JP2013080221A - Heat ray shielding material, heat shielding glass, and building material glass - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat ray shielding material that has high heat shielding performance (solar reflectance), superior heat shielding durability when pasted to glass, and favorable peeling strength and re-peeling characteristics of an adhesive layer.SOLUTION: The heat ray shielding material has an adhesive layer and a metal-particle-containing layer containing at least one type of metal particles; the metal particles have at least 60% by number of hexagonal to circular plate-shaped metal particles; the primary faces of the hexagonal to circular plate-shaped metal particles are oriented to a plane in an average range of 0° to ±30° with respect to one of the surfaces of the metal-particle-containing layer; and the adhesive layer has self-adhesiveness and re-peeling characteristics.

Description

  The present invention relates to a heat ray shielding material which is excellent in heat shielding performance and heat shielding durability, and has good removability and peel strength of an adhesive layer. The present invention also relates to a heat shielding glass and building material glass using the heat ray shielding agent.

  In recent years, heat ray shielding materials for automobiles and building windows have been developed as one of energy saving measures for reducing carbon dioxide. For example, a metal Ag thin film is generally used as a heat ray reflective material because of its high reflectance. Low-E glass (for example, manufactured by Asahi Glass Co., Ltd.) using Ag and ZnO multilayer film is widely used in buildings in order to increase visible light transmission, but the problem is high cost and heat ray shielding by DIY There has been a demand for attaching a material to an arbitrary glass, and an inexpensive heat ray shielding material that can be attached to glass has been demanded.

  As an infrared shielding filter, a filter using Ag tabular grains has been proposed (see Patent Document 1). However, the infrared shielding filter described in Patent Document 1 is intended to be used in a plasma display panel (PDP), and the Ag tabular grains are not controlled in their arrangement, and therefore mainly have wavelengths in the infrared region. It functioned as a light infrared absorber and did not function as a material that actively reflects heat rays. Therefore, when an infrared shielding filter composed of such Ag tabular grains is used for heat shielding of direct sunlight, the infrared absorbing filter itself is warmed, and the room temperature rises due to the heat, so that it functions as an infrared shielding material. Was insufficient. Moreover, in the Example of patent document 1, the dispersion | distribution which has infrared shielding property is apply | coated to a polyethylene terephthalate film, a glass plate is bonded together through the acrylic translucent adhesive material of thickness 25 micrometers, and it is optical for PDP. An example of manufacturing a filter is described.

  On the other hand, Patent Document 2 has at least 60% by number of hexagonal or circular tabular metal particles, and the main plane of the hexagonal or circular tabular metal particles is one of the metal particle-containing layers. A heat ray shielding material having a plane orientation in an average range of 0 ° to ± 30 ° with respect to the surface is disclosed. The heat ray shielding material described in Patent Document 1 can reflect near-infrared rays and is advantageous as an infrared shielding film. According to the heat ray shielding material described in Patent Document 2, it is possible to provide a low-cost, inexpensive, and highly effective heat shielding film. However, Patent Document 2 discloses a specific method for bonding the heat ray shielding material to glass, The description of the details of the adhesive sometimes used was neither disclosed nor suggested, including the examples of the same document.

  On the other hand, Patent Document 3 has an adhesive layer comprising a first adhesive layer having a carboxylic acid-modified styrene-butadiene elastomer and a second adhesive layer containing a SEPS thermoplastic elastomer and a plasticizer on a base material layer. It is described that the self-adhesive film can be repeatedly applied to and peeled from an adhesive surface such as glass. However, Patent Document 2 describes that a plastic film can be preferably used as the base material layer and that various other additives may be included in the base material layer. No consideration has been given to the use of a shielding material or metal tabular grains for the base material layer.

JP 2007-178915 A JP 2011-118347 A Japanese Patent No. 4215527

  Under such circumstances, a heat ray shielding material, which is a thin film in which the present inventors have formed a tabular metal particle-containing layer described in Patent Document 2 on a PET film, is described in Examples of Patent Document 1. When trying to attach to a glass for windows using a general acrylic translucent adhesive material, it is easy for end users to mix bubbles when such a thin film is attached with DIY. I understood. Since the window has a strong influence on the aesthetic impression of the house as seen from the outside, it has been found that if air bubbles are mixed in, the problem of aesthetic damage occurs. Acrylic polymers that have been called “adhesives” or “pressure-sensitive adhesives” have poor removability and cannot be re-attached, so they require skill in glass construction and are realistic. Carpenter construction was necessary. However, when carpentry construction is performed, the construction cost for glass becomes several steps higher than the material cost of the heat ray shielding material described in Patent Document 2, and if it is left to carpentry construction, the manufacturing cost for the end user is high. There is a problem that the merit of the heat ray shielding material described in Patent Document 2 which is low and inexpensive cannot be directly transmitted.

  In addition, the present inventors actually used a heat-shielding material described in Patent Document 2 for water on a glass using a general acrylic translucent adhesive material as described in Examples of Patent Document 1. The heat-shielding glass in a state of failing to stick, in which a large number of bubbles were mixed, was manufactured by pasting. As a result, it was found that if the heat ray shielding material was left in such a state, the heat ray shielding material was peeled off from the glass at an early stage, and the heat shielding performance could not be prolonged.

  Furthermore, the present inventors bonded the heat ray shielding material described in Patent Document 2 with the utmost care by applying water to glass using a general acrylic translucent adhesive material as described above, A thermal barrier glass almost free of bubbles was produced. However, if a simulation experiment of the temperature difference between day and night is conducted under severe conditions, the heat ray shielding material will not peel off from the glass over a long period of time, but the thermal expansion due to the temperature difference between the glass and the heat ray shielding material will occur at the edge of the heat ray shielding material. Due to the large difference, shear stress is repeatedly applied to the adhesive, resulting in disorder of the nanodisk planar arrangement. As a result, the heat ray reflectivity at the end portion is significantly reduced.

  An object of the present invention is to solve the above-described problems. That is, the problem to be solved by the present invention is that the heat shielding performance (sunlight reflectance) is high, the heat shielding durability over the entire surface bonded to the glass is excellent, and the releasability and peel strength of the adhesive layer are also good. It aims at providing a certain heat ray shielding material.

  Therefore, when a self-adhesive and re-peelable pressure-sensitive adhesive material was used as the pressure-sensitive adhesive layer, it was possible to reattach it immediately even if bubbles were mixed, and the peel strength was also good. Furthermore, the inventors have found that the heat insulation durability is improved when the temperature change during the day and night when it is bonded to glass is repeated over a long period of time.

Means for solving the above-described problems are as follows.
[1] It has a metal particle-containing layer containing at least one kind of metal particles and an adhesive layer, and the metal particles have 60% by number or more of hexagonal or circular plate metal particles, and the hexagonal shape The main plane of the flat plate-like metal particles having a circular shape is plane-oriented in an average range of 0 ° to ± 30 ° with respect to one surface of the metal particle-containing layer, and the adhesive layer is self-adhesive and removable. The heat ray shielding material characterized by having.
[2] In the heat ray shielding material according to [1], the adhesive layer preferably contains a carboxylic acid-modified thermoplastic elastomer.
[3] In the heat ray shielding material according to [1] or [2], 60% by number or more of the hexagonal or circular tabular metal particles are exposed on one surface of the metal particle-containing layer. It is preferable.
[4] In the heat ray shielding material according to [3], the surface of the metal particle-containing layer on which 60% or more of the hexagonal or circular plate-like metal particles are exposed on the surface is the adhesive. The outermost surface on the side opposite to the layer is preferable.
[5] The heat ray shielding material according to [3] or [4] is a surface of the metal particle-containing layer on which 60% or more of the hexagonal or circular plate-like metal particles are exposed on the surface. It is preferable to have a base material between the surface on the opposite side to and the adhesive layer.
[6] In the heat ray shielding material according to any one of [1] to [5], the hexagonal or circular plate-like metal particles have an average particle diameter of 70 nm to 500 nm, and the hexagonal or circular shape. It is preferable that the aspect ratio (average particle diameter / average particle thickness) of the shaped flat metal particles is 8 to 40.
[7] In the heat ray shielding material according to any one of [1] to [6], the metal tabular grain preferably contains at least silver.
[8] It is preferable that the heat ray shielding material according to any one of [1] to [7] reflects infrared light.
[9] A heat shielding glass, characterized in that a glass is adhered on the adhesive layer of the heat ray shielding material according to any one of [1] to [8].
[10] A glass for building materials, comprising the thermal barrier glass according to [9].

  According to the present invention, there is provided a heat ray shielding material having high heat shielding performance (sunlight reflectance), excellent heat shielding durability when bonded to glass, and having good removability and peeling strength of an adhesive layer. be able to. According to the heat ray shielding material of the present invention, it is possible to provide a heat shielding glass and a building material glass having high heat shielding performance (sunlight reflectance), excellent heat shielding durability, and good removability and peel strength. .

FIG. 1 is a schematic view showing an example of the heat ray shielding material of the present invention. FIG. 2 is a schematic view showing another example of the heat ray shielding material of the present invention. FIG. 3 is a schematic view showing another example of the heat ray shielding material of the present invention. FIG. 4A is a schematic perspective view showing an example of the shape of a tabular grain contained in the heat ray shielding material of the present invention, and shows a circular tabular grain. FIG. 4B is a schematic perspective view showing an example of the shape of tabular grains contained in the heat ray shielding material of the present invention, and shows hexagonal tabular grains. FIG. 5A is a schematic cross-sectional view showing the existence state of a metal particle-containing layer containing metal tabular grains in the heat ray shielding material of the present invention, and a metal particle-containing layer containing metal tabular grains (parallel to the plane of the substrate). ) And the main plane of the tabular metal particles (the plane that determines the equivalent circle diameter D). FIG. 5B is a schematic cross-sectional view showing the existence state of a metal particle-containing layer containing metal tabular grains in the heat ray shielding material of the present invention, and the metal tabular grains in the depth direction of the heat ray shielding material of the metal particle-containing layer. FIG. FIG. 5C is a schematic cross-sectional view showing an example of the presence state of a metal particle-containing layer containing metal tabular grains in the heat ray shielding material of the present invention. FIG. 5D is a schematic cross-sectional view showing another example of the existence state of the metal particle-containing layer containing the metal tabular grains in the heat ray shielding material of the present invention. FIG. 5E is a schematic cross-sectional view showing another example of the existence state of the metal particle-containing layer containing the metal tabular grains in the heat ray shielding material of the present invention. FIG. 6 is a schematic view showing an example of the thermal barrier glass of the present invention.

Hereinafter, the heat ray shielding material of the present invention will be described in detail.
The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
The “re-peelable” adhesive material in the present invention refers to a re-peeling material when it is peeled cleanly from the test support without causing any damage to the test support over a series of release rates and various holding periods at room temperature. Considered a peel-off type.
The “self-adhesive” adhesive material in the present invention means that the application to the adherend surface can be performed without using any other adhesive material, without applying further pressure or heat, , A property that can be performed without using mechanical means such as screws, staples, nails, and wires.
In the present invention, in addition to the self-adhesive property, the adhesive material is flexible, for example, is attached to the adherend surface by starting attachment from one end and proceeding to the other end to complete the attachment. It is preferred to have at least the flexibility that is possible.

[Heat ray shielding material]
The heat ray shielding material of the present invention has a metal particle-containing layer containing at least one metal particle and an adhesive layer, and the metal particles have 60% by number or more of hexagonal or circular plate-like metal particles. The main plane of the hexagonal or circular tabular metal particles is plane-oriented in an average range of 0 ° to ± 30 ° with respect to one surface of the metal particle-containing layer, and the adhesive layer is self-adhesive. And removability.
With such a configuration, the heat ray shielding material of the present invention has high heat shielding performance (sunlight reflectance), excellent heat shielding durability when bonded to glass, and good re-peelability and peel strength of the adhesive layer. is there.
The heat ray shielding material of the present invention not only provides DIY property by an adhesive layer having self-adhesiveness and removability (hereinafter referred to as an elastomer adhesive layer), but also has a remarkable improvement in characteristics characteristic of silver nanodisk thermal insulation. Detected. This is a result that the elastomer adhesive layer is much better than a normal adhesive material in the long-term stability of the heat shielding performance (sunlight reflectance, IR reflection performance).
This is a feature of the heat ray shielding material of the present invention, wherein the metal particles have 60% by number or more of hexagonal or circular plate-like metal particles, and the main feature of the hexagonal or circular plate-like metal particles. A state in which the plane is plane-oriented in an average range of 0 ° to ± 30 ° with respect to one surface of the metal particle-containing layer (hereinafter, also referred to as “nanodisk plane arrangement”) emits IR reflection. In this respect, a film in which a metal particle-containing layer and an adhesive layer are laminated due to expansion of the metal particle-containing layer (or glass) due to a difference in temperature between day and night when a normal pressure-sensitive adhesive material is laminated thereon and bonded to glass. This is due to the fact that a shear stress between the adhesive material and the film occurs at the edge portion of the film, and therefore the nanodisk planar arrangement is disturbed. Although not bound by any theory, in the case of an adhesive layer having self-adhesiveness and re-peelability (for example, an elastomer adhesive layer) used in the configuration of the heat ray shielding material of the present invention, unlike ordinary adhesive materials, Even if shear stress is applied to the edge portion due to expansion of the metal particle-containing layer (or glass) due to the difference, the shear stress is eliminated simply by sliding the interface between the glass and the adhesive layer (for example, the elastomer adhesive layer). The disc plane arrangement is not disturbed. The durability of such heat shielding performance (sunlight reflectivity) has not been studied heretofore, and the relationship between the temperature difference between day and night and the disorder of the nanodisk planar arrangement has not been known.

The heat ray shielding material of the present invention preferably has an embodiment having other layers such as an ultraviolet absorbing layer, a base material, and a metal oxide particle-containing layer as necessary.
Hereinafter, the preferable structure of the heat ray shielding material of this invention is demonstrated.

  As a layer structure of the heat ray shielding material of this invention, the aspect which has the metal particle content layer 2 containing the at least 1 sort (s) of metal tabular grain 3 and the adhesion layer 11 as shown in FIG. 1 is mentioned. Moreover, as shown in FIG. 2, the aspect which has the base material 1, the metal particle content layer 2 containing the at least 1 sort (s) of metal tabular grain 3 on this base material, and the adhesion layer 11 is mentioned. The metal tabular grains 3 may be unevenly distributed at the interface between the metal particle-containing layer 2 and the adhesive layer 11 as shown in FIGS. 1 and 2, and are appropriately dispersed in the thickness direction in the metal particle-containing layer 2. It may be (not shown). Moreover, as shown in FIG. 3, it has the base material 1, the metal particle content layer 2 on this base material, and the adhesion layer 11 on this metal particle content layer, The adhesion layer 11 of the metal particle content layer 2 The tabular metal grains 3 may be unevenly distributed on the surface on the side where no is disposed.

<1. Metal particle content layer>
The metal particle-containing layer is a layer containing at least one kind of metal particle, and there is no particular limitation as long as the metal particle has 60% by number or more of hexagonal or circular plate-like metal particles. Can be appropriately selected according to the purpose.
When the thickness of the metal particle-containing layer is d, 80% by number or more of the hexagonal or circular tabular metal particles are present in a range of d / 2 from the surface of the metal particle-containing layer. It is more preferable that it exists in the range of d / 3 from the surface of the said metal-particle content layer. It is not limited to any theory, and the heat ray shielding material of the present invention is not limited to the following production method, but a specific polymer (preferably latex) is used when producing the metal particle-containing layer. By adding it, the metal tabular grains can be segregated on one surface of the metal particle-containing layer.

1-1. Metal particles
The metal particles include 60% by number or more of hexagonal or circular tabular metal particles, and the hexagonal or circular tabular metal particles are on one surface of the metal particle-containing layer (the heat ray shielding material of the present invention). In the case of having a substrate, there is no particular limitation as long as it is plane-oriented in an average range of 0 ° to ± 30 ° with respect to the substrate surface), and it can be appropriately selected according to the purpose.
In addition, it is preferable that one surface of the said metal particle content layer is a flat plane. When the metal particle-containing layer of the heat ray shielding material of the present invention has a base material as a temporary support, it is preferably substantially horizontal with the surface of the base material. Here, the said heat ray shielding material may have the said temporary support body, and does not need to have it.
There is no restriction | limiting in particular as a magnitude | size of the said metal particle, According to the objective, it can select suitably, For example, you may have an average particle diameter of 500 nm or less.
The material of the metal particles is not particularly limited and can be appropriately selected according to the purpose. From the viewpoint of high heat ray (near infrared) reflectance, silver, gold, aluminum, copper, rhodium, nickel, Platinum or the like is preferable.

-1-2. Metal tabular grains
The shape of the metal tabular grains is not particularly limited, and can be appropriately selected according to the purpose. However, the metal tabular grains are substantially triangular tabular, substantially hexagonal tabular, and substantially disc-shaped metal with these corners removed. At least one of tabular grains is preferable.
The material of the metal tabular grain is not particularly limited as long as it contains at least silver, and can be appropriately selected according to the purpose. However, gold, aluminum, copper, rhodium, which has a high heat ray (near infrared) shielding rate, It may further contain a metal such as nickel or platinum.
There is no restriction | limiting in particular as content in the said heat ray shielding layer of the said metal tabular grain, Although it can select suitably according to the objective, In any of 1st and 2nd embodiment, 0.01 g / m ^{2 to} 1.00 g / m ² is preferable, and 0.02 g / m ^{2 to} 0.20 g / m ² is more preferable.
When the content is less than 0.01 g / m ² , the heat ray shielding may be insufficient, and when it exceeds 1.00 g / m ² , the visible transmittance may decrease. Meanwhile, the content is ^{0.02g / m 2 ~0.20g / m 2} , is advantageous in terms of sufficient heat ray shielding and visible transmittance.
In addition, content in the said heat ray shielding layer of the said metal tabular grain can be computed as follows, for example. From the observation of the super foil section TEM image and the surface SEM image of the heat ray shielding layer, the number, average particle diameter and average thickness of the metal tabular grains in a certain area are measured. Alternatively, regarding the average thickness, by applying the metal tabular grains used in the heat ray shielding layer on a glass plate in a dispersion state without adding a binder, and measuring the surface with an atomic force microscope, Accurate average thickness can be measured. The mass (g) of the tabular metal grains calculated based on the number, average grain diameter and average thickness of the tabular metal grains thus measured and the specific gravity of the tabular metal grains is divided by the constant area (m ² ). This can be calculated. Further, the metal tabular grains in a certain area of the heat ray shielding layer are eluted in methanol, and the mass (g) of the metal tabular grains measured by fluorescent X-ray measurement is divided by the constant area (m ² ). You can also.

The metal tabular grain is not particularly limited as long as it is a grain composed of two main planes (see FIGS. 4A and 4B), and can be appropriately selected according to the purpose. For example, hexagonal shape, circular shape, triangular shape Examples include shape. Among these, in terms of high visible light transmittance, a hexagonal or more polygonal shape to a circular shape is more preferable, and a hexagonal shape or a circular shape is particularly preferable.
In the present specification, the circular shape means 0 per side of a metal tabular grain having a length of 50% or more of the average equivalent circle diameter of a tabular metal grain (synonymous with tabular metal grain) described later. Say the shape that is. The circular tabular metal grains are not particularly limited as long as they have no corners and round shapes when observed from above the main plane with a transmission electron microscope (TEM), depending on the purpose. It can be selected appropriately.
In the present specification, the hexagonal shape means a shape in which the number of sides having a length of 20% or more of the average equivalent circle diameter of the metal tabular grains described later is 6 per one metal tabular grain. The same applies to other polygons. The hexagonal metal tabular grain is not particularly limited as long as it is a hexagonal shape when the metal tabular grain is observed from above the main plane with a transmission electron microscope (TEM), and is appropriately selected according to the purpose. For example, the hexagonal corner may be acute or dull, but the corner is preferably dull in that the absorption in the visible light region can be reduced. There is no restriction | limiting in particular as a grade of the dullness of an angle | corner, According to the objective, it can select suitably.
There is no restriction | limiting in particular as a material of the said metal tabular grain, The same thing as the said metal particle can be suitably selected according to the objective. The metal tabular grain preferably contains at least silver.

  Of the metal particles present in the metal particle-containing layer, hexagonal or circular plate-like metal particles are 60% by number or more, preferably 65% by number or more, and 70 by number with respect to the total number of metal particles. % Or more is more preferable. When the proportion of the metal tabular grains is less than 60% by number, the visible light transmittance may be lowered.

[1-2-1. Planar orientation]
In the heat ray shielding material of the present invention, the hexagonal or circular plate-like metal particles have a main plane on one surface of the metal particle-containing layer (when the heat ray shielding material has a substrate, the surface of the substrate). On the other hand, it is plane-oriented in the range of average 0 ° to ± 30 °, preferably plane-oriented in the range of average 0 ° to ± 20 °, and plane-oriented in the range of average 0 ° to ± 5 °. It is particularly preferable.
The presence state of the metal tabular grains is not particularly limited and may be appropriately selected depending on the intended purpose. However, it is preferable that they are arranged as shown in FIGS. 5D and 5E described later.

Here, FIG. 5A to FIG. 5E are schematic cross-sectional views showing the existence state of the metal particle-containing layer containing the metal tabular grains in the heat ray shielding material of the present invention. 5C, FIG. 5D, and FIG. 5E show the presence state of the metal tabular grain 3 in the metal particle-containing layer 2. FIG. 5A is a diagram for explaining an angle (± θ) formed by the plane of the substrate 1 and the main plane of the metal tabular grain 3 (the plane that determines the equivalent circle diameter D). FIG. 5B shows the existence region in the depth direction of the heat ray shielding material of the metal particle-containing layer 2.
In FIG. 5A, the angle (± θ) formed by the surface of the substrate 1 and the main plane of the metal tabular grain 3 or an extension line of the main plane corresponds to a predetermined range in the plane orientation. That is, the plane orientation means a state in which the inclination angle (± θ) shown in FIG. 5A is small when the cross section of the heat ray shielding material is observed. In particular, FIG. 5D shows the main surface of the substrate 1 and the metal tabular grain 3. A state where the flat surface is in contact, that is, a state where θ is 0 ° is shown. When the angle of the plane orientation of the main plane of the metal tabular grain 3 with respect to the surface of the substrate 1, that is, θ in FIG. 5A exceeds ± 30 °, a predetermined wavelength of the heat ray shielding material (for example, near the visible light region long wavelength side) The reflectance in the infrared light region is reduced.

  There is no particular limitation on the evaluation of whether or not the main plane of the metal tabular grain is plane-oriented with respect to one surface of the metal particle-containing layer (the surface of the substrate when the heat ray shielding material has a substrate). , Can be selected appropriately according to the purpose. For example, an appropriate cross section is prepared, and a metal particle-containing layer (a base material when the heat ray shielding material has a base material) and a flat metal particle are observed in this section. It may be a method of evaluating. Specifically, as a heat ray shielding material, a microtome or a focused ion beam (FIB) is used to prepare a cross-section sample or a cross-section sample of the heat ray shielding material, and this is used for various microscopes (for example, a field emission scanning electron microscope ( FE-SEM) etc.) and the method of evaluating from images obtained by observation.

  In the heat ray shielding material, when the binder covering the metal tabular grain swells with water, the sample frozen in liquid nitrogen is cut with a diamond cutter attached to a microtome, so that the cross section sample or cross section sample May be produced. Moreover, when the binder which coat | covers a metal tabular grain in a heat ray shielding material does not swell with water, you may produce the said cross-section sample or cross-section slice sample.

  As the observation of the cross-section sample or cross-section sample prepared as described above, the main surface of the metal tabular grain is one of the surfaces of the metal particle-containing layer in the sample (or the base material surface when the heat ray shielding material has a base material) If it can confirm whether the plane is plane-oriented, there is no restriction | limiting in particular, According to the objective, it can select suitably, For example, observation using FE-SEM, TEM, an optical microscope etc. is mentioned. It is done. In the case of the cross section sample, observation may be performed by FE-SEM, and in the case of the cross section sample, observation may be performed by TEM. When evaluating by FE-SEM, it is preferable to have a spatial resolution with which the shape and tilt angle (± θ in FIG. 5A) of the metal tabular grains can be clearly determined.

[1-2-2. Average particle diameter (average equivalent circle diameter) and average particle diameter (average equivalent circle diameter) particle size distribution]
There is no restriction | limiting in particular as an average particle diameter (average circle equivalent diameter) of the said metal tabular grain, Although it can select suitably according to the objective, 70 nm-500 nm are preferable, and 100 nm-400 nm are more preferable. When the average particle diameter (average equivalent circle diameter) is less than 70 nm, the contribution of absorption of the metal tabular grains becomes larger than the reflection, so that sufficient heat ray reflectivity may not be obtained. (Scattering) may increase and the transparency of the substrate may be impaired.
Here, the average particle diameter (average equivalent circle diameter) means an average value of main plane diameters (maximum lengths) of 200 tabular grains arbitrarily selected from images obtained by observing grains with a TEM. To do.
Two or more kinds of metal particles having different average particle diameters (average circle equivalent diameters) can be contained in the metal particle-containing layer. In this case, the peak of the average particle diameter (average circle equivalent diameter) of the metal particles is 2 It may have two or more, that is, two average particle diameters (average circle equivalent diameter).

In the heat ray shielding material of the present invention, the coefficient of variation in the particle size distribution of the metal tabular grains is preferably 30% or less, and more preferably 20% or less. When the coefficient of variation exceeds 30%, the reflection wavelength region of the heat ray in the heat ray shielding material may become broad.
Here, the coefficient of variation in the particle size distribution of the metal tabular grains is, for example, plotting the distribution range of the particle diameters of the 200 metal tabular grains used for calculating the average value obtained as described above, and calculating the standard deviation of the particle size distribution. It is the value (%) obtained by dividing the average value (average particle diameter (average equivalent circle diameter)) of the main plane diameter (maximum length) obtained as described above.

[1-2-3. aspect ratio]
The aspect ratio of the metal tabular grains is not particularly limited and may be appropriately selected depending on the intended purpose. However, from the viewpoint that the reflectance in the infrared light region having a wavelength of 800 nm to 1,800 nm increases, 40 is preferable and 10-35 is more preferable. When the aspect ratio is less than 8, the reflection wavelength becomes smaller than 800 nm, and when it exceeds 40, the reflection wavelength becomes longer than 1,800 nm and sufficient heat ray reflectivity may not be obtained.
The aspect ratio means a value obtained by dividing the average particle diameter (average circle equivalent diameter) of the tabular metal grains by the average grain thickness of the tabular metal grains. The average grain thickness corresponds to the distance between the main planes of the metal tabular grain, and is, for example, as shown in FIGS. 4A and 4B and can be measured by an atomic force microscope (AFM).
The method for measuring the average particle thickness by the AFM is not particularly limited and can be appropriately selected depending on the purpose.For example, a particle dispersion containing metal tabular particles is dropped onto a glass substrate and dried. For example, a method of measuring the thickness of one particle may be used.
In addition, it is preferable that the thickness of the said metal tabular grain is 5-20 nm.

[1-2-4. Range of tabular metal grains]
In the heat ray shielding material of the present invention, it is preferable that 80% by number or more of the hexagonal or circular plate-like metal particles are present in a range of d / 2 from the surface of the metal particle-containing layer, More preferably, it exists in the range, and more preferably 60% by number or more of the hexagonal or circular plate-like metal particles are exposed on one surface of the metal particle-containing layer. The presence of the metal tabular grains in the range of d / 2 from the surface of the metal particle-containing layer means that at least a part of the metal tabular grains is included in the range of d / 2 from the surface of the metal particle-containing layer. . That is, the metal tabular grain described in FIG. 5E in which a part of the metal tabular grain protrudes from the surface of the metal particle-containing layer is also in the range of d / 2 from the surface of the metal particle-containing layer. Treat as. FIG. 5E means that only a part of each metal tabular grain in the thickness direction is buried in the metal particle-containing layer, and each metal tabular grain is not stacked on the surface of the metal particle-containing layer. Absent.
Moreover, that the metal tabular grain is exposed on one surface of the metal particle-containing layer means that a part of one surface of the metal tabular grain protrudes from the surface of the metal particle-containing layer. .
Here, the distribution of the tabular metal particles in the metal particle-containing layer can be measured, for example, from an image obtained by SEM observation of a cross-sectional sample of the heat ray shielding material.

In the heat ray shielding material of the present invention, as shown in FIG. 5B, the plasmon resonance wavelength of the metal constituting the metal tabular grain 3 in the metal particle-containing layer 2 is λ, and the refractive index of the medium in the metal particle-containing layer 2 is n. When doing, it is preferable that the said metal-particle content layer 2 exists in the range of ((lambda) / n) / 4 in the depth direction from the horizontal surface of a heat ray shielding material. Within this range, the effect of increasing the amplitude of the reflected wave by the phase of the reflected wave at the interface between the upper and lower metal particle-containing layers of the heat ray shielding material is sufficiently large, and the visible light transmittance and the maximum heat ray Reflectivity is good.
The plasmon resonance wavelength λ of the metal constituting the metal tabular grain in the metal particle-containing layer is not particularly limited and can be appropriately selected according to the purpose. However, in terms of imparting heat ray reflection performance, 400 nm to 2, The thickness is preferably 500 nm, and more preferably 700 nm to 2,500 nm from the viewpoint of imparting visible light transmittance.

[1-2-5. Medium of metal particle containing layer]
There is no restriction | limiting in particular as a medium in the said metal particle content layer, According to the objective, it can select suitably. In the heat ray shielding material of the present invention, the metal-containing layer preferably contains a polymer, and more preferably contains a transparent polymer. Examples of the polymer include polyvinyl acetal resin, polyvinyl alcohol resin, polyvinyl butyral resin, polyacrylate resin, polymethyl methacrylate resin, polycarbonate resin, polyvinyl chloride resin, (saturated) polyester resin, polyurethane resin, gelatin, and cellulose. And polymers such as natural polymers. Among them, in the present invention, the main polymer of the polymer is preferably a polyvinyl alcohol resin, a polyvinyl butyral resin, a polyvinyl chloride resin, a (saturated) polyester resin, a polyurethane resin, and preferably the polyester resin and the polyurethane resin. More preferably, 80% by number or more of hexagonal or circular plate-like metal particles are present in the range of d / 2 from the surface of the metal particle-containing layer, and the heat ray shielding material of the present invention is a polyester resin. It is particularly preferable from the viewpoint of further improving the resistance to rubbing.
Moreover, in this specification, the main polymer of the polymer contained in the metal-containing layer refers to a polymer component occupying 50% by mass or more of the polymer contained in the metal-containing layer.
The refractive index n of the medium is preferably 1.4 to 1.7.
In the heat ray shielding material of the present invention, when the thickness of the hexagonal or circular plate-like metal particles is a, 80% or more of the hexagonal or circular plate-like metal particles are a / in the thickness direction. It is preferable that 10 or more is covered with the polymer, a / 10 to 10a in the thickness direction is more preferably covered with the polymer, and a / 8 to 4a is covered with the polymer. Particularly preferred. As described above, the hexagonal or circular plate-like metal particles are buried in the metal particle-containing layer at a certain ratio or more, whereby the rubbing resistance can be further increased. That is, the heat ray shielding material of the present invention is preferably in the embodiment of FIG. 5D rather than the embodiment of FIG. 5E.

[1-2-6. Area ratio of metal tabular grains]
The total area of the metal tabular grains relative to the area A of the base material when viewed from above (the total projected area A of the metal particle-containing layer when viewed from the direction perpendicular to the metal particle-containing layer) The area ratio [(B / A) × 100], which is the ratio of the value B, is preferably 15% or more, and more preferably 20% or more. When the area ratio is less than 15%, the maximum reflectance of the heat ray is lowered, and the heat shielding effect may not be sufficiently obtained.
Here, the area ratio can be measured, for example, by performing image processing on an image obtained by SEM observation of the heat ray shielding base material from above or an image obtained by AFM (atomic force microscope) observation. .

[1-2-7. Average distance between tabular grains]
As the average inter-particle distance between the tabular metal particles adjacent in the horizontal direction in the metal particle-containing layer, the average particle diameter of the tabular metal particle is 0.1 to 10 in terms of the visible light transmittance and the maximum reflectance of the heat ray. preferable.
When the horizontal average grain distance of the metal tabular grains is less than 1/10 of the average grain diameter of the metal tabular grains, the visible light transmittance is lowered. On the other hand, if it is 10 or more, the heat ray reflectance is lowered. Further, the average interparticle distance in the horizontal direction is preferably non-uniform (random) in terms of visible light transmittance. If it is not random, that is, if it is uniform, moire fringes may be seen due to diffraction scattering.

  Here, the horizontal average interparticle distance of the metal tabular grains means an average value of interparticle distances between two adjacent grains. In addition, the average inter-particle distance is random as follows: “When taking a two-dimensional autocorrelation of luminance values when binarizing an SEM image including 100 or more metal tabular grains, other than the origin. It has no significant local maximum.

[1-2-8. Layer structure of metal particle-containing layer]
In the heat ray shielding material of this invention, a metal tabular grain is arrange | positioned with the form of the metal particle content layer containing a metal tabular grain, as shown to FIG. 5A-FIG. 5E.
The metal particle-containing layer may be composed of a single layer as shown in FIGS. 5A to 5E or may be composed of a plurality of metal particle-containing layers. When comprised with a several metal particle content layer, it becomes possible to provide the shielding performance according to the wavelength range | band which wants to provide heat insulation performance. When the metal particle-containing layer is composed of a plurality of metal particle-containing layers, the heat ray shielding material of the present invention has a thickness d of the outermost metal particle-containing layer at least in the outermost metal particle-containing layer. ”, It is necessary that 80% by number or more of the hexagonal or circular plate-like metal particles are present in the range of d ″ / 2 from the surface of the outermost metal particle-containing layer. .

[1-2-9. Thickness of metal particle containing layer]
In the heat ray shielding material of the present invention, the thickness of the metal particle-containing layer is preferably 10 to 160 nm, more preferably 20 to 160 nm, and particularly preferably 20 to 100 nm. The thickness d of the metal particle-containing layer is preferably a to 10a, more preferably 2a to 8a, where a is the thickness of the hexagonal or circular plate-like metal particles.

Here, the thickness of each layer of the metal particle-containing layer can be measured, for example, from an image obtained by SEM observation of a cross-sectional sample of the heat ray shielding material.
Moreover, even when it has other layers, such as an overcoat layer mentioned later, on the said metal-particle content layer of a heat ray shielding material, the boundary of another layer and the said metal-particle content layer is determined by the same method. And the thickness d of the metal particle-containing layer can be determined. In addition, when coating on the metal particle-containing layer using the same type of polymer as the polymer contained in the metal particle-containing layer, it is difficult to determine the boundary with the metal particle-containing layer. By coating the overcoat layer after carbon deposition on the containing layer and observing the cross section by SEM, the interface between both layers can be recognized, and the thickness d of the metal particle containing layer can be determined. it can.

[1-2-10. Method for synthesizing tabular metal grains]
The method for synthesizing the metal tabular grain is not particularly limited as long as it can synthesize hexagonal or circular tabular metal particles, and can be appropriately selected according to the purpose. For example, a chemical reduction method, Examples thereof include liquid phase methods such as a photochemical reduction method and an electrochemical reduction method. Among these, a liquid phase method such as a chemical reduction method or a photochemical reduction method is particularly preferable in terms of shape and size controllability. After synthesizing hexagonal to triangular tabular metal grains, for example, by performing etching treatment with a dissolved species that dissolves silver such as nitric acid and sodium sulfite, aging treatment by heating, etc., hexagonal to triangular tabular metal grains The flat metal particles having a hexagonal shape or a circular shape may be obtained.

  As a method for synthesizing the metal tabular grains, in addition to the above, a seed crystal may be previously fixed on the surface of a transparent substrate such as a film or glass, and then metal grains (for example, Ag) may be grown in a tabular form.

  In the heat ray shielding material of the present invention, the metal tabular grains may be subjected to further treatment in order to impart desired characteristics. The further treatment is not particularly limited and may be appropriately selected depending on the purpose. For example, the formation of a high refractive index shell layer, the addition of various additives such as a dispersant and an antioxidant may be included. Can be mentioned.

-1-2-10-1. Formation of high refractive index shell layer
In order to further improve the visible light region transparency, the metal tabular grain may be coated with a high refractive index material having high visible light region transparency.
As the high refractive index material is not particularly limited and may be appropriately selected depending on the purpose, for example, TiO _x, BaTiO _3, ZnO, etc. SnO _2, ZrO _2, NbO _x and the like.

There is no restriction | limiting in particular as said coating method, According to the objective, it can select suitably, For example, Langmuir, 2000, 16 volumes, p. As reported in 2731-2735, a method of forming a TiO _x layer on the surface of silver metal tabular grains by hydrolyzing tetrabutoxytitanium may be used.

Further, when it is difficult to form a high refractive index metal oxide layer shell directly on the metal tabular grain, after synthesizing the metal tabular grain as described above, an SiO ₂ or polymer shell layer is appropriately formed, The metal oxide layer may be formed on the shell layer. When TiO _x is used as a material for the high refractive index metal oxide layer, since TiO _x has photocatalytic activity, there is a concern of deteriorating the matrix in which the metal tabular grains are dispersed. After forming the TiO _x layer on the tabular grains, an SiO ₂ layer may be appropriately formed.

-1-2-10-2. Addition of various additives-
In the heat ray shielding material of the present invention, the metal tabular grain may adsorb an antioxidant such as mercaptotetrazole or ascorbic acid in order to prevent oxidation of a metal such as silver constituting the metal tabular grain. . Further, an oxidation sacrificial layer such as Ni may be formed on the surface of the metal tabular grain for the purpose of preventing oxidation. Moreover, it may be covered with a metal oxide film such as SiO ₂ for the purpose of blocking oxygen.
For the purpose of imparting dispersibility, the metal tabular grain is, for example, a low molecular weight dispersant or a high molecular weight dispersant containing at least one of N elements such as quaternary ammonium salts and amines, S elements, and P elements. A dispersant may be added.

<2. Adhesive layer>
The heat ray shielding material of the present invention has an adhesive layer, and the adhesive layer has self-adhesiveness and removability.
The adhesive layer used for the heat ray shielding material of the present invention has self-adhesiveness and removability. Such an adhesive layer is an adhesive material that has been conventionally used as a building material, such as acrylic, silicone, polyester, polyvinyl alcohol, polyurethane, polyether, and rubber. Different from pressure sensitive adhesives.
From the viewpoint of effectively functioning as an adhesive layer, the heat ray shielding material of the present invention preferably has an adhesive layer with a thickness of 10 to 100 μm, more preferably an adhesive layer with a thickness of 10 to 50 μm, and an adhesive with a thickness of 15 to 40 μm. It is particularly preferred to have a layer. The adhesive layer is preferably applied using highly volatile acetone, toluene, methyl ethyl ketone, or the like as a solvent in order to minimize the residual solvent. In addition, when a UV-cutting agent is mixed in the adhesive layer, it is possible to reduce light deterioration with respect to the constituents of the heat ray shielding material. As the UV-cutting agent, tinuvin (manufactured by BASF) is preferable. Moreover, it is preferable that the adhesive layer takes 1 day to 1 week after the application to calm various physical properties such as internal strain.
The adhesive layer may include an ultraviolet absorber.

The material that can be used for forming the adhesive layer is not particularly limited except that it has self-adhesiveness and removability, and can be appropriately selected according to the purpose. For example, as described in Japanese Patent No. 421557 Self-adhesive and re-peelable properties with respect to a self-adhesive film using a gel polymer coating solution, a gel polymer sheet described in JP-A-2004-29673, and a conventional pressure-sensitive adhesive described in Japanese Patent No. 3532565 And an adhesive layer using a coating solution improved so as to obtain These may be used individually by 1 type and may use 2 or more types together. An adhesive layer made of these materials can be formed by coating.
Furthermore, an antistatic agent, a lubricant, an antiblocking agent and the like may be added to the adhesive layer.

  In the heat ray shielding material of the present invention, the adhesive layer preferably contains a carboxylic acid-modified thermoplastic elastomer. The pressure-sensitive adhesive layer containing the carboxylic acid-modified thermoplastic elastomer is described in Japanese Patent No. 421557, and a first adhesive layer and a second adhesive layer described later are laminated and adhered in this order to the metal particle-containing layer. An adhesive layer having self-adhesiveness is preferred. The first adhesive layer preferably includes a carboxylic acid-modified thermoplastic elastomer and a crosslinking agent, and is laminated and adhered to one side of the metal particle-containing layer. The second adhesive layer preferably includes a thermoplastic elastomer and a plasticizer, and is laminated and bonded to the first adhesive layer.

  The first adhesive layer preferably includes a carboxylic acid-modified thermoplastic elastomer and a crosslinking agent, and is a layer that is laminated and bonded to one surface of the base material layer. As the carboxylic acid-modified thermoplastic elastomer, various types such as a carboxylic acid-modified styrene-based thermoplastic elastomer can be used. Here, the carboxylic acid modification includes, for example, an aliphatic saturated monocarboxylic acid such as propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, pivalic acid, lauric acid, myristic acid, palmitic acid and stearic acid, and succinic acid. Aliphatic unsaturated monocarboxylic acids such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid, aliphatic unsaturated monocarboxylic acids such as acrylic acid, propyrolic acid, methacrylic acid, crotonic acid, isocrotonic acid and oleic acid It may be due to carboxylic acids and aliphatic unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid and mesaconic acid. Aliphatic unsaturated dicarboxylic acid modification is preferred, and maleic acid modification is most preferred.

  Such a carboxylic acid-modified styrene thermoplastic elastomer may be, for example, a hydrogenated carboxylic acid-modified styrene thermoplastic elastomer, for example, a hydrogenated carboxylic acid-modified styrene-butadiene elastomer. Good. An example of this is a hydrogenated maleic acid-modified styrene-butadiene elastomer (maleic acid-modified SEBS elastomer). When a hydrogenated maleic acid-modified styrene-butadiene elastomer is used as the carboxylic acid-modified thermoplastic elastomer in the first adhesive layer material, the melt index is, for example, 2. It is preferably 5 to 25 g / 10 minutes, more preferably 3 to 7 g / 10 minutes.

Further, when the hydrogenated carboxylic acid-modified thermoplastic elastomer is used, the hydrogenation rate is preferably substantially 100%, but may be less than that as long as the effect of the present invention is obtained. When carboxylic acid-modified SEBS is used, the mass ratio of styrene: ethylene + butylene is, for example, preferably 10:90 to 40:60, and more preferably 20:80 to 30:70. In the present invention, the acid value of the carboxylic acid-modified thermoplastic elastomer is preferably 2 to 10. When the acid value is less than 3, a colorless and transparent film can be obtained. On the other hand, when the acid value is 3 to 10, the film can be yellowish.
Examples of the carboxylic acid-modified thermoplastic elastomer include Tuftec M1911, M1913, M1943 manufactured by Asahi Kasei, and Kraton FG-1901X manufactured by Kraton Polymer.

Further, the type of the crosslinking agent used in the first adhesive layer is not particularly limited, and can be appropriately determined in consideration of, for example, the type of the carboxylic acid-modified thermoplastic elastomer. As this crosslinking agent, for example, Coronate HL (hexamethylene diisocyanate-burette type) manufactured by Nippon Polyurethane Industry can be used.
The mass ratio of the carboxylic acid-modified thermoplastic elastomer: crosslinking agent in the first adhesive layer is not particularly limited, but is preferably 100: 1 to 2: 1, and more preferably 100: 1 to 4: 1. : 1 and most preferably 50: 1 to 12: 1. Thereby, both the adhesiveness of the first adhesive layer and the metal particle-containing layer and the adhesiveness of the first adhesive layer and the second adhesive layer can be made excellent.
The first adhesive layer may contain other additives such as an antistatic agent. As the antistatic agent, for example, Elegan 264wax made by NOF Corporation can be used, and the content thereof is preferably 0.1 to 3.6% by mass based on the mass of the first adhesive layer. More preferably, it is 0.6-1.8 mass%. By using the antistatic agent at such a ratio, so-called “Yuzuhada” can be satisfactorily prevented.
The thickness of the first adhesive layer is arbitrary, but is preferably 1 to 50 μm, for example, more preferably 1 to 15 μm, and most preferably 2 to 3 μm. Desired results are obtained in terms of surfaces and processability.

The second adhesive layer preferably includes a thermoplastic elastomer and a plasticizer, and is a layer laminated and bonded to the first adhesive layer. As the thermoplastic elastomer used in the second adhesive layer, various types can be used, but it is important to select such that the cohesive force is lowered and the self-adhesion is improved by using a plasticizer in combination. is there. The thermoplastic elastomer used in the second adhesive layer is preferably a polymer composed of block segments composed of styrene monomer units and rubber monomer units. Examples of such thermoplastic elastomers include SIS, SBS, SEBS, SEPS, SI, SB, and SEP, and SEBS and SEPS are preferable. In addition, when SEPS is used as the thermoplastic elastomer of the second adhesive layer material, for example, the mass average molecular weight thereof is preferably 15,000 to 500,000, more preferably 100,000 to 500. , 000.
The second adhesive layer preferably contains 3 to 97% by mass, more preferably 10 to 90% by mass of a thermoplastic elastomer based on the mass of the second adhesive layer.

Further, the type of the plasticizer used in the second adhesive layer is not particularly limited, but when the thermoplastic elastomer has a polystyrene phase and a rubber phase, the affinity for the rubber phase is high, but the affinity for the polystyrene phase. A low molecular weight, high molecular weight compound is suitable. As such a plasticizer, for example, naphthenic oil or liquid paraffin can be used.
For example, the naphthenic oil preferably has a flash point of, for example, 100 to 300 ° C, more preferably 150 to 280 ° C. Moreover, it is preferable that the pour point is -30--5 degreeC, for example, More preferably, it is -25--10 degreeC. Moreover, it is preferable that the specific gravity is 0.83-0.87, for example, More preferably, it is 0.837-0.868. Furthermore, it is preferable that the carbon number is 3-8, for example, More preferably, it is 5-6.
On the other hand, the liquid paraffin, for example, preferably has a flash point of, for example, 100 to 300 ° C, more preferably 150 to 280 ° C. Moreover, it is preferable that the pour point is -30--5 degreeC, for example, More preferably, it is -25--10 degreeC. Moreover, it is preferable that the specific gravity is 0.89-0.91, for example, More preferably, it is 0.8917-0.9065. Furthermore, it is preferable that the carbon number is 20-35, for example, More preferably, it is 21-33.
Either the naphthenic oil or liquid paraffin can be used alone, but these can also be used in combination.

The second adhesive layer preferably contains 3 to 97% by mass, more preferably 10 to 90% by mass of a plasticizer based on its mass.
The mass ratio of the thermoplastic elastomer: plasticizer in the second adhesive layer is not particularly limited, but is preferably 5:95 to 95: 5, and more preferably 10:90 to 90:10. is there. Thereby, both the adhesiveness between the second adhesive layer and the first adhesive layer and the adhesiveness between the second adhesive layer and the adherend surface can be made excellent.
Although the thickness of the said 2nd contact bonding layer is arbitrary, it is preferable that it is 10-100 micrometers, for example, More preferably, it is 25-50 micrometers.
Further, on the second adhesive layer, if necessary, the release layer, that is, the heat ray shielding material of the present invention, covers the second adhesive layer surface of the pressure-sensitive adhesive layer at the time of storage, to the adherend surface. When pasting, a layer that is peeled off to expose the second adhesive layer surface can be provided. As the release layer, for example, silicone-treated PET, silicone-treated paper base material, polyolefin and the like can be used, and silicone-treated PET is preferable. The silicone-treated surface is preferably in contact with the second adhesive layer.

The gel polymer sheet which is an adhesive layer described in JP-A-2004-29673 can be formed from an adhesive containing an olefin base polymer. The olefin base polymer contained in the adhesive is usually a homopolymer or copolymer having in its molecule a repeating unit derived from an olefin having 3 or more carbon atoms, preferably 3 to 16 carbon atoms. As the olefin base polymer, those conventionally used as an adhesive for protective films can be used.
Since the unit derived from an olefin having 3 or more carbon atoms is a branched olefin unit having a branched structure, it exhibits non-crystallinity due to the effect of the side chain alkyl group, and usually has a glass transition temperature of room temperature (about 25 ° C.) or lower. (Tg). Thereby, moderate adhesiveness is shown. The Tg of the olefin base polymer is preferably in the range of −70 to 25 ° C., more preferably −60 to 20 ° C.

  Examples of the olefin forming the branched olefin unit include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, These are α-olefins such as 1-tetradecene, 1-pentadecene and 1-hexadecene, and alkadienes having 4 or more carbon atoms such as butadiene and isoprene. These olefins may be used alone or in combination of two or more. Moreover, an olefin base polymer may be used independently, or may mix and use 2 or more types of olefin base polymers.

  Olefin-based polymers include copolymers of olefins and one or more vinyl monomers. As the vinyl monomer, for example, styrene, ethylene (olefin having less than 3 carbon atoms), or the like can be used. Preferred examples of the olefin-based polymer include atactic polypropylene, a copolymer of atactic polypropylene and one or more vinyl monomers, a polymer of a monomer containing an olefin having 4 to 16 carbon atoms, and a block copolymer of styrene and olefin. It is a coalescence. The copolymer containing styrene is, for example, a styrene block copolymer such as a styrene-butadiene copolymer or a styrene-isoprene copolymer.

  The elastic modulus of the adhesive layer is preferably determined so that the peel strength is in the above-described range. For example, the elastic modulus G (storage elastic modulus) measured in the shear mode at a frequency of 1 rad / sec at 25 ° C. by a dynamic viscoelasticity measurement method is usually 20 to 300 kPa, preferably 30 to 200 kPa, particularly preferably. Is 50 to 100 kPa. If the elastic modulus G is too small, the removability may be lowered. Conversely, if the elastic modulus G is too large, the adhesion of the optical filter to the adherend surface is lowered, and the air interface between the adherend and the air There is a risk that In order to effectively increase the elastic modulus of the adhesive layer, it is preferable to three-dimensionally crosslink the olefin base polymer. In a crosslinked state, it may become a so-called gel state.

Moreover, in order to improve the removability of the said adhesion layer, the following methods are preferable, for example.
(I) An ethylene-olefin copolymer or styrene-olefin copolymer is used, and the proportion of ethylene units or styrene units in the molecule is increased.
(Ii) A crystalline polymer such as polyethylene is used by mixing with an olefin base polymer.
(Iii) Three-dimensionally cross-linking the olefin base polymer as described above.
These methods (i) to (iii) may be used in combination of two or more.

  The pressure-sensitive adhesive layer may contain a tackifier resin and a plasticizer as long as the effects of the present invention are not impaired. These uses are advantageous in improving the adhesion between the heat ray shielding material of the present invention and the adherend. These are preferably resins and oils made of aliphatic compounds. Moreover, unless the effect of this invention is impaired, polymers other than the above, for example, polystyrene, chloroprene, ethylene-vinyl acetate copolymer (EVA), etc. may be included in the adhesive layer.

<3. Other layers>
<< 3-1. Base material >>
The heat ray shielding material of the present invention has a base material on the surface opposite to the surface of the metal particle-containing layer on which 80% by number or more of the hexagonal or circular plate-like metal particles are unevenly distributed. It is preferable.
The substrate is not particularly limited as long as it is an optically transparent substrate, and can be appropriately selected according to the purpose. For example, the substrate has a visible light transmittance of 70% or more, preferably 80% or more. And those with high transmittance in the near infrared region.
There is no restriction | limiting in particular about the shape, a structure, a magnitude | size, material, etc. as said base material, According to the objective, it can select suitably. Examples of the shape include a flat plate shape, and the structure may be a single layer structure or a laminated structure, and the size may be the size of the heat ray shielding material. It can be appropriately selected according to the above.
The material for the substrate is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include polyolefin resins such as polyethylene, polypropylene, poly-4-methylpentene-1, and polybutene-1, polyethylene terephthalate, Polyester resins such as polyethylene naphthalate; polycarbonate resins, polyvinyl chloride resins, polyphenylene sulfide resins, polyether sulfone resins, polyethylene sulfide resins, polyphenylene ether resins, styrene resins, acrylic resins, polyamides Examples thereof include a film made of a cellulose resin such as a cellulose resin, a polyimide resin, and cellulose acetate, or a laminated film thereof. Among these, a polyethylene terephthalate film is particularly preferable.
There is no restriction | limiting in particular as thickness of this base film, It can select suitably according to the intended purpose of a solar radiation shielding film, Usually, they are about 10 micrometers-500 micrometers, 12 micrometers-300 micrometers are preferable, and 16 micrometers-125 micrometers are more. preferable.

<< 3-2. Hard coat layer >>
In order to add scratch resistance, it is also preferable that the functional film includes a hard coat layer having hard coat properties. The hard coat layer can contain metal oxide particles.
There is no restriction | limiting in particular as said hard-coat layer, The kind and formation method can be selected suitably according to the objective, for example, acrylic resin, silicone resin, melamine resin, urethane resin, alkyd resin And thermosetting or photocurable resins such as fluorine-based resins. There is no restriction | limiting in particular as thickness of the said hard-coat layer, Although it can select suitably according to the objective, 1 micrometer-50 micrometers are preferable. When an antireflection layer and / or an antiglare layer are further formed on the hard coat layer, a functional film having antireflection properties and / or antiglare properties in addition to scratch resistance is preferably obtained. The hard coat layer may contain the metal oxide particles.

<< 3-3. Overcoat layer >>
In the heat ray shielding material of the present invention, in order to prevent oxidation and sulfidation of the metal tabular grains due to mass transfer and to provide scratch resistance, the heat ray shielding material of the present invention comprises the hexagonal or circular tabular metal particles. You may have the overcoat layer closely_contact | adhered to the surface of the said metal particle content layer of the exposed one. Moreover, you may have an overcoat layer between the said metal-particle content layer and the below-mentioned ultraviolet absorption layer. The heat ray shielding material of the present invention, particularly when the metal tabular grains are unevenly distributed on the surface of the metal particle-containing layer, prevents contamination of the production process due to the peeling of the metal tabular grains, prevention of disordered arrangement of the metal tabular grains at the time of coating another layer, For example, an overcoat layer may be provided.
The overcoat layer may contain an ultraviolet absorber.
The overcoat layer is not particularly limited and may be appropriately selected depending on the intended purpose.For example, the overcoat layer contains a binder, a matting agent, and a surfactant, and further contains other components as necessary. It becomes.
The binder is not particularly limited and may be appropriately selected depending on the purpose. For example, thermosetting of acrylic resin, silicone resin, melamine resin, urethane resin, alkyd resin, fluorine resin, etc. Mold or photo-curable resin.
The thickness of the overcoat layer is preferably 0.01 μm to 1,000 μm, more preferably 0.02 μm to 500 μm, particularly preferably 0.1 to 10 μm, and particularly preferably 0.2 to 5 μm.

<4. Additives>
<< 4-1. UV absorber>
The heat ray shielding material of the present invention may have a layer containing an ultraviolet absorber.
The layer containing the ultraviolet absorber can be appropriately selected depending on the purpose, and may be an adhesive layer, or a layer (for example, an overcoat) between the adhesive layer and the metal particle-containing layer. Layer). In any case, the ultraviolet absorber is preferably added to a layer disposed on the side irradiated with sunlight with respect to the metal particle-containing layer.

  The ultraviolet absorber is not particularly limited and may be appropriately selected depending on the purpose. For example, a benzophenone ultraviolet absorber, a benzotriazole ultraviolet absorber, a triazine ultraviolet absorber, a salicylate ultraviolet absorber, Examples include cyanoacrylate ultraviolet absorbers. These may be used individually by 1 type and may use 2 or more types together.

  There is no restriction | limiting in particular as said benzophenone series ultraviolet absorber, According to the objective, it can select suitably, For example, 2,4 droxy-4-methoxy-5-sulfobenzophenone etc. are mentioned.

  The benzotriazole ultraviolet absorber is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 2- (5-chloro-2H-benzotriazol-2-yl) -4-methyl-6 -Tert-butylphenol (tinuvin 326), 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tertiarybutylphenyl) benzotriazole, 2- (2-hydroxy-3- 5-ditertiary butylphenyl) -5-chlorobenzotriazole and the like.

The triazine ultraviolet absorber is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include mono (hydroxyphenyl) triazine compounds, bis (hydroxyphenyl) triazine compounds, and tris (hydroxyphenyl) triazine compounds. Etc.
Examples of the mono (hydroxyphenyl) triazine compound include 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethyl). Phenyl) -1,3,5-triazine, 2- [4-[(2-hydroxy-3-tridecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) ) -1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-) 4-isooctyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) -4,6-bis ( 2,4-dimethylphenyl) -1,3,5-triazine, etc. Is mentioned. Examples of the bis (hydroxyphenyl) triazine compound include 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2 , 4-bis (2-hydroxy-3-methyl-4-propyloxyphenyl) -6- (4-methylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-3-methyl) -4-hexyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2-phenyl-4,6-bis [2-hydroxy-4- [3- (methoxyheptaethoxy) ) -2-hydroxypropyloxy] phenyl] -1,3,5-triazine and the like. Examples of the tris (hydroxyphenyl) triazine compound include 2,4-bis (2-hydroxy-4-butoxyphenyl) -6- (2,4-dibutoxyphenyl) -1,3,5-triazine, 2 , 4,6-Tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2,4,6-tris [2-hydroxy-4- (3-butoxy-2-hydroxypropyloxy) ) Phenyl] -1,3,5-triazine, 2,4-bis [2-hydroxy-4- [1- (isooctyloxycarbonyl) ethoxy] phenyl] -6- (2,4-dihydroxyphenyl) -1 , 3,5-triazine, 2,4,6-tris [2-hydroxy-4- [1- (isooctyloxycarbonyl) ethoxy] phenyl] -1,3,5-triazine, 2,4-bis [2 -Hydroxy-4- [1- (isooctyloxy) Carbonyl) ethoxy] phenyl] -6- [2,4-bis [1- (iso-octyloxy) ethoxy] phenyl] -1,3,5-triazine.

  The salicylate-based ultraviolet absorber is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include phenyl salicylate, p-tert-butylphenyl salicylate, p-octylphenyl salicylate, Examples include 2-ethylhexyl salicylate.

  There is no restriction | limiting in particular as said cyanoacrylate type ultraviolet absorber, According to the objective, it can select suitably, For example, 2-ethylhexyl-2-cyano-3,3-diphenylacrylate, ethyl-2-cyano-3 , 3-diphenyl acrylate and the like.

The binder is not particularly limited and may be appropriately selected depending on the intended purpose, but preferably has higher visible light transparency and higher solar transparency, and examples thereof include acrylic resin, polyvinyl butyral, and polyvinyl alcohol. . When the binder absorbs heat rays, the reflection effect by the metal tabular grains is weakened. Therefore, the ultraviolet absorbing layer formed between the heat ray source and the metal tabular grains is absorbed in the region of 450 nm to 1,500 nm. It is preferable to select a material that does not have a thickness, or to reduce the thickness of the ultraviolet absorbing layer.
The thickness of the ultraviolet absorbing layer is preferably 0.01 μm to 1,000 μm, and more preferably 0.02 μm to 500 μm. When the thickness is less than 0.01 μm, ultraviolet absorption may be insufficient, and when it exceeds 1,000 μm, the visible light transmittance may be reduced.
The content of the ultraviolet absorbing layer varies depending on the ultraviolet absorbing layer to be used and cannot be generally defined, but it is preferable to appropriately select a content that gives a desired ultraviolet transmittance in the heat ray shielding material of the present invention.
The ultraviolet transmittance is preferably 5% or less, and more preferably 2% or less. When the ultraviolet transmittance exceeds 5%, the color of the metal tabular grain layer may change due to ultraviolet rays of sunlight.

<< 4-2. Metal oxide particles >>
The heat ray shielding material of the present invention is preferable from the viewpoint of balance between heat ray shielding and production cost even if it contains at least one kind of metal oxide particles in order to absorb long wave infrared rays. In this case, for example, the overcoat layer preferably contains metal oxide particles. The overcoat layer may be laminated | stacked with the said metal oxide particle content layer through the base material. When the heat ray shielding material of the present invention is arranged so that the metal tabular grain-containing layer is on the incident direction side of heat rays such as sunlight, a part (or all) of the heat rays is reflected by the metal tabular grain-containing layer 2. After that, a part of the heat ray is absorbed by the overcoat layer, and the amount of heat directly received inside the heat ray shielding material due to the heat ray that is not absorbed by the metal oxide-containing layer and permeates the heat ray shielding material, and the heat ray The amount of heat as the total amount of heat absorbed by the metal oxide-containing layer 2 of the shielding material and indirectly transmitted to the inside of the heat ray shielding material can be reduced.
There is no restriction | limiting in particular as a material of the said metal oxide particle, According to the objective, it can select suitably, For example, a tin dope indium oxide (henceforth "ITO"), a tin dope antimony oxide (henceforth). , Abbreviated as “ATO”), zinc oxide, titanium oxide, indium oxide, tin oxide, antimony oxide, glass ceramics, and the like. Among these, ITO, ATO, and zinc oxide are more preferable, and infrared rays having a wavelength of 1,200 nm or more are preferably 90 in that they have excellent heat ray absorption ability and can produce a heat ray shielding material having a wide range of heat ray absorption ability when combined with metal tabular grains. In particular, ITO is preferable in that it has a visible light transmittance of 90% or more.
The volume average particle size of the primary particles of the metal oxide particles is preferably 0.1 μm or less in order not to reduce the visible light transmittance.
There is no restriction | limiting in particular as a shape of the said metal oxide particle, According to the objective, it can select suitably, For example, spherical shape, needle shape, plate shape, etc. are mentioned.

The content of the metal oxide particle-containing layer of the metal oxide particles is not particularly limited, as appropriate may be ^{selected, 0.1g / m 2 ~20g / m} 2 are preferred according to the purpose, more preferably ^{0.5g / m 2 ~10g / m 2} , 1.0g / m 2 ~4.0g / m 2 is more preferable.
If the content is less than 0.1 g / m ² , the amount of solar radiation felt on the skin may increase, and if it exceeds 20 g / m ² , the visible light transmittance may deteriorate. Meanwhile, the content is 1.0 g / m ² to 4.0 g / m ^2, can advantageously be avoided above two points.
The content of the metal oxide particles in the metal oxide particle-containing layer is, for example, from the observation of the super foil section TEM image and surface SEM image of the heat ray shielding layer, and the number of metal oxide particles in a certain area and It can be calculated by measuring the average particle diameter and dividing the mass (g) calculated based on the number and average particle diameter and the specific gravity of the metal oxide particles by the constant area (m ² ). . Further, metal oxide fine particles in a certain area of the metal oxide particle-containing layer are eluted in methanol, and the mass (g) of the metal oxide fine particles measured by fluorescent X-ray measurement is divided by the constant area (m ² ). This can also be calculated.

<5. Manufacturing method of heat ray shielding material>
There is no restriction | limiting in particular as a manufacturing method of the heat ray shielding material of this invention, According to the objective, it can select suitably, For example, the said metal particle content layer and the said ultraviolet absorption layer are applied to the surface of the said base material by the apply | coating method. In addition, a method of forming other layers as necessary may be mentioned.

-5-1. Method for forming metal particle-containing layer
The method for forming the metal particle-containing layer of the present invention is not particularly limited and may be appropriately selected depending on the purpose. For example, a dispersion having the metal tabular particles on the surface of the lower layer such as the substrate. May be applied by a dip coater, a die coater, a slit coater, a bar coater, a gravure coater, or the like, or may be subjected to surface orientation by a method such as an LB film method, a self-organization method, or spray coating. When producing the heat ray shielding material of the present invention, the composition of the metal particle-containing layer used in the examples described later, and by adding latex or the like, more than 80% by number of the hexagonal or circular plate metal particles are In the range of d / 2 from the surface of the metal particle-containing layer. It is preferable that 80% by number or more of the hexagonal or circular plate-like metal particles exist in a range of d / 3 from the surface of the metal particle-containing layer. Although there is no restriction | limiting in particular in the addition amount of the said latex, For example, it is preferable to add 1-10000 mass% with respect to a metal tabular grain.

  In addition, in order to accelerate | stimulate plane orientation, after apply | coating a metal tabular grain, you may accelerate | stimulate by passing through pressure bonding rollers, such as a calender roller and a laminating roller.

-5-2. Formation method of adhesive layer
The adhesive layer may be formed by coating on the metal particle-containing layer (or a substrate described later) or by bonding the metal particle-containing layer (or a substrate described later) and the adhesive layer. Although it is good, it is preferably formed by coating. For example, it can laminate | stack by application | coating on surfaces of lower layers, such as the said base material, the said metal particle content layer, and the said ultraviolet absorption layer. There is no limitation in particular as the coating method at this time, A well-known method can be used.

Among them, the method of applying a gel polymer described in Japanese Patent No. 4215527 is preferable. In this method, the above-described carboxylic acid-modified thermoplastic elastomer is introduced into a solvent such as toluene in order to produce the first adhesive layer material on the metal particle-containing layer (or base material described later). This is dissolved using a stirrer. A crosslinking agent is added to this solution, and then an antistatic agent is optionally added to produce the first adhesive layer material.
The first adhesive layer material is applied on the corona-treated surface of the base material layer. The coating method is not particularly limited as long as it can be applied in a liquid form. For example, in addition to the roller coating method, the brush coating method, the spray coating method, the dip coating method, a die coater, a bar coater A method using a knife coater is exemplified. Then, this is dried. The conditions may vary depending on the film thickness, the type of the selected solvent, etc., but can be, for example, 80 to 150 ° C. for 20 to 60 seconds, preferably 100 to 130 ° C. 30 to 50 seconds. Thereby, the 1st contact bonding layer which has a thickness of 1-50 micrometers can be provided on a base material layer.

  Then, on the first adhesive layer, the second adhesive layer material containing the thermoplastic elastomer and the cross-linking agent as described above in the content and / or mass ratio as described above, for example, any of the coating methods described above. Apply by. This is preferably dried at 80 to 150 ° C. for 0.5 to 2 minutes, more preferably at 100 to 130 ° C. for 40 seconds to 1.5 minutes, thereby forming a second adhesive layer having a thickness of 10 to 100 μm. It can be provided on the first adhesive layer. Next, if necessary, the release layer described above is provided on the second adhesive layer material. The heat ray shielding material of this invention which has an adhesion layer can be obtained by aging this for 2 to 6 days at 40-80 degreeC.

  On the other hand, an olefin gel polymer film (manufactured by Panac Co., Ltd.) described in JP-A-2004-29673 is also preferably bonded to the metal particle-containing layer (or a substrate described later).

-5-3. Method for forming overcoat layer / hard coat layer
The overcoat layer / hard coat layer is preferably formed by coating. The coating method at this time is not particularly limited, and a known method can be used. For example, a dispersion containing the ultraviolet absorber can be used as a dip coater, a die coater, a slit coater, a bar coater, a gravure coater, or the like. The method of apply | coating by etc. is mentioned.

<6. Characteristics of heat ray shielding material of the present invention>
The solar radiation reflectance of the heat ray shielding material of the present invention preferably has a maximum value in the range of 600 nm to 2,000 nm (preferably 800 nm to 1,800 nm) in that the efficiency of the heat ray reflectance can be increased. .
The visible light transmittance of the heat ray shielding material of the present invention is preferably 60% or more, and more preferably 70% or more. When the visible light transmittance is less than 60%, for example, when used as automotive glass or building glass, the outside may be difficult to see.
The ultraviolet ray transmittance of the heat ray shielding material of the present invention is preferably 5% or less, more preferably 2% or less. When the ultraviolet transmittance exceeds 5%, the color of the metal tabular grain layer may change due to ultraviolet rays of sunlight.
The haze of the heat ray shielding material of the present invention is preferably 20% or less. When the haze exceeds 20%, it may be unfavorable in terms of safety, for example, when it is used as glass for automobiles or glass for buildings, it becomes difficult to see the outside.

<7. Use Mode of Heat Ray Shielding Material>
The heat ray shielding material of the present invention is not particularly limited as long as it is an embodiment used for selectively reflecting and / or absorbing heat rays (near infrared rays), and may be appropriately selected according to the purpose. Examples include vehicle glass or film, building material glass or film, and agricultural film. Among these, the glass or film for vehicles, the glass or film for building materials are preferable from the viewpoint of energy saving effect.
In addition, in this invention, a heat ray (near infrared rays) means the near infrared rays (780 nm-2500 nm) contained about 50% in sunlight.

[Heat shield glass]
The heat-shielding glass of the present invention is characterized in that glass is adhered on the adhesive layer of the heat ray shielding material of the present invention.
There is no restriction | limiting in particular as a manufacturing method of the said glass, According to the objective, it can select suitably, The adhesive layer of the heat ray shielding material of this invention manufactured as mentioned above is used for vehicles, such as vehicles, and building materials. Can be attached to glass.

  In particular, when producing a thermal barrier glass as a vehicle glass for automobiles or the like, it is preferably produced as a laminated glass. When manufacturing the laminated glass of this invention, the heat ray shielding material of this invention can be inserted | pinched and used for the PVB intermediate film, EVA intermediate film, etc. which are used for manufacture of a normal laminated glass. Further, only the heat ray shielding layer containing the silver tabular grains and the metal oxide particles may be transferred to a PVB intermediate film, an EVA intermediate film, etc., and used with the substrate peeled off.

[Building glass]
The heat ray shielding material of the present invention can be suitably used as a building material. When using as a building material, it is preferable to make the heat ray shielding material of the present invention into the shape of a heat shielding film and affix it by an arbitrary method to make glass for building material. When the glass of the heat ray shielding material of the present invention is laminated to obtain the glass for shielding or glass for building materials of the present invention, the heat ray shielding material of any configuration of FIGS. The effect which is excellent in heat insulation durability at the time of combining can be acquired. When manufacturing the glass for building materials of this invention, it is preferable to affix the adhesion layer of the said heat insulation film on a window glass or a partition. At this time, there are a method of applying to the inside of the house and a method of applying to the outside.
An advantage of sticking the heat ray shielding material of the present invention to the inside of a house is that it is not necessary to worry about wind and rain resistance, and an inexpensive material can be used as the adhesive material. When the heat ray shielding material of the present invention is applied to the inside of a house, the surface of the metal particle-containing layer on which 60% or more of the hexagonal or circular plate-like metal particles are exposed on the surface is the adhesive. The outermost surface on the side opposite to the layer is preferable. Furthermore, between the surface opposite to the surface of the metal particle-containing layer on which 60% by number or more of the hexagonal or circular plate-like metal particles are exposed on the surface, and the adhesive layer, It is preferable to have a substrate. Specifically, as shown in FIG. 6, an embodiment in which the adhesive layer 11 of the heat ray shielding material 10 having the configuration shown in FIG. In the configuration of FIG. 6, the building material glass of the present invention is further installed by using it for window glass as a building material glass application, so that the metal particle-containing layer 2 of the heat ray shielding material 10 becomes the outermost surface on the indoor side. Antibacterial properties can also be imparted. Here, in the present specification, the antibacterial property mainly means an effect of suppressing the growth of molds, microorganisms and the like, and may include an effect of preventing the generation of unpleasant odors as a secondary matter. Such an antibacterial imparting effect is not limited to use in building glass applications, and can also be imparted to opaque glass or colored glass other than transparent glass.
As a merit of sticking the heat ray shielding material of the present invention to the outside of the house, especially in the reflective heat shield film, the heat ray is reflected on the outside, so the absorbed light to the glass can be reduced, and the heat ray cut is more effective than the inside sticking. There is a point that can be done.

In the heat ray shielding material of the present invention, since the adhesive layer has self-adhesiveness and re-peelability, it can be easily attached to glass, and can be easily attached again when necessary, such as when bubbles are mixed in or when it is replaced. be able to.
There are several types of construction methods for attaching a heat ray shielding material to glass. The main method when using the heat ray shielding material of the present invention having an adhesive layer having self-adhesiveness and removability is water adhesion, dry Pasting and electrostatic application can be mentioned.

In the case of the heat ray shielding material of the present invention, the construction method can be simply attached to the glass window in a dry state without using water. However, when pasting on a large window, the entire positioning is troublesome, and if the position is determined from the end, it is likely to cause a position shift at the opposite end.
Taking these points into account, it is reasonable to apply water to the entire positioning fine correction in the initial stage of application. Water droplets are sprayed on the entire surface of one side of the glass plate, the heat ray shielding material of the present invention made into a heat shielding film form from the adhesive material side is placed along the glass plate, and pasted while the heat shielding film can slide on the glass plate Position in the desired area. Once the position is determined, press several points on the edge strongly to stop the slide of the film, and use the squeegee or roller to push out the pinched water from the center to the edge. After that, if it is left for about one day, the adhesive strength increases and the film does not peel off. The merit of this method is that it can be installed at any site and the tools used can be general ones, so it has a wide range of applications regardless of whether it is newly built or used. Moreover, water sticking is preferable in that it can be easily attached to a glass having a small size as compared with heat lamination or electrostatic application. In addition, compared with heat laminating and electrostatic application that are generally performed in roll size, water sticking can prepare heat ray shielding material (heat shielding film) according to glass of various sizes, and waste of scrap material is lost. It is preferable also from a viewpoint applicable so that it may not arise.
In the electrostatic application method, glass is placed on a grounded metal plate, a heat ray shielding material (heat shielding film) including an adhesive layer is placed on it, and a voltage of several tens of volts is applied to the metal wire from several cm above. It is preferable that the heat ray shielding material (heat shielding film) is applied to the glass by applying an electrostatic force. Electrostatic application can produce a force to attach a film with a width of several centimeters around the metal wire, so by gradually moving the metal wire from the end to the center and the opposite end, the entire surface can be attached it can. Since static electricity becomes weaker with time, it is better to provide an adhesive layer only at a slight width at the end so that it cannot be peeled off with time. In that case, an adhesive layer should be provided with no gap at the end so that the area at the beginning of sticking becomes a bag path, and the opposite end has a gap in the pole part so that the sandwiched air can escape, After the whole surface is pasted, the procedure of sealing the gap with a highly viscous adhesive to prevent the return of air is good. This method can work smoothly as a continuous process if it is docked with a laminator and a grounded metal plate and an electrostatically applied metal wire zone are provided immediately after the lamination roll. As an advantage of this method, the glass side surface of the thermal barrier film is moderately roughened, or fine beads are dispersed in the sandwiched area, an air layer is created between the film and the glass, and the heat insulation effect is greatly enhanced. Can be mentioned. Since the haze degree increases to some extent as a whole, it is effective as a means for improving the appearance to adjust the use of an adhesive layer having increased scattering properties in accordance with the haze degree. In the case of this method, it is important that the heat shield film is made of a material that is easy to apply electrostatic. What is necessary is just to make the dielectric constant as the whole heat-shielding film high by using a fixed amount of magnesium at the time of material polymerization of the PET film to be used.

The features of the present invention will be described more specifically with reference to the following examples.
The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.

(Production Example 1)
-Synthesis of silver tabular grains-
--Synthesis process of tabular core grains--
2.5 mL of 0.5 g / L polystyrene sulfonic acid aqueous solution was added to 50 mL of 2.5 mM sodium citrate aqueous solution and heated to 35 ° C. To this solution, 3 mL of 10 mM sodium borohydride aqueous solution was added, and 50 mL of 0.5 mM silver nitrate aqueous solution was added with stirring at 20 mL / min. This solution was stirred for 30 minutes to prepare a seed solution.
--First growth step of tabular grains--
Next, 87.1 mL of ion-exchanged water was added to 132.7 mL of a 2.5 mM sodium citrate aqueous solution and heated to 35 ° C. 2 mL of 10 mM ascorbic acid aqueous solution was added to this solution, 42.4 mL of the seed solution was added, and 79.6 mL of 0.5 mM silver nitrate aqueous solution was added at 10 mL / min with stirring.
--Second growth step of tabular grains--
Next, after stirring the said solution for 30 minutes, 71.1 mL of 0.35M potassium hydroquinonesulfonate aqueous solution was added, and 200 g of 7 mass% gelatin aqueous solution was added. To this solution was added a white precipitate mixture formed by mixing 107 mL of a 0.25 M aqueous sodium sulfite solution and 107 mL of a 0.47 M aqueous silver nitrate solution. Immediately after the white precipitate mixture was added, 72 mL of 0.83 M aqueous NaOH was added. At this time, an aqueous NaOH solution was added while adjusting the addition rate so that the pH did not exceed 10. This was stirred for 300 minutes to obtain a silver tabular grain dispersion liquid a.

In this silver tabular grain dispersion liquid a, it was confirmed that silver hexagonal tabular grains having an average equivalent-circle diameter of 210 nm (hereinafter referred to as Ag hexagonal tabular grains) were formed. Moreover, when the thickness of the hexagonal tabular grains was measured with an atomic force microscope (Nanocute II, manufactured by Seiko Instruments Inc.), it was found that tabular grains having an average of 18 nm and an aspect ratio of 11.7 were produced. .
Next, about the obtained silver tabular grain and the heat ray shielding material, various characteristics were evaluated as follows. The results are shown in Table 1.

<< Evaluation of silver tabular grains >>
-Ratio of tabular grains, average grain size (average equivalent circle diameter), coefficient of variation-
The shape uniformity of the Ag tabular grains was determined by comparing the shape of 200 grains arbitrarily extracted from the observed SEM image, A for hexagonal or circular tabular metal grains, and B for irregular shaped grains such as teardrops. As a result, the ratio of the number of particles corresponding to A (number%) was determined.
Similarly, the particle diameter of 100 particles corresponding to A is measured with a digital caliper, the average value is defined as the average particle diameter (average equivalent circle diameter), and the standard deviation of the particle size distribution is the average particle diameter (average equivalent circle diameter). ) To obtain the coefficient of variation (%).

-Average particle thickness-
The obtained dispersion containing tabular silver particles is dropped on a glass substrate and dried, and the thickness of one tabular silver particle is measured using an atomic force microscope (AFM) (Nanocute II, manufactured by Seiko Instruments Inc.). It was measured. The measurement conditions using the AFM were a self-detecting sensor, DFM mode, a measurement range of 5 μm, a scanning speed of 180 seconds / frame, and a data point of 256 × 256.

-Aspect ratio-
The aspect ratio was calculated by dividing the average particle diameter (average equivalent circle diameter) by the average grain thickness from the average grain diameter (average equivalent circle diameter) and average grain thickness of the obtained silver tabular grains.

-Transmission spectrum-
The transmission spectrum of the obtained tabular silver particle dispersion was obtained by diluting the tabular silver particle dispersion 40 times with water and placing it in a quartz cell having an optical path length of 1 mm. V-670).

(Production Example 2)
In Production Example 1, a tabular silver particle dispersion b was produced in the same manner as in Production Example 1, except that 72 mL of ion-exchanged water was added instead of adding 72 mL of 0.83 M NaOH aqueous solution.

(Production Example 3)
In Production Example 1, instead of adding 87.1 mL of ion-exchanged water, changing the amount of the seed crystal solution to 127.6 mL, and instead of adding 72 mL of 0.83 M NaOH aqueous solution, 0.08 M A silver tabular grain dispersion c was prepared in the same manner as in Production Example 1 except that 72 mL of an aqueous NaOH solution was added.

(Production Example 4)
In Production Example 3, a silver flat plate was produced in the same manner as in Production Example 3, except that 132.7 mL of a 2.5 mM aqueous sodium citrate solution was not added and that the addition amount of the seed crystal solution was changed to 255.2 mL. A particle dispersion d was prepared.

(Production Example 5)
In Production Example 4, a silver tabular grain dispersion liquid e was produced in the same manner as in Production Example 4 except that 72 mL of ion-exchanged water was added instead of adding 72 mL of a 0.08 M NaOH aqueous solution.

(Production Example 6)
In Production Example 1, the amount of the seed crystal solution was changed from 42.4 mL to 21.2 mL, and 21.2 mL of ion-exchanged water was added. Produced.

[Example 1]
-Production of metal particle containing layer-
0.75 mL of 1N NaOH is added to 16 mL of the tabular silver particle dispersion e of Production Example 5 and 24 mL of ion-exchanged water is added. Then, centrifugation was performed to precipitate Ag hexagonal tabular grains. The supernatant liquid after centrifugation was discarded, 5 mL of water was added, and the precipitated Ag hexagonal tabular grains were redispersed. 1.6 mL of a 2% by mass aqueous methanol solution of a compound represented by the following structural formula (1) (water: methanol = 1: 1 (mass ratio)) was added to the dispersion to prepare a coating solution. This coating solution was applied to a wire coating bar No. 14 (manufactured by R.D.S. Webster NY) was applied onto a 50 μm thick PET film (A4300, manufactured by Toyobo Co., Ltd.) and dried to fix the Ag hexagonal tabular grains on the surface. Film was obtained. Thus, a metal particle-containing layer (hereinafter also referred to as AgND-containing layer) was produced.

-Confirmation of orientation state of Ag hexagonal tabular grains of AgND containing layer-
After depositing a carbon thin film on the obtained PET film so as to have a thickness of 20 nm, SEM observation (manufactured by Hitachi, Ltd., FE-SEM, S-4300, 2 kV, 20,000 times) was performed. It was found that the Ag hexagonal tabular grains were fixed without aggregation on the PET film, and the area ratio of the Ag hexagonal tabular grains to the substrate surface measured as follows was 45%. Moreover, it turned out that content in the said silver tabular grain surface orientation layer of the said silver tabular grain measured as follows is 0.04 g / m < ² >. At this time, Ag hexagonal tabular grains were exposed and arranged on the surface of the silver tabular grain-containing layer of the film.

-Creation of adhesive layer-
Tuftec M1911 [manufactured by Asahi Kasei maleic acid modified SEBS melt index (200 ° C., 5 kg) 3.5 g / 10 min styrene: ethylene + butylene mass ratio 30:70 acid value 2] 13 parts in propylene stirrer (13% solids). To 100 parts of this solution, 1.04 parts of Coronate HL [Hexamethylene diisocyanate-burette type manufactured by Nippon Polyurethane Industry] was mixed at room temperature. In addition, as an antistatic agent for application, Elegan 264wax [Nippon Yushi Fatty Cationic Antistatic Agent] was added to the mixed solution in 0.13 part to obtain a first adhesive layer material.
This first adhesive layer material was coated with a Mayer bar on the surface of the PET film in which the Ag hexagonal tabular grains were fixed to the surface of the metal particle-containing layer manufactured above. did. It dried at 120 degreeC for 40 second (s), and 2 micrometers of 1st contact bonding layers were provided on the surface where Ag hexagonal tabular grain is being fixed.
Next, 17% by mass of SEPS thermoplastic elastomer (mass average molecular weight 250,000) and 83% by mass of naphthenic oil plasticizer (flash point 220 ° C .; pour point −25 ° C .; specific gravity 0.8387; carbon number 5 to 6) are added to toluene. After being dissolved in the film, it was applied onto the first adhesive layer, dried at 100 ° C. for 1 minute, and provided with a second adhesive layer of 35 μm on the first adhesive layer, and then bonded to the silicone-treated PET as the release layer. . This was aged at 45 ° C. for 4 days to obtain the heat ray shielding material of Example 1. The configuration of the heat ray shielding material of Example 1 is as follows: release layer (silicone-treated PET) / adhesive layer (gel-coated second adhesive layer / first adhesive layer laminate) / metal particle-containing layer / substrate PET film Met.

-Production of thermal barrier glass (glass for building materials)-
Manufacturing glass for building materials:
The heat ray shielding material of Example 1 with an adhesive material was attached to the glass window for building materials of length 1800 mm × width 900 mm × thickness 3 mm from the indoor side. First, the heat ray shielding material of Example 1 with an adhesive material was placed along the glass window from the adhesive material side, and while the film was slid on the glass window, it was positioned in the area to be attached. After the position was determined, several portions of the end portion were strongly pressed to stop the slide of the film, and pasting was performed from the center portion toward the end portion using a squeegee to obtain the heat shielding glass of Example 1.

[Example 2]
First, a double-sided tape (manufactured by Panac Co., Ltd., PD-S1 (trade name)) having a non-self-adhesive and non-removable (ie, normal) acrylic adhesive material on both sides was produced in Example 1. The PET film in which Ag hexagonal tabular grains were fixed on the surface of the metal particle-containing layer was directly bonded to the surface on which the Ag hexagonal tabular grains were fixed.
Next, the base material of the commercially available re-peeling adhesive film which is a base material with a re-peeling adhesive layer was bonded to the opposite side of said double-sided tape PD-S1. This re-peeling adhesive film was a (product name) gel polymer sheet manufactured by Panac Corporation. The base material was a PET film having a thickness of 50 μm, and the re-peeling adhesive layer was in close contact with almost the entire surface of the PET film (the surface not adhering to the metal particle-containing layer). The re-peeling adhesive layer was an olefin gel layer having a thickness of 38 μm and containing a copolymer of α-olefin and styrene.
Furthermore, the heat-shielding material of Example 2 was obtained by pasting the re-peeling adhesive layer of the peelable adhesive film obtained above with silicone-treated PET, which is the release layer used in Example 1.
The configuration of the heat ray shielding material of Example 2 is as follows: release layer (silicone-treated PET) / re-peeling adhesive layer (adhesive layer) / base material (PET film) / PD-S1 / metal particle-containing layer / base material PET film. Met.
Thereafter, a heat-shielding glass of Example 2 was produced in the same manner as in Example 1 except that the obtained heat ray shielding material of Example 2 was used.

[Example 3]
In a 500 ml 4-neck reaction vessel equipped with a stirrer, thermometer, condenser, addition funnel, and thermowatch, 84.0 grams of IOA (isooctyl acrylate) and 75 grams of ODA (octadecyl acrylate, 48% solids in ethyl acetate), 121 grams ethyl acetate, and 0.92 grams ABP (4-acryloyl-oxybenzophenone, 26% solids in ethyl acetate). A solution containing 0.36 grams of VAZO 64 (2,2 ″ -azobis (isobutyronitrile) commercially available from DuPont) in 20 grams of ethyl acetate was added to the addition funnel. Both the solution in the reaction vessel and the material in the addition funnel were then purged with argon (or nitrogen). Thereafter, the solution in the reaction vessel was heated to 55 ° C. and an initiator was added. After about 20 hours, a conversion of 98-99% was obtained. Next, the mixture was applied to the surface of the PET film in which the Ag hexagonal tabular grains were fixed to the surface of the metal particle-containing layer produced in Example 1, on the side where the Ag hexagonal tabular grains were fixed. An adhesive solution having a coating thickness after oven drying of 0.5 to 1.0 mil (ie, 12.5 to 25 μm) was obtained. The coating was passed under UV light (PPG UV processor equipped with a 30 watt / 2.5 cm medium pressure mercury lamp) three times at 25 meters / minute to obtain a heat ray shielding material of Example 3. The configuration of the heat ray shielding material of Example 3 was in the order of adhesive material coating layer / metal particle-containing layer / substrate PET film.
Then, the heat shield glass of Example 3 was manufactured like Example 1 except having used the obtained heat ray shielding material of Example 3.

[Example 4]
In Example 1, the first adhesive layer material was formed not on the surface of the PET film on which the Ag hexagonal tabular grains were fixed but on the surface of the PET film on the opposite side instead of the surface on which the Ag hexagonal tabular grains were fixed. Except that, the heat ray shielding material of Example 4 was obtained in the same manner as Example 1. The configuration of the heat ray shielding material of Example 4 is as follows: release layer (silicone-treated PET) / adhesion layer (second adhesive layer coated with gel / laminated body of first adhesive layer) / substrate PET film / metal particle-containing layer. Met.
Then, the heat shield glass of Example 4 was manufactured like Example 1 except having used the heat ray shielding material of Example 4 obtained.

[Comparative Example 1]
A non-self-adhesive and non-removable (that is, normal) double-sided tape was fixed with Ag hexagonal tabular grains of a PET film in which Ag hexagonal tabular grains were fixed on the surface of the metal particle-containing layer produced in Example 1. The heat ray shielding material of Comparative Example 1 was obtained by directly bonding to the surface on the side. The double-sided tape used was Panac PD-S1 (trade name).
Then, the heat insulation glass of the comparative example 1 was manufactured like Example 1 except having used the heat ray shielding material of the obtained comparative example 1. FIG.

<<< Evaluation of heat ray shielding material / heat shielding glass >>>
About the obtained heat ray shielding material and heat insulation glass of each Example and comparative example, various characteristics were evaluated as follows. The results of each evaluation are shown in Table 2 below.

-Measurement of the content of silver tabular grains-
The content of the silver tabular grains in the heat ray shielding layer is obtained by eluting the silver tabular grains in a fixed area of the heat ray shielding layer (coating film) into methanol, measuring the mass of the silver tabular grains by fluorescent X-ray measurement, and calculating the mass. It was calculated by dividing by the constant area.

-Area ratio-
About the obtained heat ray shielding material, the SEM image obtained by observing with a scanning electron microscope (SEM) is binarized, and the area A of the base material when the heat ray shielding material is viewed from above (with respect to the heat ray shielding material) The area ratio [(B / A) × 100], which is the ratio of the total area B of the silver tabular grains to the total projected area A) of the heat ray shielding material when viewed from the vertical direction, was determined.

-Particle tilt angle-
After embedding the heat ray shielding material with an epoxy resin, the heat ray shielding material was cleaved with a razor in a frozen state with liquid nitrogen, and a vertical section sample of the heat ray shielding material was produced. This vertical cross-sectional sample was observed with a scanning electron microscope (SEM), and the tilt angle (corresponding to ± θ in FIG. 5A) of the 100 metal tabular grains with respect to the horizontal plane was calculated as an average value.
○: The tilt angle is ± 30 ° or less.
X: The tilt angle exceeds ± 30 °.

-Exposure of tabular metal grains-
The state of the surface opposite to the PET film of the metal particle-containing layer of the heat ray shielding material was measured by SEM.
◯: 60% by number or more of metal tabular grains exposed on one surface of the metal particle-containing layer.
X: The metal tabular grain exposed on one surface of the metal particle-containing layer is less than 60% by number.
That the metal tabular grains are exposed on the surface of the metal particle-containing layer means that 60% by area or more of one surface of the metal tabular grains is at the same position or protrudes from the surface of the metal particle-containing layer.

-Visible light transmittance and initial near infrared reflectance-
The visible light transmittance is a value obtained by measuring each heat shielding glass sample by the method described in JIS-R3106: 1998 “Testing method of transmittance, reflectance, emissivity, and solar radiation acquisition rate of plate glass” from 380 nm. It is an average value of values obtained by correcting the transmittance of each wavelength measured up to 780 nm by the spectral visibility of each wavelength. The initial near-infrared reflectance is an average value of the reflectance of each wavelength obtained by measuring each sample from 780 nm to 2,000 nm.

-Heat shielding performance-Light resistance-
Light resistance is the light resistance of the shielding performance as a percentage of the ratio of the initial near-infrared transmittance to the near-infrared transmittance after the test when a certain light resistance test is imposed on each heat-shielding glass sample. The value of The line that should be good was 90% or more. The constant light resistance test is a test in which exposure is performed at 180 W / m, 63 ° C., 30% relative humidity, and 1,000 hours with a sunshine weather meter (Suga Test Instruments, xenon lamp irradiation).

-Radio wave transmission-
The heat ray shielding material (the state of the heat shielding film) before being bonded to the glass was measured using the KEC method at the Tokyo Metropolitan Industrial Technology Center. The shielding effect of 5 dB or less was judged to be radio wave permeable.

-Measurement of haze-
Using a haze meter (NDH-5000, manufactured by Nippon Denshoku Industries Co., Ltd.), the haze (%) of the heat shielding glass obtained as described above was measured.

(Peel strength)
The peel strength is a force required to peel the adhesive layer of the heat ray shielding material from the test glass support at a special angle and peel speed. This force is expressed in Newtons per 1 centimeter (cm) wide coated sheet. The procedure is as follows.
The strip of heat-shielding material with a pressure-sensitive adhesive layer obtained in each Example and Comparative Example having a width of 0.127 dm (decimeter) is firmly attached to the horizontal surface of the test glass support of at least 1.27 lines dm (linear dm). Contact with. The strip is applied by passing a 2 kg hard rubber roller three times in each direction. If air bubbles are trapped between the test glass support and the test strip, the sample is discarded. The free end of the covering strip is folded in half so that the peel angle is about 180 °. Attach its free end to the tensile tester scale. The heat ray shielding material with the adhesive layer obtained in each example and comparative example is fastened to a jaw of a tensile tester capable of removing the heat ray shielding material from the scale at a constant speed of 2.3 meters / minute. The holding time after roll-down is 30 seconds. Record the scale reading in Newton as the tape is peeled off the glass surface.
A preferable peel strength range is 0.1 to 3.0 N / cm. An adhesive material having a peel strength exceeding 3.0 N / cm is difficult to re-peel and is a non-re-peelable adhesive material.

-Thermal insulation durability-
About each produced heat ray shielding material, the solar reflectance was calculated | required based on the method of JIS5759 from the transmittance | permeability of each wavelength measured to 350 nm-2,100 nm. This was defined as a fresh shielding factor S0. After that, a simulation experiment of the temperature difference between day and night is conducted. In a state of being attached to the glass, 100 cycles of a heating / cooling cycle of 30 ° C. for 3 hours and 5 ° C. for 3 hours (temperature pattern transition time is 30 minutes) were performed, and the subsequent shielding coefficient was S100.
From the obtained heat insulation coefficient, the heat insulation durability was calculated by (S0 / S100) × 100 [%].

(Antibacterial)
Using the heat ray shielding material with an adhesive layer obtained in each Example and Comparative Example, each 4 cm square sample was brought into contact with a flask containing E. coli solution and then stored at 27 ° C. for 3 hours. Was measured. The sterilization rate (%) is represented by the sterilization rate (%) = [(XY) / X] × 100. Here, X represents the number of initial bacteria, and Y represents the number of bacteria after 3 hours.
Based on the measured results, antibacterial properties were evaluated according to the following criteria.
○: The sterilization rate is 99% or less.
X: The sterilization rate is less than 99%.

From Table 2 above, the heat ray shielding material of the present invention has high heat shielding performance (sunlight reflectivity), excellent heat insulation durability when bonded to glass, and good re-peelability and peel strength of the adhesive layer. I found out. In Example 1, the gel was applied as a coating solution and applied to the AgND surface. The re-peelability was good, and no shear stress was applied, so it was considered that the heat insulation durability was also good. In Example 2, a commercially available gel polymer sheet was bonded to the AgND surface, and the re-peelability was good, and since the shear stress was not applied, it was considered that the heat insulation durability was also good. Example 3 is a formulation in which re-peelability is improved in the conventional adhesive material, and the peel strength is inferior to that of the gel polymer, but is acceptable, and the heat shielding durability is 91%, which is inferior to the gel polymer, but is acceptable. Met. Example 4 was superior in antibacterial property to Example 1 by making AgND indoors in Example 1.
On the other hand, it was found that Comparative Example 1 uses a conventional adhesive, has poor removability, and has no heat insulation performance and durability. Although the mechanism for unevenly distributing the surface of the metal tabular grains has not been fully elucidated, it is essential that the metal particles float on the liquid surface during coating and drying, and the surface tension that will change during drying is balanced. I think it is important.

  The heat ray shielding material of the present invention has high heat shielding performance (sunlight reflectance), excellent heat shielding durability when bonded to glass, and also has good removability and peel strength of the adhesive layer. It can be suitably used as various members that are required to prevent transmission of heat rays, such as glass for vehicles such as buses and glass for building materials.

DESCRIPTION OF SYMBOLS 1 Base material 2 Metal particle content layer 3 Metal flat particle 10 Heat ray shielding material 11 Adhesion layer 20 Glass D Diameter L Thickness F ((lambda)) Particle existing area thickness

Claims (10)

A metal particle-containing layer containing at least one metal particle and an adhesive layer;
The metal particles have 60% by number or more of hexagonal or circular tabular metal particles,
The main plane of the hexagonal or circular plate-like metal particles is plane-oriented in an average range of 0 ° to ± 30 ° with respect to one surface of the metal particle-containing layer,
The heat ray shielding material, wherein the adhesive layer has self-adhesiveness and removability.   The heat ray shielding material according to claim 1, wherein the adhesive layer contains a carboxylic acid-modified thermoplastic elastomer.   The heat ray shielding material according to claim 1 or 2, wherein 60% by number or more of the hexagonal or circular plate-like metal particles are exposed on one surface of the metal particle-containing layer.   The surface of the metal particle-containing layer on which 60% by number or more of the hexagonal or circular plate-like metal particles are exposed on the surface is the outermost surface on the side opposite to the adhesive layer. The heat ray shielding material according to claim 3.   Between the adhesive layer and the surface opposite to the surface of the metal particle-containing layer on which 60% by number or more of the hexagonal or circular plate-shaped metal particles are exposed on the surface The heat ray shielding material according to claim 3 or 4, characterized by comprising: The hexagonal or circular plate-like metal particles have an average particle diameter of 70 nm to 500 nm,
The heat ray shielding material according to any one of claims 1 to 5, wherein the hexagonal or circular plate-like metal particles have an aspect ratio (average particle diameter / average particle thickness) of 8 to 40. .   The metal tabular grain contains at least silver, The heat ray shielding material according to any one of claims 1 to 6.   Infrared light is reflected, The heat ray shielding material as described in any one of Claims 1-7 characterized by the above-mentioned.   A heat-shielding glass, wherein a glass is affixed on the adhesive layer of the heat ray shielding material according to any one of claims 1 to 8.   A glass for building materials comprising the thermal barrier glass according to claim 9.

Images