JP5559483B2 - 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 for the double-glazed glass of Patent Document 1, the silver layer and the metal layer are rusted, and the moisture resistance and acid resistance of these layers are low, and the heat ray absorbability decreases with time. was there.

  Then, an object of this invention is to provide the heat ray shielding glass which can maintain the outstanding heat ray absorptivity 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 said subject could be solved by using for shielding glass.

That is, the present invention
A transparent substrate;
A heat ray absorbing layer comprising tungsten oxide and / or composite tungsten oxide;
Have a, a heat ray reflective layer of the tungsten oxide and a metal oxide other than the composite tungsten oxide,
The transparent base material, the adhesive resin layer, the plastic film, the heat ray absorbing layer, and the heat ray reflective layer are laminated in this order,
The heat ray absorbing layer includes a binder resin,
The adhesive resin layer comprises an ethylene vinyl acetate copolymer; and
The content of tungsten oxide and / or composite tungsten oxide in the heat ray absorbing layer is 10 to 500 parts by mass with respect to 100 parts by mass of the binder resin , or
A transparent substrate;
A heat ray absorbing layer comprising tungsten oxide and / or composite tungsten oxide;
A heat ray reflective layer made of a metal oxide other than the tungsten oxide and the composite tungsten oxide, and
The transparent base material, the adhesive resin layer, the plastic film, the heat ray absorbing layer, the adhesive resin layer, the transparent base material, and the heat ray reflective layer are laminated in this order,
The heat ray absorbing layer includes a binder resin,
The adhesive resin layer comprises an ethylene vinyl acetate copolymer; and
The above problem is solved by a heat ray shielding glass, wherein the content of tungsten oxide and / or composite tungsten oxide in the heat ray absorbing layer is 10 to 500 parts by mass with respect to 100 parts by mass of the binder resin. .

  The heat ray shielding glass of the present invention has only excellent heat ray absorbability by using a heat ray absorbing layer containing tungsten oxide and / or composite tungsten oxide and a heat ray reflecting layer containing other metal oxide. In addition, this excellent heat ray absorbability can be maintained over a long period of time. Therefore, by using such a heat ray shielding glass, it becomes possible to provide a multilayer glass capable of maintaining excellent heat ray absorbability over a long period of time.

The schematic sectional drawing of the heat ray shielding glass of the reference example 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 heat ray shielding glass of the reference example 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.

Solar control glass of the present invention, as a basic configuration, the transparent substrate, heat absorbing layer comprising a tungsten oxide and / or composite tungsten oxide, and heat rays consisting of the tungsten oxide and a metal oxide other than the composite tungsten oxide A reflective layer; In order to improve the durability of the heat ray absorbent, a heat ray reflective layer is disposed as the uppermost layer, and a heat ray absorbing layer configured to be disposed between the heat ray reflective layer and a transparent substrate. If it is such a structure, the layer which has 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 reference example 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, and a heat ray reflecting layer 130 laminated on the heat ray absorbing layer 120. The heat ray absorbing layer 120 preferably includes a heat ray absorbing material 121 such as tungsten oxide or composite tungsten oxide, and a binder resin such as ethylene vinyl acetate copolymer (EVA). In addition, a hard coat layer (not shown) is disposed between the heat ray absorbing layer 120 and the heat ray reflecting layer 130 in order to improve the handleability, wear resistance, chemical resistance and moisture resistance of the heat ray absorbing glass. Preferably it is done.

In the present invention, the heat absorbing layer is being formed on a plastic film. When using a heat absorbing layer formed on a plastic film, it is on a transparent substrate you laminating the plastic film via the adhesive resin layer. FIG. 2 shows such a heat ray shielding glass.

Figure 2 shows a schematic cross-sectional view of a solar control glass 200 as good optimal embodiment of the present invention. The heat ray shielding glass 200 is formed on the transparent substrate 210, the adhesive resin layer 240 laminated on the transparent substrate 210, the plastic film 250 laminated on the adhesive resin layer 240, and the plastic film 250. A heat ray absorbing layer 220 and a heat ray reflecting layer 230 laminated on the heat ray absorbing layer 220. Thus, it is preferable to use the heat ray absorbing layer 220 formed on the plastic film 250 because the heat ray absorbing layer 220 can be easily produced and is easy to handle. As a reference example , for example, the heat ray absorbing layer 220 can be directly laminated on the adhesive resin layer 240 without using the plastic film 250.

  The heat ray absorbing layer 220 is at least one selected from the group consisting of a fluororesin, a silicone resin, an olefin resin, and an acrylic resin as a binder resin in addition to the heat ray absorbing material 221 such as tungsten oxide and composite tungsten oxide. It is preferable to include a transparent synthetic resin. By using such a binder resin, the durability of the heat ray absorbing layer 220 can be improved. The adhesive resin layer 240 preferably contains a transparent adhesive resin such as an ethylene vinyl acetate copolymer.

  The heat ray absorbing glass may have a laminated glass structure using two transparent substrates. Such a heat ray shielding glass is shown in FIGS.

FIG. 3 shows a schematic cross-sectional view of a heat ray shielding glass 300 as a reference example of the present invention. The heat ray shielding glass 300 includes a transparent base material 310A, a heat ray absorption layer 320 laminated on the transparent base material 310A, a transparent base material 310B laminated on the heat ray absorption layer 320, and the transparent base material 310B. And a heat ray reflective layer 330 laminated on the substrate. The heat ray absorbing layer 320 preferably includes a heat ray absorbing material 321 such as tungsten oxide or composite tungsten oxide, and a binder resin such as ethylene vinyl acetate copolymer (EVA). The heat ray absorbing layer 320 containing EVA has adhesiveness, and the heat ray absorbing layer 320 alone can be adhered to other layers.

FIG. 4 shows a schematic cross-sectional view of a heat ray shielding glass 400 as another preferred embodiment of the present invention. The heat ray shielding glass 400 is formed on the transparent substrate 410A, the adhesive resin layer 440A laminated on the transparent substrate 410A, the plastic film 450 laminated on the adhesive resin layer 440A, and the plastic film 450. The heat ray absorbing layer 420 formed, the adhesive resin layer 440B laminated on the heat ray absorbing layer 420, the transparent substrate 410B laminated on the adhesive resin layer 440B, and laminated on the transparent substrate 410B. And a heat ray reflective layer 430. As in the heat ray shielding glass 200 shown in FIG. 2, it is preferable to use the heat ray absorbing layer 420 formed on the plastic film 450, but as a reference example, the heat ray absorbing layer 420 is not an adhesive resin but a plastic film 450. It is also possible to form directly on the layer 440.

  The heat ray absorbing layer 420 includes at least one binder resin selected from the group consisting of a fluororesin, a silicone resin, an olefin resin, and an acrylic resin, in addition to the heat ray absorbing material 221 such as tungsten oxide and composite tungsten oxide. Is preferred. By using such a binder resin, durability of the heat ray absorbing layer can be improved. The adhesive resin layer 440 preferably contains a transparent adhesive resin such as an ethylene vinyl acetate copolymer.

  The heat ray absorbing layer 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, it is possible to provide a heat ray shielding glass having excellent heat ray absorbability even if the use of a metal layer having low durability which has been used in conventionally known multilayer glass is omitted. Can do. Furthermore, since neither the heat ray absorbing layer nor the heat ray reflecting layer contains a single metal, it is excellent in moisture resistance and acid resistance and does not generate rust. Therefore, the heat ray shielding glass of the present invention can maintain excellent heat ray shielding properties and appearance characteristics over a long period of time.

  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.

[Heat ray absorbing layer]
The heat ray absorbing layer is a layer containing tungsten oxide and / or composite tungsten oxide and a binder resin as a heat ray absorbing material.

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) acryl-maleic anhydride copolymer and ethylene-vinyl acetate- (meth) acrylate copolymer may be used . As a reference example, by using these transparent adhesive resins, a heat-absorbing layer having tackiness can be obtained, and it is possible to adhere to other layers with only the heat-absorbing layer without using an adhesive resin layer or the like. it can. As the transparent adhesive resin, EVA is particularly preferably used.

  The heat ray absorbing layer containing a transparent adhesive resin such as EVA 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, t-butylperoxy-2-ethylhexyl monocarbonate, n-butyl-4,4-bis (t-butylperoxy) valerate, 1,1-bis (t-butylperoxy) cyclohexane, 1, 1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, t-butylperoxybenzoate, benzoyl peroxide , T-butyl peroxyacetate, methyl ethyl ketone peroxide, 2,5-dimethylhexyl-2,5-bisperoxybenzoate, butyl hydroperoxide, p-menthane hydroperoxide, p-chlorobenzoyl peroxide, hydroxyheptyl peroxide Oxide, chlorohexanone peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, cumyl peroxy octoate, succinic peroxide, acetyl peroxide, m-toluoyl peroxide, t-butyl peroxide isobutyl Mention may be made of leo and 2,4-dichlorobenzoyl peroxide.

  The heat ray absorbing layer containing the transparent adhesive resin 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 the transparent adhesive resin 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 EVA.

  Heat ray absorbing layer containing transparent adhesive resin improves or adjusts various physical properties (optical properties such as mechanical strength, adhesiveness, transparency, heat resistance, light resistance, crosslinking speed, etc.), especially mechanical strength For improvement, it preferably contains 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 a transparent adhesive resin such as EVA is preferably 50 μm to 1 mm, particularly 200 to 800 μm. Thereby, the heat ray absorption layer which has the outstanding adhesiveness and heat ray shielding property is obtained.

  In order to produce a heat ray absorbing layer containing a transparent adhesive resin, for example, a composition containing a heat ray absorbing material, a transparent adhesive resin, an organic peroxide, and the like is molded by ordinary extrusion molding, calendar molding (calendering), or the like. Thus, a method of 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 preferable to set it as 40-90 degreeC, especially 50-80 degreeC.

  When producing a heat ray shielding glass using a layer containing a transparent adhesive resin, after laminating each layer used for the heat ray shielding glass, a layer containing the transparent adhesive resin is obtained by heating and pressing the obtained laminate. It is preferable to cure by crosslinking. Thereby, the layer containing transparent adhesive resin and the adjacent layer can be joined and integrated.

In the present invention, the resolver indanyl resin contained in the heat absorbing layer, a fluorine resin, silicone resin, olefin resin, and a transparent synthetic resin such as an acrylic resin is used. 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 can be produced by applying a resin composition containing a heat ray absorbing material, a transparent synthetic resin and an organic solvent on a suitable support such as a plastic film and simply drying it. At this time, the resin composition may further include a curing agent such as a polyisocyanate compound. 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.

  Moreover, it is preferable that the resin composition containing the heat ray absorbing material and the transparent synthetic resin used for forming the heat ray absorbing layer is a thermosetting or light (generally ultraviolet ray) curable resin composition. Therefore, the resin composition may further contain 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, 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, a photoinitiator can be used individually by 1 type or in mixture of 2 or more types. 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%.

  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 an acrylic resin is preferably 0.5 to 50 μm, particularly 2 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 an acrylic resin, 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 producing a heat ray absorbing layer containing a transparent synthetic resin, after applying a composition containing a transparent synthetic resin, a heat ray absorbing material, and an organic solvent on a predetermined substrate such as a plastic film or a transparent substrate, heating, Alternatively, a method of curing by irradiation with light such as ultraviolet rays, X-rays, γ rays, and electron beams is preferably used. 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 includes tungsten oxide and / or composite tungsten oxide as a heat ray absorbing material. This heat ray absorbing material 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 is obtained, and an excellent infrared cut function and transparency are 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, exhibits good infrared shielding properties, and can be used as a heat ray absorbing material 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 cutting property.

  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.

In this invention, content of the (composite) tungsten oxide in a heat ray absorption layer is 10-500 mass parts with respect to 100 mass parts of binder resin . Furthermore, it is preferable that it is 20-500 mass parts, especially 30-300 mass parts.

  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.

[Hard coat layer]
When the heat ray reflective layer is directly formed on the heat ray absorbing layer as in the heat ray shielding glass shown in FIGS. 1 and 2, it is preferable to dispose a hard coat layer between the heat ray absorbing layer and the heat ray reflective layer. According to the hard coat layer, the handleability, wear resistance, chemical resistance and moisture resistance of the heat ray shielding glass can be further improved.

  In the present invention, the hard coat layer means a layer having a hardness of H or more in a pencil hardness test specified by JIS 5600-5-4 (1999).

  The hard coat layer is a cured layer of a synthetic resin composition mainly composed of an acrylic resin, an epoxy resin, a urethane resin, a silicone resin, or the like. Usually, the thickness is 1 to 50 μm, preferably 1 to 10 μm. The synthetic resin composition is generally a thermosetting resin composition or an ultraviolet curable resin composition, and an ultraviolet curable resin composition is preferable. The ultraviolet curable resin composition is preferable because it can be cured in a short time and has excellent productivity.

  The ultraviolet curable resin composition contains an ultraviolet curable monomer and / or oligomer (and / or polymer), a photopolymerization initiator, an organic solvent, and the like. These specific compounds are the same as those of conventionally known hard coat layers.

  Further, the hard coat layer 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. In particular, it is preferable to contain an ultraviolet absorber (eg, benzotriazole-based ultraviolet absorber or benzophenone-based ultraviolet absorber), whereby the durability of the heat ray-shielding glass can be further improved. 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 hard coat layer, for example, an ultraviolet curable resin composition may be applied on the heat ray absorbing layer, dried, and then cured by irradiation with ultraviolet rays.

[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 or the heat ray absorbing layer and a layer adjacent thereto or a transparent substrate.

  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.

[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. As the metal oxide, one that can selectively transmit visible light and selectively reflect heat rays can be used.

  Specific examples of the metal oxide include tin oxide, tin-containing indium oxide (ITO), antimony-containing tin oxide (ATO), indium oxide, antimony-containing indium oxide, antimony oxide, magnesium oxide, silicon oxide, titanium oxide, and zirconium oxide. Cerium oxide, aluminum oxide, lanthanum oxide, neodymium oxide, yttrium oxide, and the like. Of these, 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 0.02 to 1 μm, particularly 0.05 to 0.1 μm. 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.

[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, as a basic structure, a transparent substrate, a heat ray absorbing layer containing tungsten oxide and / or composite tungsten oxide, and a heat ray reflecting layer containing metal oxide. In order to improve heat ray absorption durability when heat ray shielding glass is used for multi-layer glass, the heat ray reflection layer is arranged as the top layer, and the heat ray absorption layer is arranged between the heat ray reflection layer and the transparent substrate. It is particularly preferred that These layers are preferably laminated in order according to 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 a (composite) tungsten oxide 121 is produced, and the heat ray absorbing layer 120 is formed on the transparent substrate 110. After the lamination, a method of forming a heat ray reflective layer 130 made of a metal oxide on the heat ray absorbing layer 120 is used. The laminated body of the transparent substrate 110, the heat ray absorbing layer 120, and the heat ray reflecting layer 130 thus obtained is preferably cross-linked and cured by heating and pressurizing. 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 a (composite) tungsten oxide 221 is produced on the plastic film 250, and then the heat ray absorbing layer. A heat ray reflective layer 230 made of a metal oxide is formed on 220. Next, an adhesive resin layer 240 containing an adhesive resin such as EVA is manufactured. Then, the adhesive resin layer 240, the heat ray absorbing layer 220 formed on the plastic film 250, and the heat ray reflecting layer 230 are laminated on the transparent substrate 210 in this order. The laminated body thus obtained is preferably crosslinked and cured by heating and pressing the adhesive resin layer 240. Thereby, the heat ray shielding glass in which the transparent substrate 210, the adhesive resin layer 240, the heat ray absorbing layer 220 formed on the plastic film 250, and the heat ray reflective layer 230 are joined and integrated can be obtained.

  In order to produce the heat ray shielding glass 300 shown in FIG. 3, first, a heat ray absorbing layer 320 containing a transparent adhesive resin such as EVA and (composite) tungsten oxide 321 is produced, and separately from this, on the transparent substrate 310B. A heat ray reflective layer 330 made of a metal oxide is produced. Next, the heat ray absorbing layer 320, the transparent substrate 310B, and the heat ray reflecting layer 330 are laminated on the transparent substrate 310A. And it is preferable to carry out the crosslinking hardening of the heat ray absorption layer 320 by heating-pressing the laminated body obtained in this way. Thereby, the heat ray shielding glass in which the transparent base materials 310A and 310B, the heat ray absorbing layer 320, and the heat ray reflective layer 330 are joined and integrated can be obtained.

  In order to produce the heat ray shielding glass 400 shown in FIG. 4, a heat ray absorbing layer 420 containing a transparent synthetic resin such as an acrylic resin and a (composite) tungsten oxide 421 is produced on a plastic film 450 and then separately bonded with EVA or the like. Adhesive resin layers 440A and 440B containing a resin are produced. Next, the heat ray reflective layer 430 made of a metal oxide is produced on the transparent substrate 410B. And the heat ray absorption layer 420, the adhesive resin layer 440B, the transparent base material 410B, and the heat ray absorption layer 430 produced on the transparent base material 410A, the adhesive resin layer 440A, and the plastic film 450 are laminated. And it is preferable to bridge-harden adhesive resin layer 440A and 440B by heat-pressing the laminated body obtained in this way. Thereby, the heat ray shielding glass by which each layer and the transparent base material were 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 described above, the heat ray shielding glass of the present invention can maintain excellent heat ray absorbability over a long period of time. Therefore, the multilayer glass using such a heat ray shielding glass can maintain excellent heat ray absorbability over a long period of time.

  As shown in FIG. 5, the multilayer glass using the heat ray shielding glass 500 of the present invention is arranged by arranging the heat ray shielding glass 500 and another glass plate 560 so as to face each other through the hollow layer 570. can get. In the multi-layer glass, the heat ray shielding glass 500 is arranged such that a heat ray reflective layer (not shown) containing a metal oxide is on the hollow layer 570 side. The hollow layer 570 is formed by joining the heat ray shielding glass 500 and the glass plate 560 using an adhesive (not shown) with a spacer 580 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 diffusing function by surface treatment, netted glass, lined glass, tempered glass, double tempered glass, low reflection glass, high transmission glass, ceramic printing glass, heat ray and Various glasses such as special glass having an ultraviolet absorbing 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. When the double glazing 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. 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: FIG. 2)
1. Preparation of heat ray absorbing layer A composition containing the following components is applied onto a polyethylene terephthalate (PET) film (thickness: 100 μm) using an applicator, dried, and irradiated with ultraviolet light at an integrated light quantity of 500 mJ / cm ² using a high-pressure mercury lamp. By irradiation, a heat ray absorbing layer (thickness 8 μm) was produced on the PET film.

Composition of heat ray absorbing layer forming composition:
Pentaerythritol triacrylate 100 parts by weight Photopolymerization initiator (Irgacure 184) 4 parts by weight Cs _0.33 WO ₃ (average particle size 80 nm) 30 parts by weight Methyl isobutyl ketone 100 parts by weight

2. Production of Heat Ray Reflective Layer A heat ray reflective layer (thickness 0.06 μm) made of tin oxide (SnO ₂ ) was produced on the heat ray absorbing layer by sputtering using tin as a target and oxygen introduced into the apparatus.

3. 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

4). Preparation 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, and a heat ray reflecting layer were laminated in this order. 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.

5. Preparation of double-glazed glass A glass plate (thickness 3 mm) and a heat ray shielding glass were arranged to face each other through a frame-shaped aluminum spacer arranged on the peripheral edge thereof, and these were bonded with butyl rubber and silicon sealant. . 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 6 mm.

(Example 2: FIG. 4)
1. Production of heat ray absorbing layer A heat ray absorbing layer (thickness 8 μm) was produced on a PET film in the same manner as in Example 1.

2. Production of Adhesive Resin Layer In the same manner as in Example 1, two adhesive resin layers (thickness 0.4 mm) were produced.

3. Production of Heat Ray Reflective Layer A heat ray reflective layer (thickness: 0. ₂ ) made of tin oxide (SnO ₂ ) is formed on glass substrate B (thickness 3 mm) by sputtering using tin as a target and oxygen introduced into the apparatus. 06 μm).

4). Production of heat ray shielding glass On glass substrate A (thickness 3 mm), an adhesive resin layer, a heat ray absorbing layer formed on a PET film, an adhesive resin layer, and a heat ray reflective layer formed on glass substrate B The layers were laminated in this order. 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. As a result, the adhesive resin layer was cured to obtain a heat ray shielding glass (FIG. 4) in which the transparent substrate and each layer were bonded and integrated.

5. 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 1)
1. Production of heat-shielding glass Using an in-line DC sputtering device, a zinc oxide film (thickness 50 nm), a silver film (thickness 10 nm), titanium oxide on a glass substrate (thickness 3 mm) from the glass plate side A heat ray shielding glass was obtained by forming a heat ray shielding film including a film (thickness 2 nm) and a zinc oxide film (thickness 50 nm) in this order. 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.

(Evaluation)
In accordance with the procedure shown below, the multilayer glass was subjected to a weather resistance test, and then the heat ray shielding properties and appearance characteristics were evaluated. The results are summarized in Table 1.

  The multilayer glass was left for 1000 hours in an atmosphere having a temperature of 50 ° C. and a relative humidity of 90% RH while irradiating a near-ultraviolet fluorescent lamp generating near-ultraviolet light 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. Note that a day spectrophotometer (U4000 type manufactured by Hitachi High-Technologies Corporation) was used for the measurement of transmittance and reflectance. The reflection characteristic was measured with specular reflection light with an incident angle of 5 °, and the transmission characteristic was measured with an incident angle of 0 °.

  Further, the appearance characteristics of the multi-layer glass after standing were visually evaluated. The multilayer glass of Examples 1 and 2 had no change and had excellent transparency, but the multilayer glass of Comparative Example 1 showed the occurrence of rust on the silver film.

  As shown in Table 1, according to the heat ray shielding glass of this invention, it turns out that the outstanding heat ray shielding property and external appearance characteristic can be maintained over a long period of time.

  The heat ray shielding glass of the present invention and the multilayer glass using the same can maintain high heat ray shielding properties and heat insulation properties over a long period of time. Therefore, in these, the multi-layer glass is particularly suitably used as a window glass for buildings and vehicles (automobiles, railway vehicles, ships) used in warm regions such as regions with relatively low latitudes.

100, 200, 300, 400, 500: heat ray shielding glass,
110, 210, 310, 410: transparent substrate,
120, 220, 320, 420: heat ray absorbing layer,
130, 230, 330, 430: heat ray reflective layer,
240, 440: adhesive resin layer,
250, 450: Plastic film,
560: glass plate,
570: Spacer.

Claims (7)

A transparent substrate;
A heat ray absorbing layer comprising tungsten oxide and / or composite tungsten oxide;
Have a, a heat ray reflective layer of the tungsten oxide and a metal oxide other than the composite tungsten oxide,
The transparent base material, the adhesive resin layer, the plastic film, the heat ray absorbing layer, and the heat ray reflective layer are laminated in this order,
The heat ray absorbing layer includes a binder resin,
The adhesive resin layer comprises an ethylene vinyl acetate copolymer; and
Content of tungsten oxide and / or composite tungsten oxide in the heat ray absorbing layer is 10 to 500 parts by mass with respect to 100 parts by mass of the binder resin . Binder resin of the heat-ray absorbing layer, a fluorine resin, silicone resin, olefin resin, and the heat ray shielding glass according to claim 1, characterized in that it comprises at least one selected from the group consisting of acrylic resin. A transparent substrate;
A heat ray absorbing layer comprising tungsten oxide and / or composite tungsten oxide;
Have a, a heat ray reflective layer of the tungsten oxide and a metal oxide other than the composite tungsten oxide,
The transparent base material, the adhesive resin layer, the plastic film, the heat ray absorbing layer, the adhesive resin layer, the transparent base material, and the heat ray reflective layer are laminated in this order,
The heat ray absorbing layer includes a binder resin,
The adhesive resin layer comprises an ethylene vinyl acetate copolymer; and
Content of tungsten oxide and / or composite tungsten oxide in the heat ray absorbing layer is 10 to 500 parts by mass with respect to 100 parts by mass of the binder resin . Binder resin of the heat-ray absorbing layer, a fluorine resin, silicone resin, olefin resin, and the heat ray shielding glass according to claim 3, characterized in that it comprises at least one selected from the group consisting of acrylic resin. 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 to any one of claims 1 to 4, represented by ≦ 3 a it is) The placing of the heat ray shielding glass. Wherein the metal oxide is tin oxide, antimony-containing tin oxide, and the heat ray shielding glass according to claim 1 to 5, characterized in that at least one selected from the group consisting of tin-containing indium oxide. It arrange | positions so that the heat ray shielding glass of any one of Claims 1-6 and a glass plate may be opposed through a hollow layer,
The said heat ray shielding glass is arrange | positioned so that the said heat ray reflective layer may become the said hollow layer side, The multilayer glass characterized by the above-mentioned.

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