JP5640077B2 - Laminated structure and laminated body - Google Patents

Description

  INDUSTRIAL APPLICABILITY The present invention provides a laminated structure provided on the outside of a window glass attached to a building, an automobile, etc. and having a light absorption layer that absorbs infrared rays, and the laminated structure can be easily formed on the window glass. It relates to a laminate.

  In order to maintain the transparency of the window glass and suppress the incidence of infrared rays into the room, it is effective to provide a light absorption layer that absorbs infrared rays on the window glass of a building or an automobile. A light absorption layer consists of a film | membrane containing at least 1 type of electroconductive fine particles chosen from a metal oxide, a metal nitride, and a metal boride. The light absorption layer does not affect the transparency of the substrate constituting the film. For this reason, the visibility of a window glass can be maintained, the raise of room temperature can be suppressed, or cooling efficiency can be improved (refer patent document 1).

JP 2008-169074 A

  When the light absorption layer is provided on the window glass, infrared light contained in sunlight is absorbed by the light absorption layer. Then, the temperature of the light absorption layer rises. From the viewpoint that direct release of heat generated in the light absorption layer into the room can be avoided, it is effective to provide the light absorption layer outside the window glass. Thereby, summer temperature rise can be suppressed. However, when the light absorption layer is provided outside the window glass, unnecessary stress is generated in the window glass throughout the year. In summer, uncomfortable heat may be felt near the window glass. The present inventor considers such a phenomenon as follows.

  The generation of unnecessary stress is due to the fact that heat is conducted from the warmed light absorption layer to the window glass and a part of the window glass is heated. For example, when the sun is irradiated on a part of the window glass, a temperature difference occurs on the window glass. Thereby, unnecessary stress is generated. Moreover, unpleasant heat is due to the window glass being warmed by the light absorption layer, and radiant heat being emitted from the window glass into the room. Thereby, in the summer room, unpleasant heat is felt near the window glass provided with the light absorption layer. On the other hand, in winter, improvement of indoor heating efficiency and suppression of condensation occurring on the surface of the window glass are required. About these, it cannot cope only by providing the light absorption layer in the window glass.

  An object of the present invention is to provide a laminated structure capable of maintaining visibility for viewing the outside of the room, suppressing unnecessary stress generated in the window glass, and making the indoor environment easily comfortable, and the laminated structure such as a building. It is providing the laminated body which can be easily formed in a window glass.

  In order to achieve the above object, according to the first aspect of the present invention, there is provided a laminated structure provided on the outside of the window glass that partitions the outside and inside of the chamber. This laminated structure is composed of a light-absorbing layer made of a film that absorbs infrared rays by containing conductive fine particles, and a film having an independent bubble by being arranged between the window glass and the light-absorbing layer and containing hollow particles. And a heat insulating layer. When the laminated structure is laminated on a float plate glass having a thickness of 3 mm, the haze value of the laminated structure including the float plate glass is 10% or less.

  According to this configuration, since the light absorption layer is provided outside the window glass, it is possible to avoid the heat of the light absorption layer warmed by the absorption of infrared rays being directly emitted into the room. Moreover, the heat conduction from the light absorption layer to the window glass is also suppressed by the heat insulating layer provided between the window glass and the light absorption layer, and the temperature of the window glass can be brought close to room temperature. Moreover, in winter, the heat insulating effect of the heat insulating layer is also exhibited. Thereby, since the temperature of a window glass can be brought close to room temperature, the dew condensation which arises on the surface of a window glass can also be suppressed. Moreover, the indoor heating efficiency is also improved. Moreover, the haze value of the laminated structure including the float glass sheet when the laminated structure is laminated on the float glass sheet having a thickness of 3 mm is 10% or less. For this reason, the visibility which visually recognizes the outdoor is maintained.

  The laminated structure further includes a protective layer disposed outside the light absorbing layer, and the protective layer includes a water-insoluble resin component as a matrix, an antioxidant component, a light stabilizing component, an ultraviolet absorbing component, And at least one functional component selected from ultraviolet scattering components. According to this configuration, the light absorption layer is protected by the protective layer.

  In order to achieve the above object, according to a second aspect of the present invention, there is provided a laminate provided on the outside of the window glass that partitions the outside and inside of the chamber. This laminated body is disposed between a base material, a light-absorbing layer that is disposed on the base material and absorbs infrared rays by containing conductive fine particles, and between the window glass and the light-absorbing layer. And a heat insulating layer made of a film having independent bubbles. The haze value of the laminate including the float plate glass when the laminate is laminated on the float plate glass having a thickness of 3 mm is 10% or less. According to this structure, a laminated body can be affixed and used for window glass, such as a building.

  The laminate further includes a protective layer disposed outside the light absorbing layer, and the protective layer includes a water-insoluble resin component as a matrix, an antioxidant component, a light stabilizing component, an ultraviolet absorbing component, And at least one functional component selected from ultraviolet scattering components.

  In the above laminate, the substrate preferably includes a resin component, and the substrate is preferably disposed between the window glass and the light absorption layer. According to this structure, the base material containing the resin component is protected by the light absorption layer disposed on the outer side. For this reason, the weather resistance of the base material containing the resin component is improved. For example, the base material containing the resin component can be protected from ultraviolet rays by using an ultraviolet absorbing resin as the matrix resin constituting the light absorbing layer or by containing the ultraviolet absorbent in the matrix resin.

  ADVANTAGE OF THE INVENTION According to this invention, the visibility which visually recognizes the outdoor is maintained, the unnecessary stress which arises in a window glass is suppressed, the laminated structure which can make indoor environment easily comfortable, and the laminated structure is used for buildings, etc. Provided is a laminate that can be easily formed on a window glass.

(A) is a schematic cross-sectional view showing the laminated structure of the first embodiment, (b) is a schematic cross-sectional view showing the laminated structure of the second embodiment, and (c) and (d) are schematic views showing modified examples of the laminated structure. Sectional drawing. (A)-(c) is a schematic cross section which shows the example of a change of laminated structure. (A) is a schematic cross-sectional view showing the laminated structure of Comparative Example 1, (b) is a schematic cross-sectional view showing the laminated structure of Comparative Example 2, (c) is a schematic cross-sectional view showing the laminated structure of Comparative Example 3, and ( d) A schematic cross-sectional view showing a laminated structure of Comparative Example 4. (A) is a schematic cross section which shows the laminated structure of the comparative example 5, (b) is a schematic cross section which shows the laminated structure of the comparative example 6. Schematic which shows the measuring apparatus used for indoor environment evaluation.

(First embodiment)
Hereinafter, a first embodiment in which the laminated structure of the present invention is embodied as a structure provided on a window glass of a building or an automobile will be described in detail with reference to FIG.

  As shown to Fig.1 (a), the laminated body 11 is provided in the outer side of the window glass G which partitions off the inner side and the outer side of a chamber. When the laminate 11 is laminated on a float plate glass having a thickness of 3 mm, the haze value of the laminate 11 including the float plate glass is 10% or less. For this reason, the visibility from the indoor to the outdoor or the visibility from the outdoor to the indoor is maintained. The laminate 11 includes a base material B, a light absorption layer 12, and a heat insulation layer 13. The light absorption layer 12 is made of a film that absorbs infrared rays. The heat insulation layer 13 consists of a film | membrane which has an independent bubble by containing a hollow particle. The heat insulation layer 13 is disposed between the window glass G and the light absorption layer 12.

  Examples of the material constituting the base material B include glass and resin. These materials may be used alone or in combination of a plurality of types of materials. Further, the base material B may be formed by laminating a plurality of layers made of a composite material. Examples of the glass include ultra-thin glass for LCD substrates. Ultra-thin glass is produced by the overflow method. Examples of the resin include polyester resins, polyolefin resins, polycarbonate resins, acrylic resins, vinyl chloride resins, cellulose resins, vinyl acetate resins, polyimide resins, polyamide resins, polyether ether ketone resins, fluorine resins, and the like. Can be mentioned. These resins may be used alone or in combination of two or more.

  The substrate B preferably contains a resin component. In this case, the physical property of the base material B can be adjusted to a desired physical property. For example, the light absorption layer 12 and the heat insulation layer 13 can be easily applied to the base material B by adjusting the physical properties of the base material B. As for the thickness of the base material B, 25 micrometers-250 micrometers are preferable. That is, the base material B is preferably a film.

  From the standpoint that the haze value is kept small and the total light transmittance, strength, and the like are easily increased, a polyester-based resin is preferably used as the base material B, and polyethylene terephthalate is more preferably used. By using a polyester-based resin as the base material B, it can be effectively used as the laminated body 11 for preventing scattering of glass. The base material B may contain various additives such as an antioxidant, an ultraviolet absorber, and a light stabilizer.

  The light absorption layer 12 is laminated on the outer surface of the base material B. The light absorption layer 12 is made of a film containing conductive fine particles. The conductive fine particles are not particularly limited as long as they are conductive fine particles having infrared absorbing ability. Examples of the material for the conductive fine particles include at least one selected from metal oxides, metal nitrides, and metal borides.

  Examples of metal oxides include tungsten oxide compounds, titanium oxide, zirconium oxide, tantalum oxide, niobium oxide, zinc oxide, ruthenium oxide, indium oxide, tin-doped indium oxide (ITO), tin oxide, and antimony-doped tin oxide (ATO). ), And cesium oxide. An example of the metal nitride is titanium nitride. An example of the metal boride is lanthanum hexaboride.

  The average particle diameter of the conductive fine particles is, for example, 550 nm or less, and preferably 200 nm or less. In this case, the infrared absorption ability and transparency of the laminated structure can be ensured. Here, the average particle diameter is a value measured by observation with a transmission electron microscope image, and indicates an average value of the diameters of the conductive fine particles dispersed in the light absorption layer 12.

  The matrix resin constituting the light absorption layer 12 is not particularly limited. Examples of matrix resins include polyester resins, polyolefin resins, polycarbonate resins, acrylic resins, vinyl chloride resins, polyurethane resins, cellulose resins, vinyl acetate resins, polyimide resins, polyamide resins, and polyether ether ketone resins. And fluororesin. The matrix resin may be used alone or in combination of a plurality of types of matrix resins.

  The light absorption layer 12 may contain various additives such as an antioxidant, an ultraviolet absorber, and a light stabilizer. In forming the light absorption layer 12, it is preferable to use a coating agent for the light absorption layer containing a matrix resin and conductive fine particles. It does not specifically limit as a coating method of the coating agent for light absorption layers. Examples of the coating method include a dip coating method, a spin coating method, a spray coating method, a bar coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, and a gravure coating method. The thickness of the light absorption layer 12 is preferably in the range of 1 to 100 μm, for example.

  On the inner surface of the base material B, the heat insulating layer 13 is laminated. The heat insulation layer 13 consists of a film | membrane containing a hollow particle. Examples of the hollow particles include at least one of inorganic hollow particles, organic hollow particles, and organic / inorganic composite hollow particles. Examples of the inorganic hollow particles include silica hollow particles and alumina hollow particles. Examples of the organic hollow particles include acrylic hollow particles, acrylonitrile hollow particles, and polystyrene hollow particles. Examples of the organic / inorganic composite hollow particles include organic silica composite particles. Among the hollow particles, inorganic hollow particles are preferably used from the viewpoint of excellent durability and weather resistance. The average particle diameter of the hollow particles is preferably 500 nm or less, for example, from the viewpoint of ensuring transparency. Here, the average particle diameter is a value measured by observation with a transmission electron microscope image, and indicates an average value of diameters of dispersed particle diameters dispersed in the heat insulating layer 13.

  Although it does not specifically limit as matrix resin which comprises the heat insulation layer 13, The same resin as the matrix resin which comprises the light absorption layer 12 is used. The heat insulating layer 13 may contain additives such as an antioxidant, an ultraviolet absorber, and a light stabilizer. When forming the heat insulation layer 13, it is preferable to use the coating agent for heat insulation layers containing matrix resin and a hollow particle. The coating method of the coating agent is not particularly limited, and a coating method of the light absorbing layer coating agent is used. The thickness of the heat insulating layer 13 is preferably in the range of 1 to 100 μm, for example.

  In the first embodiment, a photocatalyst layer 14 is laminated on the light absorption layer 12. The photocatalyst layer 14 can suppress the adhesion of dirt to the exposed surface exposed to the outside of the laminate 11. The photocatalyst layer 14 also has a function of facilitating washing away dirt attached to the exposed surface of the laminate 11 with rain. In forming the photocatalyst layer 14, it is preferable to use a photocatalyst precursor coating agent containing a photocatalyst precursor. As a method for forming the photocatalyst layer in this case, for example, a method disclosed in JP 2009-208062 A is used. The thickness of the photocatalyst layer 14 is preferably in the range of 0.01 to 1 μm, and more preferably in the range of 0.03 to 0.3 μm.

  In the first embodiment, the adhesive layer 15 is laminated on the heat insulating layer 13. Thereby, the laminated body 11 can be easily attached to the window glass G. The adhesive layer 15 may be formed by coating a commercially available adhesive, or an adhesive tape or an adhesive sheet attached to the heat insulating layer 13. It does not specifically limit as an adhesive of the adhesion layer 15, For example, an acrylic adhesive, a urethane adhesive, a rubber adhesive, etc. are used. As window glass G, it does not specifically limit, For example, a soda-lime glass substrate, a quartz glass substrate, a borosilicate glass substrate, an alkali free glass substrate etc. are used. As window glass G, the window glass of a building building and the window glass of a motor vehicle are mentioned, for example.

  Next, the effect | action of the laminated body 11 mentioned above is demonstrated.

  The laminate 11 is attached to the outer surface of the window glass G through the adhesive layer 15. Thereby, on the outside of the window glass G, the heat insulating layer 13 is disposed between the window glass G and the light absorption layer 12. When the window glass G is irradiated with sunlight, infrared rays (particularly near infrared rays) in the sunlight are absorbed by the light absorption layer 12. Thereby, since the infrared rays which permeate | transmit the window glass G reduce, the indoor temperature rise is suppressed in summer. Further, by providing the light absorption layer 12 outside the window glass G, direct release of heat generated in the light absorption layer 12 into the room can be avoided. However, when the light absorption layer 12 is provided outside the window glass G, unnecessary stress may be generated in the window glass G throughout the year. In summer, uncomfortable heat may be felt near the window glass G. The present inventor considers such a phenomenon as follows.

  The generation of unnecessary stress is due to the fact that heat is conducted from the warmed light absorption layer 12 to the window glass G and a part of the window glass G is heated. For example, when the sun is irradiated on a part of the window glass G, a temperature difference occurs on the window glass G. Thereby, unnecessary stress is generated. The unpleasant heat is due to the window glass G being warmed by the light absorbing layer 12 and the radiation heat being emitted from the window glass G into the room. Thereby, in the summer room, unpleasant heat is felt in the vicinity of the window glass G provided with the light absorption layer 12. On the other hand, in winter, improvement of indoor heating efficiency and suppression of condensation occurring on the surface of the window glass are required. About these, it cannot cope only by providing the light absorption layer 12 in the window glass G. FIG.

  In this regard, in the laminated body 11 of the first embodiment, the heat insulating layer 13 is disposed between the window glass G and the light absorption layer 12. For this reason, since the heat conduction from the light absorption layer 12 to the window glass G is suppressed by the heat insulating layer 13, the temperature of the window glass G can be brought close to room temperature. Moreover, in the winter, the heat insulating effect by the heat insulating layer 13 is also exhibited. Moreover, by suppressing the heat conduction from the light absorption layer 12 to the window glass G, generation of unnecessary stress on the window glass G can be suppressed throughout the year. Moreover, it can suppress that unpleasant heat is felt near the window glass G in summer. Moreover, since the temperature of the window glass G approaches room temperature, the dew condensation produced on the surface of the window glass G can also be suppressed. Moreover, in the winter, the heat insulation layer 13 improves indoor heating efficiency.

  Moreover, when the laminated body 11 is laminated | stacked on the 3 mm-thick float plate glass, the haze value of the laminated body 11 containing float plate glass is 10% or less. For this reason, the influence of the laminated body 11 with respect to the transparency of the window glass G can be suppressed as much as possible. Moreover, from the viewpoint of taking sunlight into the room to make a bright indoor environment, the total light transmittance of the laminate 11 including the float plate glass when the laminate 11 is laminated on the float plate glass having a thickness of 3 mm is preferably It is 60% or more, more preferably 70% or more. The float plate glass used for the measurement of the haze value and the total light transmittance is a float plate glass having a thickness of 3 mm as defined in (JIS R 3202: 1996).

  As described above, according to the first embodiment, the following effects can be obtained.

  (1) Between the light absorption layer 12 and the window glass G, the heat insulation layer 13 is arrange | positioned. Moreover, when the laminated body 11 is laminated | stacked on 3 mm thick float plate glass, the haze value of the laminated body 11 containing float plate glass is 10% or less. Therefore, visibility for visually recognizing the outside can be maintained, unnecessary stress generated in the window glass can be suppressed, and the indoor environment can be easily made comfortable.

  (2) By using the laminated body 11 having the base material B, a laminated structure can be easily formed on a window glass such as a building.

  (3) By using the base material B containing a resin component, the physical properties of the base material B can be adjusted to desired physical properties. For example, the light absorption layer 12 and the heat insulation layer 13 can be easily applied to the base material B by adjusting the physical properties of the base material B. However, since the laminate 11 is provided outside the window glass G, the base material B containing the resin component may be deteriorated by ultraviolet rays or the like. In this respect, the laminate 11 includes a base material B between the window glass G and the light absorption layer 12. That is, since the base material B is protected by the light absorption layer 12 disposed outside the base material B, the weather resistance of the base material B is improved. For example, the base material B can be protected from ultraviolet rays by using an ultraviolet-absorbing resin as the matrix resin constituting the light-absorbing layer 12 or by including an ultraviolet absorbent in the matrix resin. Therefore, the durability and weather resistance of the laminate 11 are improved.

  (4) The light absorption layer 12 includes conductive fine particles made of at least one conductive material selected from metal oxides, metal nitrides, and metal borides. Thereby, since reflection by irradiation of sunlight is reduced, it is possible to ensure transparency while suppressing glare.

  (5) As the hollow particles of the heat insulating layer 13, organic hollow particles or inorganic hollow particles are used. Since the organic hollow particles are deteriorated by light or heat, the durability and weather resistance of the heat insulating layer 13 may not be sufficiently obtained. In this respect, the durability and weather resistance of the heat insulating layer 13 can be improved by using inorganic hollow particles as the hollow particles.

  (6) The laminate 11 includes a base material B, a light absorption layer 12 and a heat insulating layer 13. According to this structure, the laminated body 11 can be easily provided in window glass G, such as a building and a motor vehicle. Moreover, the laminated body 11 can also be replaced regularly.

(Second Embodiment)
A second embodiment that embodies the laminated structure of the present invention will be described with reference to FIG. 1B with a focus on differences from the first embodiment. In describing the second embodiment, the same reference numerals are assigned to the same components as those in the first embodiment, and the description thereof is omitted.

  As shown in FIG. 1B, a protective layer 16 that protects the light absorption layer 12 is laminated on the outer surface of the light absorption layer 12. The protective layer 16 is disposed between the light absorption layer 12 and the photocatalyst layer 14. The protective layer 16 includes a water-insoluble resin component as a matrix and at least one functional component selected from an antioxidant component, a light stabilizing component, an ultraviolet absorbing component, and an ultraviolet scattering component. The protective layer 16 is selected from the range in which the haze value of the laminated structure including the float plate glass is 10% or less when the laminated structure is laminated on the float plate glass having a thickness of 3 mm.

  The water-insoluble resin component imparts water resistance to the protective layer 16. Examples of water-insoluble resins that are water-insoluble resin components include acrylic polyol resins, polyester resins, polyolefin resins, polycarbonate resins, vinyl chloride resins, polyurethane resins, vinyl acetate resins, polyimide resins, and polyamide resins. , Polyether ether ketone resins, and fluororesins. These water-insoluble resins may be used alone or in combination of two or more.

  The antioxidant component enhances the durability of the protective layer 16. Examples of antioxidant components include vitamin C (ascorbic acid or ascorbate), vitamin E (tocopherol acetate), BHT (dibutylhydroxytoluene), BHA (butylhydroxyanisole), sodium erythorbate, propyl gallate, sodium sulfite , Sulfur dioxide, coffee bean extract (chlorogenic acid), green tea extract (catechin), and rosemary extract. These antioxidant components may be used alone or in combination of two or more.

  The light stabilizing component increases the durability of the protective layer 16. Examples of the light stabilizing component include hindered amines. Examples of hindered amines include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-succinate. Tetramethylpiperidine polycondensate, poly [6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl] [(2,2,6,6- Tetra-methyl-4-piperidyl) imino] hexamethylene [2,2,6,6-tetramethyl-4-piperidylimide], tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1, 2,3,4-butanetetracarboxylate, (mixed 2,2,6,6-tetramethyl-4-piperidyl / tridecyl) -1,2,3,4-butanetetracarboxylate, N, N -Bis (3-aminopropyl) ethylenediamine-2,4-bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro-1,3 5-triazine condensate and [N- (2,2,6,6-tetramethyl-4-piperidyl) -2-methyl-2- (2,2,6,6, -tetramethyl-4-piperidyl) Imino] propionamide. Further, as hindered amines, for example, TINUVIN (trade name, Ciba Geigy) 770, 123, 144, 622, SANOL (trade name, Sankyo Co., Ltd.) LS-770, 765, 292, 2626, and Adeka Stub (trade name, Asahi Denka Co., Ltd.) LA-52, 57, 62.

  These light stabilizing components may be used alone or in combination of two or more. The light stabilizing component may be used by mixing with a water-insoluble resin component as an additive. Moreover, the water-insoluble resin component and the light stabilizing component may be contained in the protective layer 16 by using a complex of the light stabilizing component chemically bonded to the water-insoluble resin component.

  The ultraviolet absorbing component enhances the durability of the protective layer 16 and imparts an ultraviolet shielding effect to the protective layer 16. Examples of the ultraviolet absorbing component include benzotriazoles, benzoates, cyanoacrylates, benzophenones, salicylic acid esters, and substituted acrylonitriles.

  Examples of benzotriazoles include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3′-t-butyl-5′-methylphenyl) -5 Chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-amylphenyl) benzotriazole, 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole, and 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole.

  Examples of benzoates include 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate. Examples of cyanoacrylates include ethyl-2-cyano-3,5-diphenyl acrylate. Examples of benzophenones include 2,4-dihydroxybenzophenone, 2-hydroxy-4-acetoxyethoxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, and 2,2′-dihydroxy. -4,4'-dimethoxybenzophenone, 2-hydroxy-4-o-octoxybenzophenone, 2-hydroxy-4-i-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2'-dihydroxy- 4,4'-dimethoxy-disulfobenzophenone-di-sodium salt, 2-hydroxy-4- (2-hydroxy-3-methacryloxy) propoxybenzophenone, and 2-hydroxy-4-octadecyloxybenzophenone . Examples of salicylic acid esters include phenyl salicylate, pt-butylphenyl salicylate, and p-octylphenyl salicylate. Examples of substituted acrylonitriles include ethyl 2-cyano-3,3-diphenylacrylate and 2-ethylhexyl 2-cyano-3,3-diphenylacrylate. These ultraviolet absorbing components may be used alone or in combination of two or more. The ultraviolet absorbing component may be used by mixing with the water-insoluble resin component as an additive, or by using a composite of the ultraviolet absorbing component chemically bonded to the water-insoluble resin component, A water-soluble resin component and an ultraviolet absorbing component may be included.

  The ultraviolet scattering component imparts an ultraviolet shielding effect to the protective layer 16. Examples of the ultraviolet scattering component include inorganic powder materials. Examples of inorganic powder materials include metal oxide powders such as titanium dioxide powder, zinc oxide powder and cerium oxide powder, composite inorganic material powder of titanium dioxide and iron oxide, and the surface of fine particles of cerium oxide on amorphous silica. And composite inorganic material powder coated with. These ultraviolet scattering components may be used alone or in combination of two or more. In light of sufficient scattering of ultraviolet rays, the average particle size of the ultraviolet scattering component is preferably 5 μm or less, and more preferably in the range of 10 nm to 2 μm. The protective layer 16 does not require photocatalytic activity. For this reason, when using the inorganic powder material which has photocatalytic activity as an ultraviolet-ray-scattering component, it is preferable to deactivate photocatalytic activity by forming a thin film using water glass etc. on the particle surface.

  Among these functional components, it is preferable that at least one of the ultraviolet absorbing component and the ultraviolet scattering component is contained in the protective layer 16 from the viewpoint of enhancing the function of protecting the light absorbing layer 12 from ultraviolet rays. Further, when the ultraviolet absorbing component is contained in the protective layer 16, it is preferable that at least one of the light stabilizing component and the antioxidant component is contained in the protective layer 16 from the viewpoint of enhancing the durability of the protective layer 16 itself.

  The content of the water-insoluble resin component in the protective layer 16 is preferably 50% by mass or more, more preferably 60% by mass or more, and further preferably 70% by mass or more. The content of the functional component in the protective layer 16 is, for example, in the range of 0.01 to 30% by mass. The protective layer 16 may contain, for example, a lubricant, a flame retardant, and the like. The thickness of the protective layer 16 is, for example, in the range of 0.1 to 100 μm. The protective layer 16 may be formed by coating the light absorption layer 12, or the protective layer 16 formed in advance may be attached to the light absorption layer 12.

  As mentioned above, according to 2nd Embodiment, in addition to the effect of (1)-(6) in 1st Embodiment, the following effects are acquired.

  (7) When the conductive fine particles in the light absorption layer 12 are inferior in water resistance and ultraviolet resistance, the conductive fine particles may be deteriorated by long-term use. In this regard, according to the second embodiment, the protective layer 16 includes the water-insoluble resin component as a matrix and the functional component described above. The protective layer 16 is disposed outside the light absorption layer 12. In this case, since the light absorption layer 12 is protected by the protective layer 16, the deterioration of the conductive fine particles is suppressed, and the reliability of the laminated structure can be ensured over a long period of time. Thereby, the kind of electroconductive fine particles can be selected freely.

  (8) The protective layer 16 is disposed outside the base material B. For this reason, the base material B is also protected by the protective layer 16. Therefore, the durability of the laminated structure or the laminated body 11 is further improved.

(Example of change)
You may change each said embodiment as follows.

  -You may delete the photocatalyst layer 14 from the laminated body 11. FIG. Further, instead of the photocatalyst layer 14, a layer other than the photocatalyst layer 14 functioning as an antifouling layer may be used. Examples of the antifouling layer other than the photocatalyst layer 14 include a hydrophilic layer and a water repellent layer. Examples of the material of the hydrophilic layer include a resin material having a hydrophilic group (silicon hydrophilic resin, acrylic hydrophilic resin, etc.), a resin material containing a surfactant, and the like. Examples of the water-repellent layer include a layer formed from a water-repellent resin material such as a fluorine-based resin, and a layer having a water-repellent uneven structure typified by a fractal structure and a lotus leaf structure.

  -In each embodiment, although the base material B was arrange | positioned between the heat insulation layer 13 and the light absorption layer 12, as shown in FIG.1 (c), the base material B is combined with the window glass G, the heat insulation layer 13, and You may arrange | position between. Also in this case, the effect described in the above (2) can be obtained.

  In each embodiment, the adhesive layer 15 may be omitted from the laminate 11 as shown in FIG. In this case, the heat insulation layer 13 has adhesiveness. Thus, the layer structure is simplified by attaching the laminate 11 to the window glass G by the heat insulating layer 13. Also, the coating process can be omitted. The heat-insulating layer 13 having adhesiveness is made of, for example, a film using an adhesive matrix or a film containing an adhesive. Moreover, in the case of the laminated body 11 shown in FIG.1 (c), the adhesion layer 15 may be abbreviate | omitted and adhesiveness may be provided to base material B itself.

  -In the laminated body 11 shown to Fig.1 (a)-FIG.1 (d), the base material B is arrange | positioned between the window glass G and the light absorption layer 12. FIG. For example, as shown in FIG. 2A, the base material B can be disposed outside the light absorption layer 12. Here, in the laminated structure shown in FIG. 2A, when the light absorbing layer 12 and the heat insulating layer 13 are laminated on one surface of the base material B by coating, the light absorbing layer 12 becomes a coating agent for the heat insulating layer. It is necessary to select the type of the heat insulating layer coating agent and the type of the matrix resin of the light absorbing layer 12 so as not to dissolve and adversely affect the light absorbing layer 12. In this regard, in the laminate 11 shown in FIG. 1A, the light absorption layer 12 is provided on one surface of the base material B, and the heat insulating layer 13 is provided on the other surface of the base material B. In this case, the coating agent for a light absorption layer and a heat insulation layer can be selected freely. For this reason, the weather resistance of the light absorption layer 12 and the heat insulation layer 13 can be improved, or coating conditions can be set.

  -In 2nd Embodiment, although the protective layer 16 was laminated | stacked on the light absorption layer 12, as shown in FIG.2 (b), the base material B is interposed between the protective layer 16 and the light absorption layer 12. As shown in FIG. May be. Also in this case, since the protective layer 16 is disposed outside the base material B, the base material B can be protected by the protective layer 16.

  -In 2nd Embodiment and the modification shown in FIG.2 (b), although the protective layer 16 was arrange | positioned outside the base material B, as shown in FIG.2 (c), the protective layer 16 is based on the base material B. May also be arranged inside. However, from the viewpoint that the coating agent for the light absorption layer and the heat insulation layer can be freely selected, light is absorbed on one surface of the base material B as in the modified example shown in the second embodiment and FIG. It is preferable to provide the layer 12 and provide the heat insulation layer 16 on the other surface of the base material B. In this configuration, both the base material B and the light absorption layer 12 can be protected by the protective layer 16 provided outside the light absorption layer 12.

  A release sheet may be provided on the adhesive layer 15. In this case, when the laminate 11 is attached to the window glass G, the release sheet is peeled off for use.

  -Each layer and the base material B may have a single layer structure or a multilayer structure.

  A laminated structure may be formed by sequentially applying coating using a heat insulating layer coating agent and coating using a light absorbing layer coating agent to the window glass G or the glass substrate. In this case, the base material B can be omitted. Moreover, you may apply using the coating agent for heat insulation layers, after applying an adhesive agent etc. to the window glass G or a glass substrate. Alternatively, the heat insulating layer 13 may be formed directly on the glass surface by applying a coating agent for the heat insulating layer so as to have adhesiveness with glass. Thus, the effect described in the above (1) can be obtained also by attaching a structure in which each layer is formed on a window glass in advance to a building or an automobile.

  When the light absorption layer 12 or the heat insulation layer 13 is made relatively thick, after forming at least one of the film constituting the light absorption layer 12 and the film constituting the heat insulation layer 13 in advance, the obtained film is applied to the base material B. You may laminate.

  Next, the above embodiments will be described more specifically with reference to examples and comparative examples.

Example 1
As the base material B, a PET film (manufactured by Toray Industries, Inc., trade name: Lumirror U34, thickness 50 μm) was used. The coating agent 1 for light absorption layers was apply | coated to the single side | surface of PET film so that the film thickness after drying might be set to about 10 micrometers using a Mayer bar. Then, it hardened | cured at 60 degreeC for 3 days, and formed the light absorption layer 12 on the base material B. FIG. Next, the coating agent for heat insulation layers was apply | coated to the surface on the opposite side to the light absorption layer 12 in the base material B so that thickness might be set to about 10 micrometers using a Mayer bar. Then, it hardened | cured at 60 degreeC for 3 days, and formed the heat insulation layer 13 on the base material B. FIG. Subsequently, a photocatalyst precursor coating agent was applied onto the light absorption layer 12 using a Meyer bar so that the dry thickness was 100 nm, thereby forming the photocatalyst layer 14. Next, a non-support type adhesive tape (manufactured by Soken Chemical Co., Ltd., SK2057) was attached on the heat insulating layer 13. Then, the glass sample which has the laminated structure shown to Fig.1 (a) was produced by carrying out dry lamination of the adhesive tape on the float plate glass of 220 mm x 220 mm x 3 mmt.

<Coating agent 1 for light absorption layer>
207 g of antimony-doped tin oxide fine particle dispersion slurry, 140 g of acrylic polyol resin, 18 g of isocyanate curing agent, and 4 g of ethyl acetate were mixed to prepare a coating agent 1 for a light absorbing layer. “SNS-10M” manufactured by Ishihara Sangyo Co., Ltd. was used as the antimony-doped tin oxide fine particle-dispersed slurry. The dispersion medium of the dispersion slurry is methyl ethyl ketone, and the concentration of fine particles in the dispersion slurry is 32% by mass. The primary particle diameter of the fine particles is about 20 nm, and the dispersion (secondary) average particle diameter is about 100 nm. As the acrylic polyol resin, Halus hybrid type acrylic polyol resin “Udable UV-G301 (trade name)” manufactured by Nippon Shokubai Co., Ltd. was used. “Desmodur N3200 (trade name)” manufactured by Sumika Bayer Urethane Co., Ltd. was used as the isocyanate curing agent.

<Coating agent for heat insulation layer>
8 g of hollow silica fine particles, 131 g of methyl ethyl ketone, 100 g of acrylic polyol resin, and 13 g of an isocyanate curing agent were mixed by a ball mill (manufactured by ASONE Co., Ltd., BR-2) to prepare a coating agent for a heat insulating layer. As the hollow silica fine particles, “Sirinax (trade name)” manufactured by Nippon Steel Mining Co., Ltd. was used. The primary particle diameter of the hollow silica fine particles is 80 to 130 nm, and the dispersed (secondary) average particle diameter is about 500 nm. The same thing as what was used for the coating agent for light absorption layers was used for acrylic polyol resin and an isocyanate type hardening | curing agent. For mixing by the ball mill, alumina balls having a diameter of 2 mm were used. The mixture was filled in the polycontainer and the rotation speed was adjusted to 100 rpm so that the ratio of the space volume of the container: the bulk volume of the alumina balls: the volume of the coating agent for the heat insulating layer was about 1: 1: 1.

<Photocatalyst precursor coating agent>
The photocatalyst precursor coating agent was prepared by the following steps (a) to (c).

(A) Preparation of hydrolysis condensate of titanium alkoxide To 149 g of ethyl cellosolve, 75.7 g of titanium tetraisopropoxide (manufactured by Nippon Soda Co., Ltd., trade name: A-1) was added dropwise with stirring. Thereafter, a mixed solution of 58.3 g of ethyl cellosolve, 4.55 g of distilled water and 12.6 g of 60 mass% concentrated nitric acid was added dropwise to this solution while stirring. Thereafter, this solution was stirred at 30 ° C. for 4 hours to prepare a hydrolysis-condensation liquid of titanium alkoxide.

(B) Preparation of organic component solution In a 2 L separable flask, 700 g of methyl isobutyl ketone, 337.4 g of methyl methacrylate and 42.8 g of methacryloxypropyltrimethoxysilane were added under a nitrogen atmosphere until the temperature reached 60 ° C. The mixed solution was heated. To the mixed solution, 116.6 g of methyl isobutyl ketone in which 3.32 g of azobisisobutyronitrile was dissolved was dropped to start the polymerization reaction, and stirred for 30 hours to prepare an organic component solution.

(C) Preparation of Photocatalyst Precursor Coating Agent In 42.9 g of ethyl cellosolve, 6.12 g of aluminum nitrate nonahydrate (purity 99%, manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved. Subsequently, 55.2 g of a hydrolytic condensate of titanium alkoxide was added and stirred sufficiently to obtain a solution (1). Subsequently, 7.30 g of the organic component solution, 235.8 g of methyl isobutyl ketone, 138.9 g of ethyl cellosolve, the solution (1), and colloidal silica (manufactured by Nissan Chemical Industries, Ltd., trade name: Snowtex IPA-ST, 13.9 g of primary particle size: 10 to 20 nm and dispersion (secondary) average particle size: about 20 nm) were mixed in this order. Then, it stirred for 24 hours with a 32 degreeC warm bath, and prepared the photocatalyst precursor coating agent containing colloidal silica and aluminum nitrate.

(Examples 2 and 3)
In Example 2, each layer was laminated in the same manner as in Example 1 except that the laminated structure shown in FIG. In Example 3, each layer was laminated in the same manner as in Example 1 except that the laminated structure shown in FIG.

Example 4
In Example 4, a glass sample having a laminated structure shown in FIG. First, on one side of a PET film (trade name: Lumirror U34, thickness 50 μm, manufactured by Toray Industries, Inc.) as a base material B, a light absorption layer is formed using a Meyer bar so that the film thickness after drying is about 1 μm. Coating agent 2 was applied, and light absorption layer 12 was formed on substrate B. Next, a protective layer coating agent was applied onto the light absorption layer 12 using a Mayer bar so that the film thickness after drying was about 10 μm. Thereafter, the film was cured at 60 ° C. for 3 days, and a protective layer 16 was formed on the light absorption layer 12. Next, the coating agent for heat insulation layers was apply | coated to the surface on the opposite side to the light absorption layer 12 in the base material B so that thickness might be set to about 10 micrometers using a Mayer bar. Then, it hardened | cured at 60 degreeC for 3 days, and formed the heat insulation layer 13 on the base material B. FIG. Then, the photocatalyst precursor coating agent was apply | coated on the protective layer 16 so that the dry thickness might be set to 100 nm using the Meyer bar, and the photocatalyst layer 14 was formed. Next, a non-support type adhesive tape (manufactured by Soken Chemical Co., Ltd., SK2057) was attached on the heat insulating layer 13. Then, the glass sample which has a laminated structure was produced by carrying out dry lamination of the adhesive tape on the float plate glass of 220 mmx220mmx3mmt.

<Coating agent 2 for light absorption layer>
The light absorbing layer coating agent 2 was prepared by mixing 100 g of lanthanum hexaboride dispersion slurry and 100 g of amorphous polyester resin dissolved in methyl ethyl ketone (MEK). “KHF-7A” manufactured by Sumitomo Metal Mining Co., Ltd. was used as the lanthanum hexaboride dispersion slurry. The dispersion medium of the dispersion slurry is toluene, and the concentration of fine particles in the dispersion slurry is 1.9% by mass. As an amorphous polyester resin, what melt | dissolved the amorphous polyester resin "Byron 240" by Toyobo Co., Ltd. in MEK so that it might become 40 mass% was used. The amorphous polyester resin used here does not contain the above functional components.

<Coating agent for protective layer>
Halus hybrid type acrylic polyol resin “Udable UV-G301 (trade name)” manufactured by Nippon Shokubai Co., Ltd., 12.7 g of isocyanate curing agent “Desmodur N3200 (trade name)” manufactured by Sumika Bayer Urethane Co., Ltd., and acetic acid A protective layer coating agent was prepared by mixing 58.5 g of ethyl. The Hals hybrid type acrylic polyol resin used here corresponds to a complex of an ultraviolet absorbing component and a light stabilizing component chemically bonded to a water-insoluble resin component.

(Example 5)
A glass having a laminated structure as shown in FIG. 1A by laminating each layer in the same manner as in Example 1 except that the coating agent 3 for the light absorption layer is used instead of the coating agent 1 for the light absorption layer. A sample was made.

<Coating agent 3 for light absorption layer>
36 g of lanthanum hexaboride dispersion slurry, 100 g of acrylic polyol resin, 12.7 g of an isocyanate curing agent, and 58.5 g of ethyl acetate were mixed to prepare a coating agent 3 for a light absorbing layer. “KHF-7A” manufactured by Sumitomo Metal Mining Co., Ltd. was used as the lanthanum hexaboride dispersion slurry. The dispersion medium of the dispersion slurry is toluene, and the concentration of fine particles in the dispersion slurry is 1.9% by mass. As the acrylic polyol resin, Halus hybrid type acrylic polyol resin “Udable UV-G301 (trade name)” manufactured by Nippon Shokubai was used. “Desmodur N3200 (trade name)” manufactured by Sumika Bayer Urethane Co., Ltd. was used as the isocyanate curing agent.

(Comparative Examples 1-6)
In Comparative Examples 1-4, each layer was laminated | stacked similarly to Example 1 except having changed into the laminated structure shown to Fig.3 (a)-FIG.3 (d). In Comparative Examples 5 and 6, the respective layers were laminated in the same manner as in Example 1 except that the laminated structure shown in each of FIGS. 4A and 4B was changed.

(Measurement of total light transmittance and haze value of laminated structure)
About the glass sample of each example, using a haze meter (Nippon Denshoku Co., Ltd., NDH2000), based on JISK7361-1: 1997 (ISO 13468-1: 1996), a total light transmittance and a haze value are shown. It was measured. The measurement results are shown in Table 1.

(Evaluation of indoor environment)
FIG. 5 shows a measuring device used to confirm the effects of the light absorption layer 12 and the heat insulating layer 13. As a measuring device, two polystyrene foam boxes having an inner diameter of 70 mm × 210 mm × 210 mm were prepared. On the inner surface of the bottom wall of the polystyrene foam box, a painted plate coated with black matte paint was laid on the entire surface of a 500 μm thick aluminum plate. And glass sample SA of each example was mounted on one foamed polystyrene box, and float glass simple substance SB was mounted on the other foamed polystyrene box.

  A 500 W halogen lamp L was installed above the glass sample SA and the float glass simple substance SB. The distance between the glass sample SA and the float glass simple substance SB and the halogen lamp L was 260 mm. Here, the emission spectrum of the halogen lamp L also included infrared light having a wavelength (wavelength> 2500 nm) that does not exist in the sunlight. For this reason, in order to make the light irradiated to the glass sample SA and the float glass simple substance SB approach a sunlight ray, the glass filter which is not illustrated was used.

  The glass filter was produced as follows. First, the light absorption layer 12 was formed on the PET film using the PET film described in Example 1 and the coating agent for the light absorption layer so that the film thickness after drying was about 12 μm. Next, a non-support type adhesive tape (manufactured by Soken Chemical Co., Ltd., SK2057) was pasted on the light absorption layer 12. Thereafter, the adhesive tape was dry-laminated on a 300 mm × 300 mm × 3 mmt float glass to obtain a glass filter. The glass filter was placed 160 mm away from the halogen lamp L.

  Subsequently, a thermocouple TC1A (hereinafter, this temperature is referred to as “temperature 1A”) was installed in the center of the box in which the glass sample SA was placed. A thermocouple TC1B (hereinafter, this temperature is referred to as “temperature 1B”) is also installed in the center of the box in which the float glass simple substance SB is placed. The temperature change in each box (change in the temperature in the tank) was monitored by thermocouples TC1A and TC1B.

  A thermocouple TC2A (hereinafter, this temperature is referred to as “temperature 2A”) was installed in the center of the surface facing the box of the glass sample SA. A thermocouple TC2B (hereinafter, this temperature is referred to as “temperature 2B”) was also installed at the center of the surface of the float glass simple substance SB facing the box. Changes in the glass surface temperature (glass inner surface temperature) were monitored by thermocouples TC2A and TC2B. The room temperature in which each box was placed was adjusted to about 25 ° C. Then, the temperature 1A, the temperature 1B, the temperature 2A, and the temperature 2B before the light irradiation are set to about 25 ° C., the temperature 1A−the temperature 1B = ± 0.2 ° C., and the temperature 2A−the temperature 2B = ± 0.2 ° C. Then, the halogen lamp L was irradiated with light.

  After 5 minutes from the start of light irradiation by the halogen lamp L, the in-bath temperature difference ΔT1 and the glass inner surface temperature difference ΔT2 were calculated. The bath temperature difference ΔT1 and the glass inner surface temperature difference ΔT2 are shown in the following equations.

Temperature difference in the tank ΔT1 (° C.) = (Temperature 1A after 5 minutes−temperature 1A before light irradiation) − (temperature 1B after 5 minutes−temperature 1B before light irradiation)
Glass inner surface temperature difference ΔT2 (° C.) = (Temperature 2A after 5 minutes−temperature 2A before light irradiation) − (temperature 2B after 5 minutes−temperature 2B before light irradiation)
Thereafter, the light irradiation with the halogen lamp L was continued, and the halogen lamp L was turned off when 2500 seconds had elapsed after the light irradiation was started. The temperature difference ΔT3 in the tank was calculated 500 seconds after the halogen lamp L was turned off. The tank temperature difference ΔT3 is shown in the following equation.

Temperature difference ΔT3 (° C.) in the tank = (temperature 1A after 500 seconds from turning off−temperature 1A after 2500 seconds from light irradiation) − (temperature 1B after 500 seconds from turning off−temperature 1B after 2500 seconds from the start of light irradiation)
(Evaluation of antifouling properties)
The contamination on the surface of the photocatalyst layer 14 was visually confirmed when the laminate 11 of each example was used for 3 months under the conditions actually used. The case where scale and dirt were not conspicuous was judged as good (◯), and the case where scale and dirt were conspicuous was judged as bad (x). The results are shown in Table 1.

(Evaluation of weather resistance of laminated structure)
Using a sunshine weather meter (SWM: “Sunshine Weather Meter S300” manufactured by Suga Test Instruments Co., Ltd.), an exposure test of the glass sample was performed with the surface opposite to the float plate glass facing the light source. In the exposure test, it was set to rain for 18 minutes during the irradiation with one cycle being 120 minutes, and continued for 300 hours. Details of the exposure conditions are as follows.

Setting conditions: Illuminance 255 ± 55 W / m ² , irradiation light wavelength range 250 to 1200 nm,
Black panel temperature: 63 ± 3 ℃
Relative humidity: 55 ± 5% RH
About the glass sample after an exposure test, the change of the external appearance was confirmed visually. When no change in appearance is confirmed, weather resistance is excellent (○○), when slight change in appearance is confirmed, weather resistance is good (○), and when appearance change is confirmed, weather resistance It was determined as inferior to (×). The results are shown in Table 1.

ここで、槽内温度差ΔＴ１（℃）の値が低下するにしたがって光吸収層１２による遮熱効果が向上することを示している。また、ガラス内面温度差ΔＴ２（℃）の値が低下するにしたがって光吸収層１２から窓ガラスＧへの熱伝導が抑制されることを示している。また、槽内温度差ΔＴ３（℃）の値が高くなるにしたがって室内の温度が良好に維持されることを示している。図３（ａ）に示す比較例１、図３（ｂ）に示す比較例２、及び図３（ｃ）に示す比較例３では、窓ガラスＧと断熱層１３との間に光吸収層１２を配置した。比較例１〜３のΔＴ２は、各実施例よりも高い値を示した。図３（ｄ）に示す比較例４では、断熱層１３が存在しない。比較例４のΔＴ２は、各実施例よりも高い値を示した。

Here, it is shown that the heat shielding effect by the light absorption layer 12 is improved as the value of the temperature difference ΔT1 (° C.) in the bath is lowered. Moreover, it has shown that the heat conduction from the light absorption layer 12 to the window glass G is suppressed as the value of glass inner surface temperature difference (DELTA) T2 (degreeC) falls. Moreover, it has shown that indoor temperature is favorably maintained as the value of tank temperature difference (DELTA) T3 (degreeC) becomes high. In Comparative Example 1 shown in FIG. 3A, Comparative Example 2 shown in FIG. 3B, and Comparative Example 3 shown in FIG. 3C, the light absorbing layer 12 is provided between the window glass G and the heat insulating layer 13. Arranged. ΔT2 of Comparative Examples 1 to 3 showed a higher value than each Example. In the comparative example 4 shown in FIG.3 (d), the heat insulation layer 13 does not exist. ΔT2 of Comparative Example 4 showed a higher value than each Example.

  In the comparative example 5 shown to Fig.4 (a), the laminated body 11 has been arrange | positioned inside the window glass G. FIG. ΔT2 of Comparative Example 5 showed a higher value than each Example. In Comparative Example 6 shown in FIG. 4B, the light absorption layer 12 is disposed between the window glass G and the heat insulating layer 13 inside the window glass G. In Comparative Example 6, heat conduction from the light absorption layer 12 to the window glass G was not suppressed.

  ΔT1 of each example showed the same value or a low value as each comparative example. From this, in each Example, the heat shielding effect by the light absorption layer 12 was exhibited. Moreover, Tt and Hz value of each Example also showed the value comparable as the comparative example 4, for example. From this, transparency was maintained in each Example. In Comparative Examples 5 and 6, the photocatalytic layer 14 does not exist outside the window glass G. For this reason, the evaluation result of antifouling property was unsatisfactory.

  In Example 4 and Example 5, metal boride was used as the conductive fine particles contained in the light absorption layer 12. The evaluation of the weather resistance of the laminated structure in Example 4 was superior to Example 5. Here, the metal boride used as the conductive fine particles is green. For this reason, the color was able to be confirmed with the glass sample. In Example 5, the color derived from the metal boride before the exposure test was lightened after the exposure test. On the other hand, in Example 4, the color derived from the metal boride before the exposure test was maintained after the exposure test. From this result, in Example 4, deterioration of the metal boride was suppressed by the protective layer 16, and the weather resistance was improved rather than Example 5. FIG.

  Table 2 shows the “heat shielding effect by the light absorption layer” compared based on the temperature difference ΔT1, the “heat conduction suppression effect on glass” compared based on the temperature difference ΔT2, and the “room temperature compared based on ΔT3”. Each of the “maintenance effects” is expressed as a percentage based on Comparative Example 4.

  B ... base material, G ... window glass, 11 ... laminate, 12 ... light absorption layer, 13 ... heat insulation layer, 16 ... protective layer.

Claims (5)

A laminated structure provided on the outside of the window glass that partitions the outside and inside of the chamber,
A light absorption layer composed of a film that absorbs infrared rays by containing conductive fine particles;
A heat insulating layer that is disposed between the window glass and the light absorption layer and includes a film having independent bubbles by including hollow particles;
A laminated structure, wherein a haze value of the laminated structure including the float plate glass when the laminated structure is laminated on a float plate glass having a thickness of 3 mm is 10% or less. The laminated structure according to claim 1 further includes:
A protective layer disposed outside the light absorbing layer;
The protective layer includes a water-insoluble resin component as a matrix, and includes at least one functional component selected from an antioxidant component, a light stabilizing component, an ultraviolet absorbing component, and an ultraviolet scattering component. . A laminated body provided on the outside of the window glass that partitions the outside and inside of the chamber,
A substrate;
A light absorption layer made of a film that is disposed on a substrate and absorbs infrared rays by containing conductive fine particles;
A heat insulating layer that is disposed between the window glass and the light absorption layer and includes a film having independent bubbles by including hollow particles;
A laminate having a haze value of 10% or less including the float plate glass when the laminate is laminated on a float plate glass having a thickness of 3 mm. The laminate according to claim 3 further includes:
A protective layer disposed outside the light absorbing layer;
The protective layer includes a water-insoluble resin component as a matrix, and at least one functional component selected from an antioxidant component, a light stabilizing component, an ultraviolet absorbing component, and an ultraviolet scattering component. . In the laminate according to claim 3 or 4,
The base material includes a resin component, and the base material is disposed between the window glass and the light absorption layer.

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