which is different from the above components, may be added to the near-infrared shielding coating agent of the present invention. Examples of the catalyst may include an acid or a base. Acetic acid, sodium acetate, and the like may be used. In addition, unlike the above components, an ultraviolet-shielding agent may be contained in the near-infrared-shielding coating agent of the present invention curable at normal temperature. The ultraviolet screening agent should be one of screening UV-A or UV-B. Examples thereof include organic ultraviolet screening agents (ultraviolet absorbers) such as benzophenone derivatives, p-aminobenzoic acid derivatives, p-methoxycinnamic acid derivatives, salicylic acid derivatives, and dibenzoylmethane derivatives, and inorganic ultraviolet screening agents, for example, metal oxides such as iron oxyhydroxide (goethite, FeOOH), iron oxide, cerium oxide, titanium dioxide, zinc oxide, and bismuth oxide, complex oxides using two or more of the above metal oxides, phosphoric acid compounds such as iron phosphate, titanium phosphate, cerium phosphate, and zinc phosphate, and complex phosphoric acid compounds using two or more of the above phosphoric acid compounds. For the inorganic ultraviolet-screening agent, fine particles having a small particle diameter are preferable, those having an average particle diameter of 200nm or less are more preferable, and those having an average particle diameter of 100nm or less are further preferable. The reason why fine particles are preferred is that the transparency of the coating layer in which they are mixed is not significantly reduced. In addition, the use of an ultraviolet-shielding agent that shields ultraviolet rays having a wavelength of 365nm is more preferable because entry of insects can be prevented. As such an ultraviolet screening agent, Parsol a, iron oxyhydroxide, iron oxide, titanium dioxide, zinc oxide, titanium phosphate, cerium phosphate, and the like can be used. The amounts of the catalyst and the ultraviolet screening agent added are appropriately set according to the purpose.
In addition, various additives and fillers such as a resin binder, a dispersant, a surface conditioner (a leveling agent and a wettability improver), a pH adjuster, an antifoaming agent, an emulsifier, a colorant, an extender, a fungicide, a curing aid, and a thickener may be contained as the third component within a range not to inhibit the effect of the present invention. Examples of the resin binder include organic binders such as alkyd resins, acrylic resins, polyester resins, epoxy resins, fluorine resins, and modified silicone resins. Examples of the dispersant include (1) surfactants ((a) anions (carboxylate, sulfate, sulfonate, phosphate, etc.), (b) cations (alkylamine salts, quaternary ammonium salts of alkylamine, aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts, etc.), (c) amphiprotics (betaines, amino acids, alkylamine oxides, nitrogen-containing heterocycles, etc.) and (d) non-ions (ethers, ether esters, nitrogen-containing species, etc.), (2) silicone dispersants (alkyl-modified polysiloxanes, polyoxyalkylene-modified polysiloxanes, etc.), (3) phosphate dispersants (sodium phosphate, sodium pyrophosphate, sodium orthophosphate, sodium metaphosphate, sodium tripolyphosphate, etc.), (4) alkanolamines (aminomethylpropanol, aminomethylpropanediol, etc.). The surface conditioner controls surface tension to prevent defects such as craters and craters. Examples of the surface conditioner include acrylic surface conditioners, vinyl surface conditioners, silicone surface conditioners, and fluorine surface conditioners. The amount added is appropriately set according to the purpose.
The near-infrared shielding coating agent of the present invention can be produced by mixing predetermined amounts of the above components (1) to (5). In the mixing, a catalyst, an ultraviolet screening agent or the above third component may be added as required. The mixing method is not particularly limited. For the dispersion of the inorganic near-infrared absorber, for example, a paint conditioner, a colloid mill, a ball mill, a sand mill, or a homomixer can be used.
As a method of applying the above near-infrared shielding coating agent to a substrate, a conventional method can be used. General methods such as spin coating, spray coating, roll coating, dip coating, flow coating, knife coating, electrostatic coating, bar coating, die coating, brush coating, and sponge coating can be used. For dip coating, a near infrared shielding coating may be prepared on both surfaces of the substrate. For spin coating, spray coating, roll coating, flow coating, brush coating, sponge coating, and the like, a near infrared shielding coating can be prepared on one surface of the substrate. When the coating thickness is thick, recoating may be performed. When the solvent is removed from the applied material, a near infrared shielding coating is formed. The coating formation is preferably carried out at a normal temperature of 5 to 40 ℃. Warm or cold air may be supplied in the coating formation to promote the coating formation. In addition, heating may be performed as necessary. The heating temperature may be set as appropriate depending on the heat resistance of the substrate, and specifically, is 40 to 500 ℃, preferably 40 to 200 ℃. The thickness of the near-infrared shielding coating layer can be any thickness by appropriately selecting the application method. For example, a thickness of 1 to 10nm is preferable because visible light transmittance can be improved. The thickness is more preferably 2-3 nm.
As the substrate forming the near-infrared shielding coating layer, those having various materials and various shapes can be used. For example, those having various materials such as plastic, glass, ceramic, metal, wood, and fiber may be used. In addition to transparent materials such as glass and plastic, opaque materials such as steel and ceramics, colored materials and materials with patterns can also be used as substrates. In particular, glass plates and plastic plates may be preferably used as the substrate, and the near infrared shielding coating of the present invention may be formed thereon for windows of buildings, showcases, sunroofs, and the like, and windows of automobiles, trains, and the like. In addition, those actually used may be used as the substrate. For example, near infrared shielding coatings may be formed on building windows, showcases, sunroofs, roofs, walls, and the like, as well as windows and vehicle bodies of automobiles, trains, and the like. To improve adhesion between the near-infrared shielding coating layer and the substrate, protect the substrate, and the like, a primer layer may be formed on the substrate in advance. To protect the near infrared shielding coating layer and the like, a top coat layer may be formed on the coating layer. Various inorganic binders, organic binders, and the like may be used to form the primer layer and the topcoat layer.
When the above near-infrared shielding coating agent is used and applied to at least one surface of a substrate, a near-infrared shielding coating layer may be formed. Although the properties of the near-infrared shielding coating prepared in this manner also depend on the properties of the inorganic near-infrared absorber, etc., the following is generally obtained:
(a) as for the solar radiation transmittance measured by the following method, a solar radiation transmittance of 85% or less is easily obtained, and the solar radiation transmittance is preferably 80% or less.
Method for measuring solar radiation transmittance
The near-infrared shielding coating liquid was applied to a glass plate (produced by MATSUNAMI, 53 × 76 × t1.3mm) and it was dried at normal temperature. The measurement was performed by an ultraviolet visible near infrared spectrophotometer V-570 (manufactured by JASCO Corporation, using Spectralon < manufactured by Labsphere > as a standard plate) to measure the spectral transmittance. The solar radiation transmittance (wavelength: 300-.
(b) As for the visible light transmittance of the near-infrared shielding coating layer measured by the following method, a visible light transmittance of 85% or more is easily obtained, and the visible light transmittance is preferably 90% or more.
Method for measuring visible light transmittance
The spectral transmittance was measured by the method of (a) above and the visible light transmittance (wavelength: 380-780nm) was calculated.
(c) As the pencil hardness of the near-infrared shielding coating measured by the following method, 2H is easily obtained, and the pencil hardness is preferably 4H or more.
Method for measuring pencil hardness
According to JIS K5400, tips of pencils having different hardness were polished with sandpaper, and a glass plate having a near infrared shielding coating placed on a floor was slowly scratched with a pencil tip at an angle of 45 ° to the glass plate. When the pencil hardness is higher than the coating hardness, scratches are formed on the coating surface, and conversely, when the pencil hardness is lower than the coating hardness, scratches are formed on the pencil point. Therefore, the pencil hardness at which the coating hardness exceeds the pencil hardness is regarded as the coating hardness.
As described above, the near-infrared shielding coating agent may be applied on at least one surface of the substrate to provide an article in which the near-infrared shielding coating layer is formed. The article is one in which a near-infrared shielding coating layer is formed on at least one surface of the above substrate, and may be produced by applying a near-infrared shielding coating agent to at least one surface of a substrate and drying it at a normal temperature of about 5 to 40 ℃.
Additionally, a near infrared shielding coating may be combined with the photocatalytic coating. Specifically, an article in which a photocatalytic coating is formed on at least a part of a near-infrared shielding coating can be provided. The article is obtained by forming a near-infrared shielding coating and then forming a photocatalytic coating on at least a part of the near-infrared shielding coating by a well-known method. As a method of forming the photocatalytic coating layer, a method of applying a coating agent containing a photocatalyst (hereinafter sometimes referred to as a photocatalyst coating agent) and drying it is simple and preferable. After the above near-infrared shielding coating agent is applied, the photocatalyst coating agent may be applied still in a wet state, or may be applied in a dry state. As the drying temperature, ordinary temperature of about 5 to 40 ℃ is preferable.
In addition, an article in which a near-infrared shielding coating layer is formed on one surface of a substrate and a photocatalytic coating layer is formed on the other surface of the substrate can also be provided, preferably the photocatalytic coating layer is formed on the surface of the substrate opposite to the near-infrared shielding coating layer. In this article, the above near-infrared shielding coating agent is applied to one surface of a substrate, and a photocatalytic coating layer is formed on the other surface of the substrate by a well-known method. As a method of forming the photocatalytic coating layer, a method of applying a photocatalyst coating agent and drying it is simple and preferable. The order (front or rear) of the application of the near-infrared shielding coating agent and the application of the photocatalyst coating agent may be arbitrary. As the drying temperature, ordinary temperature of about 5 to 40 ℃ is preferable. For the substrate, those having various materials and various shapes as described above can be used. Glass plates and plastic plates can be preferably used, and glass plates and plastic plates having high transparency are more general. Such articles are useful in windows for buildings, showcases, sunroofs, and the like, and windows for automobiles, trains, and the like. In addition, those used in practice can be used as the substrate. For example, the near infrared shielding coating and the photocatalytic coating may be formed on windows of buildings, showcases, sunroofs, and the like, and windows of automobiles, trains, and the like.
The above photocatalyst is a substance that exhibits photocatalytic properties when irradiated with light having energy equal to or higher than its band gap. One or two or more well-known metal compound semiconductors such as titanium oxide, zinc oxide, tungsten oxide, titanium oxide, and strontium titanate can be used. In particular, titanium oxide is desirable, which has excellent photocatalytic properties and is chemically stable and harmless. In addition to titanium oxide, titanium oxide includes those generally referred to as hydrous titanium oxide, orthotitanic acid, metatitanic acid, and titanium hydroxide. The titanium oxide may have any crystal system of anatase type, brookite type, rutile type, etc., and may have a mixed crystal system. In addition, at least one elemental metal selected from the group consisting of V, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pt, Pd and Ag, and/or a compound thereof may be contained in and/or on the surface thereof in order to improve photocatalytic performance. The particle diameter of the photocatalyst is preferably fine because it has excellent photocatalytic performance. The particle size of the photocatalyst is more preferably 1 to 500nm, still more preferably 1 to 400nm, most preferably 1 to 300 nm.
In addition, for the photocatalyst, those having a visible light response ability excited by irradiation with visible light may also be applied. Generally, only a few percent of ultraviolet rays that can excite the photocatalyst are contained in natural light, and therefore, by making the photocatalyst visible-light responsive, the natural light can be effectively used to efficiently decompose the object to be treated. For the photocatalyst having visible light response ability, well-known ones can be used. For example, those in which titanium oxide is doped with different elements such as sulfur (S), nitrogen (N), or carbon (C), those in which different metal ions are dissolved in titanium oxide, those in which a platinum halide compound, iron oxyhydroxide, or the like is supported on the surface of titanium oxide particles, those in which titanium oxide particles are complexed with a compound showing photocatalytic properties in the visible light region such as iron oxide or tungsten oxide, those in which the composition ratio of titanium to oxygen of titanium oxide is changed, or the like can be preferably used.
The photocatalyst coating agent is a composition comprising the above photocatalyst, binder and solvent, and a well-known coating agent can be used. In the near-infrared shielding coating agent of the present invention, it is preferable to use a photocatalytic coating agent using a photocatalyst in place of (1) the inorganic near-infrared absorbing agent, and using the above tetrafunctional silicon-based compound (2), the above trifunctional silicon-based compound (3), the above silane-based coupling agent (4), and the above solvent (5). Such photocatalyst coating agent does not require heating at a temperature of 200 ℃ or more, and the binder can be cured at a normal temperature of about 5 to 40 ℃. Therefore, a photocatalytic coating having a high coating hardness and less rupturable can be formed at normal temperature.
The content of the photocatalyst is preferably 5 to 98% by weight, more preferably 25 to 98% by weight, relative to the total solid content of the photocatalyst coating agent. If the content is less than 5% by weight, photocatalytic performance is lowered, which is not preferable. If the content is more than 98% by weight, the coating hardness tends to decrease, which is not preferable. In addition, the photocatalyst coating agent may contain a third component such as various additives and fillers such as a resin binder, a dispersant, a surface conditioner (a leveling agent and a wettability improver), a pH adjuster, an antifoaming agent, an emulsifier, a colorant, an extender, a fungicide, a curing assistant and a thickener, and a catalyst for hydrolysis and polycondensation.
As a method of dispersing the photocatalyst and a method of applying the photocatalyst coating agent to the substrate, the above methods can be used. When the solvent is removed from the applied material, a photocatalytic coating is formed. The coating formation is preferably carried out at a normal temperature of 5 to 40 ℃. Warm or cold air may be supplied in the coating formation to promote the coating formation. In addition, heating may be performed as necessary. The heating temperature may be set as appropriate depending on the heat resistance of the substrate, and specifically, is 40 to 500 ℃, preferably 40 to 200 ℃. The thickness of the photocatalytic coating can be any thickness by appropriately selecting the application method. For example, a thickness of 1 to 200nm is preferable because visible light transmittance can be improved. More preferably 50-100nm thick. In order to improve adhesion between the photocatalytic coating layer and the substrate, protect the substrate, and the like, a primer layer may be formed in advance on the substrate to which the photocatalytic coating agent is to be applied. To protect the photocatalytic coating layer and the like, a top coat layer may be formed on the coating layer. Various inorganic binders, organic binders, and the like may be used to form the primer layer and the topcoat layer.
The photocatalytic coating can be provided with hydrophilicity, antifogging property and antifouling property by irradiating with light of a wavelength having energy equal to or higher than the band gap. Hydrophilicity with a water contact angle of 10 ° or less, preferably 5 ° or less can be obtained by light irradiation, and droplet formation, aerosol due to water vapor solidification, and adhesion of contaminants can be prevented. In addition, substances to be treated such as harmful substances, malodorous substances and oils adhered to the photocatalytic coating can be decomposed to purify and sterilize. In particular, it is possible to target water contaminants such as oils and organic substances, air contaminants such as ammonia, mercaptans, aldehydes, amines, hydrogen sulfide, hydrocarbons, sulfur oxides and nitrogen oxides, and environmental deterioration substances such as bacteria, fungi, microorganisms and various pollutant components. As the light source for light irradiation, a light source that can emit light having energy equal to or higher than the band gap of the photocatalyst is used. For example, a natural light source such as the sun, and an artificial light source such as an ultraviolet lamp, a black light, a mercury lamp, a xenon lamp, a fluorescent lamp, and an incandescent lamp may be used. In the case of a visible light-responsive photocatalyst, light containing visible light can be used. The light irradiation amount and the irradiation time may be appropriately set depending on the amount of the substance to be treated or the like.
Examples
Examples of the present invention are explained below, but the present invention is not limited to the examples.
1. Preparation of near Infrared Shielding coating agent (examples 1 to 5 and comparative examples 1 to 3)
20 parts by weight of water and 6 parts by weight of acetic acid were placed in a synthesis vessel and stirred while the liquid temperature was maintained at 0-10 ℃. To this, components (a) to (d) having the component mixing ratios described in Table 1 were added in a total amount of 43.5 parts by weight. At this time, they were added little by little for each component and stirred for 16 hours while keeping the liquid temperature at 10 ℃.
The liquid temperature was then set to 20 ℃. 0.5 parts by weight of sodium acetate was added, and n-propanol was added so that the amount of the heated residue of the solution (the amount of the residue after drying the solution at 120 ℃ for 1 hour) became 25 to 26%.
Next, antimony-doped tin oxide (SN-100P, manufactured by ISHIHARA SANGYO KAISHA, ltd.) was added as an inorganic near-infrared absorbing agent to the above solution so that PWC (weight ratio of the inorganic near-infrared absorbing agent to all solids in the solution) was 75%, and dispersed using a paint conditioner manufactured by RedDevil to obtain a near-infrared shielding coating agent.
2. Method for forming near-infrared shielding coating
The surface of a soda glass plate (produced by MATSUNAMI, 53 × 76 × t1.3mm) was wiped with ethanol, and then air-blown to provide a substrate. Each of the near-infrared shielding coating agents synthesized by examples 1 to 5 and comparative examples 1 to 3 in the above 1 was put into a paint pot, and the above substrate was pulled out at a speed of 150-.
3. Performance test 1 of near-Infrared Shielding coating
The performance test of the near infrared shielding coating layer formed by the method in 2 above was performed by the following method. The results are shown in table 2.
(1) Initial tape adhesion: the coated surface was cross-cut by an NT cutter, and a cellophane tape was pressed on the portion and peeled off. The coating was then inspected for peeling.
(2) Coating drying property: after the coated panel was produced, it was kept in a room, and the dry state was checked by finger touch after 30 minutes.
(3) Abrasion resistance: steel wool was placed on the coated surface at a load of 100g, the surface was rubbed 10 times, and the degree of scratching on the surface was examined.
(4) Rupture over time: after the coated panel was produced, it was kept in a room for 10 days, and the coating was checked for cracking.
[ Table 2]
| Initial tape adhesion | Drying property of coating | Abrasion resistance | Break with time | |
| Example 1 | ◎ | ○ | ○ | ◎ |
| Example 2 | ◎ | ○ | ◎ | ◎ |
| Example 3 | ◎ | ◎ | ◎ | △ |
| Example 4 | ◎ | △ | ○ | ◎ |
| Example 5 | ◎ | ○ | △ | ◎ |
| Comparative example 1 | ◎ | × | × | ◎ |
| Comparative example 2 | ◎ | × | × | ◎ |
| Comparative example 3 | ◎ | ○ | ◎ | × |
Evaluation: excellent, good, o-average, Δ -slightly poor, x-poor
4. Performance test 2 of near-Infrared Shielding coating
Using a sample prepared by applying the near-infrared shielding coating agent of example 1 on a glass plate (produced by MATSUNAMI, 53 × 76 × t1.3mm) and drying it at normal temperature, the solar radiation transmittance of the near-infrared shielding coating layer and the like were measured by the following methods.
(1) Measurement of solar radiation transmittance and visible light transmittance
For the above examples, measurement was performed by an ultraviolet visible near infrared spectrophotometer V-570 (manufactured by JASCO Corporation, using Spectralon < manufactured by Labsphere > as a standard plate) to measure spectral transmittance. Then, the solar radiation transmittance (wavelength: 300 and 2500nm) was calculated in accordance with JIS R3106, resulting in 79.3%.
In addition, the visible light transmittance (wavelength: 380-780nm) was calculated from the above spectral transmittance and found to be 93.0%.
(2) The pencil hardness of the above examples was measured according to JIS K5400, and was 3H.
(3) An artificial daylight illumination apparatus was used, model SXL-501V1 (produced by SERIC ltd., light source; three xenon bulbs, 500W). The above sample was placed under a light source at a distance of 500mm, and a temperature sensor (EMPEX INSTRUMENTS, INC., TD-8182) was placed under the sample at a position 50mm from the sample. The temperature of the temperature sensor was measured when the specimen was irradiated with light for 5 minutes, and compared with the case of using a glass plate (produced by MATSUNAMI, 53 × 76 × t1.3 mm). As a result, the temperature of the above sample was low, with a difference of 10 ℃. It was thus found that when a near-infrared shielding coating is used, a temperature suppressing effect is obtained.
The near-infrared shielding coating agent of example 1 was applied to a glass plate (produced by MATSUNAMI, 53 × 76 × t1.3mm), and then a photocatalyst coating agent (ST-K253 produced by ishahara SANGYOKAISHA, ltd.) was applied to the opposite surface of the glass plate. They were dried at normal temperature.
The solar radiation transmittance and visible light transmittance of the sample were measured by the above methods. As a result, the solar radiation transmittance was 79.1%, and the visible light transmittance was 92.9%.
The intensity of ultraviolet ray applied to the sample was 0.5mW/cm2The contact angle of water was measured after 6 hours of irradiation with black light, and found to be 36 °. The contact angle of water was measured after the sample was irradiated for 24 hours, and the result was 5 °. Demonstrating photocatalytic properties.
It was found that a near-infrared shielding coating having a high coating hardness and less likely to crack can be prepared at an ordinary temperature of about 5 to 40 c by using the three tetrafunctional silicon-based compounds, the trifunctional silicon-based compounds, and the silane-based coupling agents as described above. In addition, it was found that the near infrared shielding coating layer can be combined with the photocatalytic coating layer, and hydrophilicity and the like can be provided to the substrate by the photocatalytic property in addition to the near infrared shielding property.
Example 6
The operation as in example 1 was conducted except that iron oxyhydroxide fine particles (goethite, FeOOH, produced by ISHIHARA SANGYO KAISHA, ltd.) were additionally added as an inorganic ultraviolet-shielding agent so that PWC (weight ratio of the inorganic ultraviolet-shielding agent to all solids in the solution) in example 1 was 2.3% to obtain a near-infrared shielding coating agent.
Example 7
The operation as in example 1 was carried out except that fine particles of titanium dioxide (TiO) were additionally added2Manufactured by ISHIHARA SANGYO KAISHA, ltd.) as the inorganic ultraviolet-shielding agent so that PWC (weight ratio of the inorganic ultraviolet-shielding agent to all solids in the solution) in example 1 was 2.6% to obtain a near-infrared-shielding coating agent.
The near-infrared shielding coating agents of examples 6 and 7 were each applied to a glass plate (prepared by MATSUNAMI, 53 × 76 × t1.3mm) and dried at normal temperature to prepare a near-infrared shielding coating layer. Solar radiation transmittance and visible light transmittance were measured as in 4 above.
Performance test 2 of the near infrared shielding coating.
In addition, the ultraviolet transmittance of the near infrared shielding coating layer was measured by the following method.
(4) Measurement of ultraviolet transmittance
For the above samples, measurement was performed by an ultraviolet visible near infrared spectrophotometer V-570 (manufactured by JASCO Corporation, using Spectralon < manufactured by Labsphere > as a standard plate) to measure spectral transmittance at wavelengths of 310nm and 360nm as a standard of ultraviolet shielding ability.
The results obtained are shown in table 3. It was found that examples 6 and 7 each had a lower ultraviolet transmittance than example 1 and had an ultraviolet shielding property. In particular, in example 6, the ultraviolet transmittance at 360nm was low, and in example 7, the ultraviolet transmittance at 310nm was low. Furthermore, the visible light transmittance and solar radiation transmittance of examples 6 and 7 were found to be comparable to those of example 1.
[ Table 3]
INDUSTRIAL APPLICABILITY
The near-infrared shielding coating agent can be used for preparing a near-infrared shielding coating at the normal temperature of about 5-40 ℃, and can also be applied to substrates which are easy to heat, such as plastics. Therefore, the near infrared shielding property can be provided to the surface of all the substrates.
When the near-infrared shielding coating is formed on an element such as a window of a building, near-infrared rays can be shielded to suppress an increase in indoor temperature and improve comfort.
Claims (17)
1. A near-infrared shielding coating agent curable at 5 to 40 ℃, comprising:
(1) an inorganic near infrared absorber;
(2) selected from the group consisting of Si (OR1)4At least one of tetrafunctional silicon compounds represented by (i) wherein R1 are the same or different and are an alkyl group having 1 to 10 carbon atoms, hydrolysates thereof and polycondensates thereof;
(3) selected from the general formula R2Si (OR3)3At least one of the trifunctional silicon compounds represented by the formula (I), hydrolysis products thereof and polycondensates thereof, wherein R2 and R3 are each the same or different andis an alkyl group having 1 to 10 carbon atoms;
(4) selected from the general formula Si (X)3-Y or R4Si (X)2At least one of a silane coupling agent represented by Y, a hydrolysate thereof, and a polycondensate thereof, wherein X is the same or different and represents an alkoxy group, an acetoxy group, or a chlorine atom, R4 is an alkyl group having 1 to 10 carbon atoms, and Y represents an organic group other than the alkyl group, the alkoxy group, and the acetoxy group; and
(5) a solvent, a water-soluble organic solvent,
wherein the weight ratio of the components (2) to (3) is 1:1-1: 10.
2. The near-infrared shielding coating agent curable at 5 to 40 ℃ according to claim 1, wherein the content of the component (4) is 1 to 30% by weight with respect to the total amount of the components (2) and (3).
3. The near-infrared shielding coating agent curable at 5 to 40 ℃ according to claim 1, wherein the inorganic near-infrared absorbing agent (1) is a fine particle comprising at least one selected from the group consisting of tin oxide, indium oxide, zinc oxide, and lanthanum boride as a main component.
4. The near-infrared shielding coating agent curable at 5 to 40 ℃ according to claim 3, wherein the inorganic near-infrared absorber is antimony-doped tin oxide fine particles.
5. The near-infrared shielding coating agent curable at 5 to 40 ℃ according to claim 1, wherein the content of the inorganic near-infrared absorbing agent (1) is 40 to 90% by weight relative to the total solid amount of the coating agent.
6. The near-infrared-shielding coating agent curable at 5 to 40 ℃ according to any one of claims 1 to 5, which further comprises an ultraviolet-shielding agent.
7. A near-infrared shielding coating layer formed by applying the near-infrared shielding coating agent curable at 5 to 40 ℃ according to any one of claims 1 to 6 to at least one surface of a substrate.
8. The near-infrared shielding coating according to claim 7, which has a pencil hardness of 2H or more.
9. The near-infrared shielding coating according to claim 7, which has a visible light transmittance of 85% or more and a solar radiation transmittance of 85% or less.
10. A method for preparing a near-infrared shielding coating layer, comprising applying the near-infrared shielding coating agent curable at 5 to 40 ℃ according to any one of claims 1 to 6 to at least one surface of a substrate, and drying the near-infrared shielding coating agent at 5 to 40 ℃.
11. An article comprising a near-infrared shielding coating layer formed by applying the near-infrared shielding coating agent curable at 5 to 40 ℃ according to any one of claims 1 to 6 onto at least one surface of a substrate.
12. The article of claim 11, wherein the photocatalytic coating is formed over at least a portion of the near-infrared-shielding coating.
13. The article according to claim 11, wherein the near-infrared shielding coating is formed on one surface of the substrate and the photocatalytic coating is formed on the other surface of the substrate.
14. The article according to any one of claims 11-13, wherein the substrate is a glass or plastic sheet.
15. A method for producing an article, comprising applying the near-infrared shielding coating agent curable at 5 to 40 ℃ according to any one of claims 1 to 6 to at least one surface of a substrate, and drying the near-infrared shielding coating agent at 5 to 40 ℃.
16. A method for producing an article, which comprises applying the near-infrared shielding coating agent curable at 5 to 40 ℃ according to any one of claims 1 to 6 to at least one surface of a substrate, then applying a coating agent containing a photocatalyst thereto, and drying the agent.
17. A method for producing an article, which comprises applying the near-infrared shielding coating agent curable at 5 to 40 ℃ according to any one of claims 1 to 6 to one surface of a substrate, applying a coating agent containing a photocatalyst to the other surface of the substrate, and drying the agent.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009141348 | 2009-06-12 | ||
| JP141348/2009 | 2009-06-12 | ||
| PCT/JP2010/059743 WO2010143645A1 (en) | 2009-06-12 | 2010-06-09 | Near-infrared shielding coating agent curable at ordinary temperatures, near-infrared shielding film using same, and manufacturing method therefor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| HK1176961A1 HK1176961A1 (en) | 2013-08-09 |
| HK1176961B true HK1176961B (en) | 2016-04-15 |
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