JP5559486B2 - Heat ray shielding glass and multilayer glass using the same - Google Patents

Description

  The present invention relates to a heat ray shielding glass that is suitably used for a multilayer glass having heat ray absorptivity and heat insulation properties.

  Conventionally, double glazing has been used for building openings, particularly windows, doors, roofs for lighting and glass parts of vehicles. Multi-layer glass generally has a structure in which two glass plates are arranged in parallel via an air layer. The air layer is formed by laminating two glass plates via a frame-shaped spacer. Due to the presence of the air layer, it is possible to prevent heat from entering and exiting through the multilayer glass and to impart heat insulation to the entire multilayer glass. Therefore, the energy consumed by cooling or heating can be reduced by using the double glazing.

  In recent years, a multi-layer glass that further has the ability to shield heat rays contained in sunlight is also known. For example, in Patent Document 1, a multilayer in which a heat ray-shielding glass plate in which a near-infrared reflective film is laminated on a glass plate and another glass plate are arranged to face each other with a predetermined interval (air layer) therebetween. Glass is disclosed. In the multi-layer glass, the heat ray-shielding glass plate is arranged so that the surface on which the near-infrared reflective film is laminated is the air layer side. The near-infrared reflective film is formed by laminating a metal oxide layer, a silver layer, a metal layer, and a metal oxide layer in this order. Ti, Al—Zn alloy, or the like is used for the metal layer, and tin oxide, zinc oxide, or the like is used for the metal oxide layer. By using such a heat ray-shielding glass plate, heat ray absorptivity can be imparted to the multi-layer glass, and it is possible to further reduce energy consumption and reduce heat sensation due to air conditioning.

JP 2007-70146 A

  However, in the heat ray-shielding glass plate used in the double-glazed glass of Patent Document 1, the moisture resistance and acid resistance of these layers are not sufficient, such as rusting of the silver layer and the metal layer, and heat ray shielding properties and appearance over time. There was a problem that the characteristics deteriorated.

  Then, an object of this invention is to provide the heat ray shielding glass which can maintain the outstanding heat ray shielding property and external appearance characteristic over a long period of time.

The present inventors have made of various studies in view of the above problems, heat rays in combination with heat absorbing layer comprising a tungsten oxide and / or composite tungsten oxide, and a heat ray reflective layer of such a metal oxide other than It discovered that the heat ray shielding glass which can maintain the outstanding heat ray shielding property over a long period of time by using for shielding glass was obtained.

  On the other hand, when these layers are laminated, the incident light may be reflected at the interface between the layers to produce interference fringes such as rainbow patterns. When such interference fringes occur, the appearance characteristics of the heat ray shielding glass deteriorate. According to further studies by the present inventors, the generation of interference fringes is considered to be caused by a large difference in refractive index between the heat ray absorbing layer and the heat ray reflecting layer. Therefore, in the present invention, by arranging the refractive index adjustment layer between the heat ray absorbing layer and the heat ray reflective layer, generation of interference fringes is suppressed, and excellent appearance characteristics and heat ray shielding properties are obtained over a long period of time. It has been found that a heat ray shielding glass that can be maintained can be provided.

That is, the present invention
A transparent substrate;
A heat ray absorbing layer containing tungsten oxide and / or composite tungsten oxide and a binder resin ;
A heat ray reflective layer made of a metal oxide other than the tungsten oxide and the composite tungsten oxide,
Between the ray absorbing layer and the heat ray reflective layer, at least 1 Soyu the refractive index adjusting layer,
The refractive index adjusting layer is composed of a high refractive index layer having a refractive index of 1.6 or more and 2.8 or less and a low refractive index layer having a refractive index of 1.3 or more and less than 1.6,
The above- mentioned problem is solved by a heat ray shielding glass , wherein the heat ray absorbing layer, the high refractive index layer, the low refractive index layer, and the heat ray reflective layer are laminated in this order .

  According to the heat ray shielding glass of the present invention, as described above, by using the heat ray absorbing layer containing tungsten oxide and / or composite tungsten oxide and the heat ray reflecting layer containing other metal oxide, excellent heat ray is obtained. In addition to having a shielding property, this excellent heat ray shielding property can be maintained over a long period of time. Furthermore, by arranging a refractive index adjusting layer between these layers, the occurrence of interference fringes can be suppressed and excellent appearance characteristics can be obtained. Therefore, by using such a heat ray shielding glass, it becomes possible to provide a multilayer glass capable of maintaining excellent heat ray shielding properties and appearance characteristics over a long period of time.

The schematic sectional drawing of the heat ray shielding glass of this invention is shown. The schematic sectional drawing of the heat ray shielding glass of this invention is shown. The schematic sectional drawing of the multilayer glass of this invention is shown.

  The heat ray shielding glass of the present invention includes, as a basic structure, a transparent substrate, a heat ray absorbing layer containing tungsten oxide and / or composite tungsten oxide, and heat ray reflection containing metal oxide other than the tungsten oxide and composite tungsten oxide. And at least one refractive index adjusting layer.

  The refractive index adjustment layer is a layer for suppressing the generation of interference fringes by having a refractive index different from the refractive index of the adjacent layer. The refractive index adjusting layer is disposed between the heat ray absorbing layer and the heat ray reflecting layer. Furthermore, in order to improve the durability of the heat ray shielding property, it is particularly preferable to arrange the heat ray reflective layer as the uppermost layer and arrange the heat ray absorbing layer between the heat ray reflective layer and the transparent substrate. If it is such arrangement | positioning, the layer with another function may be further arrange | positioned between each layer.

  First, the basic structure of the heat ray shielding glass of the present invention will be described below with a suitable example.

FIG. 1 shows a schematic cross-sectional view of a heat ray shielding glass 100 as a preferred embodiment of the present invention. The heat ray shielding glass 100 includes a transparent substrate 110, a heat ray absorbing layer 120 laminated on the transparent substrate 110, a refractive index adjusting layer 130 laminated on the heat ray absorbing layer 120, and the refractive index adjusting layer. And a heat ray reflective layer 140 laminated on 130. The refractive index adjustment layer 130 is a laminate of a high refractive index layer 131 having a refractive index of 1.6 or more and 2.8 or less and a low refractive index layer 132 having a refractive index of 1.3 or more and less than 1.6. Oh Ru. The heat ray absorbing layer 120 includes a heat ray absorbing material such as ( composite) tungsten oxide, and a binder resin such as an ethylene vinyl acetate copolymer (EVA).

  Moreover, the heat ray absorption layer may be formed on the plastic film. When the heat ray absorbing layer formed on the plastic film is used, it is preferable to laminate the plastic film on the transparent substrate via an adhesive resin layer. FIG. 2 shows such a heat ray shielding glass.

FIG. 2 shows a schematic cross-sectional view of a heat ray shielding glass 200 as another preferred embodiment of the present invention. The heat ray shielding glass 200 is formed on the transparent base 210, the adhesive resin layer 250 laminated on the transparent base 210, the plastic film 260 laminated on the adhesive resin layer 250, and the plastic film 260. A heat ray absorbing layer 220, a refractive index adjusting layer 230 laminated on the heat ray absorbing layer 220, and a heat ray reflecting layer 240 laminated on the refractive index adjusting layer 230. Thus, it is preferable to use the heat ray absorbing layer 220 formed on the plastic film 260 because the heat ray absorbing layer 220 of a thin film can be easily produced and is excellent in handleability. The refractive index adjustment layer 230 is a stack of a high refractive index layer 231 having a refractive index of 1.6 or more and 2.8 or less and a low refractive index layer 232 having a refractive index of 1.3 or more and less than 1.6. Karadadea Ru.

The heat ray absorbing layer 220 contains a binder resin in addition to a heat ray absorbing material such as tungsten oxide or composite tungsten oxide . The binder resin preferably contains at least one transparent synthetic resin selected from the group consisting of fluororesins, silicone resins, olefin resins, polyester resins, and acrylic resins. By using such a binder resin, the durability of the heat ray absorbing layer 220 can be improved. The adhesive resin layer 250 preferably includes a transparent adhesive resin such as an ethylene vinyl acetate copolymer.

  The heat ray absorbing layer used for the heat ray shielding glass of the present invention contains tungsten oxide and / or composite tungsten oxide, and thus has excellent heat ray absorptivity without impairing visible light transmittance. By using such a heat ray absorbing layer, a heat ray shielding glass having excellent heat ray shielding properties even if the use of a metal layer such as a low-durability silver layer that has been used in conventionally known multilayer glass is omitted. Can be provided. Furthermore, since neither a heat ray absorption layer nor a heat ray reflection layer contains a metal simple substance, it is excellent in moisture resistance and acid resistance.

  Furthermore, the refractive index adjustment layer is disposed between the heat ray absorbing layer and the heat ray reflective layer, thereby suppressing the occurrence of interference fringes and improving the durability of the heat ray shielding property without deteriorating the appearance characteristics. Is possible.

  In the present invention, the heat ray generally means infrared rays, particularly infrared rays having a wavelength of 780 nm or more that raises the temperature even among sunlight rays.

  Hereinafter, each material used for the heat ray shielding glass of the present invention will be described.

[Refractive index adjusting layer]
As the refractive index adjustment layer , a single or a plurality of refractive index adjustment layers are generally used. In the present invention, the laminate of the high refractive index layer and the low refractive index layer is needed use as a refractive index adjusting layer. Using a high refractive index layer refraction index is 1.6 or more 2.8 or less, the refractive index of the low refractive index layer is less than 1.3 to 1.6, heat absorbing layer, a high refractive index layer, A low refractive index layer and a heat ray reflective layer are laminated in this order. By using the refractive index adjustment layer as described above, the occurrence of interference fringes can be suppressed to a high level by adjusting the refractive index stepwise between the heat ray absorbing layer and the heat ray reflective layer.

  The refractive index of the high refractive index layer is preferably 1.6 or more and 2.8 or less, and particularly preferably 1.7 to 2.1. The refractive index of the low refractive index layer is preferably 1.3 or more and less than 1.6, particularly 1.4 to 1.55.

  The refractive index of each layer such as a refractive index adjusting layer, a heat ray reflecting layer, and a heat ray absorbing layer, which will be described later, is based on a refractometer (manufactured by Atago Co., Ltd., device name: Digital Abbe refractometer DR-). The value obtained by measuring the refractive index at a measurement wavelength of 589 nm in an atmosphere of 23 ° C. using M2).

  It is preferable to use a metal, a metal oxide, a synthetic resin, or the like for the refractive index adjustment layer, and adjust the refractive index with these. Therefore, the refractive index adjustment layer made of metal or metal oxide may be formed by using a vapor deposition method or the like. However, since the refractive index can be easily adjusted and manufactured, the refractive index adjusting layer is preferably a layer mainly composed of a synthetic resin.

  From such a viewpoint, the low refractive index layer is preferably made of a synthetic resin. The synthetic resin used for the low refractive index layer is a synthetic resin having a refractive index of 1.3 or more and less than 1.6, particularly 1.4 to 1.55, such as a fluororesin, a silicone resin, an olefin resin, and an acrylic resin. Polyester resin, cellulose resin, and polycarbonate resin are preferable. Particularly preferred are fluororesin and acrylic resin. According to these resins, it is easy to adjust the refractive index, and since it has excellent transparency, it is possible to provide a heat ray shielding glass excellent in appearance characteristics.

  Examples of the fluororesin having a refractive index of 1.3 or more and less than 1.6 include polytetrafluoroethylene (PTFE), tetrafluoroethylene / hexafluoropropylene copolymer (FEP), tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer Polymer (PFA), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), tetrafluoroethylene / ethylene copolymer (ETFE), fluoroethylene vinyl ether (FEVE) and ethylene chlorotrifluoroethylene copolymer ( ECTFE), the following structure:

(N = 10 to 1000)
The polymer A which has this can be mentioned. Among these, the polymer A and fluoroethylene vinyl ether (FEVE) are preferable. These (co) polymers further have functional groups (eg, alkoxysilyl groups, hydroxyl groups, amino groups, imino groups, (meth) acryloyloxy groups, epoxy groups, carboxyl groups, sulfonyl groups, acrylate type isocyanurate groups, sulfuric acid groups. Base). Preferable examples of commercially available fluororesins include Lumiflon (registered trademark, manufactured by Asahi Glass Co., Ltd.), Cytop (registered trademark, manufactured by Asahi Glass Co., Ltd.), Zaffle (registered trademark, manufactured by Daikin Chemical Co., Ltd.), And OPTOOL (registered trademark, manufactured by Daikin Chemical Co., Ltd.).

  Monomers constituting the acrylic resin having a refractive index of 1.3 or more and less than 1.6 include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) Acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, amyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) Acrylate, isooctyl (meth) acrylate, ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl Alkyl (meth) acrylates such as (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate; hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl Hydroxyalkyl (meth) acrylates such as (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 3-hydroxybutyl (meth) acrylate; phenoxyethyl (meth) acrylate, 2- Phenoxyalkyl (meth) acrylates such as hydroxy-3-phenoxypropyl (meth) acrylate; 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate Alkoxyalkyl (meth) acrylates such as 2-propoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, and 2-methoxybutyl (meth) acrylate; polyethylene glycol mono (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, Methoxypolyethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, ethoxypolypropylene glycol (meth) acrylate, nonyl Polyalkylene glycols such as phenoxy polypropylene glycol (meth) acrylate Examples include recall (meth) acrylate; pentaerythritol tri (meth) acrylate, pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerin di (meth) acrylate, and the like. Examples of the acrylic resin include homopolymers of these monomers, copolymers of two or more kinds, and copolymers of the monomers and other copolymerizable monomers.

  The thickness of the low refractive index layer made of synthetic resin is preferably 5 to 60 nm, particularly 10 to 40 nm.

  The high refractive index layer is preferably a layer containing fine particles for refractive index adjustment and a synthetic resin. Preferred examples of the synthetic resin used for the high refractive index layer include a fluororesin, a silicone resin, an olefin resin, an acrylic resin, a polyester resin, a cellulose resin, and a polycarbonate resin. Particularly preferred are fluororesin and acrylic resin.

  As the refractive index adjusting fine particles, metal particles or metal oxide particles are used. Examples of the metal particles include gold and silver particles. The metal oxide particles include aluminum oxide, tin oxide, antimony oxide, tantalum oxide, cerium oxide, lanthanum oxide, iron oxide, zinc oxide, tungsten oxide, zirconium oxide, indium oxide, titanium oxide, titanium oxide / zirconium oxide. Examples of the composite oxide include particles of titanium oxide / zirconium oxide / silicon oxide composite oxide. Among them, it is preferable to use metal oxide particles such as tin oxide, titanium oxide, zinc oxide, and zirconium oxide as the refractive index adjusting particles because they have a high refractive index and can suppress the generation of interference fringes. . These refractive index adjusting particles may be used singly or in combination of two or more.

  The average particle diameter of the refractive index adjusting particles is preferably 10 to 800 nm, particularly preferably 10 to 400 nm. Thereby, the refractive index adjustment layer excellent in transparency can be formed, and it becomes possible to improve the external appearance characteristic of heat ray shielding glass.

  The average particle size of the refractive index adjusting particles is determined by observing the cross section of the high refractive index layer with a transmission electron microscope at a magnification of about 1,000,000, and the projected area equivalent circle diameter of at least 100 refractive index adjusting particles. Obtain the number average value.

  The thickness of the high refractive index layer containing the refractive index adjusting fine particles and the synthetic resin is preferably 5 to 60 nm, particularly 10 to 40 nm.

  The refractive index adjustment layer (low refractive index layer, high refractive index layer) containing a synthetic resin is a cured layer of a resin composition containing a synthetic resin, and if necessary, refractive index adjusting particles and an organic solvent. In order to produce the refractive index adjusting layer, for example, a method in which the resin composition is coated on a suitable support such as a heat ray absorbing layer or a plastic film and simply dried is used. At this time, the resin composition may contain a curing agent such as a polyisocyanate compound. Drying is preferably performed by heating the applied resin composition at 60 to 150 ° C, particularly 70 to 110 ° C. The drying time may be about 1 to 10 minutes.

  In addition, when producing a low-refractive-index layer and a high-refractive-index layer, each layer may be apply | coated and hardened | cured one layer at a time, and you may make it harden | cure collectively after applying all the layers.

  Further, the resin composition used for forming the refractive index adjusting layer (particularly the low refractive index layer and the high refractive index layer) may be a thermosetting or light (generally ultraviolet) curable resin composition. Good. Therefore, it is preferable that the resin composition further includes a polymerization initiator. For example, it is preferable to use a thermal polymerization initiator in the case of thermosetting, and to use a photopolymerization initiator in the case of ultraviolet curing. Among these, it is particularly preferable to include a photopolymerization initiator.

  As the photopolymerization initiator, any compound suitable for the properties of the resin can be used. For example, 1-hydroxycyclohexyl phenyl ketone (Ciba Specialty Chemicals, Irgacure (registered trademark) 184) is preferably used. Generally the quantity of a photoinitiator is 0.1-10 mass% with respect to a resin composition, Preferably it is 0.1-5 mass%.

  When the resin composition is photocurable, the resin composition may further contain a polymerizable monomer or oligomer. As the polymerizable monomer or oligomer, it is preferable to mainly use a hard polyfunctional monomer such as pentaerythritol tri (meth) acrylate, pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate or the like.

  When producing a refractive index adjusting layer using a heat or photocurable resin composition, a composition containing a synthetic resin, a polymerization initiator, a refractive index adjusting layer and an organic solvent, if necessary, is used as a heat ray absorbing layer. Or after apply | coating on suitable support bodies, such as a plastic film, the method of making it harden | cure by heating or light irradiation, such as an ultraviolet-ray, a X ray, a gamma ray, an electron beam, is used preferably. The light irradiation can be performed by irradiating ultraviolet rays emitted from light rays such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, a metal halide lamp.

  Moreover, as a refractive index adjustment layer, the layer which consists of a condensate obtained by hydrolyzing a metal alkoxide and / or metal acetylacetonate, and carrying out a polycondensation can also be used. According to the sol-gel method using a metal alkoxide and a metal acetylacetonate, the refractive index can be easily adjusted and manufactured when the refractive index adjusting layer is manufactured. In the refractive index adjustment layer, metal alkoxide and metal acetylacetonate may be used alone or in combination of two or more.

  Metal acetylacetonate is a metal complex formed by bonding a metal to acetylacetone. Examples of the metal acetylacetonate include acetylacetonate of a metal such as titanium, tin, indium, zirconium, zinc, cobalt, iron, and nickel. These acetylacetonates may be acetylacetonate salts.

As the metal alkoxide, general formula (I): R ¹ _n M (OR ² ) _mn (where R ¹ and R ² represent an alkyl group having 1 to 10 carbon atoms, M represents Si, Ti, Al, and Represents an atom selected from the group consisting of Zr, m is the valence of atom M and is 3 or 4, and when m is 4, n is an integer from 0 to 2 and m is 3. Is preferably an integer of 0 to 1). Such a metal alkoxide is stable in a solvent after hydrolysis, and a refractive index adjusting layer having a desired refractive index can be easily formed.

In the general formula (I) and the general formulas (II) and (III) described later, R ¹ and R ² represent an alkyl group having 1 to 10 carbon atoms, particularly 1 to 4 carbon atoms. The alkyl group may be linear or branched. Preferably, a methyl group, an ethyl group, an isopropyl group, and a butyl group are mentioned. In the above general formula, when there are a plurality of R ¹ and OR ² , these may be the same or different.

  Since the refractive index adjusting layer can easily form a layer having a desired refractive index, it is a layer made of a condensate obtained by hydrolyzing the metal alkoxide represented by the above general formula and then polycondensing it. Is preferred. This condensate has a repeating unit of -MO- (M is as defined above) as a main skeleton.

In order to produce a low refractive index layer having a refractive index of 1.3 to 2.8, the general formula (II): R ¹ _n M ¹ (OR ² ) _4-n (where M ¹ represents Si, R ¹ and R ² each represents an alkyl group having 1 to 10 carbon atoms, and n is an integer of 0 to 2). Specific examples of such metal alkoxides include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, methyltrimethoxysilane, and ethyltrimethoxysilane. Etc.

  The thickness of the low refractive index layer produced by the sol-gel method is preferably 5 to 60 nm, particularly 10 to 40 nm.

In order to produce a high refractive index layer having a refractive index of 1.6 or more and 2.8 or less, the general formula (III): R ¹ _n M ² (OR ² ) _mn (where M ² is Ti, Zr or Al is represented, R ¹ and R ² represent an alkyl group having 1 to 10 carbon atoms, m is a valence of an atom M and is 3 or 4, and when m is 4, n is 4 A metal alkoxide represented by the following formula is preferably used: an integer of 0 to 2 and an integer of 0 to 1 when m is 3. Specific examples of such metal alkoxides include alkoxy titanium compounds such as tetramethoxy titanium, tetraethoxy titanium, tetrabutoxy titanium, tetraisopropoxy titanium, methyl triisopropoxy titanium; trimethoxy aluminum, triethoxy aluminum, triiso Examples include alkoxyaluminum compounds such as propoxyaluminum, methyldiisopropoxyaluminum, tributoxyaluminum, and diethoxyaluminum chloride; alkoxyzirconium compounds such as tetraethoxyzirconium, tetraisopropoxyzirconium, and methyltriisopropoxyzirconium.

  The thickness of the high refractive index layer produced by the sol-gel method is preferably 5 to 60 nm, particularly 10 to 40 nm.

  In order to produce the above-described refractive index adjusting layer, a sol solution containing a metal alkoxide, metal acetylacetonate, or a hydrolyzate thereof is applied onto a suitable support such as a heat ray absorbing layer or a plastic film, and applied. After the metal alkoxide or metal acetylacetonate contained in the later sol solution forms a swollen gel by hydrolysis reaction and polycondensation reaction, a method of forming a dry gel by heating the swollen gel is used.

  If necessary, a catalyst may be added to the sol solution to promote the sol-gel reaction. Examples of the catalyst include acid catalysts such as hydrochloric acid, nitric acid, trichloroacetic acid, trifluoroacetic acid, sulfuric acid, phosphoric acid, methanesulfonic acid, paratoluenesulfonic acid, and oxalic acid; N, N-dimethylbenzylamine, tripropylamine, tripropylamine, Tertiary amine catalysts such as butylamine and tripentylamine are listed. Among these, it is preferable to use an acid catalyst. The acid catalyst is usually added to the sol solution so that the pH of the sol solution is in the range of 4-7.

  The sol solution contains water and an organic solvent. As the organic solvent, alcohols such as methanol and ethanol; acetone, toluene, xylene, tetrahydrofuran and the like are preferably used.

  In order to apply the sol solution onto an appropriate support such as a heat ray absorbing layer, an appropriate method such as a bar coater method, a roll coater method, or a curtain flow method can be used.

  In the hydrolysis reaction and polycondensation reaction of the sol solution, the sol solution coated on the support is allowed to stand at a temperature of 0 to 95 ° C., particularly 70 to 90 ° C. for 100 minutes to 10 days, particularly 500 minutes to 3 days. It is preferable to do so. Thereafter, the sol solution is dried by heating at 100 to 190 ° C., particularly 1500 to 190 ° C. The heating time may be about 1 to 5 minutes.

In addition, when producing a low refractive index layer and a high refractive index layer by the sol-gel method, each sol solution may be applied one by one and dried by heating, or after all the sol solutions have been applied, they are heated and dried together. May be. By the method described above, a low refractive index layer comprising a condensate having a repeating unit of -M ¹ -O- as the main skeleton, and a high refractive index layer comprising a condensate having the repeating unit of -M ² -O- as the main skeleton. Is obtained.

  In addition, the low refractive index layer and high refractive index layer containing the synthetic resin mentioned above, and the low refractive index layer and the high refractive index layer produced by the sol-gel method can be used in combination according to each application.

[Heat ray reflective layer]
The heat ray reflective layer used for the heat ray shielding glass of the present invention is made of a metal oxide other than tungsten oxide and composite tungsten oxide.

  The refractive index of the heat ray reflective layer is preferably 1.5 to 2.8, particularly 1.6 to 2.4. By using the heat ray reflective layer having such a refractive index and the refractive index adjusting layer, generation of interference fringes can be suppressed to a high level.

  As a metal oxide used for a heat ray reflective layer, what can selectively permeate | transmit visible light and can selectively reflect a heat ray can be used. Specific examples of the metal oxide include tin oxide, tin-containing indium oxide (ITO), fluorine-containing tin oxide (FTO), antimony-containing tin oxide (ATO), indium oxide, antimony-containing indium oxide, antimony oxide, magnesium oxide, Examples thereof include silicon oxide, titanium oxide, zirconium oxide, cerium oxide, aluminum oxide, lanthanum oxide, neodymium oxide, and yttrium oxide. Of these, tin oxide, fluorine-containing tin oxide, antimony-containing tin oxide, and tin-containing indium oxide are preferable. According to these metal oxides, a heat ray reflective layer having excellent durability can be formed. Moreover, a metal oxide may be used individually by 1 type, and can also use 2 or more types together.

  The thickness of the heat ray reflective layer is preferably 50 to 500 nm, particularly preferably 100 to 400 nm. Even with such a thin heat ray reflective layer, it is possible to provide a heat ray shielding glass having excellent heat ray shielding properties by using the heat ray absorbing layer described above.

  In order to produce the heat ray reflective layer, physical vapor deposition, chemical vapor deposition, thermal spraying, and plating may be used. Examples of physical vapor deposition include vacuum vapor deposition, sputtering, and ion plating. Examples of the chemical vapor deposition (CVD) method include a thermal CVD method, a plasma CVD method, and a photo CVD method. By this method, a hard coating such as diamond-like carbon, TiN, or CrN can be formed. Examples of the thermal spraying method include an atmospheric pressure plasma spraying method and a low pressure plasma spraying method. Examples of the plating method include an electroless plating (chemical plating) method, a hot dipping method, and an electroplating method. In the electroplating method, a laser plating method can be used.

[Heat ray absorbing layer]
The heat ray absorbing layer includes tungsten oxide and / or composite tungsten oxide as a heat ray absorbing material.

  The refractive index of the heat ray absorbing layer is preferably 1.45 to 1.65, particularly 1.50 to 1.57. By using the heat ray absorbing layer having such a refractive index and the refractive index adjusting layer, generation of interference fringes can be suppressed to a high level.

  The heat ray absorbing material used for the heat ray absorbing layer can impart excellent heat ray absorptivity to the heat ray shielding glass without reducing the visible light transmittance. Therefore, by using a heat ray absorbing layer containing such a heat ray absorbing material, the thickness of the heat ray reflecting layer containing a metal oxide can be made very thin.

  Tungsten oxide is an oxide represented by the general formula WyOz (where W is tungsten, O is oxygen, 2.2 ≦ z / y ≦ 2.999). In addition, the composite tungsten oxide is the same as the above tungsten oxide, except that the element M (where M is H, He, alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co , Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br , Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, and I). As a result, free electrons are generated in WyOz, including the case of z / y = 3.0, and free electron-derived absorption characteristics are expressed in the near infrared region, which is effective as a near infrared absorbing material near 1000 nm. . In the present invention, composite tungsten oxide is preferable.

In the tungsten oxide represented by the general formula WyOz (W is tungsten, O is oxygen, 2.2 ≦ z / y ≦ 2.999), a preferable composition range of tungsten and oxygen is oxygen with respect to tungsten. When the heat ray absorbing material is described as WyOz, 2.2 ≦ z / y ≦ 2.999. If the value of z / y is 2.2 or more, it is possible to avoid the appearance of a WO ₂ crystal phase other than the objective in the heat-absorbing material, and to obtain chemical stability as a material. Therefore, it can be applied as an effective heat ray absorbing material. On the other hand, if the value of z / y is 2.999 or less, a required amount of free electrons is generated and an efficient heat ray absorbing material can be obtained.

From the viewpoint of stability, the composite tungsten oxide is generally MxWyOz (where M is H, He, alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, be, Hf, Os, Bi, 1 or more elements inner shell selected in I, W is tungsten, O is oxygen, (0.001 ≦ x / y ≦ 1, 2.2 ≦ z / y ≦ 3) An alkali metal is a group 1 element of the periodic table excluding hydrogen, and an alkaline earth metal is a group 2 of the periodic table. Elements, rare earth elements are Sc, Y and lanthanoid elements. From the viewpoint of improving optical characteristics and weather resistance as a line absorber, the M element is one or more of Cs, Rb, K, Tl, In, Ba, Li, Ca, Sr, Fe, and Sn. Is preferred.

  The composite tungsten oxide is preferably treated with a silane coupling agent. Excellent dispersibility, heat ray absorptivity, and transparency can be obtained.

  If the value of x / y indicating the addition amount of the element M is larger than 0.001, a sufficient amount of free electrons is generated, and a sufficient heat ray absorption effect can be obtained. As the amount of the element M added increases, the supply amount of free electrons increases and the heat ray absorption effect also increases. However, the value of x / y is saturated at about 1. Moreover, if the value of x / y is smaller than 1, it is preferable because an impurity phase can be prevented from being generated in the heat ray absorbing layer.

  Regarding the value of z / y indicating the control of the oxygen amount, in the composite tungsten oxide represented by MxWyOz, in addition to the same mechanism as that of the heat ray absorbing material represented by WyOz described above, z / y = Even in 3.0, since there is a supply of free electrons due to the addition amount of the element M described above, 2.2 ≦ z / y ≦ 3.0 is preferable, and 2.45 ≦ z / y ≦ 3.0 is more preferable. It is.

  Further, when the composite tungsten oxide has a hexagonal crystal structure, transmission of the oxide in the visible light region is improved, and absorption in the near infrared region is improved.

When the cation of the element M is added to the hexagonal void, the transmission in the visible light region is improved and the absorption in the near infrared region is improved. Here, generally, when the element M having a large ionic radius is added, the hexagonal crystal is formed. Specifically, Cs, K, Rb, Tl, In, Ba, Sn, Li, Ca, Sr, When Fe is added, hexagonal crystals are easily formed. Of course, other elements may be added as long as the additive element M is present in the hexagonal void formed by the WO ₆ unit, and is not limited to the above elements.

  When the composite tungsten oxide having a hexagonal crystal structure has a uniform crystal structure, the addition amount of the additive element M is preferably 0.2 or more and 0.5 or less in terms of x / y, more preferably 0.8. 33. When the value of x / y is 0.33, it is considered that the additive element M is arranged in all of the hexagonal voids.

  In addition to hexagonal crystals, tetragonal and cubic tungsten bronzes also have a heat ray absorbing effect. These crystal structures tend to change the absorption position in the near infrared region, and the absorption position tends to move to the longer wavelength side in the order of cubic <tetragonal <hexagonal. Further, the accompanying absorption in the visible light region is small in the order of hexagonal crystal <tetragonal crystal <cubic crystal. For this reason, it is preferable to use hexagonal tungsten bronze for applications that transmit light in the visible light region and shield light in the infrared region.

  Moreover, it is preferable from the viewpoint of improving the weather resistance that the surface of the composite tungsten oxide of the present invention is coated with an oxide containing one or more of Si, Ti, Zr, and Al.

  The composite tungsten oxide of the present invention is produced, for example, as follows.

  The tungsten oxide represented by the general formula WyOz and / or the composite tungsten oxide represented by MxWyOz can be obtained by heat-treating a tungsten compound starting material in an inert gas atmosphere or a reducing gas atmosphere. .

  The starting material for the tungsten compound is tungsten trioxide powder, tungsten oxide hydrate, tungsten hexachloride powder, ammonium tungstate powder, or tungsten hexachloride dissolved in alcohol and then dried. Tungsten oxide hydrate powder obtained, or tungsten oxide hydrate powder obtained by dissolving tungsten hexachloride in alcohol and then adding water to precipitate it and drying it It is preferable that it is at least one selected from a tungsten compound powder obtained by drying an aqueous ammonium solution and a metal tungsten powder.

  Here, in the case of producing tungsten oxide, it is further preferable to use tungsten oxide hydrate powder or tungsten compound powder obtained by drying ammonium tungstate aqueous solution from the viewpoint of ease of production process. Preferably, when producing a composite tungsten oxide, it is more preferable to use an aqueous ammonium tungstate solution or a tungsten hexachloride solution from the viewpoint that each element can be easily and uniformly mixed when the starting material is a solution. By using these raw materials and heat-treating them in an inert gas atmosphere or a reducing gas atmosphere, tungsten oxide and / or composite tungsten oxide having the above-described particle diameter can be obtained.

  The composite tungsten oxide represented by the general formula MxWyOz containing the element M is the same as the tungsten compound starting material of the tungsten oxide represented by the general formula WyOz described above. A tungsten compound contained in the form of a compound is used as a starting material. Here, in order to produce a starting material in which each component is uniformly mixed at the molecular level, it is preferable to mix each material with a solution, and the tungsten compound starting material containing the element M is dissolved in a solvent such as water or an organic solvent. Preferably it is possible. Examples thereof include tungstate, chloride, nitrate, sulfate, oxalate, oxide, and the like containing element M, but are not limited to these and are preferably in the form of a solution.

Here, the heat treatment condition in the inert atmosphere is preferably 650 ° C. or higher. The starting material heat-treated at 650 ° C. or higher has a sufficient coloring power and is efficient as a heat ray absorber. As the inert gas, an inert gas such as Ar or N ₂ is preferably used. As the heat treatment conditions in the reducing atmosphere, first, the starting material is heat-treated at 100 to 650 ° C. in a reducing gas atmosphere, and then heat-treated at a temperature of 650 to 1200 ° C. in an inert gas atmosphere. . The reducing gas at this time is not particularly limited, but H ₂ is preferable. When H ₂ is used as the reducing gas, the volume ratio of H ₂ is preferably 0.1% or more, more preferably 2% or more, as the composition of the reducing atmosphere. If it is 0.1% or more, the reduction can proceed efficiently.

The raw material powder reduced with hydrogen contains a magnetic phase and exhibits good heat ray absorbability, and can be used as a heat ray absorbent in this state. However, since hydrogen contained in tungsten oxide is unstable, application may be limited in terms of weather resistance. Therefore, a more stable heat ray absorbing material can be obtained by heat-treating the tungsten oxide compound containing hydrogen at 650 ° C. or higher in an inert atmosphere. The atmosphere during the heat treatment at 650 ° C. or higher is not particularly limited, but N ₂ and Ar are preferable from an industrial viewpoint. By the heat treatment at 650 ° C. or higher, a magnetic phase is obtained in the heat-absorbing material, and weather resistance is improved.

  The composite tungsten oxide of the present invention is preferably surface-treated with a coupling agent such as a silane coupling agent, a titanate coupling agent, or an aluminum coupling agent. Silane coupling agents are preferred. Thereby, the affinity with the binder resin is improved, and various physical properties are improved in addition to transparency and heat ray absorbability.

  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 -(Aminoethyl) -γ-aminopropyltrimethoxysilane and trimethoxyacrylsilane can be mentioned. Vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, and trimethoxyacrylsilane are preferred. These silane coupling agents may be used alone or in combination of two or more. Moreover, it is preferable to use content of the said compound at 5-20 mass parts with respect to 100 mass parts of composite tungsten oxides.

  The average particle diameter of the heat-absorbing material used in the present invention is preferably 10 to 800 nm, particularly 10 to 400 nm, from the viewpoint of maintaining transparency. This is because particles smaller than 800 nm do not completely block light due to scattering, can maintain visibility in the visible light region, and at the same time can efficiently maintain transparency. In particular, when importance is attached to transparency in the visible light region, it is preferable to further consider scattering by particles. When importance is attached to the reduction of scattering by the particles, the average particle size is preferably 20 to 200 nm, particularly preferably 20 to 100 nm.

  The average particle diameter of the heat-absorbing material is obtained by observing the cross section of the heat-absorbing layer with a transmission electron microscope at a magnification of about 1,000,000 times, obtaining the projected area equivalent circle diameter of at least 100 heat-ray absorbing materials, and averaging the number Value.

  The content of the (composite) tungsten oxide in the heat ray absorbing layer is preferably 10 to 500 parts by mass, more preferably 20 to 500 parts by mass, and particularly preferably 30 to 300 parts by mass with respect to 100 parts by mass of the binder resin.

  The heat ray absorbing layer preferably contains a binder resin in addition to the heat ray absorbing material described above. Binder resins include ethylene vinyl acetate copolymer (EVA), polyvinyl butyral (PVB), ethylene-methyl acrylate copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) ethyl acrylate copolymer. Polymer, ethylene- (meth) acrylic acid methyl copolymer, metal ion crosslinked ethylene- (meth) acrylic acid copolymer, partially saponified ethylene-vinyl acetate copolymer, carboxylated ethylene-vinyl acetate copolymer, ethylene Transparent adhesive resins such as ethylene copolymers such as-(meth) acrylic-maleic anhydride copolymer and ethylene-vinyl acetate- (meth) acrylate copolymer are preferably used. As the transparent adhesive resin, EVA is particularly preferably used. By using these transparent adhesive resins, a heat ray absorbing material can be highly dispersed, and a heat ray shielding glass excellent in appearance characteristics can be obtained.

  The heat ray absorbing layer containing an ethylene copolymer preferably contains an organic peroxide. By cross-linking and curing the transparent adhesive resin with an organic peroxide, the heat ray absorbing layer and the adjacent layer or transparent substrate can be 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, the one having a decomposition temperature of 70 ° C. or more with a half-life of 10 hours is preferable.

  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 Oxide, 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 peroxy isobutylene and 2,4-dichlorobenzoyl peroxide Can be mentioned.

  The heat ray absorbing layer containing the ethylene copolymer preferably contains a crosslinking aid. 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.

  The heat ray absorbing layer containing an ethylene-based copolymer may contain a silane coupling agent as an adhesion improver in order to further improve the adhesion. Examples of this silane coupling agent include γ-chloropropylmethoxysilane, vinylethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, γ-glycidoxypropyltri Methoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, vinyltrichlorosilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N- Mention may be made of β- (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.

  Heat ray absorbing layer containing ethylene copolymer improves or adjusts various physical properties (optical properties such as mechanical strength, adhesiveness, transparency, heat resistance, light resistance, crosslinking speed, etc.), especially mechanical In order to improve the strength, it is preferable to include an acryloxy group-containing compound, a methacryloxy group-containing compound, an epoxy group-containing compound, a plasticizer, and an ultraviolet absorber.

  The thickness of the heat ray absorbing layer containing the ethylene copolymer is preferably 100 μm to 1000 mm, particularly preferably 300 to 900 μm. Thereby, the heat ray absorption layer which has the outstanding adhesiveness and heat ray absorptivity is obtained.

  In order to produce a heat ray absorbing layer containing an ethylene copolymer, for example, a composition containing a heat ray absorbing material, an ethylene copolymer and an organic peroxide, and the like are subjected to normal extrusion molding, calendar molding (calendering). ) And the like to obtain a layered product. 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 preferable to set it as 40-90 degreeC, especially 50-80 degreeC.

  Also, by using an ethylene copolymer such as EVA, a heat-absorbing layer having tackiness can be obtained, and it can be adhered to other layers only with the heat-absorbing layer without using an adhesive resin layer or the like. . Therefore, as shown in FIG. 1, the heat ray shielding glass 100 including the heat ray absorbing layer containing the transparent adhesive resin includes the transparent base material 110, the heat ray absorbing layer 120, the refractive index adjusting layer 130, and the heat ray reflecting layer 140 in this order. Have a laminated structure.

  When producing a heat ray shielding glass using a layer containing an ethylene copolymer, after laminating each layer used for the heat ray shielding glass, the resulting laminate is heated and pressurized to contain a transparent adhesive resin. It is preferred to crosslink and cure the layer. Thereby, the layer containing transparent adhesive resin and the adjacent layer can be joined and integrated.

  As other binder resin contained in the heat ray absorbing layer, transparent synthetic resins such as fluororesin, silicone resin, olefin resin, and acrylic resin are used. These may be used alone or in combination of two or more. When these transparent synthetic resins are used as the binder resin, the heat ray absorbing layer is preferably a cured layer of a resin composition containing a heat ray absorbing material and a transparent synthetic resin.

  Examples of fluororesins include polytetrafluoroethylene (PTFE), tetrafluoroethylene / hexafluoropropylene copolymer (FEP), tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA), and polyvinylidene fluoride (PVDF). ), Polychlorotrifluoroethylene (PCTFE), tetrafluoroethylene-ethylene copolymer (ETFE), fluoroethylene vinyl ether (FEVE) and ethylene chlorotrifluoroethylene copolymer (ECTFE), the following structure:

(N = 10 to 1000)
The polymer A which has this can be mentioned. Among these, the polymer A and fluoroethylene vinyl ether (FEVE) are preferable. These (co) polymers further have functional groups (eg, alkoxysilyl groups, hydroxyl groups, amino groups, imino groups, (meth) acryloyloxy groups, epoxy groups, carboxyl groups, sulfonyl groups, acrylate type isocyanurate groups, sulfuric acid groups. Base). Preferable examples of commercially available fluororesins include Lumiflon (registered trademark, manufactured by Asahi Glass Co., Ltd.), Cytop (registered trademark, manufactured by Asahi Glass Co., Ltd.), Zaffle (registered trademark, manufactured by Daikin Chemical Co., Ltd.), And OPTOOL (registered trademark, manufactured by Daikin Chemical Co., Ltd.).

  Examples of silicone resins include straight silicone varnish and modified silicone varnish. Straight silicone varnish is usually produced by hydrolysis polymerization of phenyltrichlorosilane, diphenyldichlorosilane, methyltrichlorosilane, and dimethyldichlorosilane (when used, it is generally cured at 100 ° C. or higher after application). The modified silicone varnish is obtained by reacting a silicone varnish with a resin such as alkyd, polyester, acrylic, or epoxy. Preferable examples of commercially available silicone resins include silicone varnish KR series (manufactured by Shin-Etsu Chemical Co., Ltd.).

  Examples of the olefin resin monomer include polyethylene, polypropylene, and chlorinated polyethylene.

  Examples of acrylic resin monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and t-butyl (meth) acrylate. , Pentyl (meth) acrylate, amyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, ethylhexyl (meth) acrylate, nonyl (Meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylic , Alkyl (meth) acrylates such as stearyl (meth) acrylate and isostearyl (meth) acrylate; hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3- Hydroxyalkyl (meth) acrylates such as hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate; phenoxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl ( Phenoxyalkyl (meth) acrylates such as (meth) acrylate; 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-propoxyethyl (meth) acrylate, -Alkoxyalkyl (meth) acrylates such as butoxyethyl (meth) acrylate and 2-methoxybutyl (meth) acrylate; polyethylene glycol mono (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, phenoxypolyethylene Polyglycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, ethoxypolypropylene glycol (meth) acrylate, nonylphenoxypolypropylene glycol (meth) acrylate, etc. Alkylene glycol (meth) acrylate; Pentaerythri Examples include tall tri (meth) acrylate, pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and glycerin di (meth) acrylate. Examples of the acrylic resin include homopolymers of these monomers, copolymers of two or more kinds, and copolymers of the monomers and other copolymerizable monomers.

  The heat ray absorbing layer containing the heat ray absorbing material and the transparent synthetic resin is a cured layer of a resin composition containing the heat ray absorbing material, the transparent synthetic resin, and, if necessary, an organic solvent. In order to produce the heat ray absorbing layer, for example, a method in which the resin composition is applied onto a plastic film and simply dried is used. At this time, the resin composition may further contain a curing agent such as a polyisocyanate compound.

  The resin composition containing the heat ray absorbing material and the transparent synthetic resin used for forming the heat ray absorbing layer may be a thermosetting or light (generally ultraviolet ray) curable resin composition. Therefore, the resin composition may further contain a thermal polymerization initiator and a photopolymerization initiator. Among these, it is particularly preferable to include a photopolymerization initiator.

  Specific examples of the photopolymerization initiator are preferably the same as those used for the above-described refractive index adjustment layer. Generally the quantity of a photoinitiator is 0.1-10 mass% with respect to a resin composition, Preferably it is 0.1-5 mass%. When the resin composition is photocurable, the resin composition may further contain a polymerizable monomer or oligomer. As the polymerizable monomer or oligomer, it is preferable to mainly use a hard polyfunctional monomer such as pentaerythritol tri (meth) acrylate, pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate or the like.

  The thickness of the heat ray absorbing layer containing a transparent synthetic resin such as a fluororesin is preferably 0.5 to 30 μm, particularly 1 to 15 μm. Thereby, the heat ray absorption layer which has the outstanding adhesiveness and heat ray shielding property is obtained.

  Moreover, when transparent synthetic resins, such as a fluororesin, are used, manufacture becomes easy and it is excellent also in handleability, Therefore It is preferable to form a heat ray absorption layer on a plastic film. Examples of the plastic film include a polyethylene terephthalate (PET) film, a polyethylene aphthalate (PEN) film, and a polyethylene butyrate film, and a PET film is preferred. The thickness of the plastic film is preferably 10 to 400 μm, particularly 20 to 200 μm. Further, in order to improve the adhesiveness, the plastic film surface may be subjected in advance to an adhesion treatment such as a corona treatment, a plasma treatment, a flame treatment, and a primer layer coating treatment.

  When preparing a heat ray absorbing layer containing a transparent synthetic resin, a composition containing a transparent synthetic resin, a heat ray absorbing material, and an organic solvent was applied onto a predetermined substrate such as a plastic film or a transparent substrate and dried. Thereafter, a method of curing by heating or irradiation with light such as ultraviolet rays, X-rays, γ rays, and electron beams is preferably used as necessary. Drying is preferably performed by heating the resin composition coated on the plastic film at 60 to 150 ° C, particularly 70 to 110 ° C. The drying time may be about 1 to 10 minutes. The light irradiation can be performed by irradiating ultraviolet rays emitted from light rays such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, a metal halide lamp.

  The heat ray absorbing layer may contain a dye if necessary in addition to the (composite) tungsten oxide. The dye generally has an absorption maximum at a wavelength of 800 to 1200 nm. Examples include phthalocyanine dyes, metal complex dyes, nickel dithiolene complex dyes, cyanine dyes, squarylium dyes, polymethine dyes, Examples include azomethine dyes, azo dyes, polyazo dyes, diimonium dyes, aminium dyes, and anthraquinone dyes, and cyanine dyes, phthalocyanine dyes, and diimonium dyes are particularly preferable. These dyes can be used alone or in combination.

  The heat ray absorbing layer preferably contains 0.1 to 20 parts by mass, more preferably 1 to 20 parts by mass, and particularly preferably 1 to 10 parts by mass of the above dye with respect to 100 parts by mass of the binder resin.

  In the present invention, the heat ray absorbing layer may be provided with a function of adjusting color tone by imparting a neon light emission absorbing function. For this purpose, the heat ray absorbing layer may contain a neon-emitting selective absorption dye.

  Neon-emitting selective absorption dyes include cyanine dyes, squarylium dyes, anthraquinone dyes, phthalocyanine dyes, polymethine dyes, polyazo dyes, azurenium dyes, diphenylmethane dyes, and triphenylmethane dyes. it can. Such a selective absorption dye is required to have a selective absorption of neon emission near 585 nm and a small absorption at other visible light wavelengths, so that the absorption maximum wavelength is 575 to 595 nm and the absorption spectrum half width is What is 40 nm or less is preferable.

  Further, as long as the optical properties are not greatly affected, coloring dyes, ultraviolet absorbers, antioxidants and the like may be further added to the heat ray absorbing layer.

[Adhesive resin layer]
The heat ray shielding glass of the present invention may have an adhesive resin layer in order to improve the adhesion between the layers. In particular, when a heat ray absorbing layer formed on a plastic film is used, it is particularly preferable that an adhesive resin layer is used between the plastic film and a layer adjacent to the plastic film or a transparent substrate.

  For example, the heat ray shielding glass 200 using the heat ray absorbing layer 220 formed on the plastic film 260 includes a transparent substrate 210, an adhesive resin layer 250, a plastic film 260, the heat ray absorbing layer 220, as shown in FIG. The refractive index adjustment layer 230 and the heat ray reflective layer 240 have a structure in which they are laminated in this order.

  For the adhesive resin layer, ethylene-vinyl acetate copolymer (EVA), ethylene-methyl acrylate copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) ethyl acrylate copolymer, ethylene -(Meth) methyl acrylate copolymer, metal ion crosslinked ethylene- (meth) acrylic acid copolymer, partially saponified ethylene-vinyl acetate copolymer, carboxylated ethylene-vinyl acetate copolymer, ethylene- (meth) Ethylene-based copolymers such as acrylic-maleic anhydride copolymer and ethylene-vinyl acetate- (meth) acrylate copolymer can be used ("(meth) acryl" means "acryl or methacryl" Show.) In addition, for the adhesive resin layer, polyvinyl butyral (PVB) resin, epoxy resin, phenol resin, silicon resin, polyester resin, urethane resin, rubber-based adhesive, thermoplastic elastomer such as SEBS and SBS, and the like can also be used. Especially, it is preferable to use EVA for the adhesive resin layer because it has excellent adhesiveness.

  EVA used for the adhesive resin 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 resin 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.

  The adhesive resin layer preferably contains an organic peroxide in addition to EVA. Thereby, EVA can be bridge | crosslinked and an adhesive resin layer and another layer can be joined and integrated. The adhesive resin layer preferably further contains a crosslinking aid and a silane coupling agent. Specific examples of these organic peroxides, crosslinking aids, and silane coupling agents are the same as those described above in the heat ray absorbing layer, and thus detailed description thereof is omitted here.

  The adhesive resin layer has an acryloxy group for improving or adjusting various physical properties (optical properties such as mechanical strength, adhesiveness and transparency, heat resistance, light resistance, crosslinking speed, etc.), especially for improving mechanical strength. It preferably contains a containing compound, a methacryloxy group-containing compound, an epoxy group-containing compound, a plasticizer, and an ultraviolet absorber.

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

  In order to produce an adhesive resin layer containing EVA, the same method as described above in the heat ray absorbing layer is used, and thus detailed description thereof is omitted here.

[Transparent substrate]
As a transparent base material used for the heat ray shielding glass of the present invention, for example, a plastic film may be used in addition to a glass plate such as green glass, silicate glass, inorganic glass plate, and non-colored transparent glass plate. Examples of the plastic film include a polyethylene terephthalate (PET) film, a polyethylene aphthalate (PEN) film, and a polyethylene butyrate film. The thickness of the transparent substrate is generally about 1 to 20 mm.

  In the present invention, “glass” in the heat ray shielding glass means the whole transparent substrate. Accordingly, the heat ray shielding glass means a transparent substrate provided with heat ray shielding properties.

  The heat ray shielding glass of the present invention has a transparent base material, a heat ray absorbing layer containing tungsten oxide and / or a composite tungsten oxide, a heat ray reflecting layer containing a metal oxide, and a refractive index of 1.3 to 2 as basic components. .8 having a refractive index adjustment layer. In order to improve the durability of the heat ray shielding property when the heat ray shielding glass is used for the multi-layer glass, the heat ray reflective layer is preferably arranged as the uppermost layer. More preferably, the heat ray absorbing layer, the refractive index adjusting layer, and the heat ray reflecting layer are arranged in this order on the transparent substrate. Particularly preferably, the heat ray absorbing layer, the high refractive index layer, the low refractive index layer, and the heat ray reflective layer are arranged in this order on the transparent substrate. Other layers may be arranged between the layers depending on the purpose, and it is particularly preferable to use heat ray-shielding glass having the structure shown in FIGS.

  In order to produce the heat ray shielding glass 100 shown in FIG. 1, a heat ray absorbing layer 120 containing a transparent adhesive resin such as EVA and (composite) tungsten oxide, a high refractive index layer 131, a low refractive index on a transparent substrate 110. It is preferable to crosslink and cure the heat ray absorbing layer 120 by laminating the layer 132 and the heat ray reflective layer 140 and heating and pressing the resulting laminate. Thereby, the transparent base material 110, the heat ray absorption layer 120, and the heat ray reflective layer 130 can be joined and integrated.

  In order to produce the heat ray shielding glass 200 shown in FIG. 2, first, a heat ray absorbing layer 220 containing a transparent synthetic resin such as an acrylic resin and (composite) tungsten oxide is produced on the plastic film 260, and then the heat ray absorbing layer 220. A high refractive index layer 231, a low refractive index layer 232, and a heat ray reflective layer 240 are formed thereon. Next, an adhesive resin layer 250 containing an adhesive resin such as EVA is manufactured. Then, the adhesive resin layer 250, the heat ray absorbing layer 220 formed on the plastic film 250, the high refractive index layer 231, the low refractive index layer 232, and the heat ray reflective layer 240 are laminated on the transparent substrate 210 in this order. It is preferable to crosslink and cure the adhesive resin layer 250 by heating and pressing the thus obtained laminate. Thereby, the heat ray shielding glass 200 by which each layer was joined and integrated can be obtained.

In order to heat and press each laminated body, the laminated body is 1 to 120 minutes at 40 to 200 ° C., particularly 1 to 20 minutes at 60 to 150 ° C., 1.0 × 10 ³ Pa to 5.0 × 10 ⁷ Pa. It is preferable to carry out while applying pressure.

[Multilayer glass]
It is preferable that the heat ray shielding glass of the present invention is used for a multilayer glass. As above-mentioned, the heat ray shielding glass of this invention can maintain the outstanding heat ray shielding property over a long period of time. Therefore, the multilayer glass using such a heat ray shielding glass can maintain the excellent heat ray shielding property for a long period of time.

  As shown in FIG. 3, the multilayer glass using the heat ray shielding glass 300 of the present invention is formed by arranging the heat ray shielding glass 300 and another glass plate 370 so as to face each other through the hollow layer 380. can get. In the multi-layer glass, the heat ray shielding glass 300 is preferably arranged such that a heat ray reflective layer (not shown) containing a metal oxide arranged in the uppermost layer is on the hollow layer 380 side. The hollow layer 380 is formed by joining the heat ray shielding glass 300 and the glass plate 370 using an adhesive (not shown) with a spacer 390 interposed between the outer peripheral portions thereof.

  As the hollow layer, an air layer, an inert gas layer, a reduced pressure layer, or the like is used. 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 shielding layer over time.

  The air layer may use dry air by using a spacer containing a desiccant. The inert gas layer includes an inert gas such as krypton gas, argon gas, and xenon gas. The pressure of the reduced pressure layer is preferably 1.0 Pa or less, particularly 0.01 to 1.0 Pa. The thickness of the hollow layer is preferably 6 to 12 mm.

  The multilayer glass of the present invention can maintain excellent heat ray shielding properties over a long period of time by using the heat ray shielding glass described above. Such an effect can be sufficiently obtained even if an air layer is used as the hollow layer. Furthermore, it is possible not to use a desiccant or to reduce the amount of desiccant used. Therefore, it can be set as a simple structure compared with the case where an inert gas layer and a decompression layer are used as a hollow layer.

  As plate glass, 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, UV absorption Various glasses such as special glass having a function can be selected as appropriate. Moreover, about the composition of plate glass, 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.

  The double-glazed glass of the present invention has heat insulation properties and excellent heat ray shielding properties. Therefore, it is particularly preferable that the multilayer glass is used in a warm area such as a relatively low latitude area. In such an area, when the multilayer glass is used for a building or a vehicle, it is preferable that the glass plate is disposed on the indoor side and the heat ray shielding glass is disposed on the outdoor side. 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. By using in this way, the outstanding heat insulation and heat ray shielding property can be exhibited especially.

  The present invention will be described below with reference to examples. The present invention is not limited by the following examples.

Example 1
1. Preparation of heat ray absorbing layer A composition containing the following components was applied onto a polyethylene terephthalate (PET) film (thickness 100 μm) using a bar coater, dried in an oven at 80 ° C. for 2 minutes, and then subjected to a high-pressure mercury lamp. A heat ray absorbing layer (thickness: 10 μm: refractive index: 1.52) was produced on the PET film by irradiating ultraviolet rays as a UV integrated light amount of 500 mJ / cm ² .

Composition of heat ray absorbing layer forming composition:
80 parts by mass of dipentaerythritol hexaacrylate 5 parts by mass of photopolymerization initiator (Irgacure (registered trademark) 184) 20 parts by mass of Cs _0.33 WO ₃ (average particle size 80 nm) 300 parts by mass of methyl isobutyl ketone

2. Preparation of High Refractive Index Layer A composition containing the following components is applied onto a heat ray absorbing layer with a bar coater, dried at 80 ° C. for 30 seconds, and then irradiated with ultraviolet light as a UV integrated light amount of 500 mJ / cm ^{2 with} a high-pressure mercury lamp. Thus, a high refractive index layer (thickness 20 nm: refractive index 1.65) was formed.

Composition of high refractive index layer forming composition:
2 parts by mass of dipentaerythritol hexaacrylate 8 parts by mass of tin oxide particles (average particle size 15 nm) 1000 parts by mass of methyl isobutyl ketone

3. Preparation of Low Refractive Index Layer A composition containing the following components was applied onto the high refractive index layer with a bar coater and dried at 80 ° C. for 30 seconds to form a low refractive index layer (thickness 25 nm: refractive index 1.37). .

Composition of low refractive index layer forming composition:
Functional group-containing fluororesin (solid content 15% by mass, MIBK 85% by mass,
OPTOOL AR-110, manufactured by Daikin Industries, Ltd.) 70 parts by mass Methyl isobutyl ketone 1000 parts by mass

4). Production of heat ray reflective layer A heat ray reflective layer (thickness 0.3 μm: refractive index 2.0) made of fluorine-containing tin oxide was produced on the low refractive index layer by sputtering.

5. Production of Adhesive Resin Layer A sheet-like adhesive resin layer (thickness 0.4 mm) was obtained by a calendar molding method using the following composition as a raw material. 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.

Formulation of adhesive resin layer:
EVA (25 parts by mass of vinyl acetate based on 100 parts by mass of EVA,
Tosoh Corporation Ultrasen 635) 100 parts by mass,
Cross-linking agent (tert-butyl peroxy 2-ethylhexyl carbonate;
Kagome Akzo Corporation Trigonox 117) 2.5 parts by mass,
Cross-linking aid (triallyl isocyanurate;
Nippon Kasei Co., Ltd. TAIC (registered trademark)) 2 parts by mass,
Silane coupling agent (γ-methacryloxypropyltrimethoxysilane;
Shin-Etsu Chemical Co., Ltd., KBM503) 0.5 parts by mass

6). Production of heat ray shielding glass On a glass substrate (thickness 3 mm), an adhesive resin layer, a heat ray absorbing layer formed on a plastic film, a high refractive index layer, a low refractive index layer, and a heat ray reflective layer are laminated in this order. did. The obtained laminate was subjected to temporary pressure bonding 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 resin layer was cured to obtain a heat ray shielding glass (FIG. 2) in which the transparent base material and each layer were bonded and integrated.

7). Production of Multi-Layer Glass A glass plate (thickness 3 mm) and a heat ray shielding glass were arranged opposite to each other via a frame-shaped aluminum spacer arranged on the peripheral edge thereof, and these were bonded with butyl rubber. At this time, the surface on which the heat ray reflective layer of the heat ray shielding glass was formed was set to the air layer side formed by the spacer. The thickness of the air layer was 12 mm.

(Example 2)
Except that the high refractive index layer and the low refractive index layer were produced by the method described below, a heat ray shielding glass and a multilayer glass using the same were produced in the same manner as in Example 1.

1. Preparation of High Refractive Index Layer and Low Refractive Index Layer 10 g of tetrabutoxy titanium, 100 g of xylene, and 100 g of butanol were mixed to obtain a solution for forming a high refractive index layer. Separately, 10 g of tetraethoxysilane, 10 g of pure water, and 0.1 g of concentrated hydrochloric acid (35% by mass, manufactured by Kanto Chemical) were added to 10 g of ethyl alcohol and stirred to obtain a solution for forming a low refractive index layer.

  Next, a high refractive index layer forming solution is applied on the heat ray absorbing layer formed on the PET film by a roll coater method in an atmosphere of 30% humidity and 25 ° C., and then a low refractive index layer forming solution. Was applied. Thereafter, the applied solution was allowed to stand at 100 ° C. for 300 minutes, and then heated at 150 ° C. for 10 minutes. This produced the high refractive index layer (thickness 25 nm: refractive index 1.9) and the low refractive index layer (thickness 25 nm: refractive index 1.48) on the heat ray absorption layer.

(Comparative Example 1)
1. Production of heat ray shielding glass Using an in-line type DC sputtering apparatus, a heat ray containing a zinc oxide film, a silver film, a titanium oxide film, and a zinc oxide film in this order on a glass substrate (thickness 3 mm) from the glass plate side. A heat ray shielding glass was obtained by forming a shielding film. The zinc oxide film is in a 0.4 Pa reduced pressure atmosphere in which argon and oxygen are introduced at a flow ratio of 1: 9, and the silicon nitride film is 0.4 Pa in reduced pressure in which argon and nitrogen are introduced at a flow ratio of 1: 9. In the atmosphere, the other films were formed in an argon atmosphere with a pressure reduced to 0.4 Pa. The zinc oxide film, the silicon nitride film, the silver film, and the titanium oxide film were formed using zinc, silicon, silver, and titanium as targets, respectively. The titanium oxide film was formed as a titanium film, and this film was formed by oxidation in the subsequent step of forming a zinc oxide film. As the film formation conditions (applied voltage, film formation time, etc.), conditions confirmed in advance so that the film thicknesses of the respective films were the values in the table were applied. In all samples, the titanium film was formed to be 2 nm.

2. Production of Multi-layer Glass A multi-layer glass was produced in the same manner as in Example 1 using the heat ray shielding glass produced as described above.

(Comparative Example 2)
A heat ray shielding glass and a multilayer glass using the same were produced in the same manner as in Example 1 except that the heat ray reflective layer was directly produced on the heat ray absorbing layer without producing the high refractive index layer and the low refractive index layer. Produced.

(Evaluation)
1. Durability of heat ray shielding properties The multilayer glass was left for 5000 hours in an atmosphere of a temperature of 60 ° C. and a relative humidity of 90% RH while irradiating a near-ultraviolet fluorescent lamp generating near-ultraviolet rays having a wavelength of 320 nm to 400 nm. The visible light transmittance, the visible light reflectance, the solar radiation transmittance, and the solar reflectance of the multilayer glass before and after being left standing were measured based on JIS R3106-1998. In addition, the U3410 type self-recording spectrophotometer by Hitachi Ltd. was used for the measurement of the transmittance | permeability and a reflectance. The reflection characteristic was measured with specular reflection light having an incident angle of 12 °, and the transmission characteristic was measured with an incident angle of 0 °. The results are shown in Table 1.

2. Appearance characteristics (interference fringe observation)
Place the heat-shielding glass on black paper and illuminate with a three-wavelength fluorescent lamp (Matsushita Electric Industrial Co., Ltd., Parook, 20W, daylight white) to observe the interference fringes around the fluorescent lamp image. The interference fringes are determined by The results are shown in Table 1.

  A: No interference fringes are observed.

  Δ: Interference fringes are faintly recognized.

  X: Interference fringes are clearly recognized.

100, 200, 300: heat ray shielding glass,
110, 210: transparent substrate,
120, 220: heat ray absorbing layer,
130, 230: refractive index adjustment layer,
131, 231: high refractive index layer,
132, 232: low refractive index layer,
140, 240: heat ray reflective layer,
370: glass plate,
380: hollow layer,
390: Spacer.

Claims (11)

A transparent substrate;
A heat ray absorbing layer containing tungsten oxide and / or composite tungsten oxide and a binder resin ;
A heat ray reflective layer made of a metal oxide other than the tungsten oxide and the composite tungsten oxide,
Between the ray absorbing layer and the heat ray reflective layer, at least 1 Soyu the refractive index adjusting layer,
The refractive index adjusting layer is composed of a high refractive index layer having a refractive index of 1.6 or more and 2.8 or less and a low refractive index layer having a refractive index of 1.3 or more and less than 1.6,
The heat ray shielding glass , wherein the heat ray absorbing layer, the high refractive index layer, the low refractive index layer, and the heat ray reflective layer are laminated in this order . The heat ray shielding glass according to claim 1 , wherein the low refractive index layer is made of a synthetic resin. The heat ray-shielding glass according to claim 1 or 2 , wherein the high refractive index layer contains refractive index adjusting fine particles and a synthetic resin. The heat ray shielding glass according to claim 3 , wherein the refractive index adjusting fine particles are at least one selected from the group consisting of tin oxide, titanium oxide, zinc oxide, and zirconium oxide. The low refractive index layer has the general formula R ¹ _n M ¹ (OR ² ) _4-n (where M ¹ represents Si, R ¹ and R ² represent an alkyl group having 1 to 10 carbon atoms, n Is a condensate obtained by polycondensation after hydrolyzing a metal alkoxide represented by the formula ( 1 ), wherein the heat-shielding glass according to claim 1 . The high refractive index layer has the general formula R ¹ _n M ² (OR ² ) _mn (where M ² represents Ti, Zr, or Al, and R ¹ and R ² are alkyl groups having 1 to 10 carbon atoms) M is the valence of atom M and is 3 or 4, n is an integer from 0 to 2 when m is 4, and an integer from 0 to 1 when m is 3. The heat-shielding glass according to claim 1 or 5 , comprising a condensate obtained by hydrolyzing a metal alkoxide represented by The heat ray shielding glass according to any one of claims 1 to 6 , wherein the heat ray reflective layer has a refractive index of 1.5 to 2.8. Metal oxide used in the heat ray reflective layer is tin oxide, claim 1-7, characterized in that at least one selected antimony-containing tin oxide, and from the group consisting of tin-containing indium oxide 1 The heat ray shielding glass according to Item. The heat ray shielding glass according to any one of claims 1 to 8 , wherein a refractive index of the heat ray absorbing layer is 1.45 to 1.65. The tungsten oxide is represented by the general formula WyOz (W is tungsten, O is oxygen, and 2.2 ≦ z / y ≦ 2.999), and the composite tungsten oxide is Formula MxWyOz (where M is H, He, alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag , Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re , Be, Hf, Os, Bi, I , one or more elements, W represents tungsten, O represents oxygen, and 0.001 ≦ x / y ≦ 1, 2.2 ≦ z / y claim 1-9, characterized by being represented by ≦ 3 a is) Solar control glass of any one. A multilayer glass, wherein the heat ray-shielding glass according to any one of claims 1 to 10 and a glass plate are arranged so as to face each other through a hollow layer.

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