JP2017047552A - Light-transmitting laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a light-transmitting laminate capable of achieving both of adhesiveness and thermal insulation property of a surface protective layer.SOLUTION: A light-transmitting laminate 10 includes a metal thin film layer 16, a high refractive index thin film layer 14 having a refractive index higher than that of the metal thin film layer 16, a light-transmitting substrate 12, and a surface protective layer 20, in this order. The light-transmitting substrate 12 is made of a polyolefin film; the high refractive index thin film layer 14 is made of an organic thin film comprising a non-crosslinking polymer having a functional group containing at least one element selected from N, O and S, and a crosslinked polymer; the surface protective layer 20 is made of an organic inorganic hybrid material; and the content of the inorganic component in the surface protective layer 20 is 1.0 to 30 mass%.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a light transmissive laminate, and more particularly, to a light transmissive laminate excellent in heat shielding properties and heat insulation properties.

  A light-transmitting laminated film having a heat shielding property may be applied to a window glass of a building such as a building or a house or a window glass of a vehicle such as an automobile for the purpose of shielding solar radiation. It has been proposed to form a hard coat layer made of an organic-inorganic hybrid material as a protective layer of the light transmissive laminated film. Further, it has been proposed to form an organic thin film as a high refractive index thin film of a light transmissive laminated film.

JP, 2015-30109, A

  In the hard coat layer made of an organic-inorganic hybrid material, if the amount of the inorganic component is too large, the heat insulating property is lowered. On the other hand, if the amount of the inorganic component is too small, peeling occurs due to curing shrinkage.

  The problem to be solved by the present invention is to provide a light-transmitting laminate that can achieve both adhesion and heat insulation of a surface protective layer.

  In order to solve the above problems, a light transmissive laminate according to the present invention comprises a metal thin film layer, a high refractive index thin film layer having a refractive index higher than that of the metal thin film layer, a light transmissive substrate, and a surface protective layer in this order. The light-transmitting substrate is made of a polyolefin film, and the high refractive index thin film layer has a non-crosslinked polymer and a crosslinked polymer having a functional group containing at least one element selected from N, O, and S. It is composed of an organic thin film containing, the surface protective layer is composed of an organic-inorganic hybrid material, and the content of the inorganic component in the surface protective layer is in the range of 1.0 to 30% by mass. is there.

  The non-crosslinked polymer is preferably a polymer having a triazine ring. The cross-linked polymer is preferably a polyfunctional acrylate polymer or a polyfunctional methacrylate polymer. The content of the inorganic component in the surface protective layer is preferably in the range of 2.0 to 10% by mass. As the polyolefin film, a biaxially stretched polypropylene film is preferable. The polyolefin film preferably has a thickness in the range of 10 to 100 μm. The metal thin film layer is preferably made of silver or a silver alloy.

  According to the light transmissive laminate according to the present invention, the surface protective layer is made of an organic-inorganic hybrid material, and the content of the inorganic component in the surface protective layer is in the range of 1.0 to 30% by mass. The high refractive index thin film layer is composed of an organic thin film containing a non-crosslinked polymer having a functional group containing at least one element selected from N, O, and S and a crosslinked polymer. Thereby, the adhesiveness and heat insulation of a surface protective layer can be made compatible.

  When the non-crosslinked polymer is a polymer having a triazine ring, the refractive index of the organic thin film is high, and the light transmittance of the light transmissive laminate is excellent. When the crosslinked polymer is a polyfunctional acrylate polymer or polyfunctional methacrylate polymer, photocrosslinking is possible, crosslinking can be performed at a low temperature, and thermal deformation of the polyolefin film can be suppressed. Further, crosslinking in a short time with light becomes possible. When the content of the inorganic component in the surface protective layer is in the range of 2.0 to 10% by mass, the adhesiveness and the heat insulating property of the protective layer can be made more highly compatible. When the polyolefin film is a biaxially stretched polypropylene film, the stiffness is relatively strong among the polyolefin films, so that it is easy to prevent the light-transmitting laminate from being broken by the force applied at the time of reattachment. When the thickness of the polyolefin film is in the range of 10 to 100 μm, the light-peeling laminate is excellent in removability and roll-to-roll productivity. When the metal thin film layer is made of silver or a silver alloy, the adhesion with the high refractive index thin film layer made of an organic thin film is excellent. Moreover, it is excellent in light transmittance, solar shading, and heat ray reflectivity.

It is sectional drawing of the light-transmitting laminated body which concerns on one Embodiment of this invention.

  The light transmissive laminate according to the present invention will be described in detail. FIG. 1 is a cross-sectional view of a light transmissive laminate according to an embodiment of the present invention.

  The light transmissive laminate 10 includes a metal thin film layer 16, a high refractive index thin film layer 14, a light transmissive substrate 12, and a surface protective layer 20 in this order. The high refractive index thin film layer 14 is provided in contact with one surface of the light transmissive substrate 12. The metal thin film layer 16 is provided in contact with the high refractive index thin film layer 14. A high refractive index thin film layer 18 is further provided in contact with the surface of the metal thin film layer 16. The surface protective layer 20 is provided in contact with the other surface of the light transmissive substrate 12. The surface protective layer 20 is the outermost layer of the light transmissive laminate 10. On the surface of the high refractive index thin film layer 18, an adhesive layer made of an adhesive or an adhesive for attaching the light transmissive laminate 10 to an adherend such as a window or a display is provided. The surface of the adhesive layer is covered with a separator as necessary.

  The light transmissive substrate 12 is made of a polyolefin film. Since polyolefin does not have a functional group such as polyethylene terephthalate (PET), the film itself absorbs less infrared light. If it does so, it will be hard to absorb the heating heat etc. which generate | occur | produced indoors, and heat insulation will be improved more. In addition, since the polyolefin film is excellent in flexibility, it can be applied to uses requiring flexibility. In addition, the cost of the polyolefin film is lower than that of the PET film. The film is a thin film, and generally has a thickness of 200 μm or less or 250 μm or less. What is necessary is just to have the softness | flexibility which can be wound in roll shape, and if it is such, it may be 200 micrometers or more or 250 micrometers or more thick. The film is generally delivered as a roll.

  The polyolefin film is light transmissive. Light transmittance means that the transmittance value in the wavelength region of 360 to 830 nm is 50% or more. Examples of the polyolefin of the polyolefin film include chain polyolefin and cyclic polyolefin. Examples of the chain polyolefin include polyethylene, polypropylene, and ethylene-α olefin copolymer. Examples of the cyclic polyolefin include cycloolefin polymers. As the polyolefin, polypropylene is preferable from the viewpoints of light transmittance, durability, workability, and the like. In particular, from the viewpoint of light transmittance and the like, biaxially oriented polypropylene (OPP) is preferable. Biaxially stretched polypropylene is also preferred because of its relatively strong stiffness among polyolefin films.

  The polyolefin film may be subjected to a surface treatment on one or both surfaces thereof. Examples of the surface treatment include corona treatment and plasma treatment. By the surface treatment, a hydroxyl group, an oxygen group, or the like is formed on the surface of the polyolefin film, and adhesion with the layer in contact with the polyolefin film is improved.

  The thickness of the polyolefin film is preferably 10 μm or more from the viewpoint of removability during construction of the light transmissive laminate 10. More preferably, it is 15 micrometers or more, More preferably, it is 20 micrometers or more. Moreover, it is preferable that it is 100 micrometers or less from a viewpoint of being excellent in productivity by a roll to roll. More preferably, it is 50 μm or less.

  The metal thin film layer 16 is made of a metal that easily reflects far infrared rays, and can function as a solar radiation shielding layer. Examples of the metal of the metal thin film layer 16 include silver, a silver alloy, aluminum, an aluminum alloy, iron, and an iron alloy. These may be used individually by 1 type as a metal of the metal thin film layer 16, and may be used in combination of 2 or more type. Among these, silver and silver alloys are more preferable from the viewpoint of excellent light transmittance, solar shading, and heat ray reflectivity. From the viewpoint of improving durability against environment such as heat, light, and water vapor, a silver alloy is more preferable. As the silver alloy, a silver alloy containing silver as a main component and containing at least one metal element such as copper, bismuth, gold, palladium, platinum, and titanium is preferable. More preferably, a silver alloy containing copper (Ag—Cu alloy), a silver alloy containing bismuth (Ag—Bi alloy), a silver alloy containing titanium (Ag—Ti alloy), or the like is preferable.

  The film thickness of the metal thin film layer 16 is preferably 3 nm or more, more preferably 5 nm or more, and still more preferably 7 nm or more from the viewpoints of stability, solar shading. Further, from the viewpoints of light transmittance, economy and the like, it is preferably 30 nm or less, more preferably 20 nm or less, and further preferably 15 nm or less. The metal thin film layer 16 can be formed by a sputtering method or the like.

  The high refractive index thin film layers 14 and 18 are capable of exhibiting functions such as increasing light transmittance by being laminated together with the metal thin film layer 16. The high refractive index thin film layers 14 and 18 have a higher refractive index than the metal thin film layer 16. The refractive index refers to the refractive index for light of 633 nm. The refractive indexes of the high refractive index thin film layers 14 and 18 are preferably 1.6 or more. More preferably, it is 1.7 or more.

  The high refractive index thin film layers 14 and 18 are made of organic thin films. An inorganic thin film such as a metal oxide thin film is easily broken. Since the high refractive index thin film layers 14 and 18 are made of an organic thin film, cracking of the high refractive index thin film layers 14 and 18 is easily suppressed. The organic thin film contains a non-crosslinked polymer and a crosslinked polymer.

  The non-crosslinked polymer is composed of an organic polymer having a functional group containing at least one element selected from N, S, and O. Organic polymers having such functional groups tend to have a relatively high refractive index. Among N, S, and O, an organic polymer containing N and S is particularly preferable because the refractive index tends to be particularly high. These elements are elements that are strongly associated with the metal of the metal thin film layer 16, and the high refractive index thin film layers 14, 18 made of organic thin films are formed by the functional groups containing these elements. It adheres strongly to the metal thin film layer 16 in contact with the metal film, and the adhesion to the metal thin film layer 16 is improved. Among N, S, and O, N and S are elements that are strongly associated with Ag among metals, and if the organic polymer has a functional group containing N or S, adhesion to the metal thin film layer 16 containing Ag Becomes particularly good.

Examples of the functional group containing S include a sulfonyl group (—SO ₂ —), a thiol group, and a thioester group. Among these, a sulfonyl group, a thiol group, and the like are more preferable from the viewpoint of superior adhesion to the metal thin film layer 16. Examples of the polymer having a functional group containing S include polyethersulfone (PES), polysulfone, and polyphenylsulfone.

  Examples of the functional group containing O include a carboxyl group, an ester group, a ketone group, and a hydroxyl group. Among these, a carboxyl group, an ester group, and the like are more preferable from the viewpoint of excellent adhesion to the metal thin film layer 16. And as a polymer which has a functional group containing O, an epoxy resin etc. are mentioned.

  Examples of the functional group containing N include a carbazole group, an imide group, and a nitrile group. Among these, carbazole group, imide group, and the like are more preferable from the viewpoint of superior adhesion to the metal thin film layer 16. Examples of the polymer having a functional group containing N include polyvinyl carbazole (PVK) and polyimide. Moreover, the polymer which has a triazine ring is mentioned. A polymer having a triazine ring is particularly preferred because of its relatively high refractive index (1.70 or more) due to its structure.

  An organic polymer having a high refractive index, such as an organic polymer having a functional group containing at least one element selected from N, S, and O, has low elongation and poor flexibility unless it is crosslinked. An organic thin film made of such an organic polymer has low flexibility. When the organic thin film contains a crosslinked polymer in addition to such a non-crosslinked polymer, the flexibility of the organic thin film is improved. In addition, since swelling due to water is suppressed, a decrease in strength after drying is suppressed, and peeling of the high refractive index thin film layers 14 and 18 when placed in a humid heat environment is suppressed. Moreover, since a crosslinked polymer hardly generates radicals when exposed to sunlight, the weather resistance is improved by containing the crosslinked polymer.

  The crosslinking method of the crosslinked polymer is not particularly limited, and various methods such as peroxide crosslinking, sulfur crosslinking, and photocrosslinking can be mentioned. Of these, photocrosslinking is preferred. Crosslinking can be performed at a low temperature, and thermal deformation of the polyolefin film serving as a substrate can be suppressed. Further, crosslinking in a short time with light becomes possible.

  The cross-linked polymer is preferably a polyfunctional acrylate polymer or a polyfunctional methacrylate polymer from the viewpoint that photocrosslinking is possible.

  The polyfunctional acrylate or polyfunctional methacrylate is not particularly limited as long as it has two or more (meth) acrylic groups in one molecule. Specifically, ethylene glycol diacrylate, ethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, ethoxylated bisphenol A diacrylate, ethoxylated bisphenol A dimethacrylate, ethoxylated trimethylolpropane triacrylate, ethoxylated triacrylate Methylolpropane trimethacrylate, ethoxylated glycerol triacrylate, ethoxylated glycerol trimethacrylate, ethoxylated pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetramethacrylate, ethoxylated dipentaerythritol hexaacrylate, polyglycerol monoethylene oxide polyacrylate, polyglycerol polyethylene Glico Polyacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, Examples include tricyclodecane dimethanol diacrylate, tricyclodecane dimethanol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, and the like.

  When polyfunctional acrylate or polyfunctional methacrylate is used, a radical photopolymerization initiator can also be used. The radical photopolymerization initiator may be appropriately selected from known ones, and examples thereof include acetophenones, benzophenones, Michler's benzoylbenzoate, amyloxime ester, tetramethylthiuram monosulfide, and thioxanthones. When using a radical photopolymerization initiator, it is preferably used in the range of 0.1 to 15 parts by mass, more preferably in the range of 1 to 10 parts by mass, with respect to 100 parts by mass of the polyfunctional acrylate or polyfunctional methacrylate. is there.

  The film thickness of the high refractive index thin film layers 14 and 18 can be adjusted in consideration of solar shading, visibility, reflection color, and the like. The film thicknesses of the high refractive index thin film layers 14 and 18 are preferably 5 nm or more, more preferably 8 nm, from the viewpoints of easily suppressing red and yellow coloring of the reflected color and easily obtaining high light transmittance. More preferably, it is 10 nm or more. The film thickness of the high refractive index thin film layers 14 and 18 is preferably 90 nm or less, more preferably 85 nm, from the viewpoints of easily suppressing the green color of the reflected color and easily obtaining high light transmittance. Hereinafter, it is more preferably 80 nm or less.

  The organic thin film which becomes the high refractive index thin film layers 14 and 18 can be formed by preparing a coating liquid containing an organic polymer, applying the coating liquid, and drying to form a coating film. In preparing the coating liquid, a solvent for dissolving the organic polymer can be used as necessary. Examples of such solvents include alcohols such as methanol, ethanol, propanol, butanol, heptanol, and isopropyl alcohol, organic acid esters such as ethyl acetate, ketones such as acetonitrile, acetone, and methyl ethyl ketone, and cycloethers such as tetrahydrofuran and dioxane. Acid amides such as formamide and N, N-dimethylformamide, hydrocarbons such as hexane, and aromatics such as toluene and xylene. These may be used alone or in combination.

  The surface protective layer 20 is a layer disposed as the outermost layer and suppresses the surface of the light transmissive substrate 10 from being damaged. The surface protective layer 20 is made of an organic-inorganic hybrid material. An organic-inorganic hybrid material is a material containing an organic component and an inorganic component. Compared with a material that does not contain an inorganic component, by being made of an organic-inorganic hybrid material, curing shrinkage during the formation of the surface protective layer 20 can be suppressed. In addition, the scratch resistance is improved.

  Examples of the organic-inorganic hybrid material include those in which inorganic particles are blended in an organic material. In this case, the organic material includes a curable resin. Examples of the curable resin include acrylic resin, epoxy resin, and urethane resin. These may be used alone or in combination of two or more. Among these, acrylic resin and urethane resin are preferable from the viewpoint of transparency and flexibility. In addition, examples of the inorganic particles in this case include metal particles and metal oxide particles. Among these, metal oxide particles are preferable from the viewpoint of light transmittance. Examples of the metal particles and metal oxide particles include Si, Ti, and Zr. As the inorganic particles, silica particles are preferable from the viewpoints of scratch resistance, wear resistance, versatility, and the like. As the inorganic particles, nanoparticles are used from the viewpoints of dispersibility, light transmittance, and the like. The nanoparticles are nano-sized inorganic particles having a particle size of less than 1 μm. In this case, the inorganic particles become an inorganic component in the surface protective layer 20.

  In addition, organic-inorganic hybrid materials include those formed of organic materials (raw materials of organic components) and inorganic materials (raw materials of inorganic components), in which organic materials and inorganic materials are combined at the nano level or molecular level. It is done. Such an organic-inorganic hybrid material is, for example, a network in which an inorganic material dispersed in an organic material undergoes a reaction such as a polymerization reaction, and the inorganic component is highly dispersed in the organic component through a chemical bond. It has a crosslinked structure. In this case, the organic material includes a curable resin. Examples of the curable resin include acrylic resin, epoxy resin, and urethane resin. These may be used alone or in combination of two or more. In this case, examples of the inorganic material include metal compounds. Examples of the metal compound include a Si compound, a Ti compound, and a Zr compound. These may be used alone or in combination of two or more. Among these, Si compounds are more preferable from the viewpoints of scratch resistance, wear resistance, versatility, and the like. The metal compound is a compound containing an inorganic component such as Si, Ti, or Zr, and can be compounded by causing a reaction such as a polymerization reaction with a raw material of the organic component. More specifically, examples of the metal compound include organometallic compounds. Examples of organometallic compounds include silane coupling agents, metal alkoxides, metal acylates, metal chelates, and silazanes.

  The thickness of the surface protective layer 20 is preferably 2.5 μm or less from the viewpoint of excellent heat insulation (suppressing the heat transmissivity low). More preferably, it is 2.0 micrometers or less, More preferably, it is 1.5 micrometers or less. Moreover, it is preferable that it is 0.4 micrometer or more from a viewpoint of being excellent in abrasion resistance. More preferably, it is 0.6 micrometer or more, More preferably, it is 0.8 micrometer or more.

  In the light transmissive laminate 10, the surface protective layer 20 is made of an organic-inorganic hybrid material. Compared with a material that does not contain an inorganic component, by being made of an organic-inorganic hybrid material, curing shrinkage during the formation of the surface protective layer 20 can be suppressed. Thereby, distortion becomes small and it becomes easy to suppress peeling of the surface protective layer 20. At this time, the content of the inorganic component in the surface protective layer 20 is in the range of 1.0 to 30% by mass. Heat insulation is ensured by reducing the content of inorganic components. However, when there is little content of an inorganic component, the effect which suppresses the hardening shrinkage at the time of formation of the surface protective layer 20 is small. If it does so, peeling of the surface protective layer 20 will occur easily. On the other hand, the high refractive index thin film layers 14 and 18 are made of an organic thin film containing a non-crosslinked polymer having a functional group containing at least one element selected from N, O, and S and a crosslinked polymer. Thereby, the softness | flexibility of the high refractive index thin film layers 14 and 18 improves. Due to the flexibility of the high refractive index thin film layers 14 and 18, stress due to curing shrinkage at the time of forming the surface protective layer 20 is relieved, so that even if the content of the inorganic component is small, peeling of the surface protective layer 20 is suppressed. . Thereby, the adhesiveness and heat insulation of the surface protective layer 20 can be compatible. And by making content of the inorganic component in the surface protective layer 20 into the range of 2.0-10 mass%, the adhesiveness and heat insulation of the surface protective layer 20 can be compatible more highly.

  Moreover, in the light transmissive laminated body 10, the surface protective layer 20 consists of organic-inorganic hybrid material, and is excellent in abrasion resistance compared with the material which does not contain an inorganic component. In the light transmissive laminate 10, the high refractive index thin film layers 14 and 18 are organic containing a non-crosslinked polymer and a crosslinked polymer having a functional group containing at least one element selected from N, O, and S. It consists of a thin film. By containing such a non-crosslinked polymer, the refractive index is increased even for an organic thin film. Moreover, since the swelling by water is suppressed by containing a crosslinked polymer, the strength reduction after drying is suppressed, and peeling of the high refractive index thin film layers 14 and 18 when placed in a humid heat environment is suppressed. Moreover, since a crosslinked polymer hardly generates radicals when exposed to sunlight, the weather resistance is improved by containing the crosslinked polymer.

  The high refractive index thin film layers 14 and 18 preferably have a gel fraction of 20% or more. More preferably, it is 30% or more. When the gel fraction is 20% or more, the solvent resistance after the formation of the high refractive index thin film layers 14 and 18 is ensured. The high refractive index thin film layers 14 and 18 preferably have a gel fraction of 90% or less. More preferably, it is 80% or less. When the gel fraction is 90% or less, curing shrinkage during formation of the high refractive index thin film layers 14 and 18 is suppressed, and peeling of the high refractive index thin film layers 14 and 18 is suppressed. The gel fraction of the high refractive index thin film layers 14 and 18 can be adjusted by the blending ratio of the non-crosslinked polymer and the crosslinked polymer.

  In the light transmissive laminate 10, the metal thin film layer 16 is composed of one layer, and a three-layer configuration in which the high refractive index thin film layers 14 and 18 are arranged on both surfaces is shown. The laminated structure of the high refractive index thin film layers 14 and 18 is not limited to this configuration. In order from the light-transmitting substrate 12 side, a total of two or more layers such as a metal thin film layer / a high refractive index thin film layer / a metal thin film layer / a high refractive index thin film layer may be laminated. Two layers or more in total may be laminated in order from the substrate 12 side, such as high refractive index thin film layer / metal thin film layer / high refractive index thin film layer / metal thin film layer / high refractive index thin film layer.

  The light-transmitting laminate 10 is suitably used as a light-transmitting laminated film having heat shielding properties for the purpose of shielding solar radiation on window glass of buildings such as buildings and houses, and window windows of vehicles such as automobiles. it can.

  Hereinafter, the present invention will be described in detail using Examples and Comparative Examples.

  As a light transmissive laminate according to Examples and Comparative Examples, a high refractive index thin film layer composed of an organic thin film, a metal thin film layer, and a high refraction composed of an organic thin film on one surface of a light transmissive substrate composed of a polyolefin film. A light-transmitting laminate (FIG. 1) having a surface protective layer on the other surface of the light-transmitting substrate. The outline is as follows.

<Preparation of coating solution for organic thin film>
A triazine ring-containing polymer (containing "UR-108NPT3" manufactured by Nissan Chemical Industries, photopolymerization initiator, polyfunctional acrylate) with a viscosity (0.1 to 3.0 mPa · s) that can be applied with a gravure coater. By diluting (solvent: PGMEA), a coating solution for organic thin film was prepared.

<Preparation of light transmissive laminate>
Example 1
Corona treatment is performed on both sides of an OPP film ("Torayfan BO 40-2500" manufactured by Toray Industries, Inc., thickness: 40 [mu] m), and the above coating solution for organic thin film is applied on one side using a micro gravure coater. After being processed and dried at 70 ° C. for 30 seconds, an organic thin film (film thickness 20 nm) was formed by irradiating with 200 mJ / cm ² of ultraviolet rays to carry out a crosslinking treatment. Next, an Ag—Cu alloy thin film (film thickness: 7.8 nm) was formed on the first organic thin film by sputtering using a DC magnetron sputtering apparatus. Next, a second organic thin film (film thickness: 20 nm) was formed on the Ag-Cu alloy thin film in the same manner as the first organic thin film. Next, a UV curable organic-inorganic hybrid material (TG series manufactured by Dainichi Seika Kogyo Co., Ltd., inorganic component content: 1.0% by mass) is coated on the other side of the OPP film, and dried at 70 ° C. for 30 seconds. The surface protective layer (thickness 1.5 μm) made of an organic-inorganic hybrid material was formed by irradiation with 200 mJ / cm ² of ultraviolet rays. Thus, the light transmissive laminate of Example 1 was produced.

(Examples 2 to 5)
The light-transmitting laminates of Examples 2 to 5 were the same as Example 1 except that the inorganic component content (% by mass) of the UV curable organic-inorganic hybrid material (TG series manufactured by Dainichi Seika Kogyo Co., Ltd.) was changed. The body was made.

(Comparative Example 1)
Instead of using a UV curable organic-inorganic hybrid material (TG series manufactured by Dainichi Seika Kogyo Co., Ltd.), an ultraviolet curable acrylic resin (manufactured by DIC, “UVT Clear TEF-046”) was used as a material for the surface protective layer. In the same manner as in Example 1, a light transmissive laminate of Comparative Example 1 was produced.

(Comparative Example 2)
The light transmissive laminate of Comparative Example 2 was prepared in the same manner as in Example 1 except that the inorganic component content (% by mass) of the UV curable organic-inorganic hybrid material (TG series manufactured by Dainichi Seika Kogyo Co., Ltd.) was changed. Produced.

(Comparative Example 3)
Instead of UV curable organic / inorganic hybrid material (TG series manufactured by Dainichi Seika Kogyo Co., Ltd.), UV curable acrylic resin (manufactured by DIC, “UVT Clear TEF-046”) is used as the material for the surface protective layer, and organic In the preparation of the coating solution for thin film, instead of the triazine ring-containing polymer ("UR-108NPT3" manufactured by Nissan Chemical Industries, Ltd.), a triazine ring-containing polymer ("UR-108NT3" manufactured by Nissan Chemical Industries, Ltd.) was used, A light transmissive laminate of Comparative Example 3 was produced in the same manner as in Example 1 except that the organic thin film was not subjected to crosslinking treatment.

(Comparative Example 4)
In the preparation of the coating solution for organic thin films, a triazine ring-containing polymer (“UR-108NT3” manufactured by Nissan Chemical Industries, Ltd.) was used instead of the triazine ring-containing polymer (“UR-108NPT3” manufactured by Nissan Chemical Industries, Ltd.). A light transmissive laminate of Comparative Example 4 was produced in the same manner as in Example 1 except that the organic thin film was not subjected to crosslinking treatment.

(Measurement of Cu content)
The sub-element (Cu) content in the Ag—Cu alloy thin film layer was determined as follows. That is, under each film forming condition, a test piece in which an Ag—Cu alloy thin film layer was separately formed on a glass substrate was prepared, and this test piece was immersed in a 6% HNO ₃ solution and eluted with ultrasonic waves for 20 minutes. Thereafter, the obtained sample solution was used for measurement by the concentration method of ICP analysis. The Cu content was 4 atomic%.

(Measurement of film thickness of thin film layer)
The film thickness of each thin film layer was measured from the cross-sectional observation of the test piece by the field emission electron microscope (HRTEM) (manufactured by JEOL Ltd., “JEM2001F”).

  About each light-transmitting laminated body, adhesiveness and heat insulation were evaluated. In addition, the durability, scuff resistance, and heat shielding properties in a humid heat environment were also evaluated.

(Adhesiveness of surface protective layer)
It measured based on JIS K5600-5-6. Apply the blade so as to be perpendicular to the surface of the OPP film on which the surface protective layer is formed, make 6 cuts at intervals of 2 mm, then change the direction by 90 degrees and make 6 cuts perpendicular to the previous cut. Were put at intervals of 2 mm to produce 25 squares. Thereafter, a tape was applied to the cut portion of the film lattice, and the tape was rubbed. Thereafter, the tape was peeled off at an angle close to 60 degrees, and the number of remaining cells was visually confirmed. Adhesiveness is particularly good when the number of remaining masses is 25, “◎”, when the number of remaining masses is 20 or more, adhesiveness is “good”, and when the number of remaining masses is less than 20, adhesion The property was judged as “x”.

(Adhesiveness of organic thin film (high refractive index thin film layer))
A test piece in which an organic thin film was formed on one side of the OPP film was used. An acrylic adhesive sheet (“5402” manufactured by Sekisui Chemical Co., Ltd.) having a thickness of 25 μm was attached to the surface of the organic thin film, and the adhesive face of this adhesive sheet was attached to one side of the plate glass. Using a tabletop tensile tester (“AGS-1kNG” manufactured by Minebeva), a 180 ° peel test (based on JIS A5759, tensile speed 300 mm / min) was performed at the interface between the organic thin film and the OPP film, and the peeling force was measured. This was defined as the adhesive strength between layers. At this time, the one having a tensile load of 8 N / 25 mm or more was “Good”, and the one having 4-7 N / 25 mm was “Δ”, and the one having less than 4 N / 25 mm was used. It was set as "x" where adhesiveness was inferior.

(Thermal insulation properties)
An acrylic adhesive sheet (“5402” manufactured by Sekisui Chemical Co., Ltd.) having a thickness of 25 μm is pasted on the surface of the second organic thin film of the light-transmitting laminate, and the adhesive surface of this adhesive sheet is pasted on one side of the plate glass. It was. Measurement light was incident from the OPP film side, the vertical emissivities of the glass surface and the film surface were determined in accordance with JIS R3106, and the thermal conductivity (W / m ² K) was determined in accordance with JIS A5759. A heat transmissivity of 5.0 W / m ² K or less is designated as “◯”, which is excellent in heat insulation, and a heat transmissivity of 4.5 W / m ² K or less is designated as “◎”, which is particularly excellent in heat insulation. m ² K or more was defined as “x” which is inferior in heat insulation.

(Durability (moisture and heat resistance))
The light transmissive laminate was subjected to 168H treatment in a wet heat test bath at 60 ° C. and 90% RH, and then measured according to JIS K5600-5-6. Apply the blade so as to be perpendicular to the surface of the organic thin film, make 6 cuts at 2 mm intervals, then change the direction by 90 degrees and insert 6 cuts perpendicular to the previous cut at 2 mm intervals. 25 masses were produced. Thereafter, a tape was applied to the cut portion of the film lattice, and the tape was rubbed. Thereafter, the tape was peeled off at an angle close to 60 degrees, and the number of remaining cells was visually confirmed. When the remaining mass number is 25 and the thin film layer is not visually cracked or discolored, the durability (moist heat resistance) is indicated as “◯”, and the remaining mass number is less than 25, or the thin film layer is observed to crack or discolor. The case where it was made into "x" inferior to durability (moisture heat resistance).

(Abrasion resistance)
Using steel wool (“Bon Star No. 0000” manufactured by Nippon Steel Co., Ltd.), steel wool was rubbed back and forth 10 times while applying a constant load (20 g / cm ² ) to the surface of the surface protective layer of the light transmissive laminate. In this case, the scratch resistance is particularly excellent when no scratches are visually observed. “Excellent” when the scratches having a length of 10 mm or less are observed in the number of 2 or less. “O” when scratches with a length of 10 mm or less are observed in the number of 3 or more and 5 or less “△” when scratches with a length exceeding 10 mm are observed, or 10 mm A case where scratches having the following length were observed in a number exceeding 5 was defined as a poor scratch resistance “x”.

(Heat insulation)
In accordance with JIS A5759, by using a spectrophotometer (“UV3100” manufactured by Shimadzu Corporation) to measure the transmission spectrum and reflection spectrum at a wavelength of 300 to 2500 nm, the solar transmittance and solar reflectance are calculated, and the solar transmittance is calculated. It was obtained by calculating the shielding coefficient from the solar reflectance and the modified emissivity. The corrected emissivity was calculated by calculating the vertical emissivity of the entire light-transmitting laminate in accordance with JIS R3106 and correcting it with the coefficient described in JIS A5759. When the shielding coefficient is 0.69 or less, the heat shielding property is “good”, and when the shielding coefficient exceeds 0.69, the heat shielding property is “poor”.

  In Comparative Examples 1 and 3, the surface protective layer is formed of an ultraviolet curable acrylic resin, the surface protective layer does not contain an inorganic component, and the surface protective layer has poor adhesion. In Comparative Example 2, the surface protective layer is formed of an organic-inorganic hybrid material, but the content of the inorganic component is as high as 50% by mass and is inferior in heat insulation. In Comparative Example 4, the surface protective layer is formed of an organic-inorganic hybrid material and the content of inorganic components is as low as 1.0% by mass, but the organic thin film constituting the high refractive index thin film layer contains a crosslinked polymer. The adhesion of the surface protective layer is poor. On the other hand, in each example, the surface protective layer is formed of an organic-inorganic hybrid material, and the content of the inorganic component is suppressed to as low as 1.0 to 30% by mass, and the organic material constituting the high refractive index thin film layer The thin film contains a cross-linked polymer, and both the adhesion and heat insulation of the surface protective layer are achieved. Further, in Examples 2 to 4, the content of the inorganic component is in the range of 2.0 to 10% by mass, and the adhesiveness and heat insulation of the surface protective layer are made higher than those in Examples 1 and 5. Both are compatible.

  Moreover, in each Example, the organic thin film which comprises the high refractive index thin film layer contains a crosslinked polymer, and compared with the comparative examples 3 and 4, durability in a humid heat environment is improving. In each of the examples, the surface protective layer is formed of an organic-inorganic hybrid material, and the scratch resistance is improved as compared with Comparative Examples 1 and 3. Moreover, from comparison of each Example, it is excellent in abrasion resistance, so that there is much content of the inorganic component in an organic inorganic hybrid material. Moreover, each Example has a metal thin film layer and is excellent in heat-shielding property.

  Although the embodiments and examples of the present invention have been described above, the present invention is not limited to the above-described embodiments and examples, and various modifications can be made without departing from the spirit of the present invention. .

DESCRIPTION OF SYMBOLS 10 Light transmissive laminated body 12 Light transmissive board | substrates 14 and 18 High refractive index thin film layer 16 Metal thin film layer 20 Surface protective layer

Claims (7)

It has a metal thin film layer, a high refractive index thin film layer having a refractive index higher than that of the metal thin film layer, a light transmissive substrate, and a surface protective layer in this order,
The light transmissive substrate is made of a polyolefin film,
The high refractive index thin film layer is composed of an organic thin film containing a non-crosslinked polymer having a functional group containing at least one element selected from N, O, and S and a crosslinked polymer,
The said surface protective layer consists of organic-inorganic hybrid material, and content of the inorganic component in the said surface protective layer exists in the range of 1.0-30 mass%, The light-transmitting laminated body characterized by the above-mentioned.   The light transmissive laminate according to claim 1, wherein the non-crosslinked polymer is a polymer having a triazine ring.   The light-transmitting laminate according to claim 1, wherein the crosslinked polymer is a polyfunctional acrylate polymer or a polyfunctional methacrylate polymer.   4. The light transmissive laminate according to claim 1, wherein the content of the inorganic component in the surface protective layer is in the range of 2.0 to 10 mass%.   The light transmissive laminate according to any one of claims 1 to 4, wherein the polyolefin film is a biaxially stretched polypropylene film.   The thickness of the said polyolefin film exists in the range of 10-100 micrometers, The light transmissive laminated body of any one of Claim 1 to 5 characterized by the above-mentioned.   The light transmissive laminate according to claim 1, wherein the metal thin film layer is made of silver or a silver alloy.

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