JP2015217515A - Heat ray shielding film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat ray shielding film which is excellent in heat ray shielding performance, visible light transmission performance, and metal glossiness.SOLUTION: A heat ray shielding film 1 to be arranged on a window plate 5 has: a substrate film 3 composed of a transparent resin having a multilayer structure; and a layer 4 arranged on at least one surface of the substrate film and containing heat ray absorbing metal compound fine particles. In the heat ray shielding film 1, thickness per layer of the multilayer structure is 50-1,000 nm, the number of layers of the multilayer structure is 200-1,400, the heat ray absorbing metal compound is a metal or a metal oxide, the average particle diameter of the heat ray absorbing metal compound fine particles is 10-100 nm, the heat ray shielding coefficient is 0.70 or less, the visible light reflectance is 10% or more, and the visible light transmittance is 55% or more.

Description

  The present invention relates to a heat ray shielding film.

  2. Description of the Related Art Conventionally, development of a transparent film having a heat ray shielding performance has been promoted as one of energy saving measures for buildings, buildings, etc., and transportation such as trains and passenger cars. As one of the methods for that purpose, a transparent film for window plates in which a metal layer such as aluminum is uniformly deposited on a transparent film or the like has been developed.

  The metal vapor deposition film is intended to shield the heat rays by reflection, but also reflects visible light, so it has a metallic luster, but has low visible light transmittance and keeps the interior bright. It was an obstacle.

  On the other hand, there has been a demand for a transparent film for a window plate that can be installed on a window plate to give a metallic luster and enhance the decorativeness when viewed from the outside.

  Many developments have been made for transparent films for window plates. Patent Document 1 discloses a window film having a light reflection layer made of a metal vapor deposition layer or the like and an infrared absorption layer containing an infrared absorber. Patent Document 2 discloses a near infrared ray absorbing composition containing a heat ray shielding powder whose surface is coated with siliceous material.

Japanese Patent Laid-Open No. 9-249859 JP 2008-297414 A

  However, since the window film of Patent Document 1 has a metal vapor deposition layer and the like, it has a low visible light transmittance. Moreover, although the near-infrared absorption composition of patent document 2 was excellent in heat ray shielding performance and solar radiation shielding performance, it was inferior to metallic luster.

  This invention is made | formed in view of such a condition, and it makes it a subject to provide the heat ray shielding film which was excellent in the shielding performance of a heat ray and the permeation | transmission performance of visible light, and had a metallic luster feeling.

  Therefore, the present inventor has proceeded with a study on a method for imparting a metallic luster feeling without depending on a metal layer such as a metal vapor deposition layer. Conventionally, a film having a structure in which several tens to several hundreds of nm-order thin layer films are laminated can reflect light of various wavelengths at the interface of each layer, and thus has an appearance close to metallic luster. It is known. For example, Japanese Unexamined Patent Application Publication No. 2007-307893 discloses a specific example of a multilayer film having a metallic luster.

  However, such a multilayer film has a function of reflecting a part of visible light, but does not have a function of shielding heat rays. Thus, the present invention has been achieved as a result of repeated studies on a method for shielding the heat rays and not reducing the visible light transmittance while taking advantage of the characteristics of the multilayer film. That is, the present invention has the following configuration.

(1) The heat ray shielding film of the present invention is a heat ray shielding film installed on a window plate, and is provided on at least one surface of a base film made of a transparent resin having a multilayer structure and the base film. A layer containing heat ray absorbing metal compound fine particles, the multilayer structure has a thickness of 50 to 1000 nm per layer, the number of layers of the multilayer structure is 200 to 1400, and the heat ray absorbing metal The compound is a metal or a metal oxide, the heat ray absorbing metal compound fine particles have an average particle size of 10 to 100 nm, a heat ray shielding coefficient of 0.70 or less, and a visible light reflectance of 10% or more, It is a heat ray shielding film characterized by having a visible light transmittance of 55% or more.

(2) The heat ray shielding film of the present invention preferably has a heat transmissivity of less than 5.9.

(3) The heat ray shielding film of the present invention preferably has a solar radiation absorption rate of 40% or less.

(4) The heat ray shielding film of the present invention preferably has an electromagnetic wave shielding rate of 10 dB or less.

  The heat ray shielding film of the present invention is excellent in heat ray shielding performance and visible light transmission performance, and has a metallic luster.

It is typical sectional drawing which shows the layer structure of the heat ray shielding film of 1st Embodiment. It is typical sectional drawing which shows the layer structure of the heat ray shielding film of 2nd Embodiment. It is typical sectional drawing which shows the layer structure of the heat ray shielding film of a comparative example. It is typical sectional drawing which shows the layer structure of the heat ray shielding film of 3rd Embodiment. It is a spectrum figure of the transmittance | permeability and the reflectance of the heat ray shielding film of 1st Embodiment and 2nd Embodiment. It is a spectrum figure of the transmittance | permeability of the heat ray shielding film of a comparative example, and a reflectance.

  The heat ray shielding film of the present embodiment is installed on a window plate, a base film made of a transparent resin having a multilayer structure, and heat ray absorbing metal compound fine particles provided on at least one surface of the base film And a layer containing. A layer containing heat ray absorbing metal compound fine particles (hereinafter referred to as “heat ray absorbing layer”) functions as a layer that shields heat rays. Furthermore, the heat ray shielding film of this embodiment may have an adhesive layer on the window plate side in order to be installed on the window plate, and in order to prevent the surface from being damaged by external force, May have a hard coat layer. Moreover, the heat ray shielding film of this embodiment can be sandwiched between two transparent glass plates or resin plates to form a window plate.

(Electromagnetic wave, visible light, near infrared, far infrared, ultraviolet)
In the present embodiment, the electromagnetic wave refers to an electromagnetic wave having a wavelength of 10 mm to 10 km and a frequency of about 30 KHz to 30 GHz. The electromagnetic wave region is used for radio broadcasting, television broadcasting, wireless communication, cellular phone, satellite communication, and the like.
In the present embodiment, visible light means light that can be recognized with the naked eye among electromagnetic waves, and generally refers to electromagnetic waves having a wavelength of 380 to 780 nm. Near-infrared light is an electromagnetic wave having a wavelength of approximately 800 to 2500 nm and has a wavelength close to red visible light. Near-infrared rays are contained in sunlight and act to heat an object. On the other hand, far-infrared rays are electromagnetic waves having a wavelength of about 5 to 20 μm (5000 to 20000 nm), are not included in sunlight, and have a wavelength close to that emitted from an object near room temperature. Ultraviolet rays are electromagnetic waves having a wavelength of about 10 to 380 nm.
In the present embodiment, the heat ray means near infrared rays.

  Hereinafter, embodiments of the present invention will be described with reference to specific embodiments. However, embodiments of the present invention are not limited to the following embodiments.

[Heat ray shielding film of the first embodiment]
FIG. 1 is a schematic cross-sectional view showing the layer structure of the heat ray shielding film of the first embodiment.
In the heat ray shielding film 1 of 1st Embodiment, the heat ray absorption layer 4 is formed in the room inner side of the base film 3 which consists of transparent resin which has a multilayer structure. On the other hand, an adhesive layer 2 is formed on the outdoor side of the base film 3. The heat ray shielding film 1 is bonded by the window plate 5 and the adhesive layer 2. As a whole, a heat ray shielding window plate 20 (Configuration No. 20) is configured.
Hereinafter, each layer and the window plate 5 constituting the heat ray shielding film 1 of the first embodiment will be described in detail.

(Window plate 5)
In the first embodiment, the window plate 5 is a transparent plate for taking sunlight from the outside into a building, a transportation vehicle, a ship, or the like. In general, a transparent glass plate or a transparent resin plate is used as the window plate 5. As the transparent resin, various resins such as acrylic, styrene, hydrogenated cyclic resin, polycarbonate, and polyester can be used.

(Base film 3)
The base film 3 is a base material for maintaining the form as the heat ray shielding film 1, and has a function of holding the heat ray absorbing layer 4, the adhesive layer 2, and the like. Therefore, it is preferable that the base film 3 is excellent in mechanical strength, visible light transmittance, workability, and the like. The base film 3 is made of a transparent resin having a multilayer structure. By having a multilayer structure, the heat ray shielding film 1 is given a metallic luster.

  Although the base film 3 depends on the mechanical properties of the transparent resin and the like, the thickness is preferably 8 to 800 μm. More preferably, it is 12-400 micrometers.

  The base film 3 can reflect visible light irradiated from the outside in a wide wavelength region. Therefore, the base film 3 has the same metallic luster as a film having aluminum or silver deposited on the surface.

  In order to design a film that can satisfy both of the three functions of heat ray shielding performance, visible light transmission performance, and metallic luster, the present inventor has developed a transparent resin having a multilayer structure with metallic luster. The material film 3 was used as the base film.

  The base film 3 having a multilayer structure can be formed by a method using a multilayer film, a method using a liquid crystal resin coating, or the like, but a method using a multilayer film is preferable because it is easily mass-produced and has stable performance.

The multilayer film is preferably a film having a structure in which the same type of polymers having different refractive indexes or different types of polymers having different refractive indexes are alternately laminated. The thickness per layer of the multilayer structure can be adjusted by changing the extrusion thickness and the stretching ratio at the time of co-extrusion.
A method for producing a multilayer film having such a structure is described in, for example, JP-T 9-506837, JP-A 2007-307893, JP-A 2008-273186, JP-A 2013-209246, and the like. Yes.

  The base film 3 has a high reflectance in the wavelength region of visible light when the thickness per layer of the multilayer structure is 50 to 1000 nm. When the substrate film 3 is irradiated with visible light, the visible light is usually reflected at each interface of the multilayer structure having a different refractive index. In a multilayer structure, reflection occurs from the interface of each layer, and in order to increase the reflectance by shifting the phase of each reflected light, it is effective that the thickness per layer of the multilayer structure is in the above range. is there. The thickness per layer of the multilayer structure is preferably 70 to 300 nm.

  Moreover, since the multilayer structure of the base film 3 reflects visible light in a wide wavelength region, the number of layers is 200 to 1400. The number of layers is more preferably 220 to 1200. When the number of layers in the multilayer structure exceeds 1400 layers, the reflection of visible light becomes non-uniform and the reflected color becomes strong. On the other hand, when it is less than 200 layers, the reflectance of visible light is low, and the metallic gloss is inferior.

  The refractive index of the transparent resin constituting the base film 3 is preferably 1.40 to 2.00 from the viewpoint of optical design. Furthermore, the transparent resin constituting the multilayer structure is preferable in that the number of layers can be reduced by having alternately different refractive indexes. At this time, the difference in refractive index between the two is preferably 0.03 to 0.3 in terms of optical design. Here, the refractive index can be measured using an ellipsometry method.

  Specifically, as the resin constituting the base film 3, various resins such as acrylic, polycarbonate, styrene, polyester, polyolefin, hydrogenated cyclic resin, fluorine, silicone, and urethane are used. it can. Among these, from the viewpoint of interlayer strength and durability, resins such as acrylic, polycarbonate, styrene, and polyester can be used. Furthermore, from the viewpoint of the above-mentioned refractive index and the like, polyester resins such as PET, PBT, and PEN, and acrylic resins are preferable.

(Heat ray absorbing layer 4)
In the heat ray shielding film 1 of 1st Embodiment, in order to provide heat ray shielding performance, it has the heat ray absorption layer 4. FIG.

The heat ray absorbing metal compound is a metal or metal oxide having a maximum absorption wavelength peak at 800 to 2500 nm. Specific examples of heat-absorbing metal compounds include metals such as tin, silver, silver palladium alloy, gold, aluminum, cesium-containing tungsten oxide (CsWO ₃ ), antimony-containing tin oxide (ATO), tin-containing indium oxide (ITO ) And metal oxides such as gallium-containing zinc oxide (GZO).

  In these, since the metal compound excellent in electroconductivity is more excellent in heat ray absorption performance, it is preferable. Specifically, it is preferably at least one selected from tin-containing indium oxide, tin, silver, silver palladium alloy, gold, aluminum, and the like. Furthermore, tin-containing indium oxide having excellent conductivity is particularly preferable. These heat ray absorbing metal compounds may be used alone, may be used by mixing different kinds of metal compounds, or may be used by adding a trace amount of different kinds of metals.

  The resin constituting the heat ray absorbing layer 4 is not particularly limited. Specifically, various resins such as acrylic, polycarbonate, styrene, polyester, polyolefin, hydrogenated cyclic resin, fluorine, silicone, and urethane can be used. The heat-absorbing metal compound fine particles need to be uniformly dispersed in the resin.

  In the first embodiment of FIG. 1, the heat ray absorbing metal compound fine particles are added to the resin forming the hard coat layer, and the heat ray absorbing layer 4 also serves as the hard coat layer.

The average particle diameter of the heat ray absorbing metal compound is 10 to 100 nm. If it is less than 10 nm, aggregation tends to occur and the processability is poor. On the other hand, if it exceeds 100 nm, the diffusion of light increases, which is not preferable in terms of optical characteristics.
Moreover, in order to disperse | distribute microparticles | fine-particles uniformly in resin, the surface of a heat ray absorptive metal compound particle can be processed, or a dispersing agent etc. can be added suitably.
Here, the average particle size can be measured by a laser diffraction / scattering particle size distribution measuring device or the like.

  It is preferable that content of a heat ray absorptive metal compound is 5-40 mass% with respect to resin which comprises the heat ray absorption layer 4. FIG. If it is less than 5% by mass, it is necessary to increase the thickness of the resin layer, and the handling property is lowered. On the other hand, if it exceeds 40% by mass, mechanical properties such as wear resistance are lowered, and the electromagnetic wave shielding rate is increased.

  The heat ray absorbing layer 4 can be disposed on the indoor side, the outdoor side, or on either side of the base film 3. However, it is preferable to install it indoors because far-infrared reflection increases and the heat transmissivity improves.

(Adhesive layer 2)
In 1st Embodiment, in order to adhere | attach the window plate 5 and the base film 3, the contact bonding layer 2 is provided. The adhesive layer 2 preferably changes the type of adhesive depending on the object to be bonded.
In the first embodiment, the adhesive layer 2 adheres the window plate 5 and the base film 3. For example, when the purchaser of the heat ray shielding film product installs the heat ray shielding film 1 on the window plate 5 by itself, it is an adhesive layer used to bring the heat ray shielding film 1 and the window plate 5 into close contact with each other. Therefore, it is preferable to have a certain degree of adhesiveness even at room temperature. A release sheet is affixed to the adhesive layer as necessary for improving the handleability. When installing on the window plate 5, the release sheet is peeled off, and then the adhesive layer 2 is brought into close contact with the window plate 5.

  As an adhesive used in such a method of use, a pressure-sensitive adhesive generally used for glass attachment can be used. Examples of the adhesive include acrylic, silicone, urethane, butadiene, and natural rubber. Among these, acrylic and silicone are preferable from the viewpoint of durability. The thickness of the adhesive layer 2 is preferably 5 to 50 μm.

(Hard coat layer)
In order to prevent the surface of the heat ray shielding film 1 from being damaged by the external force or from being damaged, a hard coat layer can be provided as the outermost layer.
As a material used for the hard coat layer, generally, an inorganic material, an organic material, an organic inorganic material, a silicone material, or the like can be used. Among these, an ultraviolet curable acrylic resin is preferable. The thickness of the hard coat layer is preferably 0.5 to 20 μm.

  As described above, in the first embodiment of FIG. 1, the heat ray absorbing metal compound fine particles are added to the resin forming the hard coat layer, and the heat ray absorbing layer 4 also serves as the hard coat layer.

[Modification of First Embodiment]
The heat ray absorbing layer 4 may be provided with a unique layer, but the heat ray absorbing metal compound fine particles may be contained not only in the hard coat layer but also in a layer having other functions. For example, although the adhesive layer 2 exists for bonding with the window plate 5, it can be contained in the adhesive layer 2. If there is no problem in production, it can be contained in the base film 3.

  The heat ray shielding film 1 can also be installed outside the window plate 5. In this case, in FIG. 1, the description of “indoor” is replaced with “outdoor”, and the description of “outdoor” is replaced with “indoor”.

[Performance of the heat ray shielding film of the first embodiment]
Hereinafter, various performances of the heat ray shielding film 1 of the first embodiment will be described.

(Heat shielding coefficient)
In order to quantify and evaluate the heat ray shielding performance of the heat ray shielding film 1 of the first embodiment, an index called a heat ray shielding coefficient is used. The heat ray shielding coefficient is measured using a spectrophotometer according to JIS A5759. The heat ray shielding coefficient is obtained by setting the Ni value to 0.34.
The heat ray shielding coefficient of the heat ray shielding film 1 of 1st Embodiment is 0.70 or less. More preferably, it is 0.60 or less.
The numerical value of the heat ray shielding coefficient can be adjusted by the type, particle size, content, and the like of the heat ray absorbing metal compound of the heat ray absorbing layer 4.

(Visible light transmittance)
The heat ray shielding film 1 of 1st Embodiment permeate | transmits visible light with a wavelength of 380-780 nm. The visible light transmittance of the heat ray shielding film 1 is 55% or more. 60% or more is more preferable. The visible light transmittance can be measured using an infrared reflection measuring instrument in accordance with JIS A5759. The numerical value of the visible light transmittance can be adjusted by the type, particle size, content, and the like of the heat ray absorbing metal compound of the heat ray absorbing layer 4 described above, the material and the layer structure of the base film 3 and the like.

(Visible light reflectance)
The heat ray shielding film 1 of the first embodiment has a visible light reflectance of 10% or more. When the visible light reflectance is less than 10%, the metallic luster is reduced, and the decorativeness when viewed from the outside is lowered. The visible light reflectance is more preferably 20% or more. The visible light reflectance can be measured using an infrared reflection measuring instrument in accordance with JIS A5759 and JIS R3106. The numerical value of the visible light reflectance can be adjusted by the material, the layer configuration, and the like of the base film 3 described above.

(Solar radiation transmittance)
The heat ray shielding film 1 of the first embodiment suppresses transmission of visible light and near infrared light in a wavelength range of 300 to 2500 nm. The solar radiation transmittance of the heat ray shielding film 1 is preferably 70% or less. When the solar transmittance is 70% or less, the heat shielding performance is excellent. 60% or less is more preferable. The solar radiation transmittance can be measured using an infrared reflection measuring instrument in accordance with JIS A5759. The numerical value of the solar radiation transmittance can be adjusted by the material of the base film 3 described above, the layer configuration, the type of heat-absorbing metal compound, the particle size, the content, and the like.

(Solar reflectance)
The heat ray shielding film 1 of the first embodiment preferably has a solar reflectance of 10% or more. When the solar reflectance is 10% or more, the heat shielding performance is excellent. The solar reflectance is more preferably 13% or more. The solar reflectance can be measured using an infrared reflection measuring instrument in accordance with JIS A5759. The numerical value of solar radiation reflectance can be adjusted by the raw material of the base film 3, a layer structure, the kind of heat-absorbing metal compound, a particle size, content, etc. similarly to the case of the above-mentioned solar radiation transmittance.

(Solar radiation absorption rate)
The heat ray shielding film 1 of the first embodiment preferably has a solar radiation absorption rate of 40% or less. When the solar radiation absorptivity is 40% or less, the temperature of the heat ray shielding film 1 is prevented from rising and the performance is deteriorated, and the harmful effect of damaging the window plate 5 is also suppressed. The solar radiation absorption rate is more preferably 30% or less. The solar absorptance can be measured using an infrared reflection measuring instrument in accordance with JIS A5759. The numerical value of solar radiation absorptivity can be adjusted by the raw material of the base film 3, a layer structure, the kind of heat ray absorptive metal compound, a particle size, content, etc. similarly to the case of solar radiation transmittance mentioned above.
Note that the sum of the values of solar transmittance, solar reflectance, and solar absorption rate is 100%.

(Heat flow rate)
In order to quantify and evaluate the reflection efficiency of far-infrared rays by the heat ray shielding film 1 of the present embodiment, an index called heat transmissivity is used. The heat transmissivity can be measured using an infrared reflection measuring instrument in accordance with JIS A5759.
It is preferable that the heat transmissivity is less than 5.9. The heat transmissivity generally correlates to some extent with the surface resistance value of the metal compound constituting the heat ray absorbing layer 4.

(Electromagnetic wave shielding rate)
The heat ray shielding film 1 of the present embodiment uses an index called an electromagnetic wave shielding rate in order to quantify and evaluate the electromagnetic wave transmission performance. As an evaluation method, the KEC method was adopted. The measurement range of electromagnetic waves is 30 MHz to 1 GHz. For the electromagnetic wave shielding rate, a numerical value (dB) at a frequency of 800 MHz is used.
The electromagnetic wave shielding rate is preferably 10 dB or less. When the electromagnetic wave shielding rate is 10 dB or less, troubles are unlikely to occur when using a mobile phone or a mobile TV indoors or in a car. The electromagnetic wave shielding rate is more preferably 5 dB or less, and further preferably 3 dB or less.
The numerical value of the electromagnetic wave shielding rate can be adjusted by the kind, particle size, content, etc. of the heat ray absorbing metal compound described above.

[Effect of the heat ray shielding film of the first embodiment]
In the heat ray shielding film 1 of the first embodiment, since the base film 3 made of a transparent resin having a multilayer structure is present on the side close to the window plate 5, when viewed from the outside, the window plate 5 has a metallic luster. Can be granted. On the other hand, since the heat ray absorbing layer 4 also serving as a hard coat layer is present on the indoor side of the base film 3, the heat ray that has passed through the base film can be absorbed and reflected to shield the heat ray. it can. Moreover, since the heat ray shielding film 1 permeate | transmits the visible ray irradiated from the outdoors to some extent, it can keep indoors bright.
Moreover, since the heat ray shielding film 1 permeate | transmits electromagnetic waves, a mobile phone, a portable television, etc. can be used indoors.
Moreover, since the heat ray shielding film 1 of 1st Embodiment is installed in the indoor side of the window board 5, it can reduce deterioration by rain wind etc.

  As described above, the heat ray shielding film 1 of the first embodiment has a heat ray shielding performance, a visible light transmission performance, a metal, due to the combined effect of the base film 3 made of a transparent resin having a multilayer structure and the heat ray absorbing layer 4. The gloss is well balanced.

[Method for Manufacturing Heat-ray Shielding Film of First Embodiment]
The heat ray shielding film 1 of 1st Embodiment can be manufactured by forming each layer which comprises the heat ray shielding film 1 on the base film 3 one by one. A representative example of the manufacturing method for forming each layer will be described below.

  A method for forming the heat ray absorbing layer 4 will be described. First, a predetermined amount of metal compound fine particles of a predetermined type and a predetermined particle diameter are taken and added to a resin and its solvent to prepare a mixed solution. At this time, if necessary, a functional group can be attached to the surface of the metal compound fine particles, a coupling agent can be added, or a dispersant can be added.

  Next, the concentration and the like are adjusted to obtain a solution having an appropriate viscosity. The solution is coated on the base film 3 or the like. Thereafter, the heat ray absorbing layer 4 can be formed by drying.

  A method for forming the adhesive layer 2 will be described. An appropriate amount of the adhesive polymer is mixed with a solvent to prepare a solution having an appropriate viscosity. The solution is coated on the base film 3. Then, the adhesive layer 2 can be formed by drying.

  A method for forming the hard coat layer will be described. An appropriate amount of a thermosetting resin or a photocurable resin is mixed in a solvent to prepare a solution having an appropriate viscosity. The solution is coated on the base film 3 or the like. After drying, a hard coat layer can be formed by performing a curing reaction using heat or light.

[Heat ray shielding film of second embodiment]
FIG. 2 is a schematic cross-sectional view showing the layer structure of the heat ray shielding film of the second embodiment.
In the heat ray shielding film 8 of the second embodiment, a heat ray absorbing layer 6 also serving as a primer layer is formed on the outdoor side of the base film 3 made of a transparent resin having a multilayer structure. Furthermore, the adhesive layer 2 is formed on the outdoor side of the heat ray absorbing layer 6 of the base film 3. The heat ray shielding film 8 is bonded by the window plate 5 and the adhesive layer 2. As a whole, a heat ray shielding window plate 30 (Configuration No. 30) is configured.
Hereinafter, although each layer which comprises the heat ray shielding film 1 of 2nd Embodiment is demonstrated, since it is the same as that of 1st Embodiment about many layers, only the content which is not demonstrated in 1st Embodiment below is shown below. explain.

  In the second embodiment of FIG. 2, the heat-absorbing metal compound fine particles are added to the resin forming the primer layer, and the heat-ray absorbing layer 6 also serves as the primer layer.

(Primer layer)
In order to enhance the adhesion between the base film 3 and the adhesive layer 2, a primer layer can be provided on the surface of the base film 3. As a material constituting the primer layer, an ultraviolet curable acrylic resin containing a silane coupling agent or a titanium coupling agent, a thermosetting acrylic resin or a urethane resin, a thermoplastic acrylic resin or a polyester resin, etc. Can be mentioned.

  In the heat ray shielding film 8 of 2nd Embodiment, since the heat ray absorption layer 4 exists in an outdoor side with respect to the base film 3, the solar radiation reflectance falls a little and the solar radiation absorption factor has increased a little.

  Since other modifications, performance, manufacturing method, and effects of the heat ray shielding film 8 of the second embodiment are the same as those of the first embodiment, description thereof is omitted.

[Thermal ray shielding film of the third embodiment]
FIG. 4 is a schematic cross-sectional view showing the layer structure of the heat ray shielding film of the third embodiment.
The heat ray shielding film 10 of 3rd Embodiment has the structure pinched | interposed by the window board 5 from both sides, and comprises what is called a laminated glass. The heat ray shielding film 10 was obtained by further forming the adhesive layer 2 on the heat ray absorbing layer 4 of the heat ray shielding film 1 of the first embodiment. It is bonded to the second window plate 5 by the newly provided adhesive layer 2. As a whole, a heat ray shielding window plate 50 (Configuration No. 50) is configured.

When the laminated glass is constituted using the adhesive layer 2, the laminated glass can be provided with excellent penetration resistance, impact resistance, and scattering prevention effects.
Hereinafter, although each layer which comprises the heat ray shielding film 10 of 3rd Embodiment is demonstrated, since many layers are the same as that of 1st Embodiment, only the content which is not demonstrated in 1st Embodiment below is shown below. explain.

(Adhesive layer 2)
In 3rd Embodiment, in order to adhere | attach the window plate 5 and the base film 3, or in order to bond the window plate 5 and the heat ray absorption layer 4, the two-layer contact bonding layer 2 is provided. The adhesive layer 2 is not particularly limited as long as it is a resin film that is generally used as an intermediate film of laminated glass, but preferably has no absorption in the visible light region or the infrared region.

  For example, the adhesive layer 2 used in the third embodiment is applied or laminated on the base film 3 or the like as a non-adhesive adhesive at room temperature, and after laminating each material constituting the heat ray shielding window plate 50, for example. The adhesive layer exhibits adhesiveness and adhesiveness by heat treatment, and allows adhesion between the layers.

For example, when a so-called laminated glass is manufactured using two glass plates as the material of the window plate 5, as a material used for the adhesive layer 2, specifically, a polyvinyl butyral resin (PVB resin) ) And the like, and ethylene-vinyl acetate copolymer resins (EVA resins).
In the adhesive layer 2, these resins may be used alone or in combination of two or more.
The adhesive layer 2 may be manufactured using a known method, but a commercially available product may be used. Examples of commercially available products include plasticized PVB manufactured by Sekisui Chemical Co., Ltd. and Mitsubishi Plastics, EVA resin manufactured by DuPont and Takeda Pharmaceutical, and modified EVA resin manufactured by Tosoh.
The thickness of the adhesive layer 2 is preferably 100 to 1000 μm.

  In the adhesive forming the adhesive layer 2, an ultraviolet absorber, an antioxidant, an antistatic agent, a heat stabilizer, a lubricant, a filler, a colorant, an adhesion adjusting agent and the like may be appropriately added and blended.

  It does not restrict | limit especially as a method of producing the heat ray shielding window board 50 of 3rd Embodiment, What is necessary is just to use the manufacturing method of a general laminated glass. Specifically, the heat ray shielding film 10 having the adhesive layer 2 is laminated between two glass plates and pre-adhered, and the bubbles remaining after the pre-adhesion are removed by pressure bonding at high temperature and high pressure. can do.

  The heat ray shielding film 10 of the third embodiment can be used as a window plate sandwiched between two transparent glass plates or resin plates. Since the heat ray shielding film 10 of 3rd Embodiment is the structure pinched | interposed by the two window boards 5, even if which side becomes an outdoor side, deterioration by rain wind etc. can be reduced.

  Since the other modifications, performance, manufacturing method, and effects of the heat ray shielding film 10 of the third embodiment are the same as those of the first embodiment, description thereof is omitted.

[Heat shielding film of comparative example]
FIG. 3 is a schematic cross-sectional view showing a layer structure of a heat ray shielding film of a comparative example.
The heat ray shielding film 9 of the comparative example does not have a multilayer structure, and an aluminum vapor deposition layer 7 is formed on the outdoor side of the base film 3 made of one layer of transparent resin. Further, an adhesive layer 2 is formed on the outdoor side of the aluminum vapor deposition layer 7. On the other hand, as in the first embodiment, a heat ray absorbing layer 4 that also serves as a hard coat layer is formed on the indoor side of the base film 3. The heat ray shielding film 9 is bonded by the window plate 5 and the adhesive layer 2. As a whole, a heat ray shielding window plate 40 (Configuration No. 40) is configured.

  The heat ray shielding film 9 has an aluminum vapor deposition layer 7 instead of having a film made of a transparent resin having a multilayer structure, so that the metallic luster is strong but the visible light transmittance is inferior. .

  This embodiment will be described more specifically with reference to the following examples.

(Multilayer film)
Some multilayer films as a transparent resin layer having a multilayer structure used in the present invention are commercially available, and they were obtained and used for experiments. As a laminated film in which 1000 layers are alternately laminated in the thickness direction, there are Picasas GL-30 and GT-30 manufactured by Toray Industries, Inc. These have a thickness of 100 μm as a multilayer film, and the average thickness per layer of the multilayer structure is 100 nm. The optical characteristics are controlled by adjusting the refractive index of the resin. Hereinafter, it is referred to as “multilayer film”.

(Heat ray shielding film F1)
A solution was prepared by dispersing 18.5% by mass of CsWO ₃ fine particles having an average particle diameter of 20 nm in methyl isobutyl ketone (MIBK). Was added to this dispersion composition A having the following composition, to prepare a solution containing CSWO _3. The obtained solution was coated on one surface of the multilayer film GL-30 using a bar coater, and dried in a hot air oven at 100 ° C. for 2 minutes. Thereafter, the coated surface was cured by irradiating with ultraviolet rays (integrated light amount 300 mJ / cm ² ) with a high-pressure mercury lamp, and a hard coat layer containing metal compound fine particles having a thickness of about 4 μm was formed as a heat ray absorbing layer. The content of CsWO ₃ fine particles in the formed hard coat layer was 7% by mass.

  On the other hand, a composition B having the following formulation was coated on a silicone-treated separator (Mitsubishi Plastics, MRQ # 38, 38 μm thickness, hereinafter referred to as “separator”) using an applicator. Then, it was dried in a hot air oven at 100 ° C. for 2 minutes to form an adhesive layer having a thickness of about 22 μm.

<Composition A>
Dipentaerythritol polyacrylate-based ultraviolet curable resin (Arakawa Chemical Co., Ltd., Beam Set 700) 83.3 parts by mass Photopolymerization initiator (BASF, Irgacure 184) 1 part by mass Toluene Predetermined amount Heat-absorbing metal compound fine particle dispersion Liquid Specified amount

<Composition B>
Acrylic neutral pressure-sensitive adhesive (manufactured by Soken Chemical Co., Ltd., SK Dyne 2975) 100 parts by mass Curing agent (manufactured by Soken Chemical Co., Ltd., Y-75) 0.2 parts by mass Triazine UV absorber (manufactured by BASF, Tinuvin 477) 3 parts by mass Parts 100 parts by mass of toluene

  Furthermore, the said adhesive layer was laminated with the surface on the opposite side to the side in which the heat ray absorption layer of the said multilayer film GL-30 was formed, and the heat ray shielding film F1 was produced. After leaving for 7 days, the separator was peeled off, and the adhesive layer was bonded to a 3 mm thick alkali glass plate (hereinafter referred to as “glass plate”), and various performances were evaluated.

  Hereinafter, the heat ray shielding film F2 to the heat ray shielding film F14 were produced in the same manner as the heat ray shielding film F1, except that the heat ray absorbing metal compound fine particles were changed to those shown in Table 1. Specifically, it is as follows.

(Heat ray shielding film F2)
A solution was prepared by dispersing 25% by mass of GZO fine particles having an average particle diameter of 30 nm in methyl isobutyl ketone (MIBK). Using this dispersion, a layer containing GZO fine particles having a thickness of 5 μm was formed as a heat ray absorbing layer on one surface of the multilayer film GL-30 in the same manner as in the case of the heat ray shielding film F1. The content of the GZO fine particles in this layer was 50% by mass.

(Heat ray shielding film F3)
A solution was prepared by dispersing 20% by mass of ITO fine particles having an average particle diameter of 20 nm in toluene. Using this dispersion, as in the case of the heat ray shielding film F1, a layer containing ITO fine particles having a thickness of 5 μm was formed as a heat ray absorbing layer on one surface of the multilayer film GL-30. The content of ITO fine particles in this layer was 17% by mass.

(Heat ray shielding film F4)
A solution in which 20% by mass of ITO fine particles having an average particle diameter of 20 nm were dispersed in toluene and a solution in which 18.5% by mass of CsWO ₃ fine particles having an average particle diameter of 20 nm were dispersed in methyl isobutyl ketone (MIBK) were prepared. These dispersions are mixed and used in the same manner as in the case of the heat ray shielding film F1, and contain 2 μm thick ITO fine particles and CsWO ₃ fine particles as a heat ray absorbing layer on one surface of the multilayer film GL-30. A layer was formed. The content of ITO fine particles in this layer was 35% by mass, and the content of CsWO ₃ fine particles was 13% by mass.

(Heat ray shielding film F5)
A solution was prepared in which 20% by mass of ITO fine particles having an average particle diameter of 20 nm were dispersed in toluene. Using this dispersion, as in the case of the heat ray shielding film F1, a layer containing ITO fine particles having a thickness of 2 μm was formed as a heat ray absorbing layer on one surface of the multilayer film GL-30. The content of the ITO fine particles in this layer was 70% by mass.

(Heat ray shielding film F6)
A heat ray shielding film F6 was produced in the same manner as the heat ray shielding film F5 except that the multilayer film GT-30 was used instead of the multilayer film GL-30. The film thickness of the heat ray absorbing layer was 2 μm, and the content of ITO fine particles in this layer was 70% by mass.

(Heat ray shielding film F7)
A solution was prepared by dispersing 20% by mass of ITO fine particles having an average particle diameter of 20 nm in toluene. This dispersion was added to the composition C having the following composition to prepare a solution containing ITO. As in the case of the heat ray shielding film F1, a primer layer containing ITO fine particles having a thickness of 2 μm was formed as a heat ray absorbing layer on one surface of the multilayer film GL-30. The content of the ITO fine particles in the primer layer was 70% by mass.

<Composition C>
The following silane coupling agent was added to the composition A.
1 part by mass of N-phenyl-3-aminopropyltrimethoxysilane (KBM-573 manufactured by Shin-Etsu Silicone)

(Heat ray shielding film F8)
A heat ray shielding film F7 was produced in the same manner as the heat ray shielding film F1 except that a hard coat layer containing metal compound fine particles was not formed.

(Heat ray shielding film F9)
A heat ray shielding film F9 was produced in the same manner as the heat ray shielding film F8, except that the multilayer film GT-30 was used instead of the multilayer film GL-30.

(Heat ray shielding film F10)
Other than using an easy-adhesive PET film (U40, 100 μm thickness, hereinafter referred to as “PET film”) instead of the multilayer film GL-30, and not including metal compound fine particles in the hard coat layer. Were produced in the same manner as the heat ray shielding film F1 to produce a heat ray shielding film F10.

(Heat ray shielding film F11)
A heat ray shielding film F11 was prepared in the same manner as the heat ray shielding film F1, except that a PET film was used instead of the multilayer film GL-30, and the film thickness of the hard coat layer containing metal compound fine particles was 5 μm. Was made.

(Heat ray shielding film F12)
A heat ray shielding film F12 was prepared in the same manner as the heat ray shielding film F2, except that a PET film was used instead of the multilayer film GL-30, and the film thickness of the hard coat layer containing the metal compound fine particles was 2 μm. Was made.

(Heat ray shielding film F13)
Except having used PET film instead of multilayer film GL-30, it produced similarly to the heat ray shielding film F5, and produced the heat ray shielding film F13.

(Heat ray shielding film F14)
Prepared in the same manner as the heat ray shielding film F1 except that an aluminum vapor deposited PET film was used instead of the multilayer film GL-30, no heat ray absorbing layer was provided, and an adhesive layer was provided on the aluminum vapor deposition side of the PET film. Thus, a heat ray shielding film F14 was produced.

  Using the produced heat ray shielding films F2 to F14, the adhesive layer was bonded to a 3 mm thick glass plate in the same manner as in the case of the heat ray shielding film F1, and various performances were evaluated.

(Examples 1-7, Comparative Examples 1-7)
The experiments with the heat ray shielding film F1 to the heat ray shielding film F7 correspond to Examples 1 to 7, respectively. Moreover, the experiment by the heat ray shielding film F8-heat ray shielding film F14 is equivalent to the comparative example 1-the comparative example 7, respectively.
The outline of the configuration of each heat ray shielding film is summarized in Table 1. The configuration No. 20, 30, and 40 correspond to FIGS. 1, 2, and 3, respectively.

<Performance evaluation method>
In Examples and Comparative Examples, heat ray shielding coefficient, visible light transmittance, visible light reflectance, solar transmittance, solar reflectance, solar absorption rate, heat flow rate, electromagnetic wave shielding rate, performance under the conditions described below Was evaluated. In addition, evaluation was performed about the transmitted light and reflected light by irradiating a predetermined light ray from the outdoor side.

(Heat shielding coefficient)
The heat ray shielding coefficient is measured using a spectrophotometer according to JIS A5759. The heat ray shielding coefficient was determined by setting the Ni value to 0.34. When the heat ray shielding coefficient is 0.70 or less, it is determined that the heat ray shielding efficiency is excellent.
In this example, a spectrophotometer (manufactured by Shimadzu Corporation, UV3160) was used.

(Visible light transmittance)
Conforms to JIS A5759. In this example, a spectrophotometer (manufactured by Shimadzu Corporation, UV3160) was used.

(Visible light reflectance)
Conforms to JIS A5759. In this example, a spectrophotometer (manufactured by Shimadzu Corporation, UV3160) was used.

(Solar radiation transmittance)
Conforms to JIS A5759. In this example, a spectrophotometer (manufactured by Shimadzu Corporation, UV3160) was used.

(Solar reflectance)
Conforms to JIS A5759. In this example, a spectrophotometer (manufactured by Shimadzu Corporation, UV3160) was used.

(Solar radiation absorption rate)
Conforms to JIS A5759. In this example, a spectrophotometer (manufactured by Shimadzu Corporation, UV3160) was used.

(Heat flow rate)
The heat transmissivity is measured using an infrared reflectometer in accordance with JIS A5759. When the thermal conductivity is less than 5.9, it is determined that the far-infrared reflection efficiency is excellent. In this example, an infrared reflection measuring machine (manufactured by Shimadzu Corporation, FTIR8700) was used.

(Electromagnetic wave shielding rate)
Using a sample of 15 cm × 15 cm, the electromagnetic wave shielding rate was measured in the frequency range of 30 MHz to 1 GHz by the KEC method. The numerical value of the electromagnetic wave shielding rate was a value (dB) at a frequency of 800 MHz.

  The evaluation results obtained in Examples and Comparative Examples are shown in Table 1.

FIG. 5 is a spectrum diagram of transmittance and reflectance of the heat ray shielding film of Example 5 of the first embodiment and Example 7 of the second embodiment.
T1 and R1 are spectrum diagrams of transmittance and reflectance of Example 5 (heat ray shielding film F5), respectively. T2 and R2 are spectrum diagrams of transmittance and reflectance of Example 7 (heat ray shielding film F7), respectively.
Both have relatively high transmittance and reflectance in the visible light region. On the other hand, in the near-infrared region, the transmittance was close to 0, and the reflectance was considerably low. The performance of Example 5 having the heat ray absorbing layer on the indoor side was relatively better than that of Example 7 having the outdoor side.

6 is a spectrum diagram of transmittance and reflectance of the heat ray shielding films of Comparative Example 1, Comparative Example 6 and Comparative Example 7. FIG.
T3 and R3 are spectrum diagrams of transmittance and reflectance of Comparative Example 1 (heat ray shielding film F8), respectively. T4 and R4 are spectral diagrams of transmittance and reflectance of Comparative Example 6 (heat ray shielding film F13), respectively. T5 and R5 are spectral diagrams of transmittance and reflectance of Comparative Example 7 (heat ray shielding film F14), respectively.

  Although the comparative example 1 is a heat ray shielding film only of a multilayer film, it has a comparatively high reflectance in visible region. On the other hand, in the near infrared region, the transmittance was close to 90%. Comparative Example 6 is a heat ray shielding film in which an ITO fine particle-containing layer is formed on a PET film, but has a low reflectance in the visible light region and the near infrared region. On the other hand, in the near infrared region, the transmittance was close to 0%. Comparative Example 7 was an aluminum-deposited PET film, but had a moderate transmittance and reflectance in the visible light region and the near infrared region.

  Examples 1 to 7 of the present invention all had good performance in terms of heat ray shielding coefficient, visible light transmittance, visible light reflectance, solar transmittance, solar reflectance, and electromagnetic wave shielding rate. On the other hand, Comparative Examples 1-6 were inferior in heat ray shielding performance. Moreover, the comparative example 7 was inferior to visible light transmittance | permeability.

DESCRIPTION OF SYMBOLS 1 Heat ray shielding film 2 Adhesive layer 3 Base film 4 Heat ray absorption layer 5 Window plate 20 Heat ray shielding window plate

Claims (4)

It is a heat ray shielding film installed on a window plate,
A base film made of a transparent resin having a multilayer structure;
A layer containing heat-absorbing metal compound fine particles provided on at least one surface of the base film,
The thickness per layer of the multilayer structure is 50 to 1000 nm,
The number of layers of the multilayer structure is 200-1400,
The heat-absorbing metal compound is a metal or a metal oxide;
The heat ray absorbing metal compound fine particles have an average particle size of 10 to 100 nm,
The heat ray shielding coefficient is 0.70 or less,
The visible light reflectance is 10% or more,
A heat ray shielding film having a visible light transmittance of 55% or more.   The heat ray shielding film according to claim 1, wherein the heat transmissivity is less than 5.9.   The solar radiation absorption rate is 40% or less, The heat ray shielding film according to claim 1 or 2.   The heat ray shielding film according to any one of claims 1 to 3, wherein the electromagnetic wave shielding rate is 10 dB or less.

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