WO2012018000A1 - Panneau de double vitrage protégé contre les rayonnements thermiques - Google Patents

Panneau de double vitrage protégé contre les rayonnements thermiques Download PDF

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Publication number
WO2012018000A1
WO2012018000A1 PCT/JP2011/067643 JP2011067643W WO2012018000A1 WO 2012018000 A1 WO2012018000 A1 WO 2012018000A1 JP 2011067643 W JP2011067643 W JP 2011067643W WO 2012018000 A1 WO2012018000 A1 WO 2012018000A1
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Prior art keywords
heat ray
glass
heat
ray shielding
layer
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PCT/JP2011/067643
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English (en)
Japanese (ja)
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鈴木　裕二
晃人 畠中
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株式会社ブリヂストン
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/42—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating of an organic material and at least one non-metal coating
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
    • C03C17/3657—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating having optical properties
    • C03C17/366—Low-emissivity or solar control coatings

Definitions

  • the present invention relates to a multi-layer glass using a heat ray shielding glass having heat ray shielding property or heat ray reflection property.
  • a thin film of a transparent conductive film such as indium tin oxide (ITO) or tin oxide (ATO) is formed into a dry film, and a noble metal film / metal oxide film mainly composed of a metal oxide film / Ag film is laminated.
  • a heat ray shielding glass (Patent Document 1) on which a heat ray shielding film (also referred to as a Low-E film) is formed has been developed and put to practical use.
  • the Low-E film has a function (heat insulation) that transmits near-infrared rays of sunlight having a relatively short wavelength and does not escape by reflecting far-infrared rays such as heating emitted from the room.
  • Such heat ray-shielding glass (particularly, the one having the Low-E film formed thereon) should be arranged so as to face another glass plate with a predetermined distance (air layer) to form a multi-layer glass. And what improved the heat insulation is also developed (patent document 2). Thereby, the energy consumption by air conditioning can be further reduced.
  • the property of absorbing infrared rays is also known for conductive polymers, and is a transparent heat shield composed of a surface protective layer, a heat shield layer using a conductive polymer, a substrate, an ultraviolet absorbing layer, and an adhesive layer.
  • a film has been developed (Patent Document 4).
  • the Low-E film used in the heat ray shielding glass described in Patent Document 1 is formed by a vacuum film formation method such as a sputtering method, a large-sized apparatus is required, resulting in an increase in manufacturing cost.
  • the metal film is easily corroded, and there is a problem that appearance characteristics are deteriorated by long-term use. These also cause the same problem even when the multilayer glass described in Patent Document 2 is used.
  • the heat ray shielding glass described in Patent Document 3 is excellent in the function of shielding the near-infrared ray of sunlight, it is satisfactory depending on the application because it has low heat insulation properties to reflect heat rays such as heating emitted from the room. Performance may not be obtained.
  • the shielding film using the conductive polymer of Patent Document 4 cannot be said to have sufficient heat ray shielding properties.
  • a heat ray shielding glass having a heat ray reflective layer made of a conductive polymer has high heat insulation properties depending on conditions, but durability in the presence of moisture (high humidity conditions) In the invention, it is also known as “water resistance”).
  • the object of the present invention is a heat ray shielding glass product having a heat ray reflective layer made of a conductive polymer, which is excellent in heat ray shielding properties, particularly heat insulation properties, and can be formed by a low cost coating method. Another object is to provide a product having high durability in the presence of moisture (under high humidity conditions).
  • the object is to provide a spacer in which a heat ray shielding glass having a glass plate and a heat ray reflective layer made of a conductive polymer provided on the surface thereof, and another glass plate are arranged at the peripheral portion of the heat ray shielding glass.
  • the heat ray reflective layer is disposed so as to face the other glass plate with a gap, and a hollow layer is formed by the gap, and the end of the heat ray reflective layer forming range in the heat ray shielding glass.
  • the heat ray-shielding multilayer glass characterized in that the portion is inside the outer peripheral end of the spacer.
  • the end of the formation range of the heat ray reflection layer is on the outer peripheral side of the spacer arranged at the peripheral portion of the heat ray shielding glass.
  • the heat ray reflective layer made of a conductive polymer is deteriorated due to absorption of moisture in the external atmosphere from the edge of the heat ray reflective layer when it coincides with the edge or protrudes outside There is.
  • the edge part of a heat ray reflective layer exists in the inside of a spacer, or becomes the position which overlapped with the spacer, it is not exposed to external atmosphere and absorption of a water
  • the conductive polymer has the following formula (I):
  • R 1 and R 2 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, or R 1 and R 2 together may be optionally substituted carbon
  • the above polythiophene derivative Since the above polythiophene derivative has high conductivity, it is suitable as a conductive polymer used for the heat ray reflective layer in the present invention.
  • the thickness of the heat ray reflective layer is 10 to 3000 nm.
  • the heat ray shielding glass and the another glass plate have substantially the same shape.
  • the end of the heat ray reflective layer forming range is 2 mm or more inside from the outer peripheral end of the spacer. Thereby, it is possible to further prevent the moisture in the external atmosphere from being absorbed from the end of the heat ray reflective layer.
  • the heat ray shielding glass is obtained by bonding a transparent plastic film having a heat ray reflective layer formed on a surface thereof and a glass plate via an adhesive layer.
  • the edge part of the transparent plastic film which formed the heat ray reflective layer in the said heat ray shielding glass is inside the edge part of the outer peripheral side of a spacer. Thereby, it can prevent that the water
  • the adhesive layer contains an ethylene-vinyl acetate copolymer (EVA). EVA is highly transparent and excellent in weather resistance, and is therefore suitable as an adhesive used for the adhesive layer in the present invention.
  • the said spacer has a sealing material in the contact area
  • An ultraviolet absorbing layer is formed on the side of the heat ray reflective layer irradiated with sunlight. Thereby, deterioration due to ultraviolet rays of the conductive polymer can be further suppressed.
  • the spacer includes a desiccant.
  • the hollow layer is one kind of layer selected from the group consisting of a dry air layer, an inert gas layer, and a reduced pressure layer. Thereby, the heat ray reflective layer made of a conductive polymer can be more sufficiently protected from moisture.
  • the sealing material is an adhesive member or an elastic member.
  • the end of the heat ray reflection layer is inside the spacer or overlaps the spacer. Because it is located, it is not exposed to the external atmosphere and can prevent moisture from being absorbed from the end of the heat ray shielding layer, so it is possible to further suppress deterioration of the heat ray reflective layer made of a conductive polymer, It is possible to obtain a heat ray shielding glass product with higher durability.
  • FIG. 1 is a schematic sectional view showing a typical example of the heat ray-shielding multilayer glass of the present invention.
  • FIG. 2 is a schematic sectional drawing which shows another example of the heat ray shielding multilayer glass of this invention.
  • glass means a transparent substrate in general, and may be a transparent plastic substrate in addition to a glass plate. Therefore, for example, the heat ray shielding glass means a transparent substrate provided with heat ray shielding properties.
  • the heat ray shielding multilayer glass 40 of the present invention shown in FIGS. 1 and 2 includes a heat ray shielding glass 30, a glass plate 37 disposed so as to face the heat ray shielding glass 30 with a gap therebetween, and the heat ray shielding glass 30.
  • a spacer 39 disposed at the peripheral edge, a sealing material 36 for sealing the spacer 39 to the heat ray shielding glass 30 and the glass plate 37, and a hollow layer formed between the heat ray shielding glass 30 and the glass plate 37 by the spacer 39. 38.
  • the heat ray shielding glass 30 and the glass plate 37 may have different shapes, substantially the same shape as shown in FIGS. 1 and 2 is preferable in that it is easy to manufacture and use.
  • the heat ray shielding glass 30 in the heat ray shielding multilayer glass 40 of the present invention will be described.
  • an adhesive layer 22, a transparent plastic film 23, and a heat ray reflective layer 24 made of a conductive polymer are laminated and integrated in order on the surface of the glass plate 21.
  • the heat ray shielding glass 30 forms a heat ray reflective layer 24 made of a conductive polymer on one surface of the transparent plastic film 23, and then the transparent plastic film 23 is opposite to the surface on which the above layer is formed. The surface is bonded to the glass plate 21 via the adhesive layer 22.
  • the heat ray reflective layer 24 made of a conductive polymer is formed on the heat ray shielding glass 30, it is possible to effectively suppress the radiation of the heat ray and enhance the heat insulation. This is thought to be because the plasma absorption wavelength due to free electrons of the conductive polymer is shorter than the radiation of an object near the ground temperature, and reflects electromagnetic waves having a wavelength higher than the plasma absorption wavelength.
  • the surface resistance value of the heat ray reflective layer 24 made of a conductive polymer is preferably 10000 ⁇ / ⁇ or less. With this surface resistance value, the free electron density is sufficiently high and sufficient heat insulation is obtained.
  • the free electron density is preferably 1 s / cm or more.
  • the surface resistance value is preferably 1000 ⁇ / ⁇ or less, more preferably 300 ⁇ / ⁇ or less.
  • the heat ray reflective layer 24 is preferably formed on the outermost layer of the heat ray shielding glass 30 as shown in FIG. Although it is not preferable that there is another layer on the heat ray reflective layer 24, even a conductive (metal) thin film or a non-conductive organic resin hinders the radiation suppressing effect of the conductive polymer layer. If it is a thin film of an extent, it may be formed on the heat ray reflective layer 24. In this case, the surface resistance value of another layer is preferably 1 ⁇ 10 6 ⁇ / ⁇ or less, and the layer thickness is preferably 1 ⁇ m or less.
  • the heat ray reflective layer 24 made of a conductive polymer has a problem of low water resistance as described above. Therefore, in the present invention, first, as shown in the figure, the surface of the heat ray shielding layer 24 is made rainwater, condensation, moisture, etc. by disposing the heat ray shielding glass 30 so that the heat ray reflecting layer 24 faces the glass plate 37. Protects from moisture. However, even with such an arrangement, for example, as in the comparative example of the heat ray shielding multilayer glass shown in FIG. 3, the end of the formation range of the heat ray reflective layer 24 and the end on the outer peripheral side of the spacer 39 (The configuration of the heat ray shielding multilayer glass in FIG. 3 is the same as in FIGS. 1 and 2 except for the formation range of the heat ray shielding layer 24). When the moisture in the atmosphere is absorbed, the heat ray reflective layer 24 made of a conductive polymer may be deteriorated.
  • the heat ray reflective layer 24 is disposed so that the end of the formation range of the heat ray reflective layer 24 is inside the end of the spacer 39 on the outer peripheral side. That is, in FIG. 1, the end of the transparent plastic 23 on which the heat ray reflective layer 24 is formed is inside the spacer 39 (inside the end on the inner peripheral side of the spacer 39), and in FIG. The end portion of the transparent plastic 23 in which 24 is formed is located between the inner peripheral end portion and the outer peripheral end portion of the spacer 39 (in a position overlapping the spacer 39).
  • the edge part of the heat ray reflective layer 24 and the transparent plastic 23 are not exposed to the external atmosphere, the absorption of moisture from the edge part can be prevented, and the heat ray reflective layer made of the conductive polymer is further deteriorated. Can be suppressed.
  • the heat ray reflection property (heat insulation property) and visible light permeability of the heat ray reflection layer 24 can be maintained for a longer period of time.
  • the end of the heat ray reflective layer 24 may be located inside the outer peripheral end of the spacer 39, but preferably the outer peripheral end of the spacer 39 so as not to be exposed to the external atmosphere. 2 mm or more inside, more preferably 4 mm or more inside. It is particularly preferable that the end portion of the heat ray reflective layer 24 is located inside the end portion on the inner peripheral side of the spacer 39.
  • the adhesive layer 22 and the transparent plastic film 23 may be omitted.
  • the heat ray reflective layer 24 may be directly formed on the surface of the glass plate 21, or the adhesive layer 22 may be formed on the surface of the glass plate 21, and the heat ray reflective layer 24 may be formed on the surface. Also in this case, the heat ray reflective layer 24 is formed so that the end of the formation range of the heat ray reflective layer 24 is inside the end on the outer peripheral side of the spacer 39.
  • the heat ray-shielding glass 30 is easy to manufacture and has improved impact resistance and penetration resistance.
  • the transparent plastic film 23 having a heat ray reflective layer 24 formed on the surface and a glass plate are used. 21 is preferably bonded through the adhesive layer 22.
  • the transparent plastic 23 The position of the end of the is not particularly limited. It is easy to form the heat ray reflective layer 24 by coating, and it is possible to prevent moisture in the external atmosphere from being absorbed through the transparent plastic film 23. Therefore, the end portion of the transparent plastic film 23 is also the outer periphery of the spacer. It is preferable that it is inside the edge part of the side.
  • the sealing material 36 may be omitted, but in order to further prevent moisture from the external atmosphere from being absorbed from the end of the heat ray reflective layer 24, the spacer 39 is provided.
  • the sealing material 36 is preferably included.
  • the sealing material 36 seals the spacer 39, the heat ray shielding glass 30, and the glass plate 37, and is not particularly limited as long as it has a function of preventing moisture in the external atmosphere from entering the intermediate layer 38. .
  • the spacer 39 and the sealing material 36 may be integrated, or the spacer 39 having the function of the sealing material may be used.
  • the spacer 39 can be freely selected and used.
  • the spacer 39 is a hard member made of metal such as aluminum, aluminum alloy, stainless steel, or resin, and usually encloses a desiccant such as silica, and the sealing material 36 is butyl rubber, thiocol.
  • An adhesive member such as a polyisobutylene-based sealing material or an elastic member can be used.
  • the elements constituting the heat ray reflective glass 30 will be described below.
  • the conductive polymer forming the heat ray reflective layer 24 is generally an organic polymer having a conjugated double bond as a basic skeleton, specifically, polythiophene, polypyrrole, polyaniline, polyacetylene, polyparaphenylene, polyfuran, polyfluorene. , Polyphenylene vinylene, derivatives thereof, and any one or a mixture of two or more conductive polymers selected from copolymers of monomers constituting them are preferable.
  • polythiophene derivatives that are soluble or dispersible in water or other solvents and exhibit high conductivity and transparency are preferable.
  • R 1 and R 2 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, or R 1 and R 2 together may be optionally substituted carbon
  • a polythiophene derivative containing a repeating unit represented by an alkylene group having 1 to 4 atoms and n being an integer of 50 to 1000 is preferred.
  • the alkylene group having 1 to 4 carbon atoms which may be formed as a substituent formed by combining R 1 and R 2 is specifically a methylene group substituted with an alkyl group, Examples thereof include groups that form ethylene-1,2 groups, propylene-1,3 groups, butene-1,4 groups optionally substituted with alkyl groups having 1 to 12 carbon atoms or phenyl groups.
  • R1 and R2 in formula (I) preferably either a methyl group or an ethyl group, methylene group R 1 and R 2 form together an ethylene-1,2 radical or propylene-1,3 radical is there.
  • Particularly preferred polythiophene derivatives include the following formula (II):
  • p represents an integer of 50 to 1000
  • p represents an integer of 50 to 1000
  • the conductive polymer preferably further contains a dopant (electron donor).
  • a dopant electron donor
  • Preferred examples of the dopant include polystyrene sulfonic acid, polyacrylic acid, polymethacrylic acid, polymaleic acid, and polyvinyl sulfonic acid.
  • polystyrene sulfonic acid is preferable.
  • the number average molecular weight Mn of the dopant is preferably 1,000 to 2,000,000, particularly preferably 2,000 to 500,000.
  • the content of the dopant is usually 20 to 2000 parts by mass, preferably 40 to 200 parts by mass with respect to 100 parts by mass of the conductive polymer.
  • a polythiophene derivative of the formula (II) is used as a conductive polymer and polystyrene sulfonic acid is used as a dopant
  • 100 to 200 parts by mass of polystyrene sulfonic acid is preferable with respect to 100 parts by mass of polythiophene, and particularly 120 to 180 parts by mass. Part is preferred.
  • a material to which 1 to 10% by mass of a high boiling point solvent such as dimethyl sulfoxide is added it is preferable to use a material to which 1 to 10% by mass of a high boiling point solvent such as dimethyl sulfoxide is added.
  • the heat ray reflective layer 24 made of a conductive polymer can be formed by a conventionally known method.
  • a coating solution in which a conductive polymer is dissolved or dispersed is applied to the surface of the transparent plastic film 23 or the glass plate 21 or the adhesive layer 22 by a bar coater method, a roll coater method, a curtain flow method, a spray method or the like. Coating is carried out using a method, and then dried to form.
  • Solvents used in the coating liquid include water; alcohols such as methanol, ethanol and propanol; ketones such as acetophenone and methyl ethyl ketone; halogenated hydrocarbons such as carbon tetrachloride and fluorinated hydrocarbons; ethyl acetate and butyl acetate.
  • Preferred examples include esters such as tetrahydrofuran, dioxane and diethyl ether; and amides such as N, N-dimethylacetamide, N, N-dimethylformamide and N-methylpyrrolidone.
  • water and alcohols are preferable.
  • the layer thickness of the heat ray reflective layer 24 made of a conductive polymer is preferably 10 to 3000 nm, more preferably 100 to 2000 nm, particularly 150 to 1500 nm.
  • the glass plate 21 in the present invention may be a transparent substrate, for example, a glass plate such as green glass, silicate glass, inorganic glass plate, non-colored transparent glass plate, polyethylene terephthalate (PET), polyethylene naphthalate (PEN). ), A plastic substrate or film such as polyethylene butyrate or polymethyl methacrylate (PMMA) may be used.
  • a glass plate is preferable in terms of weather resistance, impact resistance and the like.
  • the thickness of the glass plate is generally about 1 to 20 mm.
  • the transparent plastic film in the present invention is not particularly limited as long as it is a transparent plastic film (meaning “transparent to visible light”).
  • plastic films include polyethylene terephthalate (PET) film, polyethylene naphthalate (PEN) film, polymethyl methacrylate (PMMA) film, polycarbonate (PC) film, polyethylene butyrate film, especially during processing.
  • PET film is preferred because of its high resistance to heat, solvent, bending and other loads, and high transparency.
  • the transparent plastic film surface may be subjected to adhesion treatment such as corona treatment, plasma treatment, flame treatment, primer layer coating treatment in advance, such as copolymer polyester resin and polyurethane resin.
  • An easily adhesive layer such as a thermosetting resin may be provided.
  • the thickness of the transparent plastic film is generally 1 ⁇ m to 10 mm, preferably 10 to 400 ⁇ m, and particularly preferably 20 to 200 ⁇ m.
  • the adhesive layer in the present invention comprises an ethylene-vinyl acetate copolymer (EVA), an ethylene-methyl acrylate copolymer, an ethylene- (meth) acrylic acid copolymer, and an ethylene- (meth) ethyl acrylate copolymer.
  • EVA ethylene-vinyl acetate copolymer
  • ethylene-methyl acrylate copolymer ethylene-methyl acrylate copolymer
  • an ethylene- (meth) acrylic acid copolymer ethylene- (meth) acrylic acid copolymer
  • ethylene- (meth) ethyl acrylate copolymer ethylene- (meth) ethyl acrylate copolymer
  • Ethylene- (meth) acrylate methyl copolymer metal ion-crosslinked ethylene- (meth) acrylic acid copolymer, partially saponified ethylene-vinyl acetate copolymer, carboxylated ethylene-vinyl acetate copolymer, ethylene- ( Ethylene copolymers such as (meth) acrylic-maleic anhydride copolymer and ethylene-vinyl acetate- (meth) acrylate copolymer can be used ("(meth) acryl” means "acrylic or methacrylic” Is shown.)
  • PVB polyvinyl butyral
  • EVA used for the adhesive layer has a vinyl acetate content of 23 to 38 parts by mass, particularly preferably 23 to 28 parts by mass with respect to 100 parts by mass of EVA. Thereby, the adhesive bond layer excellent in adhesiveness and transparency can be obtained. Further, EVA has a melt flow index (MFR) of 4.0 to 30.0 g / 10 min, and preferably 8.0 to 18.0 g / 10 min. Pre-crimping becomes easy.
  • MFR melt flow index
  • an ethylene copolymer When an ethylene copolymer is used for the adhesive layer, it is preferable to further contain an organic peroxide.
  • an organic peroxide By crosslinking and curing with an organic peroxide, adjacent layers and a glass plate can be further joined and integrated. Any organic peroxide may be used in combination as long as it decomposes at a temperature of 100 ° C. or higher and generates radicals.
  • the organic peroxide is generally selected in consideration of the film formation temperature, the adjustment conditions of the composition, the curing (bonding) temperature, the heat resistance of the adherend, and the storage stability. In particular, those having a decomposition temperature of 70 hours or more with a half-life of 10 hours are preferred.
  • organic peroxide examples 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, ⁇ , ⁇ '-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
  • the adhesive layer further contains a silane coupling agent as a crosslinking aid or an adhesion improver.
  • crosslinking aid examples 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.
  • silane coupling agents include ⁇ -chloropropylmethoxysilane, vinylethoxysilane, vinyltris ( ⁇ -methoxyethoxy) silane, ⁇ -methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, ⁇ -glycidoxypropyltrimethoxy Silane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, vinyltrichlorosilane, ⁇ -mercaptopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, N- ⁇ Mention may be made of-(aminoethyl) - ⁇ -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
  • the adhesive resin layer is used to improve or adjust various physical properties (optical properties such as mechanical strength, adhesiveness, and transparency, heat resistance, light resistance, crosslinking speed, etc.), especially to improve mechanical strength and light resistance.
  • It preferably contains an acryloxy group-containing compound, a methacryloxy group-containing compound, an epoxy group-containing compound, a plasticizer, and an ultraviolet absorber.
  • the ultraviolet absorber include benzophenone compounds, triazine compounds, benzoate compounds, and hindered amine compounds. From the viewpoint of suppressing yellowing, benzophenone compounds are preferred.
  • the ultraviolet absorber is preferably used in an amount of 0.01 to 1.5 parts by mass (particularly 0.5 to 1.0 part by mass) with respect to 100 parts by mass of the ethylene copolymer.
  • the thickness of the adhesive layer is preferably 100 to 2000 ⁇ m, particularly 400 to 1000 ⁇ m.
  • a composition containing an ethylene copolymer and an organic peroxide is formed by ordinary extrusion molding, calendar molding (calendering), or the like.
  • a method for obtaining a layered product can be used.
  • the composition is preferably mixed by heating and kneading at a temperature of 40 to 90 ° C., particularly 60 to 80 ° C.
  • the heating temperature during film formation is preferably a temperature at which the crosslinking agent does not react or hardly reacts.
  • the temperature is preferably 40 to 90 ° C, particularly 50 to 80 ° C.
  • the adhesive layer may be formed directly on the surface of a transparent plastic film or glass plate, or may be formed separately using a film-like adhesive sheet.
  • the transparent plastic film 23 on which the heat ray reflective layer 24 is formed and the glass plate 21 are prepared, and the adhesive layer 22 (the heat ray reflection of the transparent plastic film as described above) is prepared.
  • the transparent plastic film 24 and the glass plate 21 on which the heat ray reflective layer 23 is formed are formed on the surface opposite to the surface on which the layers are formed, or the adhesive sheet is laminated on the glass plate). Then, after degassing the laminated body laminated with a gap at the peripheral edge so as to be inside the outer edge of the spacer 36, it is heated (preferably at 40 to 200 ° C.
  • EVA when used for the adhesive layer 22, it is generally crosslinked at 100 to 150 ° C. (especially around 130 ° C.) for 10 minutes to 1 hour. This is carried out by degassing the laminate, pre-pressing at a temperature of, for example, 80 to 120 ° C., and heat-treating at 100 to 150 ° C. (especially around 130 ° C.) for 10 minutes to 1 hour. Cooling after crosslinking is generally performed at room temperature, and in particular, the faster the cooling, the better.
  • the end of the heat ray reflective layer 24 is located on the peripheral edge of the glass plate 21 from the end on the outer peripheral side of the spacer 36.
  • a non-formation region of the heat ray reflective layer may be provided with a masking tape or the like so as to be located inside, and the heat ray reflective layer may be applied and formed, or the heat ray reflective layer 24 is applied and formed on the entire surface of the glass plate 21. Thereafter, the heat ray reflective layer 24 at the peripheral edge may be removed with water or the like.
  • an adhesive layer 22 can be provided on the glass plate 21 in order to improve the adhesion of the heat ray reflective layer 24 to the glass plate 21.
  • an air layer, an inert gas layer, a reduced pressure layer, or the like can be used as the hollow layer 38 in the heat ray shielding multilayer glass 40 of the present invention.
  • the air layer may use dry air by using a spacer 39 containing a desiccant.
  • the inert gas layer includes an inert gas such as krypton gas, argon gas, and xenon gas.
  • the thickness of the hollow layer is preferably 6 to 12 mm.
  • the hollow layer 38 is preferably selected from any one of a dry air layer, an inert gas layer, and a reduced pressure layer. Thereby, the heat ray shielding layer 24 can be further protected from moisture, and the water resistance of the heat ray shielding multilayer glass 40 can be improved.
  • a transparent substrate similar to the glass plate 21 may be used.
  • Various glasses such as special glass having a function can be appropriately selected and used.
  • soda silicate glass, soda lime glass, borosilicate glass, aluminosilicate glass, various crystallized glass, etc. can be used.
  • the heat ray shielding multilayer glass 40 of the present invention may have layers having various functions such as another heat ray shielding layer, a neon light emitting absorption layer, and an ultraviolet absorption layer in addition to the heat ray reflection layer 24.
  • the heat ray shielding layer is a layer containing a heat ray shielding agent other than the conductive polymer.
  • the heat ray shielding agent is generally an inorganic material or an organic dye.
  • tungsten oxide and / or composite tungsten oxide indium-tin oxide, tin oxide, antimony-tin oxide, phthalocyanine dye, metal complex dye, nickel dithiolene complex dye, cyanine dye, squarylium And dyes such as dyes, polymethine dyes, azomethine dyes, azo dyes, polyazo dyes, diimonium dyes, aminium dyes and anthraquinone dyes. These dyes can be used alone or in combination.
  • the neon emission absorption layer is a layer containing a neon emission selective absorption dye.
  • selective absorption dyes for neon emission porphyrin dyes, azaporphyrin dyes, cyanine dyes, squarylium dyes, anthraquinone dyes, phthalocyanine dyes, polymethine dyes, polyazo dyes, azurenium dyes, diphenylmethane dyes, A triphenylmethane type pigment
  • dye can be mentioned.
  • Such a selective absorption dye is required to have a selective absorption of neon emission at around 585 nm and a small absorption at other visible light wavelengths. Therefore, the absorption maximum wavelength is 560 to 610 nm, and the absorption spectrum half width is small. What is 40 nm or less is preferable.
  • the ultraviolet absorption layer is a layer containing an ultraviolet absorber, and examples of the ultraviolet absorber include benzophenone compounds, benzotriazole compounds, triazine compounds, benzoate compounds, hindered amine compounds, salicylic acid compounds, and cyanoacrylate compounds. Compounds and the like can be used.
  • These layers may be formed as separate layers according to the properties (solubility, reactivity, etc.) of each compound, or may be formed as the same layer by mixing each compound.
  • a coloring pigment, an antioxidant, and the like may be further added to these layers as long as the optical properties are not greatly affected.
  • these layers may be formed on the heat ray shielding glass 30 side of the heat ray shielding multilayer glass 40, for example, on the lower layer or the upper layer (preferably the lower layer) of the heat ray reflective layer 24, or on the glass plate 37 side. May be.
  • the ultraviolet absorbing layer is formed on the side irradiated with sunlight (outside the room) with respect to the heat ray shielding layer 24. That is, when the heat ray shielding glass 30 is disposed on the outdoor side, the ultraviolet ray absorbing layer is on the lower layer of the heat ray reflecting layer 24 in the heat ray shielding glass 30 or the surface opposite to the surface on which the heat ray reflecting layer 24 of the glass plate 21 is formed. Preferably it is formed. Moreover, when the glass plate 37 is arrange
  • the shape of the heat ray-shielding multilayer glass of the present invention can be various shapes such as a rectangular shape, a round shape, and a rhombus shape depending on the application.
  • various kinds of equipment such as window glass for buildings and vehicles (automobiles, railway vehicles, ships) or equipment such as plasma displays, refrigerators, heat insulation devices, etc. It can be used for various applications such as doors and walls.
  • the glass plate When the heat ray shielding multilayer glass of the present invention is used for a building or a vehicle in a warm region such as a relatively low latitude region, the glass plate is disposed on the indoor side and the heat ray shielding glass is disposed on the outdoor side. It is preferable. This is because sunlight and the near infrared rays irradiated from the outside can be effectively shielded. On the other hand, when the heat ray shielding multilayer 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.
  • the heat ray shielding double-glazed glass of the present invention is excellent in heat insulation, it can be used more effectively in cold regions.
  • Example 1 Formation of heat ray reflective layer A poly (3,4-ethylenedioxythiophene) -containing paint (CLEVIOS PHCV4 (manufactured by HC Starck)) was applied on a PET film (thickness 100 ⁇ m) using a bar coater, It was dried at 120 ° C. for 3 minutes to form a heat ray reflective layer (thickness 600 nm) on the PET film.
  • EVA content of vinyl acetate with respect to 100 parts by mass of EVA: 25 parts by mass
  • Ultrasen 635 manufactured by Tosoh Corporation
  • EVA content of vinyl acetate with respect to 100 parts by mass of EVA: 25 parts by mass
  • Ultrasen 635 manufactured by Tosoh Corporation
  • EVA content of vinyl acetate with respect to 100 parts by mass of EVA: 25 parts by mass
  • Ultrasen 635 manufactured by Tosoh Corporation
  • Organic peroxide tert-butyl peroxy 2-ethylhexyl carbonate
  • Trigonox 117 manufactured by Kayaku Akzo
  • Cross-linking assistant triallyl isocyanurate
  • TAIC registered trademark
  • Silane coupling agent ⁇ -methacryloxypropyltrimethoxysilane
  • KBM503 manufactured by Shin-Etsu Chemical Co., Ltd.
  • UV absorber Ubinal 3049 (manufactured by BASF
  • the lamination position was adjusted so that the edge part of the PET film in which the heat ray reflective layer was formed may not cover the area
  • the obtained laminate was subjected to temporary pressure bonding by heating at 100 ° C. for 30 minutes, and then heated in an autoclave under conditions of a pressure of 13 ⁇ 10 5 Pa and a temperature of 140 ° C. for 30 minutes. Thereby, the adhesive layer was cured to obtain a heat ray shielding glass in which the glass plate and the transparent plastic film were bonded and integrated.
  • Example 2 (1) Formation of heat ray reflective layer (production of heat ray shielding glass) On a glass plate (thickness 3 mm), a poly (3,4-ethylenedioxythiophene) -containing paint (CLEVIOS PHCV4 (manufactured by HC Starck)) was applied using a bar coater and dried at 120 ° C. for 3 minutes. A heat ray reflective layer (thickness 600 nm) was formed on the glass plate. Next, the heat ray reflective layer was removed using water so that the end of the heat ray reflective layer was not covered in the region where the spacer was disposed. (2) Production of heat ray shielding multilayer glass A heat ray shielding multilayer glass was produced in the same manner as in (4) of Example 1 except that the heat ray shielding glass prepared in (1) above was used.
  • CLEVIOS PHCV4 manufactured by HC Starck
  • Example 3 A heat ray shielding multilayer glass was produced in the same manner as in Example 1 except that the thickness of the formed heat ray reflective layer was 200 nm.
  • Example 4 Except that the end of the PET film on which the heat ray reflective layer is formed is adjusted so that it is half the spacer, each member is arranged (the end of the PET film is 3 mm inside from the end on the outer peripheral side of the spacer) In the same manner as in Example 1, a heat ray shielding multilayer glass was produced (see FIG. 2).
  • Example 1 A multilayer glass was produced in the same manner as in Example 1 using two glass plates (thickness 3 mm).
  • Example 2 The heat ray shielding glass produced in (1) of Example 1 was used as a sample.
  • Example 3 A heat ray-shielding multilayer glass as in Example 1 except that the PET film on which the heat ray reflective layer is formed is laminated on the entire surface of the glass plate, and the end portion of the PET film is made to coincide with the end portion on the outer peripheral side of the spacer. was produced (see FIG. 3).
  • Example 4 A heat ray shielding multilayer glass as in Example 3 except that the PET film on which the heat ray reflective layer is formed is laminated on the entire surface of the glass plate, and the end portion of the PET film is made to coincide with the end portion on the outer peripheral side of the spacer. was produced (see FIG. 3).
  • Evaluation results Table 1 shows the evaluation results of the respective glass samples.
  • the heat ray shielding multilayer glass in which the end of the heat ray reflective layer formed of the conductive polymer of Examples 1 to 4 is inside the outer peripheral end of the spacer is a multilayer.
  • Comparative Example 2 where the heat ray reflective layer is exposed instead of glass, and Comparative Examples 3 and 4 where the end of the heat ray reflective layer coincides with the end of the spacer it is shown that the weather resistance is high. It was.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Joining Of Glass To Other Materials (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne un produit de verre protégé contre les rayonnements thermiques qui a une couche réfléchissant les rayonnements thermiques comprenant un polymère conducteur, la couche réfléchissant les rayonnements thermiques ayant d'excellentes propriétés de protection contre les rayonnements thermiques, en particulier, d'excellentes propriétés d'isolation thermique, et pouvant être produits à un coût faible. Ce produit a une durabilité élevée en présence d'eau (dans des conditions d'humidité élevée). Le panneau de double vitrage à protection contre les rayonnements thermiques est caractérisé en ce qu'un verre de protection contre les rayonnements thermiques comprenant une feuille de verre et une couche réfléchissant les rayonnements thermiques disposée sur une surface de celle-ci et comprenant un polymère conducteur et une autre feuille de verre ont été disposées séparées l'une de l'autre par un écartement formé avec un espaceur disposé le long d'une partie de bord périphérique du verre de protection contre les rayonnements thermiques, de sorte que la couche réfléchissant les rayonnements thermiques soit face à l'autre feuille de verre, l'écartement constituant une couche d'espace, et que la périphérie de la zone dans laquelle la couche réfléchissant les rayonnements thermiques a été formée dans le verre de protection contre les rayonnements thermiques est située à l'intérieur de la périphérie externe de l'espaceur.
PCT/JP2011/067643 2010-08-04 2011-08-02 Panneau de double vitrage protégé contre les rayonnements thermiques WO2012018000A1 (fr)

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JP2010175038A JP5840831B2 (ja) 2010-08-04 2010-08-04 熱線遮蔽複層ガラス
JP2010-175038 2010-08-04

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10669198B2 (en) 2015-09-07 2020-06-02 Panasonic Intellectual Property Management Co., Ltd. Vacuum glass panel, glass window, and method for producing vacuum glass panel
WO2020108673A1 (fr) * 2018-11-30 2020-06-04 Thermo Glass.eu s.r.o. Vitrage de sécurité chauffé

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5945947A (ja) * 1982-09-02 1984-03-15 Asahi Glass Co Ltd 改良された複層ガラス
DE4226757A1 (de) * 1992-08-13 1994-02-17 Bayer Ag Verbundglasscheiben
JP2004518603A (ja) * 2001-02-08 2004-06-24 カーディナル・シージー・カンパニー 被覆基材の縁部処理方法
JP2008026493A (ja) * 2006-07-19 2008-02-07 Lintec Corp 反射防止フィルム
WO2010150839A1 (fr) * 2009-06-24 2010-12-29 株式会社ブリヂストン Verre de blindage contre les rayons thermiques, et verre feuilleté de blindage contre les rayons thermiques

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5670079U (fr) * 1979-11-02 1981-06-10

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5945947A (ja) * 1982-09-02 1984-03-15 Asahi Glass Co Ltd 改良された複層ガラス
DE4226757A1 (de) * 1992-08-13 1994-02-17 Bayer Ag Verbundglasscheiben
JP2004518603A (ja) * 2001-02-08 2004-06-24 カーディナル・シージー・カンパニー 被覆基材の縁部処理方法
JP2008026493A (ja) * 2006-07-19 2008-02-07 Lintec Corp 反射防止フィルム
WO2010150839A1 (fr) * 2009-06-24 2010-12-29 株式会社ブリヂストン Verre de blindage contre les rayons thermiques, et verre feuilleté de blindage contre les rayons thermiques

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10669198B2 (en) 2015-09-07 2020-06-02 Panasonic Intellectual Property Management Co., Ltd. Vacuum glass panel, glass window, and method for producing vacuum glass panel
WO2020108673A1 (fr) * 2018-11-30 2020-06-04 Thermo Glass.eu s.r.o. Vitrage de sécurité chauffé

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