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WO2017090690A1 - Verre feuilleté, verre à vitres pour des automobiles et verre à vitres pour des bâtiments - Google Patents

Verre feuilleté, verre à vitres pour des automobiles et verre à vitres pour des bâtiments Download PDF

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Publication number
WO2017090690A1
WO2017090690A1 PCT/JP2016/084836 JP2016084836W WO2017090690A1 WO 2017090690 A1 WO2017090690 A1 WO 2017090690A1 JP 2016084836 W JP2016084836 W JP 2016084836W WO 2017090690 A1 WO2017090690 A1 WO 2017090690A1
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Prior art keywords
laminated glass
glass
thickness
transparent
value
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English (en)
Japanese (ja)
Inventor
千恵子 室伏
室伏　英伸
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AGC Inc
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Asahi Glass Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin

Definitions

  • the present invention relates to laminated glass, automotive window glass and building window glass.
  • Laminated glass with two glass plates bonded together with an intermediate film is excellent in penetration resistance, and even when broken, there is little scattering of glass fragments, so window glass for vehicles, window glass for buildings, etc. It is used as.
  • a laminated glass there is known a laminated glass provided with an infrared reflection layer or an infrared absorption layer on an intermediate film in order to suppress a temperature rise in a vehicle or a room due to solar radiation (Patent Documents 1 to 4).
  • laminated glass with an infrared reflecting layer or infrared absorbing layer on the interlayer can block infrared rays that enter from outside the vehicle or from the outside of the vehicle, but it cannot block heat conducted through the laminated glass itself.
  • outdoor heat flows through the laminated glass through the laminated glass and flows into the vehicle and the room, and in winter, heat from inside and indoor heating flows through the laminated glass and flows out of the vehicle and the outdoor.
  • a laminated glass that blocks heat conducted through the laminated glass itself, that is, has a heat insulating property, is composed of a first layer containing hollow silica fine particles and a second layer and a third layer sandwiching the interlayer.
  • Patent Document 5 has been proposed.
  • the first layer containing the hollow silica fine particles is designed to be thin in order to maintain the transmittance, so that the thermal conductivity is high and the heat insulation is insufficient.
  • the present invention provides laminated glass, automobile window glass and building window glass that have high transparency and excellent heat insulation.
  • the present invention has the following aspects. ⁇ 1> A first glass plate, a first transparent adhesive layer, a transparent heat-insulating layer having independent pores, a second transparent adhesive layer, and a second glass plate in order, wherein the independent pores The pores are directly covered with a matrix without passing through the shell, and the A value represented by the following formula (1) is 6.4 ⁇ 10 5 or less, and is represented by the following formula (2). Laminated glass whose B value is 35 or more.
  • D is the pore size (nm) of the independent pores of the transparent heat insulation layer
  • P is the porosity of the transparent heat insulation layer
  • d i is the thickness (mm) of the transparent heat insulation layer
  • d g is the first the sum of the thickness and the thickness of the second glass plate of the glass plate (mm)
  • d a is the total thickness of the first transparent adhesive layer thickness and a second transparent adhesive layer (mm) .
  • ⁇ 4> The laminated glass according to any one of ⁇ 1> to ⁇ 3>, wherein the transparent heat insulating layer is a foamed resin sheet.
  • ⁇ 5> The laminated glass according to any one of ⁇ 1> to ⁇ 4>, wherein the transparent heat insulating layer has a thickness of 0.2 to 10 mm.
  • ⁇ 6> The laminated glass according to any one of ⁇ 1> to ⁇ 5>, wherein the thickness of the first glass plate and the thickness of the second glass plate are 0.1 to 6 mm, respectively.
  • ⁇ 7> The laminated glass according to any one of ⁇ 1> to ⁇ 6>, wherein the thickness of the first transparent adhesive layer and the thickness of the second transparent adhesive layer are 0.1 to 3 mm, respectively.
  • An automotive window glass comprising the laminated glass according to any one of ⁇ 1> to ⁇ 7>.
  • ⁇ 9> A window glass for buildings comprising the laminated glass of any one of ⁇ 1> to ⁇ 7>.
  • the laminated glass, the window glass for automobiles and the window glass for buildings of the present invention have high transparency and excellent heat insulation.
  • FIG. 1 is a cross-sectional view showing an example of the laminated glass of the present invention.
  • the pore means a hole made of a void formed in the heat insulating material.
  • Independent pores means pores that are completely covered with a matrix or shell around each pore. Independent pores include independent pores that are directly covered with a matrix without passing through a shell, and independent pores that are formed by hollow particles having shells dispersed in the matrix. There are pores. The independent pores in the present invention are the former independent pores.
  • Transparent means that light can be transmitted.
  • Pore diameter is a value obtained by observing 100 pores in a cross section of a heat insulating layer using a transmission microscope and calculating a simple average of major and minor diameters when the pores are regarded as an ellipse (ie, 200 numerical values). Average).
  • Pore diameter is a value obtained by the following equation from the volume of the transparent heat insulating layer before pressing and the volume of the transparent heat insulating layer after pressing under the conditions of temperature: 200 ° C., pressure: 35 MPa, time: 10 minutes. is there.
  • Porosity 1 ⁇ (Volume of transparent heat insulating layer after pressing / Volume of transparent heat insulating layer before pressing)
  • Transmittance is a value measured in accordance with JIS R 3106: 1998 “Testing method for transmittance, reflectance, emissivity, and solar heat gain of plate glass” (ISO 9050: 1990).
  • Heat transmissivity (U value) is defined in JIS R 3107: 1998 “Method of calculating thermal resistance of sheet glass and heat transmissivity in architecture” (ISO 10292: 1994) and JIS R 3209: 1998 “Multilayer glass”. It is a value measured in compliance.
  • the “compressive modulus” is a value measured in accordance with JIS K 7181: 2011 “Plastics—How to obtain compression properties” (ISO 604: 2002).
  • FIG. 1 is a cross-sectional view showing an example of the laminated glass of the present invention.
  • the laminated glass 1 includes a first glass plate 10; a second glass plate 12; a transparent heat insulating layer 14 having independent pores disposed between the first glass plate 10 and the second glass plate 12.
  • a first transparent adhesive layer 16 that bonds the first glass plate 10 and the transparent heat insulating layer 14; and a second transparent adhesive layer 18 that bonds the second glass plate 12 and the transparent heat insulating layer 14 Have.
  • the material of the first glass plate and the second glass plate may be an inorganic glass or an organic glass, and has weather resistance, rigidity, and solvent resistance.
  • inorganic glass is preferable.
  • the materials of the first glass plate and the second glass plate may be the same or different.
  • the inorganic glass include soda lime glass, borosilicate glass, non-alkali glass, and quartz glass. Soda lime glass is preferable.
  • the organic glass include polycarbonate and acrylic resin.
  • the glass plate may be a colorless transparent glass plate or a colored transparent glass plate, and is preferably a heat ray absorbing glass plate (blue glass plate or green glass plate) rich in iron.
  • a tempered glass plate may be used to enhance safety.
  • a tempered glass plate obtained by an air cooling tempering method or a chemical tempering method can be used.
  • the shape of the glass plate may be curved or flat. Since the window glass for automobiles is often curved, when the laminated glass of the present invention is used as the window glass for automobiles, the shape of the glass plate is often curved.
  • the thickness of the glass plate is preferably 0.1 to 6 mm, more preferably 1 to 3 mm.
  • the thicknesses of the first glass plate and the second glass plate may be the same or different.
  • the thickness of the glass plate in this invention is geometric thickness. Hereinafter, the same applies to the thickness of each layer of the laminated glass of the present invention other than the glass plate.
  • the material of the first transparent adhesive layer and the second transparent adhesive layer may be any transparent resin that can adhere the glass plate and the transparent heat insulating layer.
  • the transparent resin include polyvinyl butyral, ethylene-vinyl acetate copolymer, and commercially available optically clear adhesive (OCA), and polyvinyl butyral and ethylene-vinyl acetate copolymer are preferable. Polyvinyl butyral is more preferable for applications requiring penetration resistance such as window glass.
  • the materials of the first transparent adhesive layer and the second transparent adhesive layer may be the same or different. Each transparent adhesive layer may be a laminate of two or more layers of the same or different types.
  • the transparent adhesive layer may contain an infrared absorber, an ultraviolet absorber, an antioxidant, a light stabilizer, a colorant and the like within a range not impairing the effects of the present invention.
  • the thickness of the transparent adhesive layer is preferably from 0.1 to 3 mm, and more preferably from 0.3 to 0.8 mm.
  • the thickness of the first transparent adhesive layer and the second transparent adhesive layer may be the same or different.
  • the compressive elastic modulus of the transparent heat insulating layer is preferably 4.3 MPa or more, more preferably 12 MPa or more, and further preferably 120 MPa or more.
  • the compression modulus is equal to or higher than the lower limit of the above range, the transparent heat insulating layer is excellent in mechanical strength and can withstand compression when bonded to a glass plate during the production of laminated glass.
  • the thickness of the transparent heat insulating layer is preferably 0.2 to 10 mm, more preferably 0.5 to 6 mm, and further preferably 1 to 3 mm. If the thickness of a transparent heat insulation layer is more than the lower limit of the said range, it will be further excellent in the heat insulation of a laminated glass. If the thickness of a transparent heat insulation layer is below the upper limit of the said range, the transparency of a laminated glass will become still higher.
  • the transparent heat insulating layer has independent pores (hereinafter also referred to as independent pores without a shell or simply independent pores) directly covered with a matrix without passing through a shell.
  • independent pores hereinafter also referred to as independent pores without a shell or simply independent pores
  • Examples of the transparent heat insulating layer having independent pores without a shell include a foamed resin sheet; a sheet in which generation of nanobubbles is fixed.
  • a foamed resin sheet is preferable from the viewpoint that both transparency and heat insulating properties of the laminated glass are easily achieved, manufacturing is easy, and cost is low.
  • the foamed resin sheet is a sheet in which independent pores are formed by foaming in a matrix made of a resin material.
  • Examples of the resin contained in the resin material include amorphous thermoplastic resins, crystalline thermoplastic resins, and cured products of curable resins.
  • Amorphous thermoplastic resins include polystyrene, polymethyl methacrylate, polycarbonate, amorphous polyester resin, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer, norbornene resin, amorphous fluororesin, Examples include polyether sulfone, polysulfone, polyether imide, polyarylate, polyester carbonate, triacetyl cellulose, and amorphous nylon resin.
  • thermoplastic resin examples include polypropylene, polyethylene, polyvinyl chloride, crystalline polyester resin, crystalline fluororesin, poly-4-methylpentene-1, and the like.
  • curable resin examples include epoxy resin, diethylene glycol biscarbonate, polyfunctional acrylate resin, and polyfunctional methacrylate resin.
  • the resin material is a foam nucleating agent, a colorant, an antioxidant, a light stabilizer, a mold release agent, an antiseptic, an infrared absorber, an ultraviolet absorber, a plasticizer, and a flame retardant.
  • a conductivity imparting agent, an antistatic agent, a crystal nucleating agent and the like may be contained.
  • the foamed resin sheet can be produced by a known method using a foaming agent, and it is easy to produce a foamed resin sheet having high transparency and excellent heat insulation properties.
  • a method of exposing the film to an inert gas or its supercritical fluid and then releasing the pressure at once; introducing an inert gas or its supercritical fluid into the extruder, and the pressure when the resin is extruded from the die It is preferable to manufacture by a method using a foaming method that utilizes the fact that is released at once. When importance is placed on productivity, a method of introducing an inert gas or a supercritical fluid thereof into the extruder is more preferable.
  • the method is a method for producing a foamed resin sheet by impregnating a resin material with an inert gas or a supercritical fluid thereof at a specific pressure and a specific temperature and then releasing the pressure.
  • the inert gas include carbon dioxide and nitrogen.
  • the inert gas is often impregnated into the resin material as a supercritical fluid under heating and pressurization.
  • the impregnation temperature is lower than the glass transition temperature of the amorphous thermoplastic resin, and the amorphous thermoplastic resin is sufficiently impregnated with an inert gas (hereinafter, referred to as “amorphous thermoplastic resin”).
  • amorphous thermoplastic resin A temperature higher than the glass transition temperature of the amorphous thermoplastic resin in the saturated impregnation state) is preferable.
  • the impregnation temperature is preferably lower than the melting point of the crystalline thermoplastic resin and higher than the melting point of the crystalline thermoplastic resin in the saturated impregnation state.
  • the impregnation temperature is preferably lower than the glass transition temperature of the cured product of the curable resin and higher than the glass transition temperature of the cured product of the curable resin in the saturated impregnation state. . If the impregnation temperature is at least the lower limit of the above range, the gas diffusibility is improved and the impregnation time of the inert gas can be shortened. If the impregnation temperature and the temperature at which the pressure is released are not more than the upper limit of the above range, the pore diameter of the independent pores can be reduced.
  • the impregnation pressure is preferably 8 to 50 MPa, more preferably 15 to 30 MPa. If the impregnation pressure is not less than the lower limit of the above range, the gas diffusibility can be improved, the impregnation time of the inert gas can be shortened, and the porosity of the foamed resin sheet can be increased. If the impregnation pressure is not more than the upper limit of the above range, the pore diameter of the independent pores can be reduced.
  • the impregnation time is preferably a time that allows the gas concentration in the matrix to be uniform. Depending on the type of resin material and the thickness of the resin sheet, it is preferably 0.5 to 12 hours, more preferably 1 to 2 hours. . If the impregnation time is not less than the lower limit of the above range, the porosity of the foamed resin sheet can be increased. If the impregnation time is less than or equal to the upper limit of the above range, productivity is excellent.
  • the porosity is the pore diameter multiplied by the number density of the pores.
  • the pore diameter of the independent pores without the shell is the viscosity (impregnation temperature) of the resin material when the resin material is impregnated with an inert gas or its supercritical fluid, the decompression speed (decompression time) when the pressure is released, etc.
  • the number density depends on the concentration (impregnation pressure) of the inert gas impregnated in the resin material or its supercritical fluid.
  • the impregnation temperature when the resin material is impregnated with an inert gas or its supercritical fluid is lowered to increase the viscosity of the resin material.
  • the pressure reduction rate when releasing the pressure may be reduced.
  • Obtaining a transparent heat insulating layer having independent pores without a shell having a compression modulus of 4.3 MPa or more can be achieved by increasing the compression modulus of the matrix to 6.8 MPa or more. It can also be achieved by reducing the pore diameter of the independent pores without a shell.
  • the laminated glass of the present invention has an A value represented by the following formula (1) of 6.4 ⁇ 10 5 or less, preferably 2.3 ⁇ 10 5 or less, more preferably 1.0 ⁇ 10 5 or less. .
  • the transmittance of the laminated glass is 50% or more. If the A value is 2.3 ⁇ 10 5 or less, the transmittance of the laminated glass is 70% or more.
  • the transmittance of the laminated glass is 50% or more when the A value is 6.4 ⁇ 10 5 or less, and the transmittance of the laminated glass is 70% when the A value is 2.3 ⁇ 10 5 or less. The reason for this will be described below.
  • the transmittance of the transparent heat insulation layer necessary for the transmittance of the laminated glass is determined.
  • the purpose of this derivation is to obtain a relational expression as to what the transmittance T 3 of the transparent heat insulating layer needs to be when the required numerical value of the transmittance S 6 of the laminated glass is designated.
  • the Fresnel reflection F 1 at the interface between the layer having the refractive index n 1 and the layer having the refractive index n 2 is expressed by the following equation.
  • Formula (4) is represented by the following Formula (5).
  • the refractive indexes n 1 and n 5 of a normal glass plate and the refractive indexes n 2 and n 4 of the transparent adhesive layer are about 1.5.
  • equation (5) is expressed by the following equation.
  • the transmittance T i of the transparent heat insulating layer necessary for the transmittance T L of the laminated glass to be realized can be calculated.
  • the transmittance T i of the transparent heat insulation layer is expressed as follows: the incident light intensity to the transparent heat insulation layer is I 0 , the transmitted light intensity from the transparent heat insulation layer is I, the scattering cross section of the independent pores of the transparent heat insulation layer is ⁇ , the number of pores per unit volume N, and the thickness of the transparent heat insulating layer and d i (mm), is represented by the following formula (7) (polymer Collected papers, Vol.67, No.7, pp.390 -396 (2010)).
  • the scattering cross-sectional area ⁇ is expressed by the following equation, where the pore diameter is D (mm) and the wavelength is ⁇ (nm).
  • the number N of pores per unit volume of the transparent heat insulation layer is expressed by the following formula.
  • Formula (12) is represented by the following Formula (13).
  • the thickness d i of the layer should be in the relationship of the following formula (14).
  • the unit of A value is nm 3 mm.
  • the B value represented by the following formula (2) is 35 or more, and preferably 85 or more.
  • the heat flow rate (U value) of the laminated glass which is a measure of heat insulation, is 5.0 W / m 2 K or less. If the B value is 85 or more, the U value of the laminated glass is 4.0 W / m 2 K or less.
  • the thermal conductivity of the laminated glass is U (W / m 2 K), the outdoor surface heat transfer coefficient is h ext (W / m 2 K), and the indoor surface heat transfer coefficient is h in (W / m 2 K). ), R (m 2 K / W) for the thermal resistance of each layer, d g (mm) for the total thickness of the two glass plates, ⁇ g (W / mK) for the thermal conductivity of the glass plate, transparent adhesion
  • the total thickness of the layers is d a (mm)
  • the thermal conductivity of the transparent adhesive layer is ⁇ a (W / mK)
  • the thickness of the transparent heat insulation layer is d i (mm)
  • the heat conductivity of the transparent heat insulation layer is ⁇ If i (W / mK), it is represented by the following formula (16).
  • Thermal conductivity ⁇ i of the transparent insulation layer mat the thermal conductivity of the matrix of transparent thermal insulation layer ⁇ (W / mK), the porosity of the transparent thermal insulation layer and is P, Japan University of Industrial Technology 37th (2004 Academic Lecture Meeting Applied Molecular Chemistry Group Program 5-8 “Measurement of thermal conductivity of gas hydrate simulated sediment sample” Using equation (17), b is a proportional constant Is done.
  • the hemispherical emissivity ⁇ ext of the outdoor member surface is 0.837 W / m 2 K
  • the hemispherical emissivity ⁇ in of the indoor member surface is 0.837 W / m 2 K.
  • the surface heat transfer coefficient h ext and the indoor surface heat transfer coefficient h in are as follows.
  • the thermal conductivity ⁇ g of the glass plate is approximately 1.0 W / mK even if the glass type is different, and the thermal conductivity ⁇ a of the material used for the transparent adhesive layer is approximately 0.3 W / mK. . Further, the thermal conductivity ⁇ mat of the transparent heat insulating layer matrix can be set to 1.0 W / mK as the worst case. From these, when unit (m) is unified and equation (16) is arranged, it is expressed by the following equation (18).
  • the B value is as follows.
  • the pore diameter D of the independent pores of the transparent heat insulating layer, the porosity P of the transparent heat insulating layer, the thickness d i of the transparent heat insulating layer, total d g thickness, total d a thickness of the transparent adhesive layer it can be seen that it is sufficient to relation of the following equation (22).
  • the transmittance of light having a wavelength of 500 nm of the laminated glass is preferably 50% or more, more preferably 70 to 99%, and further preferably 70 to 96%. If the transmittance
  • the heat transmissivity (U value) of the laminated glass is preferably 5.8 W / m 2 K or less from the viewpoint of improving fuel efficiency since the current laminated glass for automobiles is 5.8 W / m 2 K. More preferable is 0.0 W / m 2 K or less.
  • the thickness of the laminated glass is preferably 2 to 20 mm, more preferably 3 to 10 mm, and even more preferably 4 to 6 mm. If the thickness of the laminated glass is not less than the lower limit of the above range, the heat insulating property of the laminated glass is further improved, and the mechanical strength is also excellent. If the thickness of a laminated glass is below the upper limit of the said range, a laminated glass will not become too heavy and it is excellent also in transparency.
  • Laminated glass can be produced by a known method. For example, a second glass plate, a transparent resin sheet to be a second transparent adhesive layer, a transparent heat insulating sheet to be a transparent heat insulating layer, a transparent resin sheet to be a first transparent adhesive layer, and a first glass plate are sequentially stacked. After these are temporarily bonded, they can be manufactured by main bonding by heating and pressing. At this time, the transparent resin sheet serving as the first transparent adhesive layer and the transparent resin sheet serving as the second transparent adhesive layer may each be the same type or may be composed of two or more different types of sheets. Good.
  • the laminated glass of the present invention comprises a first glass plate, a first transparent adhesive layer, a transparent heat insulating layer having independent pores without a shell, a second transparent adhesive layer, and a second glass plate in this order.
  • the A value is 6.4 ⁇ 10 5 or less and the B value is 35 or more, and is not limited to the illustrated example.
  • the laminated glass of this invention may have a 3rd glass plate or more glass plates as needed.
  • the laminated glass of this invention may have functional layers other than a transparent heat insulation layer, such as an infrared absorption layer and an ultraviolet absorption layer.
  • the pore diameter of the independent pores in the transparent heat insulation layer is a simple average of the major and minor diameters when 100 pores are observed using a transmission microscope (manufactured by JEOL Ltd., JEM-1230) and regarded as an ellipse. Is a calculated value (that is, an average of 200 numerical values).
  • Porosity of transparent heat insulation layer It calculated
  • Porosity 1 ⁇ (Volume of transparent heat insulating layer after pressing / Volume of transparent heat insulating layer before pressing)
  • the compression elastic modulus of the transparent heat insulation layer is based on JIS K 7181: 2011 (ISO 604: 2002) for the transparent heat insulation sheet before bonding, and is a desktop precision universal testing machine (manufactured by Shimadzu Corporation, Autograph AGS-5kNX) ).
  • Heat transmissivity (U value) The U value of the laminated glass was measured using HC-074 / 630 manufactured by Eihiro Seiki Co., Ltd. in accordance with JIS R 3107: 1998 and JIS R 3209: 1998.
  • a value About the A value calculated
  • B value About the B value calculated
  • the transmittance is 70% or more and the U value is 4.0 W / m 2 K or less.
  • ⁇ The transmittance is 50% or more and the U value is 5.0 W / m 2 K or less.
  • X The transmittance is less than 50% or the U value is less than 5.0 W / m 2 K.
  • Example 1 A polycarbonate film having a thickness of 0.4 mm (manufactured by AGC Polycarbonate) was prepared. The film was placed in a pressure vessel, and liquefied carbon dioxide was supplied into the pressure vessel with a pump and heated to 120 ° C. The pressure was adjusted to maintain 20 MPa. The film was impregnated with supercritical carbon dioxide by holding for 3 hours. While maintaining the temperature, the valve of the pressure vessel was opened and the pressure was released to atmospheric pressure over 10 seconds to obtain a foamed resin sheet having a thickness of 1.2 mm. The pore diameter of closed cells in the foamed resin sheet, the porosity of the foamed resin sheet, and the compression modulus were measured.
  • both sides are sandwiched between 0.38mm thick polyvinyl butyral (PVB) films, and both sides are sandwiched between 1.6mm thick soda lime glass (Asahi Glass Co., Ltd.), which is then used in vacuum packaging bags Then, vacuum suction was performed, air remaining at the interface of each layer was degassed, and temporarily bonded at 120 ° C. for 30 minutes to obtain a laminate. Next, the laminate was put in an autoclave and was finally bonded at 120 ° C. and 1.3 MPa for 90 minutes to obtain a laminated glass. While confirming that a transparent heat insulation layer is not compressively deformed when bonding with a glass plate, the transmittance
  • Example 2 A polycarbonate film having a thickness of 0.5 mm was prepared. The film was placed in a pressure vessel, and liquefied carbon dioxide was supplied into the pressure vessel with a pump and heated to 110 ° C. The pressure was adjusted so as to maintain 26 MPa. The film was impregnated with supercritical carbon dioxide by holding for 1 hour. While maintaining the temperature, the valve of the pressure vessel was opened and the pressure was released to atmospheric pressure over 5 seconds to obtain a foamed resin sheet having a thickness of 1.3 mm. The pore diameter of closed cells in the foamed resin sheet, the porosity of the foamed resin sheet, and the compression modulus were measured.
  • a foamed resin sheet was used as a transparent heat insulating layer, both sides were sandwiched between 0.76 mm thick PVB films, and both sides were sandwiched between 1.0 mm thick soda lime glass to produce a laminated glass in the same manner as in Example 1. While confirming that a transparent heat insulation layer is not compressively deformed when bonding with a glass plate, the transmittance
  • Example 3 A polycarbonate film having a thickness of 2.0 mm was prepared. The film was placed in a pressure vessel, and liquefied carbon dioxide was supplied into the pressure vessel with a pump and heated to 95 ° C. The pressure was adjusted to maintain 25 MPa. The film was impregnated with supercritical carbon dioxide by holding for 5 hours. While maintaining the temperature, the valve of the pressure vessel was opened and the pressure was released to atmospheric pressure over 10 seconds to obtain a foamed resin sheet having a thickness of 5.8 mm. The pore diameter of closed cells in the foamed resin sheet, the porosity of the foamed resin sheet, and the compression modulus were measured.
  • a foamed resin sheet was used as a transparent heat insulating layer, both sides were sandwiched between PVB films having a thickness of 0.1 mm, both sides were sandwiched between soda lime glasses having a thickness of 2.0 mm, and laminated glass was produced in the same manner as in Example 1. While confirming that a transparent heat insulation layer is not compressively deformed when bonding with a glass plate, the transmittance
  • Example 4 A 0.2 mm thick polycarbonate film (manufactured by AGC Polycarbonate) was prepared. The film was placed in a pressure vessel, and liquefied carbon dioxide was supplied into the pressure vessel with a pump and heated to 100 ° C. The pressure was adjusted so as to maintain 26 MPa. The film was impregnated with supercritical carbon dioxide by holding for 1 hour. While maintaining the temperature, the valve of the pressure vessel was opened and the pressure was released to atmospheric pressure over 5 seconds to obtain a foamed resin sheet having a thickness of 0.5 mm. The pore diameter of closed cells in the foamed resin sheet, the porosity of the foamed resin sheet, and the compression modulus were measured.
  • the foamed resin sheet is used as a transparent heat insulating layer, and both sides are sandwiched between a PVB film having a thickness of 0.26 mm and a PVB film having a thickness of 0.5 mm. Further, both sides of the sheet are 1.0 mm thick soda lime glass and 3.0 mm thick soda.
  • Laminated glass was prepared by the same method as in Example 1 by sandwiching with lime glass. While confirming that a transparent heat insulation layer is not compressively deformed when bonding with a glass plate, the transmittance
  • Example 5 A polymethyl methacrylate (PMMA) film having a thickness of 0.5 mm was prepared. The film was placed in a pressure vessel, and liquefied carbon dioxide was supplied into the pressure vessel with a pump and heated to 70 ° C. The pressure was adjusted to maintain 28 MPa. The film was impregnated with supercritical carbon dioxide by holding for 1 hour. While maintaining the temperature, the valve of the pressure vessel was opened and the pressure was released to atmospheric pressure over 5 seconds to obtain a foamed resin sheet having a thickness of 1.2 mm. The pore diameter of closed cells in the foamed resin sheet, the porosity of the foamed resin sheet, and the compression modulus were measured.
  • PMMA polymethyl methacrylate
  • the foamed resin sheet is used as a transparent heat insulation layer, and both sides are sandwiched between two 0.38mm thick PVB films and four 0.76mm thick PVB films, and both sides are sandwiched between 2mm thick soda lime glass.
  • a laminated glass was produced in the same manner as in Example 1. While confirming that a transparent heat insulation layer is not compressively deformed when bonding with a glass plate, the transmittance
  • Example 6 A PMMA film having a thickness of 0.4 mm was prepared. The film was placed in a pressure vessel, and liquefied carbon dioxide was supplied into the pressure vessel with a pump and heated to 80 ° C. The pressure was adjusted so as to maintain 26 MPa. The film was impregnated with supercritical carbon dioxide by holding for 1 hour. While maintaining the temperature, the valve of the pressure vessel was opened and the pressure was released to atmospheric pressure over 5 seconds to obtain a foamed resin sheet having a thickness of 1.1 mm. The pore diameter of closed cells in the foamed resin sheet, the porosity of the foamed resin sheet, and the compression modulus were measured.
  • a foamed resin sheet was used as a transparent heat insulating layer, both sides were sandwiched between 0.38 mm thick PVB films, and both sides were sandwiched between 2.0 mm thick soda lime glass to produce a laminated glass in the same manner as in Example 1. While confirming that a transparent heat insulation layer is not compressively deformed when bonding with a glass plate, the transmittance
  • Example 7 A PMMA film having a thickness of 0.8 mm was prepared. The film was placed in a pressure vessel, and liquefied carbon dioxide was supplied into the pressure vessel with a pump and heated to 75 ° C. The pressure was adjusted to maintain 28 MPa. The film was impregnated with supercritical carbon dioxide by holding for 3 hours. While maintaining the temperature, the valve of the pressure vessel was opened and the pressure was released to atmospheric pressure over 5 seconds to obtain a 2.5 mm thick foamed resin sheet. The pore diameter of closed cells in the foamed resin sheet, the porosity of the foamed resin sheet, and the compression modulus were measured.
  • Example 8 A PMMA film having a thickness of 0.4 mm was prepared. The film was placed in a pressure vessel, and liquefied carbon dioxide was supplied into the pressure vessel with a pump and heated to 85 ° C. The pressure was adjusted to maintain 25 MPa. The film was impregnated with supercritical carbon dioxide by holding for 1 hour. While maintaining the temperature, the valve of the pressure vessel was opened and the pressure was released to atmospheric pressure over 5 seconds to obtain a foamed resin sheet having a thickness of 1.2 mm. The pore diameter of closed cells in the foamed resin sheet, the porosity of the foamed resin sheet, and the compression modulus were measured.
  • a foamed resin sheet was used as a transparent heat insulating layer, both sides were sandwiched between 0.38 mm thick PVB films, and both sides were sandwiched between 2.0 mm thick soda lime glass to produce a laminated glass in the same manner as in Example 1. While confirming that a transparent heat insulation layer is not compressively deformed when bonding with a glass plate, the transmittance
  • Example 9 A polystyrene film having a thickness of 0.5 mm was prepared. The film was placed in a pressure vessel, and liquefied carbon dioxide was supplied into the pressure vessel with a pump and heated to 60 ° C. The pressure was adjusted so as to maintain 16 MPa. The film was impregnated with supercritical carbon dioxide by holding for 5 hours. While maintaining the temperature, the valve of the pressure vessel was opened and the pressure was released to atmospheric pressure over 1 minute to obtain a foamed resin sheet having a thickness of 1.1 mm. The pore diameter of closed cells in the foamed resin sheet, the porosity of the foamed resin sheet, and the compression modulus were measured.
  • a foamed resin sheet was used as a transparent heat insulating layer, both sides were sandwiched between 0.38 mm thick PVB films, and both sides were sandwiched between 2.0 mm thick soda lime glass to produce a laminated glass in the same manner as in Example 1. While confirming that a transparent heat insulation layer is not compressively deformed when bonding with a glass plate, the transmittance
  • Example 10 A polystyrene film having a thickness of 0.4 mm was prepared. The film was placed in a pressure vessel, and liquefied carbon dioxide was supplied into the pressure vessel with a pump and heated to 50 ° C. The pressure was adjusted so as to maintain 26 MPa. The film was impregnated with supercritical carbon dioxide by holding for 5 hours. While maintaining the temperature, the valve of the pressure vessel was opened and the pressure was released to atmospheric pressure over 1 minute to obtain a foamed resin sheet having a thickness of 0.8 mm. The pore diameter of closed cells in the foamed resin sheet, the porosity of the foamed resin sheet, and the compression modulus were measured.
  • a foamed resin sheet was used as a transparent heat insulating layer, both sides were sandwiched between 0.76 mm thick PVB films, and both sides were sandwiched between 6.0 mm thick soda lime glass to produce a laminated glass in the same manner as in Example 1. While confirming that a transparent heat insulation layer is not compressively deformed when bonding with a glass plate, the transmittance
  • Example 1 A polycarbonate film having a thickness of 0.3 mm was prepared. The film was placed in a pressure vessel, and liquefied carbon dioxide was supplied into the pressure vessel with a pump and heated to 130 ° C. The pressure was adjusted to maintain 10 MPa. The film was impregnated with supercritical carbon dioxide by holding for 1 hour. While maintaining the temperature, the valve of the pressure vessel was opened and the pressure was released to atmospheric pressure over 5 seconds to obtain a foamed resin sheet having a thickness of 1.2 mm. The pore diameter of closed cells in the foamed resin sheet, the porosity of the foamed resin sheet, and the compression modulus were measured.
  • a foamed resin sheet was used as a transparent heat insulating layer, both sides were sandwiched between 0.38 mm thick PVB films, and both sides were sandwiched between 2.0 mm thick soda lime glass to produce a laminated glass in the same manner as in Example 1. While confirming that a transparent heat insulation layer is not compressively deformed when bonding with a glass plate, the transmittance
  • Example 2 A PMMA film having a thickness of 0.5 mm was prepared. The film was placed in a pressure vessel, and liquefied carbon dioxide was supplied into the pressure vessel with a pump and heated to 100 ° C. The pressure was adjusted to maintain 20 MPa. The film was impregnated with supercritical carbon dioxide by holding for 3 hours. While maintaining the temperature, the pressure vessel valve was opened and the pressure was released to atmospheric pressure over 5 seconds to obtain a 2.0 mm thick foamed resin sheet. The pore diameter of closed cells in the foamed resin sheet, the porosity of the foamed resin sheet, and the compression modulus were measured.
  • a foamed resin sheet was used as a transparent heat insulating layer, both sides were sandwiched between 0.38 mm thick PVB films, and both sides were sandwiched between 2.0 mm thick soda lime glass to produce a laminated glass in the same manner as in Example 1. While confirming that a transparent heat insulation layer is not compressively deformed when bonding with a glass plate, the transmittance
  • ethylene-vinyl acetate copolymer (EVA) film having a thickness of 0.4 mm was prepared.
  • the film was placed in a pressure vessel, and liquefied carbon dioxide was supplied into the pressure vessel with a pump and heated to 50 ° C. The pressure was adjusted so as to maintain 26 MPa.
  • the film was impregnated with supercritical carbon dioxide by holding for 3 hours. While maintaining the temperature, the valve of the pressure vessel was opened and the pressure was released to atmospheric pressure over 5 seconds to obtain a foamed resin sheet having a thickness of 1.1 mm.
  • the pore diameter of closed cells in the foamed resin sheet, the porosity of the foamed resin sheet, and the compression modulus were measured.
  • a foamed resin sheet was used as a transparent heat insulating layer, both sides were sandwiched between 0.38 mm thick PVB films, and both sides were sandwiched between 2.0 mm thick soda lime glass to produce a laminated glass in the same manner as in Example 1.
  • the transparent heat insulation layer was crushed and whitened when it was bonded to the glass plate. The results are shown in Table 4.
  • the laminated glasses of Examples 1 to 10 having an A value of 6.4 ⁇ 10 5 or less and a B value of 35 or more had high transparency and excellent heat insulation.
  • the laminated glass of Comparative Example 1 having an A value of over 6.4 ⁇ 10 5 and a B value of less than 35 had low transparency and poor heat insulation.
  • the laminated glass of Comparative Example 2 having an A value exceeding 6.4 ⁇ 10 5 had low transparency and poor heat insulation.
  • the laminated glass of Comparative Example 3 having a B value of less than 35 was inferior in heat insulating properties.
  • the transparent heat insulating layer was crushed and whitened when bonded to the glass plate, and the transmittance was low.
  • the laminated glass of Comparative Example 4 not provided with a transparent heat insulating layer was inferior in heat insulating properties.
  • the laminated glass of the present invention includes automotive window glass (windshield, roof window, elevating window, side fixing window, backlight, roof window, etc.), vehicle window glass such as railcar window glass, and building window glass. Useful as such.

Landscapes

  • Joining Of Glass To Other Materials (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne un verre feuilleté (1) pourvu d'une première feuille de verre (10), d'une première couche adhésive transparente (16), d'une couche d'isolation thermique transparente (14) ayant des pores indépendants sans coques, d'une seconde couche adhésive transparente (18) et d'une seconde feuille de verre (12), dans cet ordre. La valeur de A dans la formule (1), à savoir A = D3Pdi, est inférieure ou égale à 6,4 × 105 et la valeur de B dans la formule (2) est d'au moins 35 (dans les formules, D est la taille des pores (nm), P est la porosité, di est l'épaisseur (mm) de la couche d'isolation thermique transparente, dg est l'épaisseur totale (mm) des feuilles de verre et da est l'épaisseur totale (mm) des couches adhésives transparentes).
PCT/JP2016/084836 2015-11-26 2016-11-24 Verre feuilleté, verre à vitres pour des automobiles et verre à vitres pour des bâtiments Ceased WO2017090690A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110588105A (zh) * 2019-09-11 2019-12-20 信义玻璃(天津)有限公司 增厚夹层玻璃及其制作方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63170227U (fr) * 1987-04-27 1988-11-07
JPH08283049A (ja) * 1995-04-13 1996-10-29 Bridgestone Corp ガラス積層体
JPH11171604A (ja) * 1997-12-10 1999-06-29 Sekisui Chem Co Ltd 合わせガラス用中間膜及び合わせガラス
JP2010100778A (ja) * 2008-10-27 2010-05-06 Denki Kagaku Kogyo Kk シート及びその製造方法
WO2013077252A1 (fr) * 2011-11-21 2013-05-30 コニカミノルタ株式会社 Film de protection contre les infrarouges et corps de protection contre les infrarouges

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63170227U (fr) * 1987-04-27 1988-11-07
JPH08283049A (ja) * 1995-04-13 1996-10-29 Bridgestone Corp ガラス積層体
JPH11171604A (ja) * 1997-12-10 1999-06-29 Sekisui Chem Co Ltd 合わせガラス用中間膜及び合わせガラス
JP2010100778A (ja) * 2008-10-27 2010-05-06 Denki Kagaku Kogyo Kk シート及びその製造方法
WO2013077252A1 (fr) * 2011-11-21 2013-05-30 コニカミノルタ株式会社 Film de protection contre les infrarouges et corps de protection contre les infrarouges

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110588105A (zh) * 2019-09-11 2019-12-20 信义玻璃(天津)有限公司 增厚夹层玻璃及其制作方法
CN110588105B (zh) * 2019-09-11 2024-03-22 信义玻璃(天津)有限公司 增厚夹层玻璃及其制作方法

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