JP2014194446A - Heat-ray shielding material, intermediate film for laminated glass, and laminated glass - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat-ray shielding material capable of achieving both a high visible transmittance and a low total solar transmittance TTS and to provide an intermediate film having the same for a laminated glass.SOLUTION: A heat-ray shielding material includes a heat-ray reflective layer containing tabular silver particles, and a heat-ray absorbing layer containing a plurality of types of metal oxide particles. The heat-ray reflective layer contains 15-45 mg/mof the tabular silver particles, and the metal oxide particles contained in the heat-ray absorbing layer includes at least a type of particle that contains a tin-doped indium oxide, a cesium-containing tungsten oxide (CWO), or both.

Description

  The present invention relates to a heat ray shielding material, an interlayer film for laminated glass, and laminated glass.

  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.

  Such a heat ray shielding material, from the viewpoint of the heat ray shielding properties (acquisition rate of solar heat), than the heat ray absorption type in which re-radiation of absorbed light into the room (about 1/3 of the absorbed solar energy) is present, A heat ray reflection type without re-radiation is desirable, and various proposals have been made.

Patent Document 1 discloses a heat ray shielding material having a metal particle-containing layer containing at least one kind of metal particles (silver in the example of the same document) and an ultraviolet absorbing layer containing at least one kind of ultraviolet absorber. The metal particles have 60% by number or more of hexagonal or circular tabular metal particles, and the main plane of the tabular metal particles is averaged with respect to one surface of the metal particle-containing layer. With a heat ray shielding material characterized in that the surface is oriented in the range of 0 ° to ± 30 °, the visible light transmittance and the solar reflectance are high, the durability and the weather resistance are excellent, and further, the ultraviolet rays over time. It is described that discoloration can be reduced.
Furthermore, Patent Document 1 discloses an example in which the heat shielding performance is further improved by further providing a metal oxide particle layer using tin-doped acid value indium particles. However, Patent Document 1 neither discloses nor suggests combining a plurality of types of metal oxide particles.

JP 2012-215825 A

  Under such circumstances, the present inventors examined the performance of the heat ray shielding material described in Patent Document 1, and further improved from the viewpoint of achieving both high visible light transmittance and low total solar transmittance TTS. Was found to be required. In addition to the combination of a metal oxide particle layer using ITO as metal oxide particles and a metal particle-containing layer (heat ray reflective layer) using silver tabular particles, the present inventors have also used CWO as metal oxide particles. Although the combination of the metal oxide particle layer used and the metal particle-containing layer using silver tabular grains was studied, TTS was sufficient even if the amount of silver (amount of silver tabular grains) used in the metal particle-containing layer was adjusted Could not be lowered.

  The problem to be solved by the present invention is to provide a heat ray shielding material capable of achieving both high visible light transmittance and low total solar transmittance TTS.

  As a result of intensive studies by the present inventors to solve the above problems, the content of the silver tabular grains in the heat ray reflective layer is controlled within a specific range, and a plurality of types of metal oxide particles are combined in the heat ray absorbing layer. It has been found that the inclusion of both high visible light transmittance and low total solar transmittance TTS can be achieved, and the present invention has been completed.

The present invention, which is a specific means for solving the above problems, is as follows.
[1] A heat ray reflective layer containing silver tabular grains and a heat ray absorbing layer containing a plurality of types of metal oxide particles, and the silver tabular grain content in the heat ray reflective layer is 15 to 45 mg / m ^2. The heat ray shielding material characterized by being.
[2] In the heat ray shielding material of [1], the heat ray reflective layer preferably has 60% by number or more of hexagonal or circular silver tabular grains.
[3] The heat ray shielding material according to [1] or [2] has the heat ray reflective layer, the layer A having a refractive index nA, and the layer B having a refractive index nB in this order, and the following conditions It is preferable to have a multilayer structure characterized by satisfying (1) or (2).
Condition (1) nA> nB and the following formula (1) is satisfied.
Formula (1):
λ / 8 + mλ / 2−λ / 12 <nA × dA <λ / 8 + mλ / 2 + λ / 12
(In the formula (1), m represents an integer of 0 or more, λ represents a wavelength to prevent reflection, and dA represents the thickness of the layer A.)
Condition (2) nA <nB and the following formula (2) is satisfied.
Formula (2):
3λ / 8 + mλ / 2−λ / 12 <nA × dA <3λ / 8 + mλ / 2 + λ / 12
(In the formula (2), m represents an integer of 0 or more, λ represents a wavelength to prevent reflection, and dA represents the film thickness of the layer A.)
[4] In the heat ray shielding material according to [3], m is preferably 0.
[5] The heat ray shielding material according to [3] or [4] preferably includes a layer C having a refractive index nC adjacent to the layer B, and the layer B satisfies the following condition (3). .
Condition (3) nA> nB and nB <nC, or nA <nB and nB> nC are satisfied, and the following formula (3) is satisfied.
Formula (3):
λ / 4 + Lλ / 2−λ / 12 <nB × dB <λ / 4 + Lλ / 2 + λ / 12
(In the formula (3), L represents an integer of 0 or more, λ represents a wavelength to prevent reflection, and dB represents the film thickness of the layer B.)
[6] In the heat ray shielding material according to [5], the L is preferably 0.
[7] In the heat ray shielding material according to [5] or [6], the layer B is a stacked body of a plurality of layers B ″ having different refractive indexes, and any layer included in the layer B ″ It is preferable to satisfy the formula (3).
[8] The heat ray shielding material according to any one of [3] to [7], wherein the heat ray reflective layer satisfies the condition (1) or (2) on the opposite side of the layer A and the layer B. It is preferable to have the second layer A and the second layer B in the order of the layer A, the layer B, the second layer (A), and the second layer (B).
[9] In the heat ray shielding material according to any one of [3] to [8], it is preferable that the wavelength λ to be prevented from being reflected is 400 nm to 700 nm.
[10] In the heat ray shielding material according to any one of [1] to [9], at least one of the metal oxide particles contained in the heat ray absorbing layer contains tin-doped indium oxide (ITO) and cesium. It is preferably any of tungsten oxide (CWO).
[11] In the heat ray shielding material according to any one of [1] to [10], the metal oxide particles contained in the heat ray absorbing layer are tin-doped indium oxide (ITO) and cesium-containing tungsten oxide (CWO). It is preferable that both are included.
[12] In the heat ray shielding material according to any one of [1] to [11], the content of cesium-containing tungsten oxide (CWO) contained in the heat ray absorbing layer is 0.3 to 1.3 g / m. ² is preferred.
[13] The heat ray shielding material according to any one of [1] to [12] further includes a support, and the heat ray reflective layer and the heat ray absorption layer are disposed on opposite sides of the support. It is preferable.
[14] An interlayer film for laminated glass comprising the heat ray shielding material according to any one of [1] to [13].
[15] A laminated glass comprising the interlayer film for laminated glass according to [14] and at least two glass plates, wherein the interlayer film for laminated glass is inserted into the two sheets of glass. .

  According to the present invention, it is possible to provide a heat ray shielding material capable of achieving both high visible light transmittance and low total solar transmittance TTS.

FIG. 1 is a schematic view showing an example of the laminated glass of the present invention including the heat ray shielding material of the present invention. FIG. 2 is a schematic view showing the laminated glass of Comparative Example 3 including the heat ray shielding material of Comparative Example 3. FIG. 3 is a schematic view showing another example of the laminated glass of the present invention including the heat ray shielding material of the present invention. FIG. 4 is a schematic view showing an example of the laminated glass of the present invention including the heat ray shielding material of the present invention. FIG. 5 is a schematic view showing an example of the laminated glass of the present invention including the heat ray shielding material of the present invention. FIG. 6A is a schematic cross-sectional view showing the existence state of a heat ray reflective layer containing silver tabular grains in the heat ray shielding material of the present invention, and a heat ray reflective layer containing silver tabular grains (parallel to the plane of the substrate); The figure explaining angle ((theta)) with the main plane (surface which determines circle equivalent diameter D) of a silver tabular grain is shown. FIG. 6B is a schematic cross-sectional view showing the existence state of a heat ray reflective layer containing silver tabular grains in the heat ray shielding material of the present invention, and the presence of silver tabular grains in the depth direction of the heat ray shielding material of the heat ray reflective layer. It is a figure which shows an area | region. FIG. 6C is a schematic cross-sectional view showing an example of the presence state of a heat ray reflective layer containing metal tabular grains in the heat ray shielding material of the present invention. FIG. 7A is a schematic perspective view showing an example of the shape of a silver tabular grain preferably used in the heat ray shielding material of the present invention, and shows a circular silver tabular grain. FIG. 7B is a schematic perspective view showing an example of the shape of silver tabular grains preferably used in the heat ray shielding material of the present invention, and shows hexagonal silver tabular grains.

  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.

[Heat ray shielding material]
The heat ray shielding material of the present invention has a heat ray reflective layer containing silver tabular grains and a heat ray absorption layer containing a plurality of types of metal oxide particles, and the silver tabular grain content in the heat ray reflective layer is 15. characterized in that it is a ~45mg / m ^2.
With such a configuration, the heat ray shielding material can achieve both high visible light transmittance and low total solar transmittance TTS.
Hereinafter, the more preferable aspect of the heat ray shielding material of this invention is demonstrated concretely.

<Characteristics of heat ray shielding material>
The visible light transmittance of the heat ray shielding material of the present invention is preferably 60% or more, more preferably 65% or more, particularly preferably 70% or more, and preferably 72% or more. More particularly preferred. When the visible light transmittance is 60% or more, for example, when used as glass for automobiles or glass for buildings, the outside is easy 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 from the viewpoint of shielding sunlight, preventing an increase in room temperature, and cutting ultraviolet rays harmful to health. 1% or less is particularly preferable, and 0.5% or less is particularly preferable.

<Configuration of heat ray shielding material>
The heat ray shielding material of this invention has a heat ray reflective layer and the heat ray absorption layer containing a multiple types of metal oxide particle in this order from the external light side. Furthermore, the aspect which has other layers, such as an easily bonding layer, an undercoat layer, an overcoat layer, an adhesion layer, a support body (henceforth a base material), a backcoat layer as needed, is also preferable.
Hereinafter, the preferable structure of the heat ray shielding material of this invention is demonstrated based on drawing.

FIG. 1 is an example of laminated glass, in which a heat ray shielding material is sandwiched between a glass plate 21 and an intermediate film 22. Details of the laminated glass will be described later.
As a preferred embodiment of the heat ray shielding material of the present invention, as shown in FIG. 1, the heat ray shielding material of the present invention comprises a heat ray reflecting layer 2 containing silver tabular grains and a heat ray absorption containing a plurality of types of metal oxide particles. And a heat ray reflecting layer 2 and a heat ray absorbing layer 14 on opposite sides of the support 1. By setting it as such an aspect, the heat ray shielding material which can make high visible light transmittance | permeability and low total solar transmittance TTS compatible can be provided.

As a preferred embodiment of the heat ray shielding material of the present invention, as shown in FIG. 3, the heat ray shielding material of the present invention is a heat ray absorbing layer 14 containing a plurality of types of metal oxide particles, the support 1, and The layer 5B (1 and 5B) having a refractive index of nB, the layer 5A (undercoat layer 5A) having a refractive index of nA, and the heat ray reflective layer 2 in this order, and the following condition (1) or (2) It is a mode to satisfy. By adopting an embodiment having the heat ray reflective layer 2, the layer 5A, and the layer 5B in this order, an antireflection function is imparted, and the amount of reflection of light incident from the front side, particularly obliquely (for example, 60 °) is suppressed. From the viewpoint of being able to do so.
Condition (1) nA> nB and the following formula (1) is satisfied.
Formula (1):
λ / 8 + mλ / 2−λ / 12 <nA × dA <λ / 8 + mλ / 2 + λ / 12
(In the formula (1), m represents an integer of 0 or more, λ represents a wavelength to prevent reflection, and dA represents the thickness of the layer A.)
Condition (2) nA <nB and the following formula (2) is satisfied.
Formula (2):
3λ / 8 + mλ / 2−λ / 12 <nA × dA <3λ / 8 + mλ / 2 + λ / 12
(In the formula (2), m represents an integer of 0 or more, λ represents a wavelength to prevent reflection, and dA represents the film thickness of the layer A.)

  In said Formula (1) and said Formula (2), m represents an integer greater than or equal to 0, and it is preferable from a viewpoint of the robustness of manufacturing cost or a film thickness that it is an integer of 0-5.

  In the heat ray shielding material of the present invention, m is preferably 0 from the viewpoint of suppressing reflection and reflection of obliquely incident light, from the viewpoint of improving productivity due to the thin film thickness and easy film thickness control. . By setting the resonance mode of the heat ray reflective layer containing silver tabular grains to the lowest order m = 0 (in the vicinity of 1 / 8λ in the case of a high refractive index and in the vicinity of 3 / 8λ in the case of a low refractive index), it is 60 ° oblique with respect to the front incidence. Both can be provided with an antireflection effect, and both visible light transmittance and suppression of reflection can be achieved.

  Note that m may be an integer of 1 to 5 from the viewpoint of achieving a design that achieves both suppression of reflection of visible light and enhancement of reflection of near-infrared light. In this case, 1 is 1 to suppress reflection of visible light and 1000 nm. It is preferable from the viewpoint of enhancing reflection of near infrared rays in the vicinity. Further, if m> 5, the film thickness becomes too large, and precise control of the film thickness becomes difficult, so m <= 5 is preferable from the viewpoint of productivity.

  The range of film thickness (optical path difference) at which the antireflection effect is obtained includes the range of optically allowable deviation. In consideration of optical effects, the antireflection effect can be sufficiently obtained in the range of ± λ / 12. Therefore, in the formulas (1) and (2), the term of −λ / 12 and + λ / 12 A term is provided. The deviation is preferably within this film thickness range, and more preferably within a range of ± λ / 16.

That is, the formula (1) preferably satisfies the following formula (1 ′), and the formula (2) preferably satisfies the following formula (2 ′).
Formula (1 ′):
λ / 8 + mλ / 2−λ / 16 <nA × dA <λ / 8 + mλ / 2 + λ / 16
(In the formula (1 ′), m represents an integer of 0 or more, λ represents a wavelength to prevent reflection, and dA represents a film thickness of the layer A.)
Formula (2 ′):
3λ / 8 + mλ / 2−λ / 16 <nA × dA <3λ / 8 + mλ / 2 + λ / 16
(In the formula (2 ′), m represents an integer of 0 or more, λ represents a wavelength to prevent reflection, and dA represents a film thickness of the layer A.)
The preferred range of m in the formula (1 ′) and the formula (2 ′) is the same as the preferred range of m in the formula (1) and the formula (2).

  The layers 5A and 5B are not limited to the configuration shown in FIG. For example, the layer 5A may be a functional layer other than the undercoat layer, and the layer 5B may be a functional layer or support other than the undercoat layer. Examples of other functional layers include an easily adhesive layer.

In the configuration of FIG. 3, particularly when the layer B is a support, a support having a refractive index of 1.5 or more, which is higher than ordinary glass (refractive index n is 1.5 or less) at a wavelength λ to prevent reflection. By using the body, it is easy to make the refractive index larger than the refractive index n2 of the layer A, which is preferable from the viewpoint that the support itself can be used as the layer B utilizing the refractive index of the support itself. Further, when the layer B is a support, it is more preferable to use a support having a refractive index of 1.55 or more, and it is particularly preferable to use a support having a refractive index of 1.61 or more.
The preferable range of the layer B in FIG. 3 is the same as the preferable range of the layer B in FIGS.

  As a preferred embodiment of the heat ray shielding material of the present invention, as shown in FIG. 4, a layer 5A having a refractive index of nA is provided as an undercoat layer 5A, and a layer 5B having a refractive index of nB is provided as a second undercoat. It has the layer 5B, the layer C as the support 1, and an embodiment that satisfies the condition (1) or the condition (2). By having an aspect having the heat ray reflective layer, the layer A, and the layer B in this order, an antireflection function is imparted, and the amount of reflection of light incident from the front, particularly obliquely (for example, 60 °) is suppressed. It is preferable from the viewpoint that can be achieved.

In the configuration of FIG. 4, the layer B preferably satisfies the following formula (3) from the viewpoint of obtaining a better antireflection effect. In particular, when both the layer A and the layer C sandwiching the layer B are dielectrics, the layer B preferably satisfies the following formula (3) from the viewpoint of antireflection.
Condition (3) nA> nB and nB <nC, or nA <nB and nB> nC are satisfied, and the following formula (3) is satisfied.
Formula (3):
λ / 4 + Lλ / 2−λ / 12 <nB × dB <λ / 4 + Lλ / 2 + λ / 12
(In the formula (3), L represents an integer of 0 or more, λ represents a wavelength to prevent reflection, and dB represents the film thickness of the layer B.)
A preferable range of the formula (3) will be described. In addition, the preferable range of the said Formula (3) below is the same also in the heat ray shielding material of this invention other than the structure of FIG.
In said Formula (3), L represents an integer greater than or equal to 0, it is preferable that it is 0-5, and the viewpoint by which reflection and reflection of obliquely incident light are suppressed that 0 is the production | generation by thin film thickness. It is more preferable from the viewpoint of improvement of the property and easy control of the film thickness. By setting the resonance mode of the heat ray reflective layer containing silver tabular grains to the lowest order L = 0, it is possible to provide an antireflection effect for both front incidence and oblique 60 °, and the visible light transmittance and reflection It is possible to achieve both suppression of jamming.

In consideration of optical effects, the antireflection effect can be sufficiently obtained in the range of ± λ / 12. Therefore, the term of −λ / 12 and the term of + λ / 12 are provided in the equation (3). The deviation is preferably within this film thickness width, and more preferably within a range of ± λ / 16.
That is, the formula (3) preferably satisfies the following formula (3 ′).
Formula (3 ′):
λ / 4 + Lλ / 2−λ / 16 <nB × dB <λ / 4 + Lλ / 2 + λ / 16
(In the formula (3 ′), L represents an integer of 0 or more, λ represents a wavelength to prevent reflection, and dB represents the film thickness of the layer B.)
The preferable range of L in the formula (3 ′) is the same as the preferable range of L in the formula (3).

  In the formulas (1) to (3), the wavelength λ to be prevented from being reflected is not particularly limited, and examples thereof include visible light, infrared light, and ultraviolet light bands. Light is preferable from the viewpoint of use as a heat ray shielding material, and the heat ray reflective material of the present invention preferably has a wavelength λ of 400 to 700 nm, more preferably 550 nm ± 50 nm, to prevent reflection.

  In the configuration of FIG. 4, the refractive index nc at the wavelength λ at which reflection of the layer C is to be prevented is larger than the refractive index nB at the wavelength λ at which reflection of the layer B is to be prevented. However, it is preferable from the viewpoint that optical interference with the reflected light of the heat ray reflective layer occurs and a better antireflection effect can be obtained. In particular, when the layer C is a support, by using a support having a refractive index of 1.5 or more, which is higher than ordinary glass (refractive index n is 1.5 or less) at a wavelength λ to prevent reflection, It is preferable from the viewpoint that the refractive index can be easily larger than the refractive index n2 of the layer B, and can be used as the layer C by utilizing the refractive index of the support itself. Further, when the layer C is a support, it is more preferable to use a support having a refractive index of 1.55 or more.

  As a preferred embodiment of the heat ray shielding material of the present invention, as shown in FIG. 5, a heat ray absorbing layer 14, a support 1, a layer 5B (undercoat layer 5B) having a refractive index of nB, and a layer 5A having a refractive index of nA ( The second undercoat layer 5 </ b> A), the heat ray reflective layer 2, and the layer 4 (overcoat layer 4) having a refractive index of nA ′ are provided in this order and satisfy the above condition (1) or (2). By making it the aspect which has the layer 4, the heat ray reflective layer 2, the layer 5A, and the layer 5B in this order, it is preferable from a viewpoint of reducing a reflection further.

In addition, in the heat ray shielding material of the present invention, the layer B is a laminate composed of a plurality of layers B ″, and each layer B ″ satisfies the formula (3) to prevent reflection. (This embodiment is not shown).
The heat ray shielding material of the present invention preferably has a configuration in which the layer C satisfies the formula (3). In the case of this configuration, a layer satisfying the formula (3) may be further provided on the layer C.
Thus, by having a plurality of layers satisfying the above formula (3), it is possible to suppress reflection at the wavelength λ where reflection is desired.

Moreover, the heat ray shielding material of this invention is the 2nd layer A 'and 2nd layer B' which satisfy | fill the said conditions (1) or (2) on the opposite side of the said layer A and the said layer B of a heat ray reflective layer. A mode in which the layer A, the layer B, the second layer A ′, and the second layer B are included in this order is also preferable. By adopting such an embodiment, interference layers can be provided on both sides of the heat ray reflective layer, providing a more antireflection function, and the amount of reflection of light incident from the front, particularly obliquely (for example, 60 °) can be further increased. The effect that it can suppress is acquired.
In addition, it is not necessary for the heat ray shielding material of the present invention to include all of the above-described interference layers (layer A, layer B, layer C, layer A ′, layer B ′, etc.), as shown in FIG. A known intermediate film (for example, PVB layer) used when forming the intermediate film or the laminated glass may have a part of the functions of the interference layer. In FIG. 5, the intermediate film is used as the layer B ′, and the overcoat layer 4 and the intermediate film 22 are used as the second layer A ′ and the second layer B ′ that satisfy the above condition (1) or (2). An embodiment was shown.

(Arrangement of each layer and form of multilayer structure)
In the heat ray shielding material of the present invention, plasmon resonance caused by silver particles contained in the heat ray reflective layer is achieved by satisfying the condition (1) or (2) and having the layer structure as shown in FIGS. Among reflections by wavelength, reflection at a desired wavelength λ can be suppressed by optical interference.
Here, in the heat ray shielding material of the present invention, the heat ray reflective layer, the layer A, the layer B, the layer C, the second layer A ′, and the second layer B ′ are adjacent to each other. Even if it arrange | positions, it may be arrange | positioned through a 30 nm or less layer. The effect of suppressing the reflection of the wavelength λ of the present invention by optical interference is in particular the layer C, the layer B, the layer A, the heat ray reflective layer, the second layer A ′, and the second layer B ′. This is prominent when the layers are arranged adjacent to each other. That is, the layer C and the layer B are preferably arranged adjacent to each other, and more preferably directly bonded together. The layer B and the layer A are preferably arranged adjacent to each other, and more preferably directly bonded to the entire surface. The layer A and the heat ray reflective layer are preferably disposed adjacent to each other, and more preferably directly bonded to the entire surface. The heat ray reflective layer and the second layer A ′ are preferably disposed adjacent to each other, and more preferably directly bonded together. The second layer A ′ and the second layer B ′ are preferably disposed adjacent to each other, and more preferably directly bonded to the entire surface.

  Moreover, even if the heat ray shielding material of this invention is a sheet-like state, the state wound up by roll shape may be sufficient. In addition, when the heat ray shielding material of this invention is the state wound up by roll shape, it is preferable that it is wound by the core with a diameter of 50-250 mm.

<Configuration of each layer>
(Heat ray absorbing layer)
The heat ray shielding material of the present invention has a heat ray absorbing layer containing a plurality of types of metal oxide particles. It is preferable from the viewpoint of shielding performance that the heat ray absorbing layer is laminated on the inner side (the side opposite to the incident light or outside light side) than the support. When the heat ray shielding material of the present invention is arranged so that the heat ray reflective layer is on the incident direction side of the heat ray such as sunlight, a part (or all) of the heat ray is reflected by the heat ray reflective layer, and then the metal oxide The physical particle layer absorbs a part of the heat rays, and the amount of heat directly received inside the heat ray shielding material due to the heat rays that are not absorbed by the metal oxide particle layer and pass through the heat ray shielding material, and the heat ray shielding material The amount of heat as the total amount of heat absorbed by the metal oxide particle layer 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"), cesium containing tungsten (henceforth, Abbreviated as “CWO.” The composition is not particularly limited, but is preferably Cs _0.33 WO ₃ ), antimony-doped tin oxide (hereinafter abbreviated as “ATO”), zinc oxide, zinc antimonate, Examples thereof include titanium oxide, indium oxide, tin oxide, antimony oxide, glass ceramics, lanthanum hexaboride (LaB ₆ ), and a plurality of these are selected.
Among these, ITO and CWO are excellent in that they can excel in 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, have high infrared shielding ability, and can maintain visible light transmittance. It is particularly preferable to select
The volume average particle size of the primary particles of the metal oxide particles is preferably 100 nm or less, more preferably 80 nm or less, and most preferably 60 nm or less in order not to reduce the visible light transmittance and not to generate haze. .
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.

There is no restriction | limiting in particular as total content of the said metal oxide particle, Although it can select suitably according to the objective, 0.5-5.0 g / m < ² > is preferable, 0.5-4.0 g / m ² is more preferable, and 1.0 to 3.0 g / m ² is more preferable.
If the total content is less than 0.5 g / m ² , the amount of solar radiation felt on the skin may increase, and if it exceeds 5 g / m ² , the visible light transmittance may deteriorate.
When using a CWO, the content of CWO, preferably ^{0.3~1.3g / m 2, 0.6~1.3g / m} 2 is more preferable.
When ITO and CWO are used in combination, the mass ratio of ITO and CWO is preferably 5 to 95:95 to 5, more preferably 10 to 90:90 to 10, and further preferably 20 to 80:80 to 20. .
The content of the metal oxide particles can be calculated from, for example, the absorbance of the heat ray absorption layer measured. It can also be calculated by fluorescent X-ray analysis.

  In the heat ray shielding material of the present invention, the film thickness of the heat ray absorbing layer is not particularly limited, but is 0.5 to 10 μm from the viewpoint of providing sufficient heat ray absorbing ability and maintaining coatability. Is preferable, and it is preferable that it is 1.0-3.0 micrometers.

(Heat ray reflective layer)
The heat ray shielding material of this invention has a heat ray reflective layer containing a silver tabular grain, and content of a silver tabular grain is 15-45 mg / m < ² >.
The content of silver tabular grains are 15~45mg / m ^2, preferably ^{15~35g / m 2, 20~35g / m} 2 is more preferable.
When the thickness of the heat ray reflective layer is d, it is preferable that 80% by number or more of the hexagonal or circular tabular silver particles are present in a range of d / 2 from the surface of the heat ray reflective layer. More preferably, it exists in the range of d / 3 from the surface of the heat ray reflective layer. The present invention 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 added when producing the heat ray reflective layer. By doing so, the silver tabular grains can be segregated on one surface of the heat ray reflective layer.

1-1. Silver tabular grains
In the heat ray shielding material of the present invention, the silver tabular grain preferably has 60% by number or more of tabular silver particles, and more preferably has 60% by number or more of hexagonal or circular tabular silver particles.
In the heat ray reflective layer, the presence form of hexagonal or circular tabular silver particles is relative to one surface of the heat ray reflective layer (when the heat ray shielding material of the present invention has a substrate, the surface of the substrate). The main planes of hexagonal or circular tabular silver particles are preferably plane-oriented within an average range of 0 ° to ± 30 °, and plane-oriented within an average range of 0 ° to ± 20 °. Is more preferable, and it is particularly preferable that the plane orientation is in the range of 0 ° to ± 10 ° on average.
In addition, it is preferable that one surface of the said heat ray reflective layer is a flat plane. When the said heat ray reflective layer of the heat ray shielding material of this invention has a base material as a temporary support body, it is preferable that it is a substantially horizontal surface with the surface of a 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 silver tabular grain, According to the objective, it can select suitably, For example, you may have an average particle diameter of 500 nm or less.
In addition, the heat ray reflective layer may contain other metal particles in addition to the silver tabular grains. Other metal particles are not particularly limited and can be appropriately selected according to the purpose. However, gold, aluminum, copper, rhodium, nickel, platinum, and the like are preferable because of high reflectance of heat rays (near infrared rays). preferable.

-1-2. Silver tabular grains
The silver tabular grain is not particularly limited as long as it is a grain composed of two main planes (see FIGS. 7A and 7B), 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 this specification, the circular shape means 0 per side of a silver tabular grain having a length of 50% or more of the average equivalent circle diameter of silver tabular grains (synonymous with tabular silver grains) described later. Say the shape that is. The circular silver tabular 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 silver tabular grains described later is 6 per silver tabular grain. The same applies to other polygons. The hexagonal tabular silver particles are not particularly limited as long as they are hexagonal when the silver tabular grains are observed from above the main plane with a transmission electron microscope (TEM), and are appropriately selected according to the purpose. For example, the hexagonal corners may be acute or dull, but the corners are 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.

  Of the metal particles present in the heat ray reflective layer, the hexagonal or circular tabular silver particles are preferably 60% by number or more, more preferably 65% by number or more based on the total number of silver particles. 70% by number or more is particularly preferable. When the proportion of the silver tabular grains is 60% by number or more, the visible light transmittance is increased.

-2-1-1. Planar orientation
In the heat ray shielding material of the present invention, the hexagonal or circular tabular silver particles have a principal plane that is on one surface of the heat ray reflective layer (the surface of the substrate when the heat ray shielding material has a substrate). The average orientation is preferably 0 ° to ± 30 °, more preferably the average 0 ° to ± 20 °, and the average 0 ° to ± 10 °. It is particularly preferable that the film is plane-oriented.
The presence state of the silver tabular grains is not particularly limited and may be appropriately selected depending on the purpose.

Here, FIGS. 6A to 6C are schematic cross-sectional views showing the existence state of the heat ray reflective layer containing silver tabular grains in the heat ray shielding material of the present invention. 6A, 6B and 6C show the presence state of the silver tabular grains 3 in the heat ray reflective layer 2. FIG. FIG. 6A is a diagram for explaining an angle (± θ) formed by the plane of the base material 1 and the main plane of the silver tabular grain 3 (the plane that determines the equivalent circle diameter D). FIG. 6B shows the existence region in the depth direction of the heat ray shielding material of the heat ray reflective layer 2.
In FIG. 6A, the angle (± θ) formed by the surface of the substrate 1 and the main plane (plane determining the equivalent circle diameter D) of the silver tabular grains 3 or an extension line of the main plane is a predetermined value in the plane orientation described above. Corresponds to the range. That is, the plane orientation refers to a state where the inclination angle (± θ) shown in FIG. 6A is small when the cross section of the heat ray shielding material is observed. In particular, the surface of the substrate 1 and the main plane of the silver tabular grain 3 are in contact with each other. In other words, a state where θ is 0 ° is preferable. When the angle of the plane orientation of the main plane of the silver tabular grain 3 with respect to the surface of the substrate 1, that is, θ in FIG. 6A 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.

  As an evaluation of whether or not the main surface of the silver tabular grain is plane-oriented with respect to one surface of the heat ray reflective layer (the surface of the substrate when the heat ray shielding material has a substrate), there is no particular limitation, It can be selected appropriately according to the purpose. For example, an appropriate cross section is prepared, and a heat ray reflective layer (a base material when the heat ray shielding material has a base material) and silver tabular grains in this section are observed. The method of evaluating may be used. 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 silver tabular grains swells with water, the cross-section sample or cross-section sample is obtained by cutting a sample frozen in liquid nitrogen by a diamond cutter mounted on a microtome. May be produced. Moreover, when the binder which coat | covers silver 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 plane of the silver tabular grain with respect to one surface of the heat ray reflective layer (or the surface of the base material when the heat ray shielding material has a base material) in the sample As long as it can be confirmed whether or not the film is plane-oriented, there is no particular limitation, and it can be appropriately selected according to the purpose. For example, observation using an FE-SEM, TEM, optical microscope, or the like can be given. . 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 inclination angle (± θ in FIG. 6A) of the silver tabular grains can be clearly determined.

-1-2-2. Coefficient of variation in particle size distribution of average particle diameter (average equivalent circle diameter)
In the heat ray shielding material of the present invention, the coefficient of variation in the particle size distribution of the silver tabular grains is preferably 35% or less, more preferably 30% or less, and particularly preferably 20% or less. The coefficient of variation is preferably 35% or less because the reflection wavelength region of heat rays in the heat ray shielding material becomes sharp.
Here, the coefficient of variation in the particle size distribution of the silver tabular grains is, for example, plotting the distribution range of the particle diameters of the 200 silver 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. Silver tabular grain thickness and aspect ratio
In the heat ray shielding material of the present invention, the thickness of the silver tabular grains is preferably 14 nm or less, more preferably 5 to 14 nm, and particularly preferably 5 to 12 nm.
There is no restriction | limiting in particular as an aspect-ratio of the said silver tabular grain, Although it can select suitably according to the objective, From the point from which the reflectance in the infrared region of wavelength 800nm-1800nm becomes high, it is 6 ~ 40 is preferable and 10-35 is more preferable. When the aspect ratio is less than 6, 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 equivalent circle diameter) of the tabular silver grains by the average grain thickness of the tabular silver grains. The average grain thickness corresponds to the distance between the main planes of the silver tabular grains, and is, for example, as shown in FIGS. 7A and 7B 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 silver tabular grains is dropped onto a glass substrate and dried. For example, a method of measuring the thickness of one particle may be used.

-1-2-4. Existence range of silver tabular grains-
In the heat ray shielding material of the present invention, the thickness of the existing region of the silver tabular grains is preferably 5 to 60 nm, and more preferably 5 to 20 nm.
In the heat ray shielding material of the present invention, 80% by number or more of the hexagonal or circular tabular silver particles are preferably present in a range of d / 2 from the surface of the heat ray reflective layer, and in a range of d / 3. More preferably, 60% by number or more of the hexagonal or circular tabular silver particles are exposed on one surface of the heat ray reflective layer. That the silver tabular grains are present in the range of d / 2 from the surface of the heat ray reflective layer means that at least a part of the silver tabular grains is contained in the range of d / 2 from the surface of the heat ray reflective layer. That is, a silver tabular grain in which a part of the tabular silver grain protrudes from the surface of the heat ray reflective layer is also treated as a silver tabular grain present in the range of d / 2 from the surface of the heat ray reflective layer.
Moreover, that the silver tabular grain is exposed on one surface of the heat ray reflective layer means that a part of one surface of the silver tabular grain protrudes from the surface of the heat ray reflective layer.
Here, the silver tabular grain presence distribution in the heat ray reflective 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. 6B, when the plasmon resonance wavelength of silver constituting the silver tabular grain 3 in the heat ray reflective layer 2 is λ and the refractive index of the medium in the heat ray reflective layer 2 is n The heat ray reflective layer 2 is preferably present in the range of (λ / n) / 4 in the depth direction from the horizontal plane of the heat ray shielding material. Within this range, the effect of increasing the amplitude of the reflected wave due to the phase of the reflected wave at the interface between the upper and lower heat ray reflective layers of the heat ray shielding material is sufficiently great, and the visible light transmittance and maximum heat ray reflection are achieved. The rate is good.
The plasmon resonance wavelength λ of silver constituting the silver tabular grains in the heat ray reflective layer is not particularly limited and can be appropriately selected according to the purpose, but is 400 nm to 2,500 nm in terms of imparting heat ray reflection performance. It is preferable that it is 700 nm-2500 nm from the point which provides visible light transmittance | permeability.

-1-2-5. Medium of heat ray reflective layer
There is no restriction | limiting in particular as a medium in the said heat ray reflective layer, According to the objective, it can select suitably. In the heat ray shielding material of the present invention, the heat ray reflective 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 the tabular silver grains of hexagonal or circular tabular silver grains are preferably present in the range of d / 2 from the surface of the heat ray reflective layer, and are polyester resin and polyurethane resin. It is particularly preferable from the viewpoint of further improving the rubbing resistance of the heat ray shielding material of the present invention.
Among the polyester resins, a saturated polyester resin is more particularly preferable from the viewpoint of imparting excellent weather resistance since it does not contain a double bond. Moreover, it is more preferable to have a hydroxyl group or a carboxyl group at the molecular terminal from the viewpoint of obtaining high hardness, durability, and heat resistance by curing with a water-soluble / water-dispersible curing agent or the like.
Commercially available polymers can be preferably used as the polymer, and examples thereof include Plus Coat Z-867, which is a water-soluble polyester resin manufactured by Kyoyo Chemical Industry Co., Ltd.
Moreover, in this specification, the main polymer of the polymer contained in the heat ray reflective layer refers to a polymer component occupying 50% by mass or more of the polymer contained in the heat ray reflective layer.
It is preferable that content of the said polyester resin and polyurethane resin with respect to the said silver particle contained in the said heat ray reflective layer is 1-10000 mass%, It is more preferable that it is 10-1000 mass%, It is 20-500 mass%. It is particularly preferred. By setting the binder contained in the heat ray reflective layer to be in the above range or more, physical properties such as rubbing resistance can be improved.
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 tabular silver particles is a, 80% by number or more of the hexagonal or circular tabular silver 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 tabular silver particles are buried in the heat ray reflective layer at a certain ratio or more, thereby improving the rub resistance.

-1-2-6. Area ratio of silver tabular grains-
The total value B of the area of the silver tabular grains with respect to the area A of the base material when the heat ray shielding material is viewed from above (the total projected area A of the heat ray reflective layer when viewed from the direction perpendicular to the heat ray reflective layer) The area ratio [(B / A) × 100] as a ratio 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-
The average distance between the tabular grains adjacent to each other in the horizontal direction in the heat ray reflective layer is preferably 1/10 or more of the average grain diameter of the tabular silver grains in terms of the visible light transmittance and the maximum reflectance of the heat rays.
When the average distance between grains in the horizontal direction of the silver tabular grains is less than 1/10 of the average grain diameter of the silver tabular grains, the maximum reflectance of the heat rays 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, absorption of visible light occurs, and the transmittance may decrease.

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

-1-2-8. Layer structure of heat ray reflective layer
In the heat ray shielding material of the present invention, the silver tabular grains are arranged in the form of a heat ray reflective layer containing silver tabular grains as shown in FIGS. 6A to 6C.
The heat ray reflective layer may be composed of a single layer as shown in FIGS. 6A to 6C or may be composed of a plurality of heat ray reflective layers. When it comprises a plurality of heat ray reflective layers, it becomes possible to impart shielding performance according to the wavelength band to which thermal insulation performance is desired. When the heat ray reflective layer is composed of a plurality of heat ray reflective layers, the heat ray shielding material of the present invention has at least the outermost heat ray reflective layer, and the thickness of the outermost heat ray reflective layer is d ′. It is preferable that 80% by number or more of the hexagonal or circular tabular silver particles are present in a range of d ′ / 2 from the surface of the outermost heat ray reflective layer.

-1-2-9. Heat ray reflective layer thickness
In the heat ray shielding material of the present invention, the thickness of the heat ray reflective layer is preferably 5 to 80 nm, and more preferably 6 to 20 nm. The thickness d of the heat ray reflective layer is preferably a to 10a, more preferably 2a to 8a, more preferably 1a to 5a, where a is the thickness of the hexagonal or circular tabular silver particles. It is particularly preferred that

Here, the thickness of each layer of the heat ray reflective 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 heat ray reflective layer of a heat ray shielding material, the boundary of another layer and the said heat ray reflective layer can be determined by the same method. And the thickness d of the heat ray reflective layer can be determined. When coating the heat ray reflective layer using the same type of polymer as the polymer contained in the heat ray reflective layer, the boundary between the heat ray reflective layer and the heat ray reflective layer can usually be discriminated by an image observed by SEM. The thickness d of the heat ray reflective layer can be determined.

-1-2-10. Methods for synthesizing silver tabular grains
The method for synthesizing the silver tabular grains is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a liquid phase method such as a chemical reduction method, a photochemical reduction method, an electrochemical reduction method, or the like may be used. It is mentioned as what can synthesize circular tabular silver particles. 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 silver grains, hexagonal to triangular tabular silver grains, for example, by etching with a dissolved species that dissolves silver such as nitric acid and sodium sulfite, and aging by heating Hexagonal or circular tabular silver particles may be obtained.

  As a method for synthesizing the silver tabular grains, in addition to the above, a seed crystal may be fixed in advance 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 silver 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
The silver tabular grains may be coated with a high refractive index material having high visible light range transparency in order to further enhance the visible light range 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 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 silver tabular grains, after synthesizing the silver tabular grains 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 silver 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, when the heat ray reflective layer contains a polymer and the main polymer of the polymer is a polyester resin, it is preferable to add a crosslinking agent from the viewpoint of film strength. The crosslinking agent is not particularly limited, and examples thereof include epoxy-based, isocyanate-based, melamine-based, carbodiimide-based, and oxazoline-based crosslinking agents. Of these, carbodiimide and oxazoline crosslinking agents are preferred. Specific examples of the carbodiimide-based crosslinking agent include, for example, Carbodilite V-02-L2 (manufactured by Nisshinbo Industries, Ltd.). It is preferable to contain the component derived from 1-20 mass% crosslinking agent with respect to all the binders in the said heat ray reflective layer, More preferably, it is 2-20 mass%.
Moreover, in the heat ray shielding material of this invention, when the said heat ray reflective layer contains a polymer, it is preferable from a viewpoint from which generation | occurrence | production of a repellency is suppressed and a favorable planar layer is obtained. As the surfactant, a specific example of a surfactant that can use a known surfactant such as an anionic or nonionic surfactant is, for example, Lapisol A-90 (manufactured by NOF Corporation), Narrow Acty HN-100 (manufactured by Sanyo Chemical Industries, Ltd.). It is preferable to contain 0.05-10 mass% surfactant with respect to all the binders in the said heat ray reflective layer, More preferably, it is 0.1-5 mass%.

The silver tabular grains may adsorb an antioxidant such as mercaptotetrazole or ascorbic acid in order to prevent oxidation of silver or the like constituting the silver tabular grains. Further, for the purpose of preventing oxidation, an oxidation sacrificial layer such as Ni may be formed on the surface of the silver tabular grain. 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 silver tabular grains are, for example, low molecular weight dispersants and high molecular weight dispersants containing at least one of N elements such as quaternary ammonium salts and amines, S elements, and P elements. A dispersant may be added.

<Support>
The heat ray shielding material of the present invention preferably has a support.
There is no restriction | limiting in particular as said support body, A well-known support body can be used.
The thickness of the support is not particularly limited and can be appropriately selected according to the purpose of use of the heat ray shielding material. Usually, the thickness is about 10 μm to 500 μm, but is thinner from the viewpoint of the demand for thinning. preferable. The thickness of the support is preferably 10 μm to 100 μm, more preferably 15 to 80 μm, and particularly preferably 20 to 75 μm. When the thickness of the support is sufficiently thick, adhesion failure tends to hardly occur. Moreover, when the thickness of the said support body is thin enough, when it bonds together to a building material or a motor vehicle as a heat ray shielding material, there exists a tendency for the construction as it is not too strong and to become easy to construct. Furthermore, when the support is sufficiently thin, the visible light transmittance is increased, and the raw material cost tends to be suppressed.

The support is not particularly limited as long as it is an optically transparent support and can be appropriately selected according to the purpose. For example, the visible light transmittance is 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 support body, 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 support is not particularly limited as long as it is an optically transparent support and can be appropriately selected according to the purpose. For example, the visible light transmittance is 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 support body, 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.
There is no restriction | limiting in particular as a material of the said support body, According to the objective, it can select suitably, For example, polyolefin resin, such as polyethylene, a polypropylene, poly 4-methylpentene-1, 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.

  The thickness of the support is not particularly limited and can be appropriately selected according to the purpose of use of the heat ray shielding material. Usually, the thickness is about 10 μm to 500 μm, but is thinner from the viewpoint of the demand for thinning. preferable. The thickness of the support is preferably 10 μm to 100 μm, more preferably 20 to 75 μm, and particularly preferably 35 to 75 μm. When the thickness of the support is sufficiently thick, adhesion failure tends to hardly occur. Moreover, when the thickness of the said support body is thin enough, when it bonds together to a building material or a motor vehicle as a heat ray shielding material, there exists a tendency for the construction as it is not too strong and to become easy to construct. Furthermore, when the support is sufficiently thin, the visible light transmittance is increased, and the raw material cost tends to be suppressed.

<Other layers>
(UV absorbing layer)
The heat ray shielding material of the present invention may have an ultraviolet absorbing layer on the outside light side of the heat ray reflective layer.
The ultraviolet absorbing layer may be provided as a single functional layer or a layer having other functions, but the ultraviolet absorbing layer may be a layer having other functions to reduce the number of laminated layers. Therefore, it is preferable from the viewpoint of reducing the thickness of the heat ray shielding material. Also, the number of stacked layers is not particularly limited, and may include only one layer or a plurality of layers, but having only one layer can reduce the number of stacked layers and reduce the thickness of the heat ray shielding material. It is preferable from the viewpoint.

  In the heat ray shielding material of the present invention, the transmittance at 390 nm of the ultraviolet absorbing layer is preferably 50% or less, and the heat ray reflective layer is deteriorated by ultraviolet rays of sunlight, or 40% or less, or It is more preferable from the viewpoint of preventing a person in the room from being exposed to harmful ultraviolet rays and fading of indoor furnishings, and particularly preferably 30% or less.

-UV absorber-
In the heat ray shielding material of the present invention, the content and type of the ultraviolet absorber contained in the ultraviolet absorbing layer is not particularly limited, except that the transmittance at 390 nm of the ultraviolet absorbing layer can be controlled to be within the characteristic range.

  The content of the ultraviolet absorber in the ultraviolet absorbing layer varies depending on the ultraviolet absorbing layer to be used and cannot be generally defined, but the content that gives the desired ultraviolet transmittance in the heat ray shielding material of the present invention is appropriately selected. It is preferable to do.

  Examples of the ultraviolet absorber include triazine, benzotriazole, cyclic imino ester, benzophenone, merocyanine, cyanine, dibenzoylmethane, cinnamic acid, cyanoacrylate, benzoate, and the like. It is done. These may be used individually by 1 type and may use 2 or more types together. Specifically, compounds described in paragraphs 0040 to 0088 of JP2012-136919A can be used, and the contents thereof are incorporated in the present specification.

-Binder for UV absorbing layer-
The binder for the ultraviolet absorbing layer is not particularly limited and may be appropriately selected depending on the intended purpose. However, the one having higher visible light transparency is preferable, and examples thereof include acrylic resin, polyvinyl butyral, polyvinyl alcohol, and polyester resin. Can be mentioned. 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.

-Film thickness of UV absorbing layer-
In the heat ray shielding material of the present invention, it is preferable that the thickness of the ultraviolet absorbing layer is sufficiently increased from the viewpoint of sufficiently blocking ultraviolet rays, the thickness of the ultraviolet absorbing layer is more preferably 5 μm or more, and is preferably 10 μm or more. It is particularly preferred. Therefore, a configuration in which an ultraviolet absorber is included in the pressure-sensitive adhesive, the intermediate film, or the support is preferable.
In the case where the coating layer has a layer with low light resistance, it is preferable to have an ultraviolet absorbing layer on the outside light side of the layer, and in that respect, an adhesive or an intermediate film is preferable.
The upper limit of the thickness of the ultraviolet absorbing layer is preferably 200 μm from the viewpoint of visible light transmittance, and more preferably 100 μm.
The ultraviolet absorbing layer may be adjusted in refractive index or thickness by changing the composition so as to satisfy the condition (1) or (2).
The refractive index can be adjusted by adjusting the refractive index of the binder or by adding fine particles having different refractive indexes. In order to lower the refractive index, it is desirable to add a low refractive index binder or low refractive index fine particles in the binder. Examples of the low refractive index binder include a fluorine-containing polymer. Examples of the low refractive index fine particles include fine particles of magnesium fluoride and silica. In particular, silica fine particles are preferable in terms of refractive index, dispersion stability, and cost. In order to further reduce the refractive index, it is preferable to use hollow silica fine particles, and the hollow silica fine particles have a refractive index of 1.17 to 1.40, more preferably 1.17 to 1.35, still more preferably. 1.17 to 1.30. The refractive index here represents the refractive index of the entire particle, and does not represent the refractive index of only the outer shell silica forming the hollow silica particles. The average particle size of the fine particles is preferably 30 nm to 100 nm, more preferably 35 nm to 80 nm, and still more preferably 40 nm to 60 nm.
Conversely, in order to increase the refractive index, it is preferable to add high refractive index fine particles in the binder. The high refractive index fine particles are made of an oxide of at least one metal selected from titanium, zirconium, aluminum, indium, zinc, tin, and antimony, and have an average particle size of 0.2 μm or less, preferably 0.1 μm. Hereinafter, it is preferable that an inorganic filler of 0.06 μm or less is contained.

(Adhesive layer)
The heat ray shielding material of the present invention preferably has a pressure-sensitive adhesive layer (hereinafter also referred to as a pressure-sensitive adhesive layer).
The material that can be used for forming the pressure-sensitive adhesive layer is not particularly limited as long as it does not impair the transparency, and can be appropriately selected according to the purpose. For example, polyvinyl butyral (PVB) resin, acrylic Examples thereof include resins, styrene / acrylic resins, urethane resins, polyester resins, and silicone resins. These may be used individually by 1 type and may use 2 or more types together. The pressure-sensitive adhesive layer made of these materials may be formed by bonding or may be formed by coating. In the case of forming by bonding, it is preferable to use a substrate-less pressure-sensitive adhesive from the viewpoint that the thickness can be reduced.
Furthermore, an antistatic agent, a lubricant, an antiblocking agent and the like may be added to the pressure-sensitive adhesive layer.

  The thickness of the pressure-sensitive adhesive layer is preferably 0.1 μm to 30 μm, and more preferably 5 to 20 μm.

(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 is further formed on the hard coat layer, it is preferable that antireflection properties are obtained in addition to scratch resistance. Moreover, the said hard-coat layer may serve as the heat ray absorption layer which has the said metal oxide particle and has the said metal oxide particle.

(Overcoat layer)
In the heat ray shielding material of the present invention, in order to prevent oxidation and sulfidation of silver tabular grains due to mass transfer, and to impart scratch resistance, the heat ray shielding material of the present invention comprises the hexagonal or circular tabular metal particles. You may have an overcoat layer closely_contact | adhered to the surface of the exposed said heat ray reflective layer. The heat ray shielding material of the present invention, particularly when silver tabular grains are unevenly distributed on the surface of the heat ray reflective layer, prevents contamination of the production process due to the peeling of the silver tabular grains, prevents silver tabular grain arrangement disorder during coating of different layers, etc. Therefore, it may have an overcoat layer.
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 5 μm, more preferably 0.05 to 1 μm. Moreover, it is also preferable that the overcoat layer is adjusted in refractive index or thickness by changing the composition so as to satisfy the condition (1) or (2). As a method of adjusting the refractive index of the overcoat layer, the same method as the method of adjusting the refractive index of the ultraviolet absorbing layer can be used, and preferable components used for adjusting the refractive index are also the same.

(Undercoat layer)
On the other hand, in the heat ray shielding material of the present invention, an undercoat layer may be provided between the support and the heat ray reflective layer. There is no restriction | limiting in particular as said undercoat layer, According to the objective, it can select suitably. A plurality of the undercoat layers may be provided.
It is preferable that the undercoat layer is adjusted in refractive index or thickness by changing the composition so as to satisfy the condition (1) or (2). The preferred composition of the undercoat layer is the same as the preferred composition of the overcoat layer. As a method of adjusting the refractive index of the undercoat layer, the same method as the method of adjusting the refractive index of the ultraviolet absorbing layer can be used, and preferable components used for adjusting the refractive index are also the same.

(Back coat layer)
On the other hand, in the heat ray shielding material of the present invention, a back coat layer may be provided on the surface of the support opposite to the heat ray reflective layer. The backcoat layer is not particularly limited and may be appropriately selected depending on the intended purpose. However, the backcoat layer may be a layer containing a compound having absorption in the infrared region, and heat ray absorption having the metal oxide particles described above. It is good also as a layer. It is preferable that the back coat layer is adjusted in refractive index or thickness by changing the composition so as to satisfy the condition (1) or (2). The preferred composition of the backcoat layer when it is not the layer containing the compound having absorption in the infrared region or the heat ray absorbing layer having the metal oxide particles is the same as the preferred composition of the overcoat layer. As a method for adjusting the refractive index of the backcoat layer, a method similar to the method for adjusting the refractive index of the ultraviolet absorbing layer can be used, and preferable components used for adjusting the refractive index are also the same.

<Method for producing heat ray shielding material>
There is no restriction | limiting in particular as a method to manufacture the heat ray shielding material of this invention, According to the objective, it can select suitably.

-1. Formation method of undercoat layer, overcoat layer, and backcoat layer-
There is no restriction | limiting in particular as a formation method of the said undercoat layer, an overcoat layer, a backcoat layer, and an ultraviolet absorption layer, According to the objective, it can select suitably.
In the case of forming a layer that is a support and an ultraviolet absorbing layer, [0094] to [0155] of JP2012-136919A, or [0086] to [0148] of JP2012-122000A. An ultraviolet absorber can be included in the support using the described method.

  Although there is no restriction | limiting in particular as a formation method in the case of forming the said ultraviolet absorption layer as an adhesion layer, an undercoat layer, an overcoat layer, or a backcoat layer, It is preferable to form by application | 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.

-2. Formation method of heat ray reflective layer
The method for forming the heat ray reflective layer is not particularly limited and can be appropriately selected depending on the purpose. For example, the dispersion liquid having the silver tabular grains on the surface of the lower layer such as the base material is dipped. Examples thereof include a method of coating by a coater, a die coater, a slit coater, a bar coater, a gravure coater, and the like, and a method of plane orientation by a method such as an LB film method, a self-organization method, and spray coating. When producing the heat ray shielding material of the present invention, the number of the tabular silver particles of the hexagonal or circular tabular silver particles is 80 by setting the composition of the heat ray reflective layer used in the examples described later and adding latex. % Or more is preferably present in the range of d / 2 from the surface of the heat ray reflective layer. More preferably, 80% by number or more of the silver tabular grains of the hexagonal or circular tabular silver grains are present in a range of d / 3 from the surface of the heat ray reflective 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 silver tabular grain.

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

-3. Formation method of adhesive layer
The pressure-sensitive adhesive layer can be formed by coating. For example, it can be laminated on the surface of a lower layer such as the heat ray reflective layer, the overcoat layer, or the metal oxide particle-containing layer. There is no limitation in particular as the coating method at this time, A well-known method can be used.

(Adhesive layer lamination by dry lamination)
When laminating the pressure-sensitive adhesive layer on the surface of the heat ray reflective layer, it is possible to apply a coating solution containing a pressure-sensitive adhesive directly on the surface, but various additives, plasticizers, solvents used, etc. contained in the pressure-sensitive adhesive However, in some cases, the arrangement of silver particles in the heat ray reflective layer may be disturbed, or the silver particles themselves in the heat ray reflective layer may be altered. In order to minimize such an adverse effect, a film in which an adhesive is applied and dried on a release film in advance is prepared, and the adhesive surface of the film and the heat ray reflection of the heat ray shielding material of the present invention are prepared. It is effective to perform lamination in a dry state by laminating the layer surface.

<Use of heat ray shielding material>
The heat ray shielding material of the present invention may be used alone as a heat ray shielding material, or may be laminated with other functional layers. Moreover, the heat ray shielding material of the present invention may be bonded to glass or the like to form heat shielding glass. Moreover, the heat ray shielding material of the present invention may be sandwiched between laminated glasses or used as laminated glass.
The heat ray shielding material of the present invention is not particularly limited as long as it is an embodiment used for selectively reflecting near infrared rays (absorbing as necessary), and may be appropriately selected according to the purpose. Examples thereof include a film for a vehicle and a laminated structure, a film for a building material, a laminated structure, and an agricultural film. Among these, in terms of energy saving effect, a vehicle film and a laminated structure, a building material film and a laminated structure are preferable.

(Heat shield glass)
It is good also as heat insulation glass by which glass was affixed on the said adhesive layer of the heat ray shielding material of this invention. In the case of an internal application, the glass, the adhesive layer, the heat ray reflective layer, and the heat ray absorption layer are attached in this order from the outside light side. On the other hand, in the case of an external application, the heat ray reflection layer, the heat ray absorption layer, the adhesive layer, and the glass are attached so as to be in this order from the outside light side.
By setting it as such a structure, heat insulation performance becomes favorable.

[Interlayer film for laminated glass / Laminated glass]
The interlayer film for laminated glass of the present invention includes the heat ray shielding material of the present invention.
Moreover, the laminated glass of the present invention has the interlayer film for laminated glass of the present invention and at least two glass plates, and the interlayer film for laminated glass is inserted in the two sheets of glass. To do. When the heat ray shielding material of the present invention is laminated on the interlayer film of laminated glass, the heat ray reflection layer and the heat ray absorption layer are used in this order from the outside light side, and the heat shielding performance is good. Become.
1 and 3 to 5 show preferred embodiments of the laminated glass of the present invention. 1 and 3 to 5, the intermediate films 22 are laminated on both surfaces of the heat ray shielding material of the present invention to constitute the intermediate film for laminated glass of the present invention. Furthermore, the interlayer film for laminated glass of the present invention obtained in the two pieces of glass 21 is inserted.

<Configuration>
(Interlayer film)
The interlayer film for laminated glass of the present invention includes an interlayer film. It is preferable that the interlayer film for laminated glass of the present invention further includes a second interlayer film. Further, the compositions of the first and second intermediate films may be the same or different.

The thickness of the first and second intermediate films is preferably 100 to 1000 μm, and more preferably 200 to 800 μm. The first and second intermediate films may be thickened by overlapping a plurality of sheets.
The brittleness of the first and second interlayer films is preferably 100 to 800%, more preferably 100 to 600%, more preferably 200 to 500%. It is particularly preferred that

  The first and second intermediate films are preferably resin intermediate films. The resin interlayer is preferably a polyvinyl acetal-based resin film. There is no restriction | limiting in particular as said polyvinyl acetal type-resin film, For example, what is described in Unexamined-Japanese-Patent No. 6-000926, Unexamined-Japanese-Patent No. 2007-008797 etc. can be used preferably. Among the polyvinyl acetal resin films, a polyvinyl butyral resin film is preferably used in the present invention. The polyvinyl butyral resin film is not particularly defined as long as it is a resin film mainly composed of polyvinyl butyral, and a widely known polyvinyl butyral resin film as an interlayer film for laminated glass can be employed. Among them, in the present invention, the intermediate film is preferably a resin intermediate film mainly composed of polyvinyl butyral or a resin intermediate film mainly composed of ethylene vinyl acetate, and a resin intermediate film mainly composed of polyvinyl butyral. It is particularly preferred that In addition, resin which is a main component means resin which occupies the ratio of 50 mass% or more of the said resin intermediate film.

(Glass)
Although there is no restriction | limiting in particular as glass used for a laminated glass, Clear glass is used as the glass of the side used as the outside light side (incident light side), and clear glass is used as the glass which becomes an inner side (opposite side to incident light). Alternatively, it is preferable to use green glass.
Here, in the present specification, a glass referred to as a laminated glass generally includes a glass substitute resin. That is, instead of the glass sandwiching the interlayer film for laminated glass of the present invention, a glass substitute resin formed body or a combination of a glass substitute resin formed body and glass can be used. Examples of glass substitute resins include polycarbonate resins, acrylic resins, and methacrylic resins. It is also possible to use a glass substitute resin coated with a hard coat layer. Examples of hard coat layers include acrylic hard coat materials, silicone hard coat materials, melamine hard coat materials, and inorganic fine particles such as silica, titania, alumina, and zirconia dispersed in these hard coat materials. Things can be raised.

<Method for producing interlayer film / laminated glass for laminated glass>
There is no restriction | limiting in particular as an intermediate film for laminated glasses of this invention, and the manufacturing method of laminated glass, A well-known method can be used.

  As a method for producing the interlayer film for laminated glass of the present invention, for example, the heat ray shielding material of the present invention is preferably overlapped and thermocompression bonded between the first and second interlayer films.

It is preferable that the manufacturing method of the laminated glass of this invention includes the process of crimping | bonding, heating the intermediate film for laminated glasses of this invention clamped by the said glass plate.
The lamination of the interlayer film for laminated glass of the present invention sandwiched between the glass plates and the glass plate is performed, for example, after pre-pressing at a temperature of 80 to 120 ° C. for 30 to 60 minutes under reduced pressure with a vacuum bag or the like. In addition, it can be laminated in an autoclave under a pressure of 1.0 to 1.5 MPa at a temperature of 120 to 150 ° C. to obtain a laminated glass in which a laminate is sandwiched between two glasses. Moreover, you may bond together using an adhesive material etc.
At this time, it is preferable that the time of thermocompression bonding at a temperature of 120 to 150 ° C. under a pressure of 1.0 to 1.5 MPa is 20 to 90 minutes.
After the thermocompression bonding, there is no particular limitation on the method of cooling, and the laminated glass body may be obtained by cooling while releasing the pressure as appropriate. In the present invention, it is preferable to lower the temperature while maintaining the pressure after completion of the thermocompression bonding from the viewpoint of further improving the wrinkles and cracks of the obtained laminated glass body. Here, when the temperature is lowered while maintaining the pressure, the pressure inside the apparatus at the time of thermocompression bonding (preferably 130 ° C.) is such that the pressure inside the apparatus at 40 ° C. becomes 75% to 100% at the time of thermocompression bonding. It means to cool down. The method of lowering the temperature while maintaining the pressure is not particularly limited as long as the pressure when the temperature is lowered to 40 ° C. is within the above range, but the pressure inside the pressure device naturally decreases as the temperature decreases. In addition, a mode in which the temperature is lowered without leaking pressure from the inside of the apparatus or a mode in which the temperature is lowered while further pressurizing from outside so that the internal pressure of the apparatus does not decrease as the temperature decreases is preferable. In the case where the temperature is lowered while maintaining the pressure, it is preferable to cool to 120 ° C. to 150 ° C. and then cool to 40 ° C. over 1 to 5 hours.
In the present invention, it is preferable to include a step of releasing the pressure after the temperature is lowered while the pressure is maintained. Specifically, it is preferable to lower the temperature by releasing the pressure after the temperature in the autoclave becomes 40 ° C. or lower after the temperature is lowered while the pressure is maintained.
As mentioned above, the laminated glass of this invention is the temperature of 120-150 degreeC under the process which clamps the intermediate film for laminated glasses of this invention with at least two glass plates, and 1.0-1.5 MPa after that. It is preferable to include a step of thermocompression bonding, a step of lowering the temperature while maintaining the pressure, and a step of releasing the pressure.

  The range in which the glass plate and the interlayer film for laminated glass of the present invention are thermocompression bonded may be a range over the entire area of the glass plate, but may be only the peripheral edge of the glass plate, Generation | occurrence | production can also be suppressed more.

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.

  As a support, Cosmo Shine A4300 (manufactured by Toyobo Co., Ltd., 38 μm), which is a PET film subjected to double-sided easy adhesion treatment, was used.

<Preparation of undercoat layer>
A coating solution for an undercoat layer having the composition shown below was prepared.
Composition of coating solution for undercoat layer:
Polyurethane aqueous solution: Hydran HW-350
(Manufactured by DIC Corporation, solid content concentration 30% by mass) 3.23 parts by mass Surfactant A: Lipal 8780P
(Manufactured by Lion Corporation, solid content 1% by mass) 0.96 parts by mass Surfactant B: NAROACTY CL-95
(Manufactured by Sanyo Chemical Industries, Ltd., solid content 1% by mass) 1.18 parts by mass water 64.63 parts by mass methanol 30 parts by mass

  On the support body, the coating liquid for undercoat layers was apply | coated so that the average thickness after drying might be set to 180 nm using the wire bar. Then, it heated at 130 degreeC for 1 minute, dried and solidified, and formed the undercoat layer.

<Preparation of heat ray reflective layer>
(Preparation of silver tabular grain-containing dispersion B1)
―Synthesis of silver tabular grains―
2.5 mL of 0.5 g / L polystyrene sulfonic acid aqueous solution was added to 50 mL of 2.5 mmol / L (2.5 mM) sodium citrate aqueous solution and heated to 35 ° C. To this solution, 3 mL of 10 mmol / L sodium borohydride aqueous solution was added, and 50 mL of 0.5 mmol / L silver nitrate aqueous solution was added with stirring at 20 mL / min. This solution was stirred for 30 minutes to prepare a seed solution.
In a reaction kettle, 87.1 mL of ion-exchanged water was added to 132.7 mL of a 2.5 mmol / L sodium citrate aqueous solution and heated to 35 ° C. 2 mL of 10 mmol / L ascorbic acid aqueous solution is added to the above solution in the reaction kettle, 42.4 mL of the seed solution is added, and 79.6 mL of 0.5 mmol / L silver nitrate aqueous solution is added with stirring at 10 mL / min. did. After stirring for 30 minutes, 71.1 mL of a 0.35 mol / L potassium hydroquinonesulfonate aqueous solution was added to the reaction kettle, and 200 g of a 7 mass% gelatin aqueous solution was added to the reaction kettle. To the above solution in the reaction kettle, a white precipitate mixed solution of silver sulfite formed by mixing 107 mL of a 0.25 mol / L aqueous sodium sulfite solution and 107 mL of a 0.47 mol / L aqueous silver nitrate solution was added. Immediately after the white precipitate mixture was added, 72 mL of a 0.17 mol / L aqueous NaOH solution was added to the reaction kettle. 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, it was confirmed that silver hexagonal tabular grains (hereinafter referred to as Ag hexagonal tabular grains) having an average equivalent circle diameter of 200 nm were formed. SEM images were observed for 400 grains in the silver tabular grain dispersion A1, and image analysis was performed with tabular grains mainly having a hexagonal shape being A and other irregular grains being B. The ratio of the number of particles (number%) was 96%. Further, the obtained silver tabular grain dispersion A1 is dropped on a glass substrate and dried, and the thickness of each metal tabular grain corresponding to A is measured with an atomic force microscope (Nanocute II, manufactured by Seiko Instruments Inc.). As a result, it was found that tabular grains having an average of 12 nm and an aspect ratio of 16.7 were formed. 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.

  The silver tabular grain dispersion liquid (800 mL) was kept at 40 ° C., and adjusted to pH = 10 using 1N NaOH and / or 1N sulfuric acid. Water-insoluble phenyl mercaptotetrazole (trade name: 5-mercapto-1-phenylmercaptotetrazole, manufactured by Wako Pure Chemical Industries, Ltd.) was further added as a dispersant, and stirring was continued for 10 minutes. The addition amount was 1.0% in terms of a molar ratio with respect to silver. This was centrifuged at 9000 rpm for 60 minutes with a centrifuge (Hitachi Koki Ghimac CR-GIII, angle rotor), and 760 mL of the supernatant was discarded. The precipitated silver tabular grains were transferred to a desktop homogenizer (Mitsui Denki Seiki Co., Ltd., SpinMix08), 160 mL of 0.2 mmol / L NaOH aqueous solution was added, and dispersed at 12000 rpm for 20 minutes. 200 mL of 0.2 mmol / L NaOH aqueous solution was added to the obtained dispersion liquid, and this was made into silver tabular grain dispersion liquid B1.

(Preparation of coating solution containing silver tabular grains)
A coating solution for a heat ray reflective layer having the composition shown below was prepared.
Composition of coating solution for heat ray reflective layer:
Polyurethane aqueous solution: Hydran HW-350
(DIC Co., Ltd., solid content concentration 30% by mass) 0.27 parts by mass Surfactant A: Lipal 8780P
(Manufactured by Lion Corporation, solid content 1% by mass) 0.96 parts by mass Surfactant B: NAROACTY CL-95
(Sanyo Chemical Industries, Ltd., solid content: 1% by mass) 1.19 parts by mass Silver tabular grain dispersion B1 32.74 parts by mass 1- (5-methylureidophenyl) -5-mercaptotetrazole (Wako Pure Chemical ( Co., Ltd., solid content 2% by mass) 0.61 parts by mass water 34.23 parts by mass methanol 30 parts by mass

<Heat ray reflective layer (production of silver tabular grain containing layer)>
On the undercoat layer formed on the support, a coating solution for silver tabular grain-containing layer was applied using a wire bar so that the average thickness after drying was 20 nm.

<Coating solution for overcoat layer>
A coating solution for an overcoat layer having the composition shown below was prepared.
Composition of coating solution for overcoat layer:
Modified polyvinyl alcohol PVA203 (manufactured by Kuraray Co., Ltd.) 10 parts by mass Glutaraldehyde 0.5 parts by mass Water 371 parts by mass Methanol 119 parts by mass

  On the heat ray reflective layer (silver tabular grain-containing layer) formed on the support through the undercoat layer, the coating liquid for the overcoat layer is dried to a thickness of 30 nm using a wire bar. It applied so that it might become. Then, it heated at 100 degreeC for 2 minute (s), dried and solidified, and formed the overcoat layer.

<Coating liquid for heat ray absorbing layer>
IR-1 to IR-7 shown in Table 1 below (in terms of solid content) were prepared as coating solutions for the heat ray absorbing layer. In Table 1 below, the ITO dispersion represents PI (20% by mass manufactured by Mitsubishi Materials Corporation), and the CWO dispersion was a cesium-containing tungsten oxide Cs _0.33 WO ₃ dispersion (trade name YMF-02 18.5% by mass). , Manufactured by Sumitomo Metal Mining Co., Ltd.), the photopolymerization initiator represents Irgacure 819 (manufactured by BASF), and MIBK represents methyl isobutyl ketone (manufactured by Wako Pure Chemical Industries, Ltd.).

Apply the coating solution IR-1 for heat ray absorbing layer to the support surface on the side opposite to the overcoat layer of the film in which the support, the undercoat layer, the silver tabular grain-containing layer and the overcoat layer are laminated with # 8 bar. Applied. Thereafter, the film was dried at a film surface temperature of 90 ° C. for 1 minute, and then irradiated with ultraviolet rays using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) of 160 W / cm to form a metal oxide-containing layer. . The UV-A irradiation amount was 200 mJ / cm ² .
The heat ray shielding material obtained in the above manner, in which the heat ray absorbing layer, the support, the undercoat layer, the silver tabular grain-containing layer, and the overcoat layer (external light side) are laminated in this order, is the heat ray shielding material of Example 1. It was.

[Examples 2-5, Comparative Examples 1-2, 4-5]
The coating amount of the heat ray reflective layer and the kind and the coating amount of the heat ray absorbing layer are prepared, and the heat ray shielding materials of Examples 2 to 5 and Comparative Examples 1 to 2 and 4 to 5 having the compositions described in Table 2 below are prepared. did.

<Evaluation of heat ray shielding material>
(Confirmation of the existence range of silver tabular grains in the heat ray reflective layer)
About the heat ray shielding material of each Example and a comparative example, when the thickness of the said heat ray reflective layer is set to d, the range where 80 number% or more of the said hexagonal shape or circular silver tabular grain exists is a perpendicular | vertical cross section of a multilayered structure. It calculated from the image which observed the sample by SEM.
As a result, it was confirmed that 80% or more of the hexagonal or circular silver tabular grains were present in the d / 2 range in the heat ray shielding materials of each Example and Comparative Example.

(Confirmation of particle inclination angle of heat ray reflective layer)
After embedding the heat ray reflective layer of the heat ray shielding material of each Example and Comparative Example with an epoxy resin, it was cleaved with a razor in a state frozen with liquid nitrogen, and a multilayer structure vertical direction cross section sample was produced. This vertical cross-sectional sample was observed with a scanning electron microscope (SEM), and the inclination angle (corresponding to ± θ in FIG. 6A) of the main plane of 100 metal tabular grains with respect to the horizontal plane was calculated as an average value.
(Evaluation criteria)
A: Inclination angle is ± 10 ° or less B: Inclination angle exceeds ± 10 ° As a result, the heat ray shielding materials of each Example and Comparative Example were evaluated as A.

<Production of laminated glass>
A polyvinyl butyral interlayer film for laminated glass (thickness: 380 μm) and the heat ray shielding materials of Examples 1 to 5 and Comparative Examples 1 to 2 and 4 to 5 prepared above were stacked on a clear glass having a thickness of 2 mm. Furthermore, a polyvinyl butyral interlayer film for laminated glass (thickness: 380 μm) and a clear glass having a thickness of 2 mm were stacked thereon in that order. This laminate was pre-pressed under vacuum at 95 ° C. for 30 minutes, and then pressure-bonded while heating in an autoclave at 1.3 MPa and 120 ° C., Examples 1 to 5, Comparative Examples 1 and 2, 4-5 laminated glass was produced.

<Evaluation of laminated glass>
(Visible light transmittance and TTS)
About the laminated glass of each Example and Comparative Example, the transmission and reflection spectra (wavelength 300 to 2500 nm) measured from the outside light side (heat ray reflective layer side) were measured with ultraviolet and visible near-infrared with an integrating sphere unit ISN-723 attached. It measured using the spectroscope (JASCO Corporation make, V-670).
The results of calculating the visible light transmittance and TTS based on the visible light transmittance and TTS calculation method described in ISO13837 are shown in Table 2 below.

(Comprehensive evaluation)
When the silver amount of the heat ray reflective layer or the ITO / CWO coating amount of the heat ray absorbing layer is increased, both the visible light transmittance and TTS are lowered. Therefore, in order to compare the optical performance, it is necessary to compare the visible light transmittance or TTS. When the visible light transmittance is converted to 72% by fine adjustment of the silver amount of the heat ray reflective layer,
TTS 55% or more, or fine adjustment of the amount of silver in the heat ray reflective layer cannot adjust the visible light transmittance to 72%: D
TTS 53% to less than 55%: C
TTS 51% or more and less than 53%: B
TTS less than 51%: A
It was. Practically, it is necessary to have A or B evaluation.
The obtained results are shown in Table 2 below.

From Table 2 above, it was found that the laminated glass of the present invention can achieve both high visible light transmittance and low total solar transmittance TTS.
On the other hand, from Comparative Example 1, it was found that when only ITO particles were used alone as the heat ray absorbing layer, it was impossible to achieve both high visible light transmittance and low total solar transmittance TTS. From Comparative Example 2, it was found that even when only CWO particles were used alone as the heat ray absorbing layer, it was impossible to achieve both high visible light transmittance and low total solar transmittance TTS.
Further, if the silver tabular grain content is outside the range of 15 to 45 mg / m ² from Comparative Examples 4 and 5, the visible light transmittance cannot be adjusted to 72% by fine adjustment of the silver amount of the heat ray reflective layer. I understood.

[Example 6]
Using the heat ray reflective layer produced using IR-3 under the conditions of Example 3, the following interference layer was further added to examine the evaluation of the amount of reflection.

<High refractive index layer (undercoat layer A)>
A coating solution for undercoat layer A (layer A) having the composition shown below was prepared.
Composition of coating solution for undercoat layer A (layer A):
Polyurethane aqueous solution: Hydran HW-350
(Manufactured by DIC Corporation, solid content concentration 30% by mass) 3.23 parts by mass Surfactant A: Lipal 8780P
(Manufactured by Lion Corporation, solid content 1% by mass) 0.96 parts by mass Surfactant B: NAROACTY CL-95
(Manufactured by Sanyo Chemical Industries, Ltd., solid content 1% by mass) 1.18 parts by mass water 64.63 parts by mass methanol 30 parts by mass

<Low refractive index layer (undercoat layer B)>
A coating solution B2 for an undercoat layer B (layer B) having the composition shown below was prepared.
Composition of coating liquid B2 for undercoat layer B (layer B):
Polyurethane aqueous solution: Hydran HW-350
(DIC Corporation, solid content concentration 30% by mass) 1.83 parts by mass Silica particle IPA dispersion: Through rear 4110
(Manufactured by JGC Catalysts & Chemicals Co., Ltd., solid content concentration 20.5%) 4.06 parts by mass Surfactant B: NAROACTY CL-95
(Manufactured by Sanyo Chemical Industries, Ltd., solid content 1% by mass) 1.18 parts by mass water 64.63 parts by mass IPA 25.94 parts by mass

In Example 6, on a Cosmo Shine A4300 (PET having a refractive index of 1.66) used as a support, a low refractive index layer (Layer B) having a refractive index of 1.4 described in Table 3 below, and the following table The high refractive index layer (layer A) having a refractive index of 1.6 described in 1 was applied so that the dry film thicknesses were 105 nm (layer B) and 55 nm (layer A), respectively. A heat ray reflective layer (silver tabular grain-containing layer) was formed thereon by coating in the same manner as in Example 3. However, the overcoat layer was not applied. Furthermore, the heat ray absorption layer was provided in the back surface of the support body using IR-3 similarly to Example 3. The obtained film was used as the heat ray reflective material of Example 6.
A laminated glass was produced in the same manner as in Example 3 using the heat ray reflective material of Example 6. The obtained laminated glass was used as the laminated glass of Example 6. The layer adjacent to the layer B was a support (corresponding to the layer C), and the refractive index nC was 1.66.
The laminated glass of Example 6 was configured as shown in FIG.

[Example 7]
In Example 7, a heat ray shielding material was obtained in the same manner as in Example 6 except that the coating thickness of the coating liquid for the undercoat layer A (layer A) was changed so that the dry film thickness of the undercoat layer A was 220 nm. And the laminated glass of a structure as shown in FIG. 4 was manufactured.
Here, the laminated glass of Example 7 corresponds to the case where the relationship between the layer A and the layer B is m = 1 in the formula (1).

[Example 8]
In Example 8, a heat ray reflective layer was formed and the coating liquid A2 was further used to change the overcoat layer A ′ so that the dry film thickness was 55 nm. Then, a heat ray shielding material and a laminated glass having a structure as shown in FIG. 5 were produced.

[Example 9]
In Example 9, Example 6 was carried out except that the heat ray reflective layer (silver tabular grain-containing layer) was formed directly on the support without applying the undercoat layer B or the undercoat layer A on the support. In the same manner as described above, a heat ray shielding material and a laminated glass having the structure shown in FIG. 1 were produced.

[Example 10]
Example 10 was carried out except that the undercoat layer B having a refractive index of 1.4 was applied so that the dry film thickness was 155 nm without applying the undercoat layer B on the support. In the same manner as in Example 6, a heat ray shielding material and a laminated glass having a configuration as shown in FIG. 3 were produced. In this layer configuration, the support also serves as the layer B.

[Example 11]
In Example 11, a low refractive index layer (layer B ″ 3) having a refractive index of 1.4, a high refractive index layer (layer B ″ 2) having a refractive index of 1.6, and a refractive index of 1. The low refractive index layer (layer B "1) 4 and the high refractive index layer (layer A) having a refractive index of 1.6 have dry film thicknesses of 105 nm (layer B" 3) and 95 nm (layer B "2), respectively. , 105 nm (layer B ″ 1), 55 nm (layer A), except that the coating was changed to be the same as in Example 6, the heat ray shielding material and FIG. 4 (however, layer B has a three-layer structure) A laminated glass having a structure as shown in FIG.

[Comparative Example 3]
In Comparative Example 3, a heat ray shielding material and a laminated glass having the structure shown in FIG. 2 were produced in the same manner as in Example 6 except that the heat ray absorbing layer was not provided.

[Evaluation]
(Visible light transmittance, TTS, comprehensive evaluation)
About the laminated glass of Examples 6-11 and the comparative example 5, it carried out similarly to Example 1, measured visible light transmittance | permeability and TTS, and performed comprehensive evaluation.
The obtained results are shown in Tables 3 and 4 below.

(Amount of reflection)
About the laminated glass of each Example and Comparative Example, the absolute light reflectance unit ARV-474S was attached to the external light side (heat ray reflective layer side), the transmission measured from an oblique angle of 60 °, and the reflection spectrum (wavelength 300 to 2500 nm). It measured using the ultraviolet visible near-infrared spectrometer (the JASCO make, V-670). The visible light reflectance described in ISO13837 was defined as the amount of reflection.
The obtained results are shown in Tables 3 and 4 below.

From the said table | surface, the laminated glass of this invention can make high visible light transmittance | permeability and low total solar radiation transmittance | permeability TTS compatible, and also under conditions which satisfy | fill a specific condition to a heat ray absorption layer like Example 6. FIG. It was found that, by providing a coating layer as an interference layer, it is possible to simultaneously achieve reflection suppression in addition to high visible light transmittance and low total solar transmittance TTS. Further, it was found that the effect of suppressing reflection can be further enhanced by providing interference layers (antireflection layers) satisfying specific conditions on both sides as in Example 8. However, as in Example 9, it was found that only the heat-absorbing layer can achieve both high visible light transmittance and low total solar transmittance TTS, but the reflection is large. Although the film thickness of the adjacent layer is large as in Example 7 and m = 1 in Equation (1), both high visible light transmittance and low total solar transmittance TTS can be achieved, but Equation (1) It was found that the reflection could not be suppressed as compared with Examples 6 and 8 in which m = 0.
On the other hand, it was found that the total solar transmittance TTS was increased and the performance was inferior when only the interference layer was used, as in the laminated glass of Comparative Example 9 having a configuration not using the heat ray absorbing layer.

  Since the heat ray shielding material of the present invention can achieve both high visible light transmittance and low total solar transmittance TTS, for example, films for automobiles, buses, etc., laminated structures, films for building materials, and laminated structures As a body etc., it can utilize suitably as various members calculated | required to prevent permeation | transmission of a heat ray.

DESCRIPTION OF SYMBOLS 1 Support body 2 Heat ray reflective layer (metal particle content layer)
3 Silver tabular grain 4 Overcoat layer 5A, 5B, 5C, 5A ′ Layer A, Layer B, Layer C, Layer A ′
14 Heat-absorbing layer (metal oxide particle-containing layer)
21 Glass 22 Intermediate film D Diameter L Thickness f (λ) Particle existence region thickness

Claims (15)

A heat ray reflective layer containing silver tabular grains;
A heat-absorbing layer containing a plurality of types of metal oxide particles,
Content of the silver tabular grain in the said heat ray reflective layer is 15-45 mg / m < ² >, The heat ray shielding material characterized by the above-mentioned.   The heat ray shielding material according to claim 1, wherein the heat ray reflective layer has 60% by number or more of hexagonal or circular silver tabular grains. It has the multilayer structure characterized by having the heat ray reflective layer, the layer A having a refractive index nA, and the layer B having a refractive index nB in this order and satisfying the following condition (1) or (2) The heat ray shielding material according to claim 1 or 2.
Condition (1) nA> nB and the following formula (1) is satisfied.
Formula (1):
λ / 8 + mλ / 2−λ / 12 <nA × dA <λ / 8 + mλ / 2 + λ / 12
(In the formula (1), m represents an integer of 0 or more, λ represents a wavelength to prevent reflection, and dA represents the thickness of the layer A.)
Condition (2) nA <nB and the following formula (2) is satisfied.
Formula (2):
3λ / 8 + mλ / 2−λ / 12 <nA × dA <3λ / 8 + mλ / 2 + λ / 12
(In the formula (2), m represents an integer of 0 or more, λ represents a wavelength to prevent reflection, and dA represents the film thickness of the layer A.)   The heat ray shielding material according to claim 3, wherein the m is 0. The heat ray shielding material according to claim 3 or 4, which has a layer C having a refractive index nC adjacent to the layer B, and the layer B satisfies the following condition (3).
Condition (3) nA> nB and nB <nC, or nA <nB and nB> nC are satisfied, and the following formula (3) is satisfied.
Formula (3):
λ / 4 + Lλ / 2−λ / 12 <nB × dB <λ / 4 + Lλ / 2 + λ / 12
(In the formula (3), L represents an integer of 0 or more, λ represents a wavelength to prevent reflection, and dB represents the film thickness of the layer B.)   The heat ray shielding material according to claim 5, wherein L is 0.   The heat ray shielding material according to claim 5 or 6, wherein the layer B is a stacked body of a plurality of layers B '' having different refractive indexes, and each layer included in the layer B '' satisfies the formula (3). .   On the opposite side of the heat ray reflective layer from the layer A and the layer B, the second layer (A) and the second layer (B) satisfying the condition (1) or (2) The heat ray shielding material according to any one of claims 3 to 7, which has the layer B, the second layer (A), and the second layer (B) in this order.   The heat ray shielding material according to any one of claims 3 to 8, wherein a wavelength λ to be prevented from being reflected is 400 nm to 700 nm.   The at least one kind of the metal oxide particles contained in the heat ray absorbing layer is any one of tin-doped indium oxide (ITO) and cesium-containing tungsten oxide (CWO). The heat ray shielding material as described.   The heat ray shielding material according to any one of claims 1 to 10, wherein the metal oxide particles contained in the heat ray absorbing layer contain both tin-doped indium oxide (ITO) and cesium-containing tungsten oxide (CWO). The content of cesium-containing tungsten oxide contained in the heat absorbing layer (CWO) is, the heat ray shielding material according to any one of claims 1 to 11 is 0.3~1.3g / m ^2. Furthermore, it has a support,
The heat ray shielding material according to any one of claims 1 to 12, wherein the heat ray reflective layer and the heat ray absorption layer are disposed on opposite sides of the support.   An interlayer film for laminated glass comprising the heat ray shielding material according to claim 1.   A laminated glass comprising the interlayer film for laminated glass according to claim 14 and at least two glass plates, wherein the interlayer film for laminated glass is inserted into the two sheets of glass.

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