JP2012121277A - Heat ray shielding glass, and double-glazed glass using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat ray shielding glass that has superior heat ray shielding properties, especially, thermal insulation, is manufactured at low cost, has high visible light transmittance, and has durability in the presence of water.SOLUTION: The heat ray shielding glass 10 includes: a glass plate 11; and a heat ray reflective layer 14 disposed on a surface of the glass plate and made of a conductive polymer. A low-refractive index layer 15 is formed on a surface of the heat ray reflective layer 14, and a refractive index of the low-refractive index layer 15 is lower than that of the heat ray reflective layer 14. A double-glazed glass using the heat ray shielding glass is also provided.

Description

  The present invention relates to a heat ray shielding glass having heat ray shielding property or heat ray reflection property, and a multilayer glass using the heat ray shielding glass.

  Conventionally, in order to reduce the air conditioning load of buildings such as office buildings and buses, passenger cars, trains, etc., railways, etc., these windows have a function of shielding near infrared rays (heat rays) in sunlight, There is a demand for a function of reflecting and insulating heat rays radiated from the room. As a glass that shields or reflects heat rays, a kneading type heat ray absorbing glass in which ions such as Fe, Cr, Ti, etc. are introduced into the glass itself to give heat ray absorption, or a heat ray reflecting glass in which a metal oxide film is deposited. A thin film of a transparent conductive film such as indium tin oxide (ITO) or tin oxide (ATO) is formed into a dry film, and a noble metal film / metal oxide film mainly composed of a metal oxide film / Ag film is laminated. A heat ray shielding glass (Patent Document 1) on which a heat ray shielding film (also referred to as Low-E film) is formed has been developed and put into practical use. Among these, the Low-E film has a function (heat insulation) that transmits near infrared rays of sunlight having a relatively short wavelength and does not escape by reflecting far infrared rays such as heating emitted from the room.

  Such heat ray-shielding glass (particularly, the one on which the Low-E film is formed) is arranged to be opposed to another glass plate with a predetermined interval (air layer) to form a multilayer glass. And what improved the heat insulation is also developed (patent document 2). Thereby, the energy consumption by air conditioning can be further reduced.

  However, since the Low-E film is formed by a vacuum film formation method such as a sputtering method, a large-sized apparatus is required, and the manufacturing cost of the heat ray shielding glass using the device increases. Further, the metal film is easily corroded, and there is a problem that the appearance characteristics are deteriorated by long-term use.

  Further, as heat ray shielding glass having high heat ray shielding properties and realizing high visible light transmittance, fine particles of tungsten oxide and / or composite tungsten oxide (also referred to as (composite) tungsten oxide) and UV excitation coloring. The thing which formed the coating film containing an inhibitor on the glass substrate is developed (patent document 3). Such a heat ray-shielding glass is excellent in the function of shielding the near-infrared rays of sunlight, but since the heat insulation property that reflects the heat rays emitted from the room is low, satisfactory performance can be obtained depending on the application. There may not be.

  Furthermore, the property of absorbing infrared rays is also known for conductive polymers, and is a transparent heat shield composed of a surface protective layer, a heat shield layer using a conductive polymer, a substrate, an ultraviolet absorbing layer, and an adhesive layer. A film has been developed (Patent Document 4).

JP 2001-226148 A JP 2007-70146 A JP 2007-269523 A JP 2005-288867 A

  However, it cannot be said that the shielding film using the conductive polymer of Patent Document 4 has sufficient heat ray shielding properties. When the heat ray shielding property is increased, there is a problem that sufficient visible light transmittance cannot be obtained (see Patent Document 4, Table 1).

  Further, according to the study by the present inventors, a heat ray shielding glass having a heat ray reflective layer made of a conductive polymer has high heat insulation properties depending on conditions, but durability in the presence of moisture (high humidity conditions) The problem of low water resistance (also referred to as “water resistance” in the invention) has also become apparent.

  Accordingly, an object of the present invention is a heat ray that has excellent heat ray shielding properties, particularly heat insulation properties, can be produced at low cost, has high visible light transmittance, and has high durability in the presence of moisture (high humidity conditions). It is to provide a shielding glass.

  Moreover, the objective of this invention is also providing the multilayer glass using this heat ray shielding glass.

  The object is a heat ray shielding glass comprising a glass plate and a heat ray reflective layer comprising a conductive polymer provided on the surface thereof, wherein a low refractive index layer is formed on the surface of the heat ray reflective layer, and This is achieved by a heat ray shielding glass characterized in that the refractive index of the low refractive index layer is lower than that of the heat ray reflective layer.

  The heat ray reflective layer made of a conductive polymer needs to have a sufficiently high free electron density in order to obtain high heat ray reflectivity (heat insulation). Therefore, in order to improve the visible light transmittance or to improve the water resistance, when a material having high physical properties and water resistance is mixed in the conductive polymer layer, the free electron density is generally lowered, Sufficient heat insulation cannot be obtained. Also, normally, when another layer (for example, a protective layer) is formed on the surface of the conductive polymer layer, sufficient heat insulation cannot be obtained due to infrared absorption of the other layer.

  In the present invention, by forming a low refractive index layer having a refractive index lower than that of the heat ray reflective layer on the surface of the heat ray reflective layer made of a conductive polymer, high heat insulation of the heat ray reflective layer made of the conductive polymer is achieved. Without damaging, it is possible to improve the visible light transmittance and protect the heat ray reflective layer from moisture such as rain water, condensation, and moisture. Thereby, it can be set as the heat ray shielding glass with high visible light transmittance, sufficient water resistance (durability in the presence of moisture (high humidity condition)), and heat insulation performance maintained for a long period of time. . Further, since the conductive polymer is made of an organic polymer, it is possible to form a layer by a low cost coating method or the like, and the heat ray shielding glass of the present invention can be manufactured at a low cost.

  Preferred embodiments of the heat ray shielding glass of the present invention are as follows.

(1) The layer thickness of the low refractive index layer is 50 to 350 nm. If the thickness of the layer formed on the surface of the heat ray reflective layer made of a conductive polymer is too thick, the heat insulation property of the heat ray reflective layer may be impaired, and if it is too thin, the visible light transmittance and water resistance are improved. You may not get enough. Therefore, the thickness of the low refractive index layer is preferably in the above range. The layer thickness of the low refractive index layer is more preferably 50 to 250 nm, and particularly preferably 50 to 150 nm.
(2) The refractive index of the low refractive index layer is 1.48 or less. The refractive index is more preferably 1.45 or less, and particularly preferably 1.42 or less. Thereby, visible light transmittance can be improved more sufficiently.
(3) The low refractive index layer includes at least one refractive index adjusting material selected from the group consisting of porous fine particles, hollow fine particles, oxide fine particles, and fluororesin fine particles. Examples of the porous fine particles include porous oxide fine particles such as porous silica fine particles, and examples of the hollow fine particles include hollow oxide fine particles such as hollow silica fine particles. These refractive index adjusting materials are suitable materials for forming the low refractive index layer.
(4) The low refractive index layer contains a fluororesin or a silicone resin. An organic thin film containing these refractive index adjusting materials is also preferable as the low refractive index layer.
(5) The conductive polymer has the following formula (I):

(In the formula, R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, or R ¹ and R ² together may be optionally substituted carbon. An alkylene group having 1 to 4 atoms, and n represents an integer of 50 to 1000). Since the above polythiophene derivative has high conductivity, it is suitable as a conductive polymer used for the heat ray reflective layer in the present invention.
(6) The surface resistance value of the heat ray reflective layer is 100000Ω / □ or less.
(7) The heat ray reflective layer has a thickness of 10 to 3000 nm.

  Further, the object is to arrange the heat ray shielding glass of the present invention and another glass plate so that the low refractive index layer faces the other glass plate with a gap therebetween, and the gap forms a hollow layer. It is also achieved by a double-glazed glass characterized in that is formed.

  By making such a double-glazed glass, heat insulation by the hollow layer is imparted, and further, the heat ray reflective layer can be protected from moisture such as rainwater, condensation, moisture, etc. Can be maintained. In addition, it is preferable that the said hollow layer is formed when the said heat ray shielding glass and said another glass plate are arrange | positioned through a spacer. Furthermore, it is preferable to put a desiccant in the spacer.

  According to the present invention, the heat ray reflective layer of the heat ray shielding glass is formed of a conductive polymer, and a low refractive index layer having a refractive index lower than that of the heat ray reflective layer is formed on the surface thereof. Reflects heat rays such as heating that does not escape and does not take the heat of the outside into the room Improves the visible light transmittance without impairing the heat insulation of the heat ray reflective layer, and makes the heat ray reflective layer rainwater, condensation, moisture It can be protected from moisture such as.

  Therefore, it can be said that the heat ray shielding glass of the present invention is a heat ray shielding glass having excellent heat insulation, high visible light transmittance, sufficient external light, and high water resistance. Further, since the conductive polymer is made of an organic polymer, it is possible to form a layer by a low cost coating method or the like, and it can be said that the heat ray shielding glass of the present invention can be manufactured at a low cost.

  Furthermore, since the heat ray shielding glass of the present invention is used for the multilayer glass of the present invention, it can be said that the multilayer glass is excellent in heat insulation, durability and weather resistance, and inexpensive.

FIG. 1 is a schematic sectional view showing a typical example of the heat ray shielding glass of the present invention. FIG. 2 is a schematic sectional view showing a typical example of the multilayer glass of the present invention.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. FIG. 1 is a schematic sectional view showing a typical example of the heat ray shielding glass of the present invention. In the present invention, “glass” in the heat-shielding glass means a transparent substrate in general, and may be a transparent plastic substrate in addition to a glass plate. Accordingly, the heat ray shielding glass means a transparent substrate provided with heat ray shielding properties.

  In the heat ray shielding glass 10 shown in FIG. 1, an adhesive layer 12, a transparent plastic film 13, a heat ray reflective layer 14 made of a conductive polymer, a refractive index adjusting material and a binder resin are formed on the surface of the glass plate 11. The low refractive index layer 15 is laminated and integrated in this order. Here, the refractive index of the low refractive index layer 15 is lower than the refractive index of the heat ray reflective layer 14. Usually, the heat ray-shielding glass 10 forms a heat ray reflective layer 14 made of a conductive polymer on one surface of a transparent plastic film 13, and further forms a low refractive index layer 15 on the surface, and then a transparent plastic film. 13 is bonded to the glass plate 11 through the adhesive layer 12 on the surface opposite to the surface on which the heat ray reflective layer 14 is formed. The heat ray shielding glass 10 of the present invention can effectively shield near-infrared rays and exhibit heat insulation properties by forming the heat ray reflective layer 14 made of a conductive polymer. This is thought to be because the plasma absorption wavelength due to free electrons of the conductive polymer is shorter than the radiation of an object near the ground temperature, and reflects electromagnetic waves having a wavelength higher than the plasma absorption wavelength.

  However, the heat ray-shielding glass on which the conductive polymer layer is formed has a problem that the visible light transmittance is low and a water resistance of the conductive polymer layer is low. In order to improve the visible light transmittance or to improve the water resistance, when a material having high physical properties or high water resistance is mixed in the conductive polymer layer, in general, the free electron density is lowered and sufficient. Insulation cannot be obtained. Moreover, normally, when another layer (for example, protective layer) is formed on the surface of the conductive polymer layer, sufficient heat insulation cannot be obtained due to infrared absorption of the other layer.

  In the present invention, the low refractive index layer 15 having a refractive index lower than that of the heat ray reflective layer 14 is formed on the surface of the heat ray reflective layer 14 made of a conductive polymer, so that the heat ray reflective layer 14 made of the conductive polymer is formed. The visible light transmittance can be improved without impairing the radiation suppressing effect, and the high heat insulating property is not impaired, and the heat ray reflective layer 14 can be protected from moisture such as rain water, condensation, and moisture.

  The layer thickness of the low refractive index layer 15 is not particularly limited as long as the effects of the present invention can be achieved. However, if it is too thick, the heat insulation property of the heat ray reflective layer 14 made of a conductive polymer may be impaired. In some cases, the effects of improving the visible light transmittance and water resistance cannot be sufficiently obtained. Therefore, the layer thickness of the low refractive index layer 15 is preferably 50 to 350 nm, more preferably 50 to 250 nm, and particularly preferably 50 to 150 nm.

  Moreover, the low refractive index layer 15 should just be a refractive index lower than the heat ray reflective layer 14 which consists of conductive polymers. The one where the difference of both refractive indexes is large can improve the visible light transmittance of heat ray shielding glass. The refractive index of the heat ray reflective layer 14 made of a conductive polymer is generally 1.5 or more, preferably 1.51 to 1.54. Therefore, the refractive index of the low refractive index layer is preferably 1.48 or less, more preferably 1.45 or less, and particularly preferably 1.42 or less.

  A high refractive index layer having a higher refractive index than that of the heat ray reflective layer 14 may be formed between the heat ray reflective layer 14 and the low refractive index layer 15 (not shown). Thereby, since the refractive index difference at the interface of the surface of the heat ray shielding glass can be further increased, the visible light transmittance can be further improved. The refractive index of the high refractive index layer is preferably 1.54 or more, more preferably 1.60 or more, and particularly preferably 1.69 to 1.80.

  The low refractive index layer 15 may be formed of any material as long as the above refractive index is obtained. For example, a composition in which a refractive index adjusting material such as porous fine particles, hollow fine particles, oxide fine particles and fluororesin fine particles is dispersed in a binder resin such as a thermosetting resin or an ultraviolet curable resin, which will be described later, is applied and cured. Can be formed.

  Since the porous fine particles and the hollow fine particles contain air inside, the refractive index can be lowered. Any material may be used, but oxide porous fine particles and hollow fine particles are preferable, and porous silica fine particles and hollow silica fine particles are particularly preferable. Examples of the oxide fine particles include fine particles of oxides such as silica, aluminum oxide, and zirconia, and silica fine particles are particularly preferable. The porous silica fine particles can be obtained, for example, by forming an aggregate of silica fine particles by spray drying a colloidal solution of silica fine particles. The hollow silica fine particles can be obtained, for example, by covering the surface of the porous silica fine particles with an organosilicon compound and closing the pore entrance. Hollow silica fine particles can be preferably used because they exhibit a refractive index (about 1.24 to 1.44) lower than that of ordinary silica fine particles (about 1.46).

  Examples of the fluororesin fine particles include FET (fluoroethylene / propylene copolymer), PTFE (polytetrafluoroethylene), ETFE (ethylene / tetrafluoroethylene), PVF (polyvinyl fluoride), PVD (polyvinylidene fluoride), and the like. Fine particles consisting of

  When fine particles are used as the refractive index adjusting material in the low refractive index layer 15, the average particle diameter is preferably 1 to 200 nm. With this average particle size, the transparency can be prevented from being greatly affected. When hollow silica fine particles are used, the average particle size is preferably 5 to 200 nm, more preferably 10 to 100 nm, and particularly preferably 20 to 70 nm.

Although the compounding quantity of microparticles | fine-particles does not have a restriction | limiting in particular, 5-90 mass parts is preferable with respect to 100 mass parts of binder resins, such as ultraviolet curable resin, and 10-70 mass parts is still more preferable.
Moreover, the low refractive index layer 15 is good also as an organic thin film layer containing a fluororesin, a silicone resin, or an acrylic silicone resin. Examples of the fluororesin include the same fluororesins as the above-mentioned fluororesin fine particles. In the case of forming an organic thin film, for example, these refractive index adjusting materials can be formed by applying and curing a composition in which a binder resin such as an ultraviolet curable resin described later is mixed.

When a high refractive index layer is formed between the heat ray reflective layer 14 and the low refractive index layer 15, for example, a composition in which a refractive index adjusting material such as metal oxide fine particles is dispersed in a binder resin such as an ultraviolet curable resin described later. It can be formed by applying and curing an object. As metal oxide fine particles used for the high refractive index layer, ITO, ATO, Sb ₂ O ₅ , Sb ₂ O ₃ , SbO ₂ , In ₂ O ₃ , SnO ₂ , ZnO, ZrO ₂ , ZnO doped with Al, TiO ₂ and the like. As the metal oxide fine particles, those having an average particle diameter of 10 to 50 nm are preferable, and ZrO ₂ fine particles are particularly preferable. When forming a high refractive index layer, the thickness of the high refractive index layer is preferably 20 to 300 nm, and more preferably 40 to 200 nm.

  In the present invention, the surface resistance value of the heat ray reflective layer 14 made of a conductive polymer is preferably 100000Ω / □ or less. With this surface resistance value, even if the low refractive index layer 15 is formed, the free electron density is sufficiently high and sufficient heat insulation is obtained. The surface resistance value is more preferably 10000Ω / □ or less, particularly 1000Ω / □ or less.

  The layer thickness of the heat ray reflective layer 14 made of a conductive polymer is preferably 10 to 3000 nm, more preferably 100 to 2000 nm, and particularly 150 to 1500 nm.

  In the present invention, the adhesive layer 12 and the transparent plastic film 13 may be omitted, and the heat ray reflective layer 14 may be directly formed on the surface of the glass plate 11.

[Heat ray reflective layer]
The conductive polymer forming the heat ray reflective layer 14 is generally an organic polymer having a conjugated double bond as a basic skeleton, specifically, polythiophene, polypyrrole, polyaniline, polyacetylene, polyparaphenylene, polyfuran, polyfluorene. , Polyphenylene vinylene, derivatives thereof, and any one or a mixture of two or more conductive polymers selected from copolymers of monomers constituting them are preferable. Among these, polythiophene derivatives that are soluble or dispersible in water or other solvents and exhibit high conductivity and transparency are preferable. In particular, the following formula (I):

(In the formula, R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, or R ¹ and R ² together may be optionally substituted carbon. A polythiophene derivative containing a repeating unit represented by an alkylene group having 1 to 4 atoms and n represents an integer of 50 to 1000 is preferable.

In the formula (I), R ¹ and R ² are combined to form an alkylene group having 1 to 4 carbon atoms which may be used as a substituent, specifically, a methylene group substituted with an alkyl group, Examples thereof include groups that form ethylene-1,2 groups, propylene-1,3 groups, butene-1,4 groups optionally substituted with alkyl groups having 1 to 12 carbon atoms or phenyl groups.

As R1 and R2 in formula (I), preferably either a methyl group or an ethyl group, methylene ^{group R 1} and ^{R 2} form together an ethylene-1,2 radical or propylene-1,3 radical is there. Particularly preferred polythiophene derivatives include the following formula (II):

(Wherein p represents an integer of 50 to 1000), that is, a polythiophene derivative having a poly (3,4-ethylenedioxythiophene) unit.

  The conductive polymer preferably further contains a dopant (electron donor). Preferred examples of the dopant include polystyrene sulfonic acid, polyacrylic acid, polymethacrylic acid, polymaleic acid, and polyvinyl sulfonic acid. In particular, polystyrene sulfonic acid is preferable. By these, the electroconductivity of a conductive polymer can be improved and the near-infrared shielding effect of the heat ray reflective layer 14 can be improved. The number average molecular weight Mn of the dopant is preferably 1,000 to 2,000,000, particularly preferably 2,000 to 500,000.

  Content of a dopant is 20-2000 mass parts normally with respect to 100 mass parts of conductive polymers, Preferably, it is 40-200 mass parts. For example, when the polythiophene derivative of the formula (II) is a conductive polymer and polystyrene sulfonic acid is used as a dopant, 100 to 200 parts by mass of polystyrene sulfonic acid is preferable with respect to 100 parts by mass of polythiophene, and particularly 120 to 180 parts by mass. Part is preferred.

  The heat ray reflective layer made of a conductive polymer can be formed by a conventionally known method. For example, a coating solution in which a conductive polymer is dissolved or dispersed is applied to the surface of a transparent plastic film or glass plate or an adhesive layer using an appropriate method such as a bar coater method, a roll coater method, a curtain flow method, or a spray method. Apply and dry to form. Solvents used in the coating liquid include water; alcohols such as methanol, ethanol and propanol; ketones such as acetophenone and methyl ethyl ketone; halogenated hydrocarbons such as carbon tetrachloride and fluorinated hydrocarbons; ethyl acetate and butyl acetate. Preferred examples include esters such as tetrahydrofuran, dioxane and diethyl ether; and amides such as N, N-dimethylacetamide, N, N-dimethylformamide and N-methylpyrrolidone. In particular, water and alcohols are preferable.

[Binder resin]
The binder resin used for the low refractive index layer 15 (high refractive index layer as necessary) is not particularly limited as long as the heat ray reflective layer 14 can be protected from moisture such as rainwater, condensation, moisture, etc. In order to protect from physical damage such as scratches and notches, it is preferable to use an ultraviolet curable resin or a thermosetting resin which is a curable synthetic resin. In particular, an ultraviolet curable resin is preferable because it can be cured in a shorter time and has excellent productivity. Examples of the ultraviolet curable resin or thermosetting resin include phenolic resin, resorcinol resin, urea resin, melamine resin, epoxy resin, acrylic resin, urethane resin, furan resin, and silicone resin. An ultraviolet curable resin composition is used together with a photopolymerization initiator and the like, and a thermosetting resin is used as a thermosetting resin composition together with a thermal polymerization initiator and the like.
Examples of the ultraviolet curable resin (monomer, oligomer) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2-ethylhexyl polyethoxy (meth) acrylate. , Benzyl (meth) acrylate, isobornyl (meth) acrylate, phenyloxyethyl (meth) acrylate, tricyclodecane mono (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, acryloylmorpholine , N-vinylcaprolactam, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, o-phenylphenyloxyethyl (meth) acrylate, neopentylglyce Di (meth) acrylate, neopentyl glycol dipropoxy di (meth) acrylate, neopentyl glycol di (meth) acrylate hydroxypivalate, tricyclodecane dimethylol di (meth) acrylate, 1,6-hexanediol di (meth) Acrylate, nonanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, tris [(meth) acryloxyethyl] isocyanurate, ditrimethylolpropane (Meth) acrylate monomers such as tetra (meth) acrylate; polyol compounds (for example, ethylene glycol, propylene glycol, neopentyl glycol, , 6-hexanediol, 3-methyl-1,5-pentanediol, 1,9-nonanediol, 2-ethyl-2-butyl-1,3-propanediol, trimethylolpropane, diethylene glycol, dipropylene glycol, polypropylene Polyols such as glycol, 1,4-dimethylolcyclohexane, bisphenol A polyethoxydiol, polytetramethylene glycol, the polyols and succinic acid, maleic acid, itaconic acid, adipic acid, hydrogenated dimer acid, phthalic acid, isophthalic acid Polyester polyols which are reaction products of polybasic acids such as acid and terephthalic acid or acid anhydrides thereof, polycaprolactone polyols which are reaction products of the polyols and ε-caprolactone, the polyols and the above, Polybasic acid or this Reaction products of these acid anhydrides with ε-caprolactone, polycarbonate polyols, polymer polyols, etc.) and organic polyisocyanates (for example, tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, diphenylmethane-4,4′-diisocyanate, diisocyanate) Cyclopentanyl diisocyanate, hexamethylene diisocyanate, 2,4,4′-trimethylhexamethylene diisocyanate, 2,2′-4-trimethylhexamethylene diisocyanate, etc.) and a hydroxyl group-containing (meth) acrylate (for example, 2-hydroxyethyl (meta ) Acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylic Rate, cyclohexane-1,4-dimethylol mono (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerin di (meth) acrylate, etc.) (Meth) such as bisphenol type epoxy (meth) acrylate, which is a reaction product of bisphenol type epoxy resin such as polyurethane (meth) acrylate, bisphenol A type epoxy resin, bisphenol F type epoxy resin and (meth) acrylic acid which is a reaction product Examples include acrylate oligomers. These compounds can be used alone or in combination.

  These ultraviolet curable resins may be used as a thermosetting resin together with a thermal polymerization initiator.

  In order to make the low refractive index layer 15 a hard coat layer, among the above-mentioned ultraviolet curable resins (monomer, oligomer), pentaerythritol tri (meth) acrylate, pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meta) ) It is preferable to mainly use hard polyfunctional monomers such as acrylate and trimethylolpropane tri (meth) acrylate.

  As the photopolymerization initiator used together with the ultraviolet curable resin, any compound suitable for the properties of the ultraviolet curable resin can be used. For example, acetophenone such as 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropane-1 Benzoin series such as benzyl dimethyl ketal, benzophenone, 4-phenylbenzophenone, benzophenone series such as hydroxybenzophenone, thioxanthone series such as isopropylthioxanthone, 2-4-diethylthioxanthone, and other special types include methylphenyl glyoxylate Etc. can be used. Particularly preferably, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropane-1, Examples include benzophenone. These photopolymerization initiators may be optionally selected from one or more known photopolymerization accelerators such as benzoic acid type or tertiary amine type such as 4-dimethylaminobenzoic acid. It can be used by mixing at a ratio. Moreover, it can be used by 1 type, or 2 or more types of mixture of only a photoinitiator. Particularly preferred is 1-hydroxycyclohexyl phenyl ketone (Irgacure 184, manufactured by Ciba Specialty Chemicals). Generally the quantity of a photoinitiator is 0.1-10 mass% with respect to a resin composition, Preferably it is 0.1-5 mass%.

  Examples of the thermal polymerization initiator used together with the thermosetting resin include organic peroxides and cationic polymerization initiators which are compounds containing a functional group that initiates polymerization by heating, and organic peroxides are preferred. For example, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane (2,5-dimethyl) Preferred examples include -2,5-bis (t-butylperoxy) hexane, t-butylperoxy 2-ethylhexanate, t-butylperoxybenzoate, and t-hexylperoxyisopropyl monocarbonate. Are 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane and 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane. The amount of the thermal polymerization initiator is generally 0.01 to 10% by mass relative to the resin composition. Mashiku is 0.1 to 5 mass%.

  The low refractive index layer 15 may contain a small amount of an ultraviolet absorber, an infrared absorber, an anti-aging agent, a paint processing aid, a colorant, and the like, if necessary. The amount thereof is generally 0.1 to 10% by mass, preferably 0.1 to 5% by mass, based on the resin composition.

  In order to form the low refractive index layer 15 (a high refractive index layer as necessary), for example, the refractive index adjusting material, the binder resin composition (preferably an ultraviolet curable resin and a photopolymerization initiator, or thermosetting). Resin and thermal polymerization initiator) and, if necessary, a coating solution containing other additives is applied to the surface of the heat ray reflective layer 14 and then dried, followed by curing by ultraviolet irradiation or curing by heat treatment. do it.

  In the case of an ultraviolet curable resin, as a specific method of coating, a gravure coater or the like is used to coat a coating solution obtained by dissolving an ultraviolet curable resin composition containing an acrylic monomer or the like with a solvent such as toluene, and then dried. Then, a method of curing with ultraviolet rays can be mentioned. This wet coating method has the advantage that the film can be uniformly formed at high speed at low cost. After this coating, for example, by irradiating with ultraviolet rays and curing, effects of improving adhesion and increasing the hardness of the film can be obtained.

  In the case of an ultraviolet curable resin, when it is cured in a nitrogen atmosphere, polymerization inhibition due to oxygen in the air can be eliminated, so that the low refractive index layer 15 having higher hardness can be obtained. In the present invention, since the low refractive index layer is preferably a thin layer having a thickness of 50 to 350 nm, ultraviolet curing under a nitrogen atmosphere can be made into a thin and higher hardness low refractive index layer 15. It is effective in.

  In the case of ultraviolet curing, many light sources that emit light in the ultraviolet to visible range can be used as the light source, such as ultra-high pressure, high pressure, low pressure mercury lamp, chemical lamp, xenon lamp, halogen lamp, mercury lamp, carbon arc lamp, incandescent lamp. And laser light. The irradiation time cannot be determined unconditionally depending on the type of lamp and the intensity of the light source, but is about several seconds to several minutes. Moreover, in order to accelerate curing, the laminate may be preheated to 40 to 120 ° C. and irradiated with ultraviolet rays.

  When a high refractive index layer is formed between the heat ray reflective layer 14 and the low refractive index layer 15, the high refractive index layer and the low refractive index layer 15 are applied to the surface of the heat ray reflective layer 14 in this order, and then once. It may be cured by ultraviolet irradiation or the like, and a high refractive index layer is coated on the surface of the heat ray reflective layer 14 and cured by ultraviolet irradiation or the like, and then a low refractive index layer 15 is coated and cured by ultraviolet irradiation or the like. May be. Since the coating layer before curing is easily damaged, it is preferable to cure each layer.

  Below, the other element which comprises the heat ray shielding glass of this invention is demonstrated.

[Glass plate]
The glass plate in the present invention may be a transparent substrate, for example, a glass plate such as green glass, silicate glass, inorganic glass plate, non-colored transparent glass plate, polyethylene terephthalate (PET), polyethylene naphthalate (PEN). Alternatively, a plastic substrate or film such as polyethylene butyrate or polymethyl methacrylate (PMMA) may be used. A glass plate is preferable in terms of weather resistance, impact resistance and the like. As for the thickness of a glass plate, about 1-20 mm is common.

[Transparent plastic film]
The transparent plastic film in the present invention is not particularly limited as long as it is a transparent plastic film (meaning “transparent to visible light”). Examples of plastic films include polyethylene terephthalate (PET) film, polyethylene naphthalate (PEN) film, polymethyl methacrylate (PMMA) film, polycarbonate (PC) film, polyethylene butyrate film, especially during processing. A PET film is preferred because of its high resistance to heat, solvent, bending and other loads, and high transparency. Moreover, in order to improve adhesiveness, the transparent plastic film surface may be subjected to adhesion treatment such as corona treatment, plasma treatment, flame treatment, primer layer coating treatment in advance, such as copolymer polyester resin and polyurethane resin. An easily adhesive layer such as a thermosetting resin may be provided. The thickness of the transparent plastic film is generally 1 μm to 10 mm, preferably 10 to 400 μm, and particularly preferably 20 to 200 μm.

[Adhesive layer]
The adhesive layer in the present invention comprises an ethylene-vinyl acetate copolymer (EVA), an ethylene-methyl acrylate copolymer, an ethylene- (meth) acrylic acid copolymer, an ethylene- (meth) ethyl acrylate copolymer. , Ethylene- (meth) acrylate methyl copolymer, metal ion cross-linked ethylene- (meth) acrylic acid copolymer, partially saponified ethylene-vinyl acetate copolymer, carboxylated ethylene-vinyl acetate copolymer, ethylene- ( Ethylene-based copolymers such as (meth) acrylic-maleic anhydride copolymer and ethylene-vinyl acetate- (meth) acrylate copolymer can be used ("(meth) acryl" means "acrylic or methacrylic" Is shown.) For the adhesive layer, polyvinyl butyral (PVB) resin, epoxy resin, phenol resin, silicone resin, polyester resin, urethane resin, rubber adhesive, thermoplastic elastomer such as SEBS and SBS, and the like can also be used. Among these, EVA is preferably used because it exhibits excellent adhesiveness and high transparency.

  EVA used for the adhesive layer has a vinyl acetate content of 23 to 38 parts by mass, particularly preferably 23 to 28 parts by mass with respect to 100 parts by mass of EVA. Thereby, the adhesive bond layer excellent in adhesiveness and transparency can be obtained. Moreover, it is preferable that the melt flow index (MFR) of EVA is 4.0-30.0 g / 10min, especially 8.0-18.0g / 10min. Pre-crimping becomes easy.

  When using an ethylene-type copolymer for an adhesive bond layer, it is preferable to contain an organic peroxide further. By crosslinking and curing with an organic peroxide, adjacent layers and a glass plate can be further joined and integrated. Any organic peroxide may be used in combination as long as it decomposes at a temperature of 100 ° C. or higher and generates radicals. The organic peroxide is generally selected in consideration of the film formation temperature, the adjustment conditions of the composition, the curing (bonding) temperature, the heat resistance of the adherend, and the storage stability. In particular, those having a decomposition temperature of 70 hours or more with a half-life of 10 hours are preferred.

Examples of this organic peroxide include 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane-3-di- t-butyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, dicumyl peroxide, α, α′-bis (t-butylperoxy) Isopropyl) benzene, n-butyl-4,4-bis (t-butylperoxy) valerate, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) -3 , 3,5-trimethylcyclohexane, t-butyl peroxybenzoate, benzoyl peroxide, t-butyl peroxyacetate, methyl ethyl ketone pero Side, 2,5-dimethylhexyl-2,5-bisperoxybenzoate, butyl hydroperoxide, p-menthane hydroperoxide, p-chlorobenzoyl peroxide, hydroxyheptyl peroxide, chlorohexanone peroxide, octanoyl peroxide Oxide, decanoyl peroxide, lauroyl peroxide, cumyl peroxy octoate, succinic acid peroxide, acetyl peroxide, m-toluoyl peroxide, t-butyl peroxyisobutylene and 2,4-dichlorobenzoyl peroxide Can be mentioned.
The adhesive layer preferably further contains a silane coupling agent as a crosslinking aid or adhesion improver.

  Examples of the crosslinking aid include polyfunctional compounds such as esters obtained by esterifying a plurality of acrylic acid or methacrylic acid with glycerin, trimethylolpropane, pentaerythritol, and the like, triallyl cyanurate, and triallyl isocyanurate.

  Examples of silane coupling agents include γ-chloropropylmethoxysilane, vinylethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, γ-glycidoxypropyltrimethoxy. Silane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, vinyltrichlorosilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β Mention may be made of-(aminoethyl) -γ-aminopropyltrimethoxysilane. These silane coupling agents may be used alone or in combination of two or more. Moreover, it is preferable that content of the said compound is 5 mass parts or less with respect to 100 mass parts of ethylene-type copolymers.

  The adhesive resin layer is used to improve or adjust various physical properties (optical properties such as mechanical strength, adhesiveness, and transparency, heat resistance, light resistance, crosslinking speed, etc.), especially to improve mechanical strength and light resistance. It preferably contains an acryloxy group-containing compound, a methacryloxy group-containing compound, an epoxy group-containing compound, a plasticizer, and an ultraviolet absorber. Examples of the ultraviolet absorber include benzophenone compounds, triazine compounds, benzoate compounds, and hindered amine compounds. From the viewpoint of suppressing yellowing, benzophenone compounds are preferred. The ultraviolet absorber is preferably used in an amount of 0.01 to 1.5 parts by mass (particularly 0.5 to 1.0 part by mass) with respect to 100 parts by mass of the ethylene copolymer.

  The thickness of the adhesive layer is preferably 100 to 2000 μm, particularly 400 to 1000 μm.

  In order to produce an adhesive layer containing an ethylene copolymer, for example, a composition containing an ethylene copolymer and an organic peroxide is formed by ordinary extrusion molding, calendar molding (calendering), or the like. For example, a method for obtaining a layered product can be used. The composition is preferably mixed by heating and kneading at a temperature of 40 to 90 ° C, particularly 60 to 80 ° C. The heating temperature during film formation is preferably a temperature at which the crosslinking agent does not react or hardly reacts. For example, it is preferably 40 to 90 ° C, particularly 50 to 80 ° C. The adhesive layer may be formed directly on the surface of a transparent plastic film or glass plate, or may be formed separately using a film-like adhesive sheet.

In order to produce the heat ray shielding glass according to the present invention, for example, a transparent plastic film having a heat ray reflecting layer (if necessary, the heat ray shielding layer may be formed on the lower layer side of the heat ray reflecting layer), and glass Prepare a plate, through the adhesive layer as described above (formed on the surface opposite to the surface on which the heat ray reflective layer etc. of the transparent plastic film is formed, or laminate the adhesive sheet on the glass plate), After deaeration of the laminate obtained by laminating the transparent plastic film and the glass plate on which the heat ray reflective layer or the like is formed, heating is performed (preferably at 40 to 200 ° C. for 1 to 120 minutes, particularly at 60 to 150 ° C. for 1 to 20). It is sufficient that the pressure is pressed (preferably a pressure of 1.0 × 10 ³ Pa to 5.0 × 10 ⁷ Pa) for one minute to bond and integrate. These steps can be performed, for example, by a vacuum bag method, a nip roll method, or the like.

For example, when EVA is used for the adhesive layer, it is generally crosslinked at 100 to 150 ° C. (particularly around 130 ° C.) for 10 minutes to 1 hour. This is performed by degassing the laminated body, and pre-pressing at a temperature of, for example, 80 to 120 ° C., and performing a heat treatment at 100 to 150 ° C. (particularly around 130 ° C.) for 10 minutes to 1 hour. Cooling after crosslinking is generally performed at room temperature, and in particular, the faster the cooling, the better.
Even when a transparent plastic film is not used, an adhesive layer can be provided on the glass plate in order to improve the adhesion of the heat ray shielding layer and the heat ray reflective layer to the glass plate.

[Multilayer glass]
It is preferable that the heat ray shielding glass of the present invention is used for a multilayer glass. By making the heat ray shielding glass of the present invention into a multilayer glass, the heat ray reflective layer can be further protected from moisture such as rain water, condensation, moisture and the like, as well as from physical damage such as scratches and scratches. Further, the performance can be maintained for a longer period.

  FIG. 2 is a schematic cross-sectional view showing a typical example of the multilayer glass of the present invention. As shown in the drawing, the multilayer glass 30 of the present invention is composed of a heat ray shielding glass 20 of the present invention (an adhesive layer 22, a transparent plastic film 23, a heat ray reflective layer 24 made of a conductive polymer on the surface of a glass plate 21, a low The refractive index layer 25 is laminated and integrated in order), another glass plate 27 disposed so as to face the heat ray shielding glass 20 with a gap, and an adhesive (not shown) disposed on the outer peripheral portion thereof. ), And a hollow layer 28 formed between the heat ray shielding glass 20 and the glass plate 27 by the spacer 29. By forming the hollow layer 28, further heat insulation is imparted. In the multi-layer glass 30, the heat ray shielding glass 20 is disposed so that the heat ray reflective layer 24 having the low refractive index layer 25 formed on the surface thereof faces the glass plate 27. As a result, the heat ray reflective layer 24 can be protected from moisture such as rain water, dew condensation, moisture and the like, and can be protected from physical damage such as scratches and scratches. Performance can be maintained.

  An air layer, an inert gas layer, or the like is used as the hollow layer. According to these hollow layers, it is possible to improve the heat insulating properties required for the multilayer glass and to suppress the deterioration of the heat ray reflective layer 24 over time. The air layer may use dry air by placing a desiccant in the spacer 29. The inert gas layer includes an inert gas such as krypton gas, argon gas, and xenon gas. The thickness of the hollow layer is preferably 6 to 12 mm.

  As described above, the multilayer glass of the present invention can maintain excellent heat ray shielding properties over a long period of time. Since the heat ray reflective layer of the heat ray shielding glass of the present invention is protected by the low refractive index layer, such an effect can be sufficiently obtained even when an air layer is used as the hollow layer. In this case, the desiccant is not used or the amount of the desiccant used can be reduced, and a simpler configuration can be obtained.

  As glass plates, float glass, template glass, ground glass with light diffusion function by surface treatment, netted glass, lined glass, tempered glass, double tempered glass, low reflection glass, high transmission plate glass, ceramic printing glass, heat ray Various glass such as special glass having a UV absorbing function can be selected as appropriate. Moreover, about the composition of a glass plate, soda silicate glass, soda lime glass, borosilicate glass, aluminosilicate glass, various crystallized glass, etc. can be used.

  The shape of the multi-layer glass can be various shapes such as a rectangular shape, a round shape, and a rhombus shape depending on applications. As for the use of double glazing, doors of various devices such as window glass for buildings and vehicles (automobiles, railway vehicles, ships), and equipment elements such as plasma displays, refrigerators, heat insulation devices, etc. It can be used for various applications such as walls.

When the double-glazed glass of the present invention is used for a building or vehicle in a warm area such as a relatively low latitude area, the glass plate is on the indoor side and the heat ray shielding glass is on the outdoor side. Preferably it is arranged. This is because sunlight and the near infrared rays irradiated from the outside can be effectively shielded. On the other hand, when the double-glazed glass of the present invention is used in a cold region such as a region having a relatively high latitude, it is preferable that the glass plate is disposed on the outdoor side and the heat ray shielding glass is disposed on the indoor side.
This is because infrared rays such as heating emitted from the room are reflected and not escaped (heat insulation), and the heating efficiency can be improved. Since the double-glazed glass of the present invention is excellent in heat insulating properties, it can be used more effectively in cold regions.

  Hereinafter, the present invention will be described in more detail with reference to examples.

1. Preparation of heat ray shielding glass [Example 1]
(1) Formation of heat ray reflective layer An aqueous dispersion of a mixture of poly (3,4-ethylenedioxythiophene) and polystyrenesulfonic acid on a PET film (thickness 100 μm) (PT-400MF (manufactured by Nagase Chemtech)) A solid content of 1.3% by mass was applied using a bar coater and dried at 135 ° C. for 1 minute to form a heat ray reflective layer (thickness 300 nm) on the PET film.
(2) Formation of a low refractive index layer A coating liquid having the following composition was applied to the surface of the heat ray reflective layer by a roll coater, dried at 80 ° C. for 1 minute, and then irradiated with ultraviolet rays (high pressure mercury lamp, irradiation distance). 20 cm, irradiation time 5 seconds), and a low refractive index layer having a thickness of 90 nm was formed.
(Combination)
Dipentahexaacrylate (DPHA): 20 parts by mass Photopolymerization initiator (Irgacure (registered trademark) 184 (manufactured by Ciba Specialty Chemicals)): 2 parts by mass Hollow silica fine particles (average particle size 60 nm) (Thruria 1420 (manufactured by Catalyst Kasei Co., Ltd.)) (solid content 20%): 200 parts by mass (3) Production of Adhesive Layer A composition having the following composition was rolled into a sheet by a calendering method, and an adhesive layer (thickness 0) 4 mm). The blend was kneaded at 80 ° C. for 15 minutes, the calender roll temperature was 80 ° C., and the processing speed was 5 m / min.
(Combination)
EVA (content of vinyl acetate with respect to 100 parts by mass of EVA: 25 parts by mass; Ultrasen 635 (manufactured by Tosoh Corporation)): 100 parts by mass,
Organic peroxide (tert-butyl peroxy-2-ethylhexyl carbonate; Trigonox 117 (manufactured by Kayaku Akzo)): 2.5 parts by mass,
Cross-linking assistant (triallyl isocyanurate; TAIC (registered trademark) (manufactured by Nippon Kasei Co., Ltd.)): 2 parts by mass,
Silane coupling agent (γ-methacryloxypropyltrimethoxysilane; KBM503 (manufactured by Shin-Etsu Chemical Co., Ltd.)): 0.5 part by mass UV absorber: (Ubinal 3049 (manufactured by BASF)): 0.5 part by mass (4) Production of heat ray shielding glass On a glass plate (thickness 3 mm), an adhesive layer and the PET film (a heat ray reflective layer and a low refractive index layer were formed in this order on the surface) were laminated in this order. The obtained laminate was temporarily pressed by heating at 100 ° C. for 30 minutes, and then heated in an autoclave for 30 minutes under conditions of a pressure of 13 × 10 ⁵ Pa and a temperature of 140 ° C. Thereby, the adhesive layer was cured to obtain heat ray shielding glass (FIG. 1) in which the glass plate and the PET film were bonded and integrated.

[Example 2]
As a polythiophene derivative of the heat ray reflective layer, an aqueous dispersion of a mixture of poly (3,4-ethylenedioxythiophene) and polystyrenesulfonic acid (Baytron P HC V4 (HC Starck Co., Ltd., solid content: 1.3% by mass)) is used. A heat ray shielding glass was produced in the same manner as in Example 1 except that.

[Example 3]
A heat ray shielding glass was produced in the same manner as in Example 1 except that the thickness of the low refractive index layer was 200 nm.

[Example 4]
A heat ray shielding glass was produced in the same manner as in Example 2 except that the thickness of the low refractive index layer was 200 nm.

[Example 5]
A heat ray shielding glass was produced in the same manner as in Example 1 except that a coating liquid having the following composition was used for the low refractive index layer.
(Combination)
Dipentahexaacrylate (DPHA): 10 parts by mass Photopolymerization initiator (Irgacure (registered trademark) 184 (manufactured by BASF Japan)): 2 parts by mass Fluororesin (OPTOOL AR-110 (manufactured by Daikin Industries) (solid content 15) % By mass): 200 parts by mass Methyl isobutyl ketone: 10 parts by mass

[Example 6]
A heat ray shielding glass was produced in the same manner as in Example 2 except that a coating liquid having the following composition was used for the low refractive index layer.
(Combination)
Dipentahexaacrylate (DPHA): 10 parts by mass Photopolymerization initiator (Irgacure (registered trademark) 184 (manufactured by BASF Japan)): 2 parts by mass Fluororesin (OPTOOL AR-110 (manufactured by Daikin Industries) (solid content 15) % By mass): 200 parts by mass Methyl isobutyl ketone: 10 parts by mass

[Comparative Example 1]
A heat ray shielding glass was prepared in the same manner as in Example 1 except that an acrylic resin layer using a coating liquid having the following composition was formed instead of the low refractive index layer.
(Combination)
Dipentahexaacrylate (DPHA): 40 parts by mass Photopolymerization initiator (Irgacure (registered trademark) 184 (manufactured by BASF Japan)): 2 parts by mass Methyl isobutyl ketone: 180 parts by mass

[Comparative Example 2]
(1) Formation of heat ray reflective layer A heat ray reflective layer (thickness 300 nm) was formed in the same manner as in Example 1 (1).
(2) Production of adhesive layer An adhesive layer was produced in the same manner as in Example 1 (3).
(3) Production of heat ray shielding glass A heat ray shielding glass was produced in the same manner as in Example 1 (4) except that the low refractive index layer was not formed.

[Comparative Example 3]
(1) Production of adhesive layer An adhesive layer was produced in the same manner as in Example 1 (3).
(2) Production of laminated glass An adhesive layer and a PET film (thickness 100 μm) were laminated on a glass plate (thickness 3 mm). The obtained laminate was temporarily pressed by heating at 100 ° C. for 30 minutes, and then heated in an autoclave for 30 minutes under conditions of a pressure of 13 × 10 ⁵ Pa and a temperature of 140 ° C. As a result, the adhesive layer was cured to obtain a laminated glass in which the glass plate and the PET film were bonded and integrated.

2. Evaluation Method (1) Emissivity Measured according to JIS R3106.
(2) Visible light transmittance Using the transmission spectrum measured by a spectrophotometer UV3100PC (manufactured by Shimadzu Corporation), Y of the tristimulus value of the XYZ color system is calculated to obtain luminous transmittance (Y). It was. The calculation method was performed using a C light source of 2 ° (JIS Z8722-2000).
(3) Weather resistance Each glass sample was left in an atmosphere of a temperature of 40 ° C. and a humidity of 90% RH for 1000 hours to evaluate the appearance. The case where there was no change in appearance was marked as ◯, and the case where there was a change in appearance such as film peeling was marked as x.

3. Evaluation results Table 1 shows the evaluation results of the respective glass samples.

  As shown in Table 1, the heat ray shielding glasses of Examples 1 to 6 in which the low refractive index layer is formed have the same emissivity as Comparative Examples 1 and 2 without the low refractive index layer, and high heat insulation is maintained. It was confirmed that the visible light transmittance was improved. Furthermore, it was shown that the weather resistance was improved and protected from moisture as compared with Comparative Example 2 having no protective layer on the surface.

  In addition, this invention is not limited to said embodiment and Example, A various deformation | transformation is possible within the range of the summary of invention.

  It is possible to provide heat ray shielding glass or multi-layer glass that can reduce the air-conditioning load of buildings such as office buildings and buses, passenger cars, trains and other vehicles and railways over a long period of time.

10: Heat ray shielding glass 11, 21, 27: Glass plate 12, 22: Adhesive layer 13, 23: Transparent plastic film 14, 24: Heat ray reflective layer 15, 25: Low refractive index layer 28: Hollow layer 29: Spacer 30 : Multi-layer glass

Claims (9)

  A heat ray shielding glass comprising a glass plate and a heat ray reflective layer made of a conductive polymer provided on the surface thereof, wherein a low refractive index layer is formed on the surface of the heat ray reflective layer, and the low refractive index A heat ray-shielding glass, wherein the refractive index of the layer is lower than that of the heat ray reflective layer.   The heat ray-shielding glass according to claim 1, wherein the low refractive index layer has a thickness of 50 to 350 nm.   The heat ray shielding glass according to claim 1 or 2, wherein a refractive index of the low refractive index layer is 1.48 or less.   The low refractive index layer includes the low refractive index layer containing at least one refractive index adjusting material selected from the group consisting of porous fine particles, hollow fine particles, oxide fine particles, and fluororesin fine particles. Heat ray shielding glass given in any 1 paragraph.   The heat ray shielding glass according to any one of claims 1 to 4, wherein the low refractive index layer contains a fluororesin or a silicone resin. The conductive polymer has the following formula (I):

(In the formula, R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, or R ¹ and R ² together may be optionally substituted carbon. The heat ray shielding glass according to any one of claims 1 to 5, which is a polythiophene derivative containing a repeating unit represented by an alkylene group having 1 to 4 atoms and n representing an integer of 50 to 1000.   The heat ray shielding glass according to any one of claims 1 to 6, wherein a surface resistance value of the heat ray reflective layer is 100,000 Ω / □ or less.   The layer thickness of the said heat ray reflective layer is 10-3000 nm, The heat ray shielding glass of any one of Claims 1-7.   The heat ray-shielding glass according to any one of claims 1 to 8 and another glass plate are disposed so that the low refractive index layer faces the other glass plate with a gap therebetween, A multilayer glass, wherein a hollow layer is formed by a gap.

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