JP2018075797A - Far-infrared reflecting substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a far-infrared reflecting substrate excellent in corrosion resistance.SOLUTION: The far-infrared reflecting substrate is configured to have a metal layer [C] and a silicon-containing layer [D] between a base material [A] and a protective layer [B] and satisfies the following (1)-(4): (1) the metal layer [C] contains 50 mass% or more of silver based on the whole metal layer [C]; (2) the silicon-containing layer [D] is in direct contact with the metal layer [C]; (3) the silicon-containing layer [D] contains 40 atom% or more of silicon based on the whole silicon-containing layer [D]; and (4) the far-infrared reflectance is 60% or more.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a far-infrared reflective substrate.

  2. Description of the Related Art Conventionally, for example, as a means for imparting energy saving performance to a window of a building or a moving body, it is known to install a laminated body having far-infrared reflection performance on the window. The laminated body having the far-infrared reflecting performance reflects radiant heat mainly composed of far infrared rays generated indoors and suppresses the radiant heat from flowing out of the indoors to the outdoors. And many laminates having far-infrared reflective performance are known in which a metal layer mainly composed of silver is laminated on a base material such as a plastic film and a surface protective layer is further provided thereon. It has been.

  Here, the surface protective layer is known to be made of glass, resin, or the like, but in order to return more radiant heat mainly composed of far infrared rays to the room, that is, far infrared reflection performance. It is also known that it is preferable to make the surface protective layer thin in order to make the surface more excellent. As the thin surface protective layer, an organic surface protective layer (see Patent Document 1) formed using a process such as wet coating, an organic silicon compound such as hexamethyldisiloxane, or the like is used as a material. An inorganic surface protective layer made of silicon oxide, aluminum oxide or the like formed by a chemical vapor deposition (CVD) process or the like is known (see Patent Document 2).

Japanese Patent Laid-Open No. 10-286900 Special table 2002-539004 gazette

  Among infrared rays, far-infrared rays emitted indoors by heating heat in the winter are absorbed not only by glass and plastic films but also by the surface protective layer. Therefore, in order to obtain the performance to prevent the thermal energy from flowing out outdoors by reflecting far infrared rays, that is, to realize the high infrared reflectance of the infrared reflecting substrate, the infrared reflecting substrate is made of a thick surface protective layer. As described above, it is necessary to reduce the thickness of the surface protective layer without taking a protective structure. However, when the surface protective layer is thinned, the present inventors faced the problem that contamination by chemical substances is easily received, and deterioration due to corrosion or the like of the metal layer reflecting infrared rays easily proceeds. That is, the thin surface protective layer described in the cited references 1 and 2 gives excellent far-infrared reflection performance to the laminate having far-infrared reflection performance, but the metal layer provided in the laminate having far-infrared reflection performance. The present inventor has faced the problem that deterioration due to corrosion or the like tends to proceed.

  Therefore, the subject of this invention is providing the far-infrared reflective board | substrate which provided the outstanding corrosion resistance to the board | substrate which has favorable far-infrared reflective performance.

The present invention employs the following means in order to solve such problems. That is,
The far-infrared reflective substrate satisfying the following (1) to (4) having a configuration having a metal layer [C] and a silicon-containing layer [D] between the substrate [A] and the protective layer [B]. .
(1) The metal layer [C] contains 50% by mass or more of silver with respect to the entire metal layer [C]. (2) The silicon-containing layer [D] is in direct contact with the metal layer [C]. Layer [D] contains 40 atomic% or more of silicon with respect to the entire silicon-containing layer [D]. (4) Far-infrared reflectance is 60% or more.

  In the far-infrared reflective substrate of the present invention, the silicon-containing layer [D] containing 40 atomic% or more of silicon is in direct contact with the metal layer [C]. Even if the silicon-containing layer [D] has a thin thickness that hardly reduces the light transmittance, the silicon-containing layer [D] can extremely effectively suppress the corrosion of the metal layer [C] containing silver. . Therefore, according to the present invention, it is possible to provide an infrared reflective substrate having excellent far-infrared reflectivity with a far-infrared reflectivity of 60% or more and excellent corrosion resistance.

It is a cross-sectional schematic diagram of the 1st form example of the infrared reflective board | substrate of this invention, Specifically, base material [A], internal buffer layer [F], 1st high refractive index layer [E], 1st Silicon-containing layer [D], metal layer [C], second silicon-containing layer [D], second high refractive index layer [E], inorganic protective layer [B1], and organic protective layer [B2] ] Is a schematic cross-sectional view of a configuration in which the layers are stacked in this order. It is a cross-sectional schematic diagram of the 2nd form example of the infrared reflective board | substrate of this invention, Specifically, base material [A], internal buffer layer [F], 1st high refractive index layer [E], silicon containing It is a cross-sectional schematic diagram of a structure formed by laminating a layer [D], a metal layer [C], a second high refractive index layer [E], and an inorganic protective layer [B1] in this order. It is a cross-sectional schematic diagram of the 3rd example of the infrared reflective board | substrate of this invention, Specifically, base material [A], internal buffer layer [F], 1st high refractive index layer [E], metal layer It is a cross-sectional schematic diagram of a structure formed by laminating [C], a silicon-containing layer [D], a second high refractive index layer [E], and an inorganic protective layer [B1] in this order. It is a cross-sectional schematic diagram of a conventional infrared reflective substrate, which is a base [A], an internal buffer layer [F], a first high refractive index layer [E], a metal layer [C], a second high refractive index layer [ E] and the inorganic protective layer [B1] are laminated in this order.

The infrared reflective substrate of the present invention comprises the following (1) to (4) having a structure having a metal layer [C] and a silicon-containing layer [D] between a base material [A] and a protective layer [B]. Satisfied.
(1) The metal layer [C] contains 50% by mass or more of silver with respect to the entire metal layer [C]. (2) The silicon-containing layer [D] is in direct contact with the metal layer [C]. The layer [D] contains 40 atomic% or more of silicon with respect to the entire silicon-containing layer [D]. (4) The far-infrared reflectance is 60% or more.

  As a result of extensive studies by the inventors, the far-infrared reflective substrate having a structure in which the silicon-containing layer [D] containing silicon is in direct contact with the metal layer [C] is used to corrode the metal layer [C]. It came to obtain the far-infrared reflective board | substrate which shows tolerance with respect to this.

  Moreover, as an example of the form which the far-infrared reflective board | substrate of this invention can take, a form like FIGS. 1-3 can be illustrated.

  First, as shown in FIG. 1, the first is a substrate [A] 1, an internal buffer layer [F] 2, a first high refractive index layer [E] 3, and a first silicon-containing layer [D]. 4, metal layer [C] 5, second silicon-containing layer [D] 6, second high refractive index layer [E] 7, inorganic protective layer [B1] 9, and organic protective layer [B2] 10 In this order. In this infrared reflective substrate, a first silicon-containing layer [D] 4 and a second silicon-containing layer [D] 6 are formed on both surfaces of the metal layer [C] 5, respectively. It has a content layer [D]. Note that the infrared reflecting substrates of Examples 2 and 8 described later belong to this embodiment.

  Secondly, as shown in FIG. 2, the substrate [A] 1, the internal buffer layer [F] 2, the first high refractive index layer [E] 3, the silicon-containing layer [D] 11, the metal layer It is an infrared reflective substrate having [C] 5, a second high refractive index layer [E] 7, and an inorganic protective layer [B1] 9 in this order. In this infrared reflective substrate, a silicon-containing layer [D] 11 is formed between the base [A] 1 and the metal layer [C] 5, and has one silicon-containing layer [D]. In addition, the infrared reflective board | substrate of Example 3 mentioned later belongs to this embodiment example.

  Third, as shown in FIG. 3, the substrate [A] 1, the internal buffer layer [F] 2, the first high refractive index layer [E] 3, the metal layer [C] 5, the silicon-containing layer [ D] 11, an infrared reflective substrate having a second high refractive index layer [E] 7 and an inorganic protective layer [B1] 9 in this order. In this infrared reflective substrate, the silicon-containing layer [D] 11 is formed between the metal layer [C] 5 and the inorganic protective layer [B1] 9, and has one silicon-containing layer [D]. In addition, the infrared reflective board | substrate of Example 5 mentioned later belongs to this embodiment example.

  Further, as a conventional infrared reflective substrate having no silicon-containing layer, as shown in FIG. 4, a base material [A] 1, an internal buffer layer [F] 2, a first high refractive index layer [E] 3, Examples include those having a metal layer [C] 5, a second high refractive index layer [E] 7 and an inorganic protective layer [B1] 9 in this order. It belongs to a form example.

  Each configuration in the present invention will be described below.

[Base material]
Although it does not specifically limit as base material [A] used for this invention, The thing which consists of inorganic oxides and resin, such as glass, can be used. In order to facilitate continuous processing and handling, the substrate [A] is more preferably a flexible resin film. Examples of the resin film material include aromatic polyesters represented by polyethylene terephthalate and polyethylene-2,6-naphthalate, aliphatic polyamides represented by nylon 6 and nylon 66, aromatic polyamides, polyethylene and polypropylene, and the like. Examples thereof include acrylics represented by polyolefin, polycarbonate, polymethyl methacrylate film and the like. Among these, aromatic polyesters are preferable in terms of cost, ease of handling, and heat resistance to heat received when processing the laminate, and polyethylene terephthalate or polyethylene-2,6-naphthalate is more preferable, polyethylene. A terephthalate film is particularly preferred. Moreover, the biaxially stretched film which raised mechanical strength is preferable, and especially a biaxially stretched polyethylene terephthalate film is preferable. The film thickness is preferably in the range of 5 μm to 250 μm, and more preferably 15 μm to 150 μm, from the viewpoint of ease of handling and productivity improvement by lengthening the processing unit.

  In addition, various additives such as antioxidants, heat stabilizers, weather stabilizers, ultraviolet absorbers, organic lubricants, pigments, dyes, organic or inorganic fine particles, fillers, anti-static agents are also included in the resin film. An agent, a nucleating agent, etc. may be added to such an extent that the properties of the resin film are not deteriorated.

  In order to improve the adhesion between the base material [A] made of a resin film or the like and a layer other than the base material [A] such as an internal buffer layer [F] to be described later, for example, JP-A-2004-107627 As described in the above, the base [A] is at least polyester, acrylic, polyurethane, acrylic on the side of the base [A] on which the internal buffer layer [F] and the metal layer [C] are laminated. It is one of preferred embodiments to provide a primer layer containing various resins such as graft polyester.

[Protective layer]
As the protective layer [B] used in the present invention, an inorganic protective layer, an organic protective layer, or a combination of an inorganic protective layer and an organic protective layer can be employed. The protective layer is provided to protect the far-infrared reflective substrate from defects such as scratches and corrosion due to chemicals, etc., but the far-infrared reflective performance will deteriorate due to the absorption of the far-infrared by the protective layer. In order to obtain a good far-infrared reflection performance, it is necessary to make the protective layer sufficiently thin. Therefore, when a hard film such as glass or an acrylic hard coat resin is used for the protective layer, the thickness of the protective layer is preferably 5 μm or less, more preferably 2 μm or less, and 0.5 μm or less. Further preferred. In addition, in order to prevent the change in the thickness of the protective layer and the change in the observation angle from being easily observed as a change in the color tone of the transmitted light or reflected light of the visible light, the thickness of the protective layer is 0.2 μm or less. It is preferable that it is 0.1 μm or less, more preferably 0.05 μm or less. On the other hand, as described above, in order to protect the far-infrared reflective substrate from defects such as scratches and corrosion due to chemicals, the thicker the protective layer, the better. In order to obtain a continuous and uniform protective layer, the thickness of the protective layer is preferably 2 nm or more, more preferably 5 nm or more, and even more preferably 10 nm or more.

  In order to obtain a hard protective layer with a thinner film thickness, the protective layer is one or more oxynitrides selected from the group consisting of silicon oxide, aluminum oxide, silicon nitride, and aluminum nitride It is a preferable aspect that the inorganic protective layer [B1] contains 50% by mass or more of the total amount of the inorganic protective layer [B1]. For the purpose of obtaining a dense and high-hardness protective film, it is preferable that 70% by mass or more of silicon oxide or the like is contained in the entire inorganic protective layer [B1], and 90% by mass or more. More preferably it is contained. Here, the mass% of at least one oxynitride selected from the group consisting of silicon oxide, aluminum oxide, silicon nitride, and aluminum nitride represents the entire inorganic protective layer [B1]. Is a sum of mass% of silicon, aluminum, oxygen, and nitrogen.

Further, in order to obtain more uniform characteristics against penetration of moisture and the like, the organic protective layer containing a resin having a resin skeleton composed of — (CH ₂ ) — or — (CF ₂ ) — or the like. [B2] is a preferred embodiment. In order to prevent moisture and the like from penetrating into the infrared reflective substrate, the contact angle of the organic protective layer [B2] with respect to water is preferably 60 ° or more, more preferably 80 ° or more. Preferably, it is more preferably 100 ° or more. It is assumed that the organic protective layer [B2] contains a fluorine resin or a silicone resin as a component, and that the organic protective layer [B2] is the outermost layer of the far-infrared reflective substrate. This is a preferred embodiment for increasing the contact angle of water with water. Moreover, in addition to the above, when the above-mentioned aspect is taken, when removing this adhesive from the far-infrared reflective substrate in which an adhesive such as a tape is attached on the surface of the organic protective layer [B2], This is also a preferred embodiment because the layer formed on the substrate [A] is prevented from peeling off. The reason why the layer formed on the substrate [A] is prevented from peeling off is that the adhesive force between the organic protective layer [B2] and the adhesive is, for example, the inorganic protective layer [B1]. This is considered to be because the adhesive strength between the layer and the adhesive is low.

  In addition, as a method of modifying the surface hardness and optical properties of the organic protective layer [B2], inorganic or organic particles or a combination thereof may be used, and one or more particles may be combined to form the organic protective layer [B2 ] And can be used. For example, as the inorganic particles, silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, zinc oxide, germanium oxide, indium oxide, tin oxide, tin-doped indium oxide (ITO), cerium oxide, or the like can be used. As organic fine particles, styrene resin, styrene-acrylic copolymer resin, styrene-acrylic copolymer resin, acrylic resin, divinylbenzene resin, silicone resin, urethane resin, melamine resin, styrene-isoprene resin, benzoguanamine resin, polyamide resin Polyester resin or the like can be used. The shape of the particle includes a spherical shape, a hollow shape, a porous shape, a rod shape, a plate shape, a fiber shape, an indefinite shape, and the like, and can be appropriately selected according to necessary characteristics. Furthermore, by performing a surface treatment that introduces a functional group to the particle surface, a crosslinking reaction occurs between the crosslinkable resin and the particle surface, thereby modifying the characteristics of the organic protective layer [B2]. be able to. As the surface treatment for introducing a functional group, for example, an organic compound containing a polymerizable unsaturated group can be bonded to the particles. The polymerizable unsaturated group is not particularly limited, and examples thereof include acryloyl group, methacryloyl group, vinyl group, propenyl group, butadienyl group, styryl group, ethynyl group, cinnamoyl group, maleate group and acrylamide group. .

  In order to protect the far-infrared reflective substrate from defects such as scratches and corrosion due to chemicals, it is a preferable aspect to have both the inorganic protective layer [B1] and the organic protective layer [B2].

[Metal layer]
Examples of the purpose of providing the metal layer [C] in the present invention include obtaining electrical conductivity, electromagnetic wave prevention, and heat shielding and heat insulation performance by infrared reflection. In order to obtain good infrared reflection performance, it is necessary to use a metal exhibiting excellent conductivity for the metal layer [C], and an example of such a metal is silver (Ag). Optically excellent by having a layer containing 50% by mass or less of silver (Ag) showing little excellent conductivity in the visible light region and the mass of the layer being 100% by mass. A far-infrared reflective substrate can be obtained. For the purpose of obtaining good infrared reflectance and visible light transmittance of the metal layer [C], it is preferable that 70% by mass or more of silver (Ag) is contained in the whole layer, and 90% by mass. It is more preferable that it is contained in an amount of at least%. On the other hand, the upper limit of the content of silver (Ag) is not particularly limited, and the content of silver (Ag) is 100% by mass, that is, even if the metal layer [C] is made of only silver (Ag). Good. In order to prevent silver (Ag) from deteriorating due to reaction with sulfur, oxygen, etc., or to prevent defects due to aggregation, Au, Pt, Pd, Cu, Bi, Nd, Mg, Zn, It is preferably used as an alloy of one or more metals selected from Al, Ti, Y, Eu, Pr, Ce, Sm, Ca, Be, Cr, Co, Ni and the like and silver (Ag).

  Further, when the total mass of the metal layer [C] is 100% by mass, the proportion of silver (Ag) contained in the metal layer [C] is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 90% by mass. If it is at least%, the far-infrared shielding effect tends to be even better.

  The film thickness of the metal layer [C] is preferably 5 nm or more, and more preferably 10 nm or more. By setting the film thickness of the metal layer [C] to 5 nm or more, the thickness unevenness of the metal layer [C] is suppressed, and the metal layer [C] can exhibit stable far-infrared reflection performance. On the other hand, the thickness of the metal layer [C] is preferably 30 nm or less, and more preferably 25 nm or less. By making the film thickness of the metal layer [C] 30 nm or less, the visible light transmission performance of the far-infrared reflective substrate can be further improved.

  In addition, as a method for forming the metal layer [C], various metal and alloy targets are used to obtain a thin film by a sputtering process, resistance heating by an evaporation process, electron beam, laser, high frequency induction heating, arc, etc. Examples include a method of obtaining a thin film by depositing various metals and alloys vaporized by the method. Among these, a method of obtaining a thin film by a sputtering process is preferable from the viewpoint of excellent control of film thickness and film quality and obtaining good film adhesion.

  Further, from the viewpoint of protecting the metal layer [C] from corrosion and oxidation, the metal layer [C] and the metal layer [C1] containing 50% by mass or more of silver with respect to the whole and Y, Ti, Zr, Nb, Ta , Cr, Mo, W, Ru, Ir, Pd, Pt, Ni, Cu, Au, Al, Ce, Nd, Sm, and a metal thin film [C2] made of a mixture thereof, or a mixture thereof. Furthermore, it is preferable that the metal layer [C1] is provided with the metal thin film [C2] on one side or both sides. In order to sufficiently protect the metal layer [C] from corrosion and oxidation, the thickness of the metal thin film [C2] is preferably 0.5 nm or more. In order to obtain good visible light transmission performance, the thickness of the metal thin film [C2] is preferably 10 nm or less. In order to achieve both the protection performance and the visible light transmission performance, the film thickness of the metal thin film [C2] is more preferably 1 nm or more and 5 nm or less. The metal thin film [C2] is a layer provided to protect the metal layer [C] from corrosion and has little influence on properties such as infrared reflection performance. Therefore, when considering the thickness of the metal layer [C] for characteristics such as infrared reflection performance, the metal thin film [C2] is excluded. In addition, the metal thin film [C2] may contain silver (Ag), but in that case, the silver content in the metal thin film [C2] is when the mass of the layer is 100% by mass. It is preferable that it is less than 50 mass%. In addition, it is more preferable that the metal thin film [C2] does not contain silver (Ag).

[Silicon-containing layer]
In the far-infrared reflective substrate of the present invention, excellent corrosion resistance is obtained by adopting a structure in which the silicon-containing layer [D] is in direct contact with the metal layer [C].
The silicon-containing layer [D] can impart excellent corrosion resistance by containing 40 atomic% or more of silicon with respect to the entire silicon-containing layer [D].
In addition, it is one of the possible modes of the present invention that the silicon-containing layer [D] is made of two or more kinds of elemental semiconductors including carbon and germanium which are elemental semiconductors such as SiC.
In addition, elements other than silicon, carbon, and germanium can be added and used within a range that does not significantly change the characteristics of the silicon-containing layer [D].
For the purpose of obtaining an optically and chemically stable far-infrared reflective substrate, silicon is contained in the silicon-containing layer [D] in an amount of 45 atomic% or more with respect to the entire silicon-containing layer [D]. It is more preferable that 50 atomic% or more is contained in the silicon-containing layer [D], and it is particularly preferable that 90 atomic% or more is contained in the silicon-containing layer [D].

  The silicon-containing layer [D] is preferably disposed between the metal layer [C] and the protective layer [B], more preferably disposed between the substrate [A] and the metal layer [C]. It is further preferable to dispose both between the substrate [A] and the metal layer [C] and between the metal layer [C] and the protective layer [B]. The reason why the corrosion resistance of the far-infrared reflective substrate can be obtained by providing the silicon-containing layer [D] is not clear, but the metal layer [C] and the resin or metal oxide forming the substrate and the high refractive index layer are directly used. It is thought that the defect of the interlayer structure that occurs when the layers are stacked is reduced through the silicon-containing layer [D]. The reason why it is preferable to dispose between the substrate [A] and the metal layer [C] is more preferable than disposing between the metal layer [C] and the protective layer [B]. Defects in the interlayer structure when the metal layer [C] is directly formed on the resin or metal oxide forming the metal layer, and defects in the interlayer structure when the metal oxide or resin is formed on the metal layer [C] Therefore, it is considered that the effect of reducing the structural defects generated between the substrate [A] and the metal layer [C] by the silicon-containing layer [D] becomes larger. Obtaining superior corrosion resistance by disposing the silicon-containing layer [D] between the substrate [A] and the metal layer [C] and between the metal layer [C] and the protective layer [B]. A far-infrared reflective substrate with good adhesion can be obtained.

  Since the silicon-containing layer [D] hinders transmission of visible light, in order to obtain good transparency, the thickness of the silicon-containing layer [D] is preferably 10 nm or less, and more preferably 5 nm or less. More preferably, it is 3 nm or less. On the other hand, in order to obtain good corrosion resistance, the thickness of the silicon-containing layer [D] is preferably 1 nm or more, more preferably 3 nm or more, and further preferably 5 nm or more.

  Further, when the silicon-containing layer [D] contains a large amount of oxygen or nitrogen, there is a tendency that good corrosion resistance cannot be obtained. The reason for this is not clear, but the silicon-containing layer containing a large amount of oxygen and nitrogen is close to the chemical properties of the metal oxide, which may increase the number of interlayer defects generated between the metal layer [C]. thinking. The content ratio of oxygen (O) to silicon (Si) in the silicon-containing layer [D] is x, the content ratio of nitrogen (N) to silicon (Si) in the silicon-containing layer [D] is y, and the silicon-containing layer [D] The content ratio of other elements (M) to silicon (Si) is z, and the element content ratio of the silicon-containing layer [D] is SiOxNyMz (where M means an element other than silicon, oxygen and nitrogen). When expressed, the value of x + y is preferably 1.2 or less, more preferably 0.6 or less, and still more preferably 0.3 or less. From the same viewpoint, the bond energy value BE-T ([D]) indicated by the silicon peak top obtained when the silicon-containing layer [D] is analyzed by X-ray photoelectron spectroscopy is the same as that of silicon oxide or nitride. It is preferably smaller than the bond energy value indicated by the peak top. That is, the value of BE-T ([D]) is preferably 102 eV or less, more preferably 101 eV or less, and even more preferably 100 eV or less.

[High refractive index layer]
The far-infrared reflective substrate of the present invention has a refractive index of 1.7 or more between the base material [A] and the metal layer [C] and at least one of the metal layer [C] and the protective layer [B]. The high refractive index layer [E] having a different constituent element or the content ratio of constituent elements from the silicon-containing layer [D] is formed by visible light at the interface between the metal layer [C] and other layers. It is preferable to have a high refractive index layer [E] between the substrate [A] and the metal layer [C] and between the metal layer [C] and the protective layer [B]. Further preferred.

  Materials of the high refractive index layer [E] include oxides such as titanium oxide, zirconium oxide, yttrium oxide, niobium oxide, tantalum oxide, zinc oxide, tin-doped indium oxide (ITO), tin oxide and bismuth oxide, and nitriding A nitride such as silicon, a mixture thereof, a metal or a metal such as aluminum or copper doped with them, a carbon-containing doped metal, or the like can be appropriately selected and used. Depending on the refractive index and thickness of the high refractive index layer [E], it is possible to adjust the color of the interface reflection, reflected light, and transmitted light of the far-infrared reflective substrate. The higher the refractive index of the high refractive index layer [E], the greater the effect that can be obtained with a thinner film thickness. Therefore, the refractive index is preferably 1.7 or more, and more preferably 1.9 or more. . In addition, the high refractive index layer [E] is used to target various metals, metalloids, semiconductor elements and alloys, oxides, nitrides, suboxides, subnitrides, oxynitrides, oxynitrides, and the like. Method to obtain a thin film by sputtering process that reacts with gas such as oxygen or nitrogen if necessary, Method to obtain thin film by CVD process that reacts vaporized organometallic compound and gas such as oxygen or nitrogen with plasma or the like The film can be formed by a method of obtaining a thin film by a wet coating process in which an organometallic compound diluted in a solvent is dried and cured. In the case where the metal layer [C] is formed by the sputtering process, it is advantageous to form the high refractive index film [E] also by the sputtering process in order to form the metal layer [C] continuously. Therefore, it is preferable.

  In order to control the visible light transmission performance and infrared reflection performance of the entire far-infrared reflective substrate, for example, a high refractive index layer and a metal such as (high refractive index layer) m (/ metal layer / high refractive index layer) n are used. Examples thereof include those in which a plurality of layers are laminated (where m is 0 or 1 and n is an integer of 1 or more). Here, it is effective to adjust the visible light transmittance and infrared reflection performance of the far-infrared reflective substrate to adjust the number of repeating structures n and the refractive index and film thickness of the high refractive index layer and the metal layer. Means.

  In addition, the number “n” of the (/ metal layer [C] / high refractive index layer [E]) of the far-infrared reflective substrate of the present invention is 1 or more, and the infrared reflective performance and visible light transmission performance are excellent. A far-infrared reflective substrate can be obtained. Furthermore, it is preferable that the number “n” of (/ metal layer [C] / high refractive index layer [E]) be 2 or more because infrared reflection performance and visible light transmission performance can be further improved. Further, the upper limit of the number “n” of (/ metal layer [C] / high refractive index layer [E]) is not particularly limited, but the complexity of the manufacturing process and the obtained infrared reflection performance and visible light transmission performance 3 or less is preferable from the viewpoint of balance.

  On the other hand, in order to make the far-infrared reflective substrate more excellent in weather resistance, the base material [A], metal layer [C], silicon-containing layer [ D] or the protective layer [B] and the internal buffer layer [F] described later are preferably firmly adhered. Here, for example, in Patent Document 2 (Special Table 2002-539004), in order to improve the adhesion between the polymer substrate and the transparent metal oxide layer, aluminum or silver is interposed between the polymer substrate and the transparent metal oxide layer. Although a technique for providing a metal layer such as an adhesion improving layer is shown and can be applied to the technique of the present invention, the metal layer reflects and absorbs visible light. Tend to decrease. Therefore, the present inventor sets the content mass% of tin contained in the high refractive index film [E] to 50 mass with respect to the sum of the metal elements, metalloid elements and semiconductor elements contained in the high refractive index film [E]. % To 90% by mass, and the total mass of zinc contained in the high refractive index film [E] relative to the sum of the metal elements, metalloid elements and semiconductor elements contained in the high refractive index film [E] 10% by mass or more and 50% by mass or less, and further, the high refractive index film [E] can be formed on the base [A], the metal layer [C], the silicon-containing layer [D], or the protective layer which can be adjacent thereto. [B] By directly laminating at least one of the internal buffer layers [F] described later, the high refractive index layer [E] without reducing the visible light transmittance of the far-infrared reflective substrate. And the weather resistance of the far-infrared reflective substrate can be improved. , The form is preferred. The reason why the above-described configuration improves the adhesion between the layers and the weather resistance of the far-infrared reflective substrate is not clear, but by making the composition of the high refractive index layer [E] as described above, a high refractive index is obtained during film formation. It may be because the distortion generated in the film [E] and the damage to the base material [A], the metal layer [C], the silicon-containing layer [D] and the internal buffer layer [F] to be described later are reduced. Conceivable. In addition, when the metal layer [C] or the silicon-containing layer [D] is formed, the strain generated in the metal layer [C] or the silicon-containing layer [D] and the damage given to the high refractive index layer [E] are reduced. I guess that.

  In the present invention, the metal and semi-metal / semiconductor elements exclude H, He, N, O, F, Ne, S, Cl, Ar, As, Br, Kr, I, Xe, At, and Rn. Is.

[Internal buffer layer]
The internal buffer layer is to suppress damage to the interface between the substrate [A] and the protective layer [B], the metal layer [C], the silicon-containing layer [D], and the high refractive index layer [E]. It is a layer to be provided. In the far-infrared reflective substrate of the present invention, an internal buffer layer is formed between the base [A] and the protective layer [B], the metal layer [C], the silicon-containing layer [D], and the high refractive index layer [E]. [F] is preferably provided. Thereby, it can prevent that stress concentrates on the inside of each layer which a far-infrared reflective board has, and the interface between layers, and it breaks. Moreover, the optical characteristics of the far-infrared reflective substrate can be improved by designing the surface shape of the internal buffer layer [F]. The thickness of the internal buffer layer [F] is in the range of 0.2 μm to 10 μm, and can be appropriately selected depending on the configuration of the far infrared reflecting substrate, the composition of each layer, and the use of the far infrared reflecting substrate.

  The material of the internal buffer layer [F] depends on the combination of the base material [A], the protective layer [B], the metal layer [C], the high refractive index layer [E] and the high refractive index layer [E]. In order to prevent stress concentration in each layer of the far-infrared reflective substrate or at the interface between the layers, the far-infrared reflective performance or visible light transmission performance of the far-infrared reflective substrate, or the metal layer [C] or the high refractive index layer [ E] and the internal buffer layer [F] can be selected as appropriate from the standpoint of adhesion. And to meet the requirements for each characteristic such as adhesion, scratch resistance, moist heat resistance or weather resistance, an organic film mainly composed of a crosslinkable resin, an inorganic material mainly composed of metal, oxygen, carbon, etc. Appropriately selected from organic membranes and organic-inorganic hybrid membranes such as those in which inorganic fine particles are dispersed in organic membranes, those using organic modified materials of inorganic membrane materials, or those using a mixture thereof Can be used.

  For example, the internal buffer layer [F] is an organic film mainly composed of a crosslinkable resin such as acrylic, urethane, or melamine. It is preferable because the film characteristics can be adjusted relatively easily depending on the type and amount of the contained particles. Examples of the method for obtaining an organic film include a method of drying and curing a coating solution obtained by diluting a resin composition containing (meth) acrylate as a main component in a solvent.

  The fact that the organic film is an acrylic crosslinked resin obtained by crosslinking (meth) acrylate controls the curing of the organic film with energy rays such as ultraviolet rays by blending a photopolymerization initiator and the like. It is preferable because the physical properties can be easily controlled by curing the organic film. Examples of (meth) acrylates include 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, polyethylene glycol diacrylate, hydroxypivalate neopentyl glycol diacrylate, and dicyclopenta Nyl diacrylate, caprolactone-modified dicyclopentenyl diacrylate, ethylene oxide-modified phosphate diacrylate, allylated cyclohexyl diacrylate, isocyanurate diacrylate, trimethylolpropane triacrylate, dipentaerythritol triacrylate, propionic acid-modified dipentaerythritol triacrylate , Pentaerythritol triacrylate, propylene oxide modified trimethylolpropane tri Chryrate, tris (acryloxyethyl) isocyanurate, dipentaerythritol pentaacrylate, propionic acid modified dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, caprolactone modified dipentaerythritol hexaacrylate, various urethane acrylates, melamine acrylate, ethylene glycol di Methacrylate, triethylene glycol dimethacrylate, 1.4-butanediol dimethacrylate, neopentyl glycol dimethacrylate, 1.6-hexanediol dimethacrylate, 1.9-nonanediol dimethacrylate, 1.10-decanediol dimethacrylate Glycerin dimethacrylate, dimethylol-tricyclodecane dimethacrylate, Such as trimethylol propane trimethacrylate or ethoxylated trimethylolpropane trimethacrylate and the like. Generally, the higher the number of functional groups, the higher the surface hardness of the organic film. These may be used alone, but the characteristics of the organic film can be adjusted by using two or more polyfunctional (meth) acrylates or a resin having an unsaturated group having a low functional group number. The (meth) acrylate may be used as a monomer or a prepolymer, or may be used by mixing a plurality of types of monomers and prepolymers. Also, the internal buffer layer [F] is modified by adding at least one selected from the group consisting of polyester resin, polyurethane resin, polyester urethane resin, and silicone resin to the internal buffer layer [F] or by adding a plurality of types. It is preferable to improve the adhesion between the metal layer or the high refractive index layer and the internal buffer layer [F]. In particular, when an acrylic cross-linked resin is used as the internal buffer layer [F], it is preferable to use a silicone resin as the additive resin because the compatibility between the cross-linked resin and its solvent and the additive resin is excellent. The amount to be added is appropriately selected according to the physical properties and durability of the combination of the entire far-infrared reflective substrate. In order to obtain a sufficient modification effect and to suppress the adverse effect on the physical properties of the internal buffer layer [F]. The resin is preferably added in the range of 0.1% by mass to 30% by mass and more preferably 0.1% by mass to 15% by mass with respect to 100% by mass of the internal buffer layer [F]. preferable.

  As another method for modifying the shrinkage, surface hardness, optical properties, and surface shape of organic films, inorganic or organic particles or a combination of them is added to the organic film in combination of one or more types. Can be used. For example, as the inorganic particles, silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, zinc oxide, germanium oxide, indium oxide, tin oxide, tin-doped indium oxide (ITO), cerium oxide, or the like can be used. As organic fine particles, styrene resin, styrene-acrylic copolymer resin, styrene-acrylic copolymer resin, acrylic resin, divinylbenzene resin, silicone resin, urethane resin, melamine resin, styrene-isoprene resin, benzoguanamine resin, polyamide resin Polyester resin or the like can be used. The shape of the particle includes a spherical shape, a hollow shape, a porous shape, a rod shape, a plate shape, a fiber shape, an indefinite shape, and the like, and can be appropriately selected according to necessary characteristics. Furthermore, by performing a surface treatment that introduces a functional group on the particle surface, a cross-linking reaction occurs between the cross-linkable resin and the particle surface, thereby modifying the characteristics of the internal buffer layer [F]. Can do. As the surface treatment for introducing a functional group, for example, an organic compound containing a polymerizable unsaturated group can be bonded to the particles. The polymerizable unsaturated group is not particularly limited, and examples thereof include acryloyl group, methacryloyl group, vinyl group, propenyl group, butadienyl group, styryl group, ethynyl group, cinnamoyl group, maleate group and acrylamide group. .

  Further, for example, the internal buffer layer [F] is an inorganic film mainly composed of a metal, a semimetal, or a semiconductor element such as silica, alumina, zirconia, or diamond-like carbon (DLC), oxygen, nitrogen, carbon, or the like. This is because the compatibility with the metal layer [C] and the high refractive index layer [E] is good and the process compatibility is high, such as being able to be continuously processed by a dry coating process such as sputtering. preferable. When the internal buffer layer [F] is an inorganic film, since it is easy to obtain a dense film, it has advantages such as easy to obtain high hardness, while it is difficult to increase the film thickness because the film forming speed is slow, There may be a limitation that the strain received by the far-infrared reflective substrate is likely to increase due to the shrinkage stress generated during film formation. Examples of methods for obtaining inorganic films include targets for various metals, metalloids, semiconductor elements and alloys, oxides, nitrides, suboxides, subnitrides, oxynitrides, oxynitrides, etc. And a method of obtaining the internal buffer layer [F] by a sputtering process that reacts with a gas such as oxygen or nitrogen as required.

  As the internal buffer layer [F], an organic-inorganic hybrid film can be used as a combination of the advantages of the organic film and the inorganic film described above. As an example of a method for obtaining an organic-inorganic hybrid film, CVD is performed by reacting a vaporized organic-inorganic compound and a gas such as oxygen or nitrogen with plasma or the like using an organic-inorganic compound such as an alkyl silicate or an alkyl titanate as a raw material. There are a method of obtaining the internal buffer layer [F] by a process, a method of obtaining the internal buffer layer [F] by a wet coating process in which an organic-inorganic compound diluted in a solvent is dried and cured.

  In order to obtain physical properties such as scratch resistance and surface hardness, it is preferable to increase the thickness of the internal buffer layer [F], and to suppress distortion such as curling due to stress generated when the internal buffer layer [F] is formed. Since it is preferable to reduce the thickness of the internal buffer layer [F], the thickness of the internal buffer layer [F] is preferably 0.1 μm to 10 μm, and more preferably 0.2 μm to 5 μm. More preferably, the thickness is 0.4 μm to 3 μm.

  When the internal buffer layer [F] is an organic film mainly composed of a crosslinkable resin, the flexibility of the internal buffer layer [F] is increased and the followability to deformation is improved, but the film hardness is reduced. It is necessary to adjust the thickness of the internal buffer layer [F] to 0.4 μm or more, more preferably 0.5 μm or more, and further preferably 1 μm to 3 μm.

[Far infrared reflection board]
For example, by providing a far-infrared reflecting substrate inside the window, it is possible to prevent indoor thermal energy from flowing out as far-infrared rays, and to expect the effect of reflecting the indoor window surface and returning the thermal energy into the room. At that time, the higher the far-infrared reflectance, the more heat energy can be reflected. Therefore, the far-infrared reflectance of the far-infrared reflective substrate of the present invention is 60% or more, preferably 70% or more, and more preferably 80% or more. Here, in order to make the far-infrared reflectance of the far-infrared reflective substrate 60% or more, it is possible to reduce the thickness of the protective layer [B] as described above.

  Further, when the far-infrared reflective substrate of the present invention is used by being bonded to the inside of a window, the far-infrared reflective substrate preferably has a high visible light transmittance (that is, transparency), and the far-infrared reflective substrate of the present invention. The substrate is composed of a base material [A], a protective layer [B], a metal layer [C], a high refractive index layer [E], an internal buffer layer [F], a surface protective film, and other constituent layers. By adjusting the film thickness, the visible light transmittance can be designed according to the application. The visible light transmittance of the far-infrared reflective substrate is preferably 40% or more, more preferably 60% or more, and further preferably 70% or more.

  In addition, when the far-infrared reflective substrate of the present invention is used by being bonded to the inside of a window, a poster or the like is temporarily displayed using an adhesive tape or the like on the surface of the far-infrared reflective substrate of the present invention. It is supposed to be pasted. And in order to suppress more that each layer which forms a far-infrared reflective board | substrate peels when removing an adhesive tape etc., it described in the adhesion | attachment section of the characteristic evaluation method of the following Example. It is preferable that it is a far-infrared reflective board whose determination by an evaluation method is A.

[Usage]
The far-infrared reflective substrate of the present invention takes advantage of its excellent chemical resistance and reflects heat energy that flows in and out of windows and walls of buildings and vehicles, home appliances, etc., thereby improving energy efficiency such as improving the cooling and heating effect. It can be used as a transparent heat insulating material, a heat shielding window material, an electromagnetic wave shielding material or the like having a function of improving.

  In the far-infrared reflective substrate of the present invention as described above, each constituent film such as the protective layer [B] described above is shown on the surface of the base [A] described above, for example, in the paragraph of the brief description of the drawings. In addition, it is manufactured by laminating.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated, this invention is not necessarily limited to these.
[Characteristic evaluation method]
The evaluation method of the characteristics of the far-infrared reflective substrate used in this example is as follows.

(1) Corrosion resistance 1
1) Preparation of test specimen for evaluation a. The far-infrared reflective substrate is cut into a 50 mm square.
A. An adhesive layer is formed on the base material side surface of the sample cut in the item (a).
C. Next, it pastes to 3 mm-thick float glass through the adhesion layer formed by (i) term, and obtains the test specimen for evaluation.
2) Determination of test specimen for evaluation a. An evaluation liquid (a solution in which 2.5 g of lactic acid and 5 g of NaCl are dissolved in 50 ml of water) is dropped onto the surface of the prepared test specimen for evaluation, and exposed in an environment of 60 ° C. × 90% RH for 2 hours.
A. Rinse the test specimen for evaluation with water.
3) Judgment of the test specimen for evaluation The location under the evaluation droplet on the test specimen for evaluation is observed with a laser microscope for the presence or absence of a discoloration point due to corrosion of the test specimen for evaluation and the presence or absence of surface peeling.
・ Measuring equipment: VK-X110 (manufactured by Keyence Corporation)
-Objective lens: Standard lens 10 times-Optical zoom: 1.0 times a. Criteria A: No discoloration point and no surface layer peeling.
B: There is a color change point and no surface layer peeling.
C: There is a discoloration point and there is surface peeling.
Here, although the corrosion of the metal layer [C] is slight, a discoloration point appears as the metal layer [C] progresses, and further, surface peeling occurs when the corrosion of the metal layer [C] greatly progresses. That is, as the determination of the corrosion resistance, the determination A is the most excellent, the determination B is the second best after the determination A, and the determination C is inferior. The evaluation specimen of judgment A is one in which no signs of corrosion are observed. On the other hand, the evaluation test specimen of judgment B tends to be difficult to understand visually as the appearance deteriorates, but it is expected that corrosion will progress over time. And in the test specimen for evaluation of judgment C, there is a tendency that the corrosion progresses so that the appearance deterioration can be seen visually.

(2) Corrosion resistance 2
An evaluation solution (dissolving 2.5 g of lactic acid and 5 g of NaCl in 50 ml of water) was dropped on the surface of the prepared test specimen for evaluation, and the exposure was performed for 4 hours in a 60 ° C. × 90% RH environment. Corrosion resistance 2 was evaluated in the same manner as the “corrosion resistance 1” evaluation method.

(3) Adhesion 1) Preparation of test specimen for evaluation a. The far-infrared reflective substrate is cut into a 50 mm square.
A. An adhesive layer is formed on the substrate side surface of the sample cut in item a.
C. It sticks to 3 mm-thick float glass through the adhesion layer formed by (i) term, and obtains the glass paste of a far-infrared reflective substrate.
D. Using the cross-cut spacing spacer (Cortech Co., Ltd .: model number CROSSSCUT GUIDE1.0) and a cutter knife, the far-infrared reflective substrate is cut 6 times in the vertical direction and 6 times in the horizontal direction. Test specimens for evaluation placed at intervals of 1 mm are obtained (this operation creates a 5 × 5 = 25 grid on the far-infrared reflective substrate surface).
2) Determination of test specimen for evaluation A transparent pressure-sensitive adhesive tape (manufactured by Nitto Denko Corporation: model number 31B) is pressure-bonded onto the lattice of the prepared test specimen, and the pressure-bonded tape is peeled off in a direction of about 60 degrees.
A. Criteria A: No peeling on all 25 grids.
B: Separation occurred in a grid of 1 square or more out of 25 squares.
It can be said that the far-infrared reflective substrate with the adhesion determination of A has better adhesion than the far-infrared reflective substrate with the adhesion determination of B.

(4) Visible light transmittance 1) Preparation of test specimen for evaluation a. The far-infrared reflective substrate is cut into a 50 mm square.
A. A transparent adhesive layer is formed on the substrate side surface of the sample cut in the item a.
C. Next, it pastes to 3 mm-thick transparent float glass through the adhesion layer formed by a term, and obtains the test body for evaluation.
2) Determination of test specimen for evaluation Visible light transmittance was measured according to JIS R 3106 (1998), and the value obtained from the spectral transmittance at a wavelength of 380 to 780 nm was defined as the visible light transmittance (%). .
・ Measurement device: UV-visible near-infrared spectrophotometer UV-3600 manufactured by Shimadzu Corporation
-Wavelength range: 380-780nm
・ Slit width: (20)
・ Scanning speed: High speed ・ Sampling: 1 nm
・ Grating: 720nm
Measurement content: 5 samples were measured, and the average value of 3 samples excluding the sample showing the maximum value and the sample showing the minimum value was determined.

(5) Far-infrared reflective performance 1) Preparation of test specimen for evaluation a. The far-infrared reflective substrate is cut into a 50 mm square.
A. A transparent adhesive layer is formed on the substrate side surface of the sample cut in the item a.
C. Next, it pastes to 3 mm-thick transparent float glass through the adhesion layer formed by a term, and obtains the test body for evaluation.
2) Judgment of test specimen for evaluation The measurement of far-infrared reflectance is performed according to JIS R 3106 (1998), and the reflectance for thermal radiation of 283K is obtained from the spectral reflectance of wavelength 5 to 25 μm. Far infrared reflectance (%).
・ Measuring device: Fourier transform infrared spectrophotometer IR Prestige-21 manufactured by Shimadzu Corporation
・ Specular reflection measurement unit: SRM-8000A
-Wave number range: 400-2000cm ^-1
-Measurement mode:% Transmittance
・ Abodoid coefficient: Happ-Genzel
・ Number of integration: 40
Decomposition: 4.0
Measurement content: 5 samples were measured, and the average value of 3 samples excluding the sample showing the maximum value and the sample showing the minimum value was determined.

(6) Thickness of protective layer [B], metal layer [C], silicon-containing layer [D], high refractive index layer [E] STEM (SEM) observed using a field emission electron microscope (JEM2100F manufactured by JEOL Ltd.) The thickness was measured from a scanning transmission electron microscope (Scanning Transmission Electron Microscopy) image.
Sample preparation: FIB microsampling method (FB-2100μ-Sampling System manufactured by Hitachi)
STEM image observation conditions: acceleration voltage 200 kV, beam spot size of about 1 nmφ, measurement n number: 1.

(7) Content mass% of metal layer [C]
From EDX spectrum obtained by measurement using EDX (detector: JED-2300T manufactured by JEOL Ltd., software: Analysis Station manufactured by JEOL Ltd.) mounted on a field emission electron microscope (JEM2100F manufactured by JEOL Ltd.), mass% Was calculated. Note that elements whose mass% was less than 1% were excluded in the calculation of mass%.
Sample preparation: FIB microsampling method (FB-2100μ-Sampling System manufactured by Hitachi)
STEM image observation conditions: acceleration voltage 200 kV, beam spot size of about 1 nmφ Observation element: C to U
-Number of measurement n: 1.

(8) Number of atoms of silicon-containing layer [D], content ratio EDX (detector: JED-2300T manufactured by JEOL Ltd.) mounted on field emission electron microscope (JEM2100F manufactured by JEOL Ltd.), software: Analysis Station manufactured by JEOL Ltd. ), And the atomic percentage was calculated from the obtained EDX spectrum. Note that elements whose atomic percentage was less than 1% were excluded in the calculation of atomic percentage. The content ratio of oxygen (O) to silicon (Si) in the silicon-containing layer [D] is x, the content ratio of nitrogen (N) to silicon (Si) in the silicon-containing layer [D] is y, and the silicon-containing layer [D] X and y used for calculation of the value of x + y when the content ratio of other elements (M) to silicon (Si) is expressed as z and the element content ratio of the silicon-containing layer [D] is expressed as SiOxNyMz Obtained from the equation.
x = “number of oxygen atoms obtained” / “number of silicon atoms%”
y = “number of nitrogen atoms obtained” / “number of silicon atoms%”
Sample preparation: FIB microsampling method (FB-2100μ-Sampling System manufactured by Hitachi)
STEM image observation conditions: acceleration voltage 200 kV, beam spot size 1 nmφ
Observation element: C to U
-Number of measurement n: 1.

(9) Refractive index The refractive index in wavelength 589nm was calculated | required with the following method.
1) Measuring method The change of the polarization state of the reflected light from the measurement sample was measured by the following apparatus and measurement conditions, and the optical constants (refractive index and extinction coefficient) were calculated. In the calculation, the spectrum of Δ (phase difference) and ψ (amplitude reflectance) measured on the sample is compared with (Δ, ψ) calculated from the calculation model, and the dielectric is so close to the measured value (Δ, ψ). Fitting is performed by changing the function. The fitting result shown here is the result of the best fit (mean square error converges to the minimum) between the measured value and the theoretical value.
2) Apparatus / High-speed spectroscopic ellipsometer M-2000 (manufactured by JA Woollam)
・ Rotation compensator type (RCE: Rotating Compensator Ellipsometer)
-300 mm R-Theta stage 3) Measurement conditions-Incident angle: 65 degrees, 70 degrees, 75 degrees-Measurement wavelength: 195 nm to 1680 nm
・ Analysis software: WVASE32
・ Beam diameter: 1 × 2mm
-Number of measurement n: 1.

(10) Contact angle to water The contact angle to water was determined by using a static method in accordance with JIS R 3257 (1999).

[Example 1]
A hard coat film (Toughtop (registered trademark) THS: manufactured by Toray Film Processing Co., Ltd.) was used as the substrate [A] having an internal buffer layer [F] having a thickness of 2.5 μm.
On the inner buffer layer [F] of the film, a metal oxide having a tin content of 70% and a zinc content of 30% with respect to the sum of metal elements, metalloid elements and semiconductor elements Using a target, sputtering was performed under a film forming gas condition in which the pressure ratio of argon / carbon dioxide / nitrogen was 85% / 10% / 5%, and the first high refractive index layer [E] having a thickness of 32 nm was formed. Formed. The refractive index of the first high refractive index layer [E] was 2.0.

  Subsequently, using a Si target, sputtering was performed under a film forming gas condition of 100% argon to form a first silicon-containing layer [D] having a thickness of 2 nm. Subsequently, a metal target having a silver (Ag) content mass of 97% and a gold content mass% of 3% with respect to the sum of the metal elements, metalloid elements, and semiconductor elements was set to 100% argon. Sputtering was performed under film forming gas conditions to form a metal layer [C] having a thickness of 13 nm. Subsequently, using a Si target, sputtering was performed under a film forming gas condition of 100% argon to form a second silicon-containing layer [D] having a thickness of 2 nm. Subsequently, using a metal oxide target in which the content percentage of tin is 70% and the content percentage of zinc is 30% with respect to the sum of the metal elements, metalloid elements, and semiconductor elements, argon / carbon dioxide / Sputtering was performed under a film forming gas condition in which the nitrogen pressure ratio was 85% / 10% / 5% to form a second high refractive index layer [E] having a thickness of 32 nm. The refractive index of the second high refractive index layer [E] was 2.0.

  Further, using an Si target, sputtering was performed under a film forming gas condition in which the pressure ratio of argon / carbon dioxide / nitrogen was 45% / 40% / 15%, and an inorganic protective layer [B1 with a thickness of 20 nm] ] To obtain a far-infrared reflective substrate. One or more oxynitrides selected from the group consisting of silicon oxide, aluminum oxide, silicon nitride, and aluminum nitride in the inorganic protective layer [B1] were 99% by mass. Table 1 shows the configuration of the far-infrared reflective substrate of Example 1, and Table 2 shows the evaluation results.

[Example 2]
As in Example 1, the substrate [A], the internal buffer layer [F], the first high refractive index layer [E], the first silicon-containing layer [D], the metal layer [C], and the second silicon-containing material Layer [D] 2, second high refractive index layer [E] 2, and inorganic protective layer [B1] were formed.

  Subsequently, on the inorganic protective layer [B1], Novec 1720 (manufactured by 3M, active ingredient 0.1 wt%) was applied using a bar coater (counter No. 3) and dried at 80 ° C. for 3 minutes. Thus, an organic protective layer [B2] was formed to obtain a far-infrared reflective substrate. The contact angle of water on the surface of the organic protective layer [B2] with respect to water was 107 °. Table 3 shows the configuration of the far-infrared reflective substrate of Example 2, and Table 4 shows the evaluation results.

[Example 3]
In the same manner as in Example 1, a base material [A], an internal buffer layer [F], and a first high refractive index layer [E] were formed. Subsequently, using a Si target, sputtering was performed under a film forming gas condition of 100% argon to form a silicon-containing layer [D] having a thickness of 4 nm. Subsequently, a metal layer [C] was formed in the same manner as in Example 1. Subsequently, as in Example 1, the second high refractive index layer [E] and the inorganic protective layer [B1] were formed to obtain a far-infrared reflective substrate. Table 1 shows the configuration of the far-infrared reflective substrate of Example 3, and Table 2 shows the evaluation results.

[Example 4]
As in Example 1, the substrate [A], the internal buffer layer [F], the first high refractive index layer [E], the silicon-containing layer [D], the metal layer [C], the second high refractive index layer [ E] and an inorganic protective layer [B1] were formed.

  Subsequently, an organic protective layer [B2] was formed on the inorganic protective layer [B1] in the same manner as in Example 2 to obtain a far-infrared reflective substrate. Table 3 shows the configuration of the far-infrared reflective substrate of Example 4, and Table 4 shows the evaluation results.

[Example 5]
In the same manner as in Example 1, a base material [A], an internal buffer layer [F], and a first high refractive index layer [E] were formed. Subsequently, a metal layer [C] was formed in the same manner as in Example 1. Subsequently, using a Si target, sputtering was performed under a film forming gas condition of 100% argon to form a silicon-containing layer [D] having a thickness of 4 nm. Subsequently, in the same manner as in Example 1, a second high refractive index layer [E] and an inorganic protective layer [B1] were formed to obtain a far-infrared reflective substrate. Table 1 shows the configuration of the far-infrared reflective substrate of Example 5, and Table 2 shows the evaluation results.

[Example 6]
As in Example 5, the substrate [A], the internal buffer layer [F], the first high refractive index layer [E], the metal layer [C], the silicon-containing layer [D], the second high refractive index layer [ E] and an inorganic protective layer [B1] were formed.

  Subsequently, an organic protective layer [B2] was formed on the inorganic protective layer [B1] in the same manner as in Example 2 to obtain a far-infrared reflective substrate. Table 3 shows the configuration of the far-infrared reflective substrate of Example 6, and Table 4 shows the evaluation results.

[Example 7]
In the same manner as in Example 1, a base material [A], an internal buffer layer [F], and a first high refractive index layer [E] were formed. Subsequently, using a Si target, sputtering was performed under a film forming gas condition of 100% argon to form a first silicon-containing layer [D] having a thickness of 4 nm. Subsequently, a metal layer [C] was formed in the same manner as in Example 1. Subsequently, using a Si target, sputtering was performed under a film forming gas condition of 100% argon to form a second silicon-containing layer [D] having a thickness of 4 nm. Subsequently, in the same manner as in Example 1, a second high refractive index layer [E] and an inorganic protective layer [B1] were formed to obtain a far-infrared reflective substrate. Table 1 shows the configuration of the far-infrared reflective substrate of Example 7, and Table 2 shows the evaluation results.

[Example 8]
Similar to Example 7, substrate [A], internal buffer layer [F], first high refractive index layer [E], first silicon-containing layer [D], metal layer [C], second silicon-containing A layer [D], a second high refractive index layer [E], and an inorganic protective layer [B1] were formed.

  Subsequently, an organic protective layer [B2] was formed on the inorganic protective layer [B1] in the same manner as in Example 2 to obtain a far-infrared reflective substrate. Table 3 shows the configuration of the far-infrared reflective substrate of Example 8, and Table 4 shows the evaluation results.

[Example 9]
In the same manner as in Example 1, a base material [A], an internal buffer layer [F], and a first high refractive index layer [E] were formed. Subsequently, using a Si target, sputtering was performed under a film forming gas condition of 100% argon to form a first silicon-containing layer [D] having a thickness of 8 nm. Subsequently, a metal layer [C] was formed in the same manner as in Example 1. Subsequently, using a Si target, sputtering was performed under a film forming gas condition of 100% argon to form a second silicon-containing layer [D] having a thickness of 8 nm. The silicon content of the second silicon-containing layer [D] was 95 atomic%, and the value of x + y when the element content ratio was expressed as SiOxNyMz was 0.1. The binding energy value BE-T ([D]) indicated by the peak top of silicon obtained when the second silicon-containing layer [D] was analyzed by X-ray photoelectron spectroscopy was 99 eV. Subsequently, in the same manner as in Example 1, a second high refractive index layer [E] and an inorganic protective layer [B1] were formed to obtain a far-infrared reflective substrate. Table 1 shows the configuration of the far-infrared reflective substrate of Example 9, and Table 2 shows the evaluation results.

[Comparative Example 1]
In the same manner as in Example 1, a base material [A], an internal buffer layer [F], and a first high refractive index layer [E] were formed. Subsequently, a metal layer [C] was formed in the same manner as in Example 1. Subsequently, in the same manner as in Example 1, a second high refractive index layer [E] and an inorganic protective layer [B1] were formed to obtain a far-infrared reflective substrate. Table 1 shows the configuration of the far-infrared reflective substrate of Comparative Example 1, and Table 2 shows the evaluation results.

[Comparative Example 2]
As in Comparative Example 1, the substrate [A], the internal buffer layer [F], the first high refractive index layer [E], the metal layer [C], the second high refractive index layer [E], and the inorganic protective layer [B1] was formed.

  Subsequently, an organic protective layer [B2] was formed on the inorganic protective layer [B1] in the same manner as in Example 2 to obtain a far-infrared reflective substrate. Table 3 shows the configuration of the far-infrared reflective substrate of Comparative Example 2, and Table 4 shows the evaluation results.

[Comparative Example 3]
In the same manner as in Example 1, a base material [A], an internal buffer layer [F], and a first high refractive index layer [E] were formed. A Si-containing layer [D] having a thickness of 8 nm was formed by performing sputtering using a Si target under a film forming gas condition in which the pressure ratio of argon / carbon dioxide / nitrogen was 45% / 40% / 15%. The silicon content of the silicon-containing layer [D] is 32 atomic%, and the element content ratio is expressed as SiOxNyMz (where M represents an element other than silicon, oxygen, and nitrogen). The value was 2. Moreover, the bond energy value BE-T ([D]) indicated by the silicon peak top obtained when the silicon-containing layer [D] was analyzed by X-ray photoelectron spectroscopy was 103 eV. Subsequently, a metal layer [C] was formed in the same manner as in Example 1. Subsequently, in the same manner as in Example 1, a second high refractive index layer [E] and an inorganic protective layer [B1] were formed to obtain a far-infrared reflective substrate. Table 1 shows the configuration of the far-infrared reflective substrate of Comparative Example 3, and Table 2 shows the evaluation results.

  The far-infrared reflective substrate of the present invention makes use of its excellent corrosion resistance and is a transparent heat insulation and shielding provided with a metal layer in order to improve the cooling and heating effect by blocking the heat energy flowing in and out of windows of buildings and vehicles. It can be used as a thermal window material or an electromagnetic shielding material.

1: Substrate [A]
2: Internal buffer layer [F]
3: First high refractive index layer [E]
4: First silicon-containing layer [D]
5: Metal layer [C]
6: Second silicon-containing layer [D]
7: Second high refractive index layer [E]
8: Protective layer [B]
9: Inorganic protective layer [B1]
10: Organic protective layer [B2]
11: Silicon-containing layer [D]

Claims (6)

A far-infrared reflective substrate satisfying the following (1) to (4) having a configuration having a metal layer [C] and a silicon-containing layer [D] between a substrate [A] and a protective layer [B].
(1) The metal layer [C] has a layer made of one or more layers of metal, and at least one of the layers contains 50% by mass or more of silver when the mass of the layer is 100% by mass (2 The silicon-containing layer [D] is in direct contact with the metal layer [C]. (3) The silicon-containing layer [D] contains 40 atomic% or more of silicon with respect to the entire silicon-containing layer [D]. Infrared reflectance is 60% or more   The far-infrared reflective substrate according to claim 1, wherein the silicon-containing layer [D] is formed between the base [A] and the metal layer [C].   The far-infrared reflective substrate according to claim 1, wherein the silicon-containing layer [D] is formed on both surfaces of the metal layer [C].   Furthermore, it has the high refractive index layer [E] whose refractive index is 1.7 or more, and the high refractive index layer [E] is between the substrate [A] and the metal layer [C], and the metal layer [C]. ] And the protective layer [B], The far-infrared reflective substrate according to claim 1, wherein the far-infrared reflective substrate is formed between the protective layer [B] and the protective layer [B]. The protective layer [B] has an inorganic protective layer [B1],
50% by mass or more of at least one selected from the group consisting of silicon oxide, silicon nitride, aluminum oxide and aluminum nitride is used as the inorganic protective layer [B1]. The far-infrared reflective substrate according to claim 1, wherein the far-infrared reflective substrate is contained.   The far-infrared reflective substrate according to claim 1, wherein the protective layer [B] has an organic protective layer [B2].

Images