JP2018149753A - Far-infrared reflective substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a far-infrared reflective substrate excellent in corrosion resistance.SOLUTION: There is provided a far-infrared reflective substrate having a layer [C] 6, a layer [D] 5 in direct contact with the layer [C] 6, and a layer [E] 4 in direct contact with the layer [D] 5 from a layer [G] 10 side in this order between a substrate [A] 1 and the layer [G] 10, far-infrared reflection rate of 60% or more and satisfying following (1) to (4). (1) The layer [C] 6 has a layer consisting of one or a plurality of layers of a metal, and contains silver of 50 atom number % or more based on whole layer [C] 6. (2) The layer [D] 5 contains silicon or contains silicon and carbon and total content thereof is 40 atom number % or more. (3) The layer [E] 4 contains nitrogen or contains nitrogen and oxygen and nitrogen content of the layer [E] 4 is 2 atom number % or more and oxygen content of the layer [E] 4 is 0 to 45 atom number %. (4) Total content of nitrogen and oxygen (atom number %) in the layer [E] 4 is larger than that in the layer [D] 5.SELECTED DRAWING: Figure 3

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, although the thin surface protective layer described in References 1 and 2 contributes to the improvement of the far-infrared reflection performance of the laminate having the far-infrared reflection performance, the metal layer provided in the laminate having the far-infrared reflection performance The present inventor has faced problems such as deterioration due to corrosion or the like, and that delamination is likely to proceed in at least a part of the layers formed by the layers of the far-infrared reflective substrate.

  Accordingly, an object of the present invention is to provide a far-infrared reflective substrate having excellent corrosion resistance while being a far-infrared reflective substrate having good far-infrared reflective performance.

The present invention employs the following means in order to solve such problems. That is,
Between the substrate [A] and the layer [G], the layer [C], the layer [D] directly in contact with the layer [C], and the layer [D] are in direct contact from the layer [G] side. The far-infrared reflective board | substrate which has layer [E], a far-infrared reflectance is 60% or more, and satisfies the following (1)-(4).
(1) The layer [C] has a layer made of one or more layers of metal, and contains 50 atomic% or more of silver with respect to the entire layer [C]. (2) The layer [D] contains silicon. Or silicon and carbon are contained, and the total content of silicon and carbon in the layer [D] with respect to the entire layer [D] is 40 atomic% or more. (3) Layer [E] contains nitrogen Or the nitrogen content of the layer [E] is 2 atomic% or more with respect to the whole layer [E], and the oxygen content of the layer [E] is the whole layer [E]. (4) The total content of nitrogen and oxygen in the layer [E] (number of atoms%) in the layer [E] is 0 to 45 atomic% relative to the total amount of nitrogen and oxygen in the layer [D]. It is larger than the total content (number of atoms%) with respect to the entire layer [D].

  In the far-infrared reflective substrate of the present invention, the layer [D] is in direct contact with the layer [C] and the layer [E]. And by said structure, corrosion of the layer [C] containing silver can be suppressed, suppressing the fall of the far-infrared reflectance of a far-infrared reflective board | substrate, and visible-light transmittance. 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 far-infrared reflective board | substrate of this invention, Specifically, base material [A], layer [B], 1st layer [F], layer [E], layer It is a cross-sectional schematic diagram of a structure formed by laminating [D], a layer [C], a second layer [F], and an inorganic layer [G1] in this order. It is a cross-sectional schematic diagram of the 2nd form example of the far-infrared reflective board | substrate of this invention, Specifically, base material [A], layer [B], 1st layer [F], layer [E], layer It is a cross-sectional schematic diagram of a structure formed by laminating [D], layer [C], layer [H], second layer [F], and inorganic layer [G1] in this order. It is a cross-sectional schematic diagram of the 3rd form example of the far-infrared reflective board | substrate of this invention, Specifically, base material [A], layer [B], 1st layer [F], layer [E], layer [D], layer [C], layer [H], second layer [F], inorganic layer [G1], and organic layer [G2] 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 4th form example of the far-infrared reflective board | substrate of this invention, Specifically, base material [A], layer [B], layer [E], layer [D], layer [C] FIG. 6 is a schematic cross-sectional view of a configuration in which a layer [H], a layer [I], and an inorganic layer [G1] are stacked in this order. It is a cross-sectional schematic diagram of the 5th form example of the far-infrared reflective board | substrate of this invention, Specifically, base material [A], layer [B], component layer [K] of layer [E], layer [E] ], The layer [J], the layer [D], the layer [C], the layer [H], the layer [I], the inorganic layer [G1], and the organic layer [G2] stacked in this order. FIG. It is a cross-sectional schematic diagram of a far-infrared reflective board | substrate which does not have a layer [E], and is a base material [A], a layer [B], a 1st layer [F], a layer [D], a layer [C], 2nd The layer [F] and the inorganic layer [G1] are laminated in this order.

The far-infrared reflective substrate of the present invention includes a layer [C], a layer [D] in direct contact with the layer [C], in order from the layer [G] side, between the base [A] and the layer [G], and It has a layer [E] that is in direct contact with the layer [D], has a far-infrared reflectance of 60% or more, and satisfies the following (1) to (4).
(1) The layer [C] includes a single layer or a plurality of layers of metal, and contains 50 atomic% or more of silver with respect to the entire layer [C].
(2) Layer [D] contains silicon or contains silicon and carbon, and the total content of silicon and carbon in layer [D] with respect to the entire layer [D] is 40 atomic% or more.
(3) The layer [E] contains nitrogen or contains nitrogen and oxygen, and the nitrogen content of the layer [E] is 2 atomic% or more with respect to the whole layer [E], and the layer [E] ] Is 0 to 45 atomic% with respect to the whole layer [E].
(4) The total content (atomic%) of the nitrogen and oxygen layer [E] in the layer [E] is the total content (atom in the layer [D] of the nitrogen and oxygen layer [D]. Several percent).

  As a result of intensive studies by the inventor, the far-infrared reflective substrate of the present invention has a layer [E], a layer [D], a layer [C], and a layer [G] in this order from the base [A] side. The layer [C] having a specific composition is in direct contact with the layer [D] having a specific composition, and the layer [D] is in direct contact with the layer [E] having a specific composition. In order to make the far-infrared reflecting substrate excellent in far-infrared reflecting performance, for example, even if the far-infrared reflecting substrate has a thin layer [G], the far-infrared reflecting substrate has excellent corrosion resistance. They found out that

  Moreover, as an example of the form which the far-infrared reflective board | substrate of this invention can take, a form like FIGS. 1-5 can be illustrated.

  First, as shown in FIG. 1, the first is the substrate [A] 1, layer [B] 2, first layer [F] 3, layer [E] 4, layer [D] 5, layer [ C], a far-infrared reflective substrate having a second layer [F] 9 and an inorganic layer [G1] 11 in this order. In addition, the far-infrared reflective board | substrate of Example 1 mentioned later belongs to this embodiment example.

  Second, as shown in FIG. 2, the substrate [A] 1, the layer [B] 2, the first layer [F] 3, the layer [E] 4, the layer [D] 5, and the layer [C ], A layer [H] 7, a second layer [F] 9, and an inorganic layer [G1] 11 in this order. In this far-infrared reflective substrate, the layer [D] 5 and the layer [H] 7 are formed on both sides of the layer [C] 6 and has two silicon-containing layers. In addition, the infrared reflective board | substrate of Example 2 mentioned later belongs to this embodiment example.

  Third, as shown in FIG. 3, substrate [A] 1, layer [B] 2, first layer [F] 3, layer [E] 4, layer [D] 5, layer [C ], [H] 7, second layer [F] 9, inorganic layer [G1] 11, and organic layer [G2] 12 in this order. This far-infrared reflective substrate has two layers, an inorganic layer [G1] 11 and an organic layer [G2] 12. In addition, the infrared reflective board | substrate of Example 6 mentioned later belongs to this embodiment example.

  Fourth, as shown in FIG. 4, the substrate [A] 1, layer [B] 2, layer [E] 4, layer [D] 5, layer [C] 6, layer [H] 7, It is a far-infrared reflective board | substrate which has layer [I] 8 and inorganic type layer [G1] 11 in this order. This far-infrared reflective substrate has two layers, layer [E] 4 and layer [I] 8. In addition, the infrared reflective board | substrate of Example 4 mentioned later belongs to this embodiment example.

As a fifth example, as shown in FIG. 5, the substrate [A] 1, layer [B] 2, layer [E] 4, layer [D] 5, layer [C] 6, layer [H] 7, layer A far-infrared reflective substrate having [I] 8, an inorganic layer [G1] 11, and an organic layer [G2] 12 in this order. In this far-infrared reflective substrate, the layer [E] has two constituent layers, a constituent layer [J] 13 and a constituent layer [K] 14.
In addition, the far-infrared reflective board | substrate of Example 8 mentioned later belongs to this embodiment example.

  In addition, the layer [E], the layer [D], and the layer [C] are sequentially provided from the substrate [A] side, the layer [E] and the layer [D] are in direct contact, and further, the layer [D] and the layer [C] As a far-infrared reflective substrate that does not have a configuration in direct contact with [C], as shown in FIG. 6, a base material [A] 1, a layer [B] 2, a first layer [F] 3, The layer [D] 5, the layer [C] 6, the second layer [F] 9, and the inorganic layer [G1] 11 are included in this order. The infrared reflective substrate of Comparative Example 1 described later belongs to this embodiment.

  Each configuration in the present invention will be described below.

(Substrate [A])
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 adhesiveness between the base material [A] made of a resin film and the like and a layer other than the base material [A] such as a layer [B] described later, for example, Japanese Patent Application Laid-Open No. 2004-107627 As described, the base material [A] is made of various materials such as polyester, acrylic, polyurethane, and acrylic graft polyester on the surface on which the layer [B] or the layer [C] of the base material [A] is laminated. It is one of preferred embodiments that a primer layer containing a resin is provided.

(Layer [C])
Examples of the purpose of providing the layer [C] in the present invention include obtaining electrical conductivity and electromagnetic wave prevention, and heat shielding and heat insulation by infrared reflection. In order to obtain good infrared reflection performance, it is necessary to use a metal exhibiting excellent conductivity for the layer [C], and an example of such a metal is silver (Ag). Optically superior by having a layer containing 50% by number or more of silver (Ag), which absorbs less visible light and exhibits very good conductivity, with respect to the entire layer [C]. A far-infrared reflective substrate can be obtained.
For the purpose of obtaining good infrared reflectance and visible light transmittance of the layer [C], it is preferable that silver (Ag) is contained at 70 atomic% or more with respect to the entire layer [C]. , More preferably 90 atomic percent or more. 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 atomic%, that is, even if the layer [C] consists only of 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). The layer [C] preferably contains gold (Au) in addition to silver (Ag), and gold (Au) in addition to silver (Ag) because the far-infrared reflective substrate has better corrosion resistance. It is more preferable to contain Au) and copper (Cu).

  The film thickness of the layer [C] is preferably 5 nm or more, and more preferably 10 nm or more. By setting the film thickness of the layer [C] to 5 nm or more, the thickness unevenness of the layer [C] is suppressed, and the layer [C] can exhibit stable far-infrared reflecting performance. On the other hand, the film thickness of the layer [C] is preferably 30 nm or less, and more preferably 25 nm or less. By making the film thickness of the 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 layer [C], a method of obtaining a thin film by a sputtering process using various metal or alloy targets, a method of resistance heating, electron beam, laser, high frequency induction heating, arc, etc. by a vapor deposition process And a method of obtaining a thin film by depositing various metals and alloys vaporized in (1). 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 layer [C] from corrosion and oxidation, the layer [C] is composed of the layer [C1] containing at least 50 atomic% of silver and Y, Ti, Zr, Nb, Ta, Cr. , Mo, W, Ru, Ir, Pd, Pt, Ni, Cu, Au, Al, Ce, Nd, Sm, Sn, Zn, Cr, and a metal thin film [C2] comprising a mixture thereof Furthermore, it is preferable that the metal thin film [C2] is provided on one side or both sides of the layer [C1]. In order to sufficiently protect the 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 layer [C] from corrosion and has little influence on properties such as infrared reflection performance. Therefore, when considering the thickness of the 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). In this case, the silver content in the metal thin film [C2] is 50 atoms relative to the metal thin film [C2]. It is preferable that it is less than%. In addition, it is more preferable that the metal thin film [C2] does not contain silver (Ag).

(Layer [D])
In the far-infrared reflective substrate of the present invention, the layer [D] disposed between the substrate [A] and the layer [C] employs a structure in direct contact with the layer [C], thereby providing good corrosion resistance. To get. The reason for this is not clear, but if the layer [D] is arranged between the substrate [A] and the layer [C], the layer [C] is formed on the resin or metal oxide forming the substrate or layer. Compared to the case of direct formation, the effect of reducing the defects of the interface structure is great, and it is considered that good corrosion resistance is exhibited.

  The layer [D] contains silicon or contains silicon and carbon, and the total content of the silicon and carbon layer [D] in the layer [D] is 40 atomic% or more. Thus, excellent corrosion resistance can be imparted to the far-infrared reflective substrate.

  Further, as described above, the layer [D] may contain silicon and carbon, which are elemental semiconductors, such as SiC, that is, may contain two or more kinds of elemental semiconductors. The layer [D] may contain germanium or the like as an elemental semiconductor other than silicon or carbon.

  And layer [D] may contain elements other than silicon, carbon, and germanium in the range which does not change the characteristic of layer [D] significantly.

  For the purpose of obtaining an optically and chemically stable far-infrared reflective substrate, the total content of the silicon and carbon layer [D] in the layer [D] is preferably 45 atomic% or more, It is more preferably 50 atomic percent or more, and particularly preferably 90 atomic percent or more.

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

  Moreover, when layer [D] contains many oxygen and nitrogen, the tendency for the favorable corrosion resistance of a far-infrared reflective board | substrate to be not acquired is seen. The reason for this is not clear, but the layer containing a lot of oxygen and nitrogen has a chemical property close to that of the metal oxide, and it is thought that the number of defects generated between the layers [C] increases. Yes. The content ratio of oxygen (O) to silicon (Si) in layer [D] is x, the content ratio of nitrogen (N) to silicon (Si) in layer [D] is y, and the content ratio of silicon (Si) in layer [D] is relative to silicon (Si). When the content ratio of the other element (M) is z and the element content ratio of the layer [D] is expressed as SiOxNyMz (where M means an element other than silicon, oxygen, and nitrogen (for example, carbon)) 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 layer [D] is analyzed by X-ray photoelectron spectroscopy is the peak top of silicon oxide or nitride. Is preferably smaller than the binding energy value indicated by 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.

  The far-infrared reflective substrate of the present invention may have a layer [H] in addition to the layer [D]. And as a concrete example of this far-infrared reflective board, layer [E], layer [D], layer in order from base [A] side between base [A] and layer [G] A far-infrared reflective substrate having [C] and a layer [H], in which the layer [C] and the layer [H] are in direct contact with each other can be exemplified (specifically, the substrate [A] / Layer [E] / layer [D] / layer [C] / layer [H] / layer [G]). In the far-infrared reflective substrate having the above configuration, the corrosion resistance can be further improved. The reason for this is not clear, but it is assumed that it is possible to suppress the occurrence of defects in the interface structure on both sides of the layer [C]. In addition, about the composition and thickness of layer [H], the description about the composition and thickness of said layer [D] is employ | adopted as it is. The layer [H] may have the same configuration as the layer [D] or a different configuration.

(Layer [E])
In the far-infrared reflective substrate of the present invention, the layer [D] disposed between the substrate [A] and the layer [C] is in direct contact with the layer [C] and the layer [E]. ] Is a layer having a nitrogen content of 2 atomic% or more with respect to the entire layer [E] and an oxygen content of 0 to 45 atomic% with respect to the entire layer [E]. And the far-infrared reflective board | substrate of this invention of said structure becomes the excellent corrosion resistance.

  About the detail of the mechanism in which the corrosion resistance of the far-infrared reflective board | substrate of this invention of said structure is excellent, it estimates as follows. In other words, in the far-infrared reflective substrate of the present invention, it is presumed that the generation of defects in the interface structure between the layer [C] and the layer [E] is suppressed. More specifically, in the layer [E], the nitrogen content is 2 atomic% or more with respect to the whole layer [E], and the oxygen content is 0 to 45 atoms with respect to the whole layer [E]. By being several percent, the degree of localization of positive charges and negative charges in the layer [E] is reduced, and the occurrence of defects in the interface structure between the layer [C] and the layer [E] is suppressed. I guess.

  Here, from the reason that the corrosion resistance of the far-infrared reflective substrate is more excellent, the nitrogen content of the layer [E] should be 10 atomic% or more with respect to the entire layer [E]. Preferably, it is 20 atomic% or more. Moreover, about the oxygen content of layer [E], since the corrosion resistance of a far-infrared reflective board | substrate becomes more excellent, and the adhesiveness of a far-infrared reflective board | substrate becomes excellent, layer [E It is preferably 40 atomic percent or less, more preferably 30 atomic percent or less, and even more preferably 20 atomic percent or less based on the total.

  Further, the upper limit of the nitrogen content in the layer [E] is not particularly limited, but is preferably smaller than a value obtained by completely nitriding each element included in the layer [E].

  Moreover, it is preferable that layer [E] contains many nitrogen and oxygen from the reason that the transparency of a far-infrared reflective board | substrate is made more excellent. Specifically, the total content of the layer [E] with respect to the nitrogen and oxygen layer [E] is preferably 20 atomic% or more, more preferably 30 atomic% or more, and 40 atomic%. It is still more preferable that it is above. Further, as described above, the far-infrared reflective substrate has a higher corrosion resistance in the far-infrared reflective substrate as the content of nitrogen in the layer [E] is larger and the content of oxygen is smaller. From the reason that both transparency and corrosion resistance of the layer are excellent, the content of the layer [E] with respect to the layer [E] is as small as 0 to 40 atomic%, and the layer [E] The content of nitrogen in E] is preferably 20 atomic percent or more with respect to the entire layer [E]. In addition, the nitrogen content in the layer [E] is more preferably 30 atomic% or more, and further preferably 40 atomic% or more with respect to the entire layer [E].

  In the far-infrared reflective substrate of the present invention, the total content (number of atoms%) of the nitrogen and oxygen layer [E] in the layer [E] is the entire nitrogen and oxygen layer [D] in the layer [D]. Is greater than the total content (number of atoms%). And by this structure, the corrosion resistance of the far-infrared reflective board | substrate of this invention becomes the outstanding thing.

  The layer [E] may contain one or more elements selected from the group consisting of silicon, tin, and zinc in addition to nitrogen and oxygen. For example, in the case where the layer [E] contains silicon, it becomes easy to obtain a layer having excellent far-infrared reflective substrate adhesion. In addition, when the layer [E] contains tin and zinc (the refractive index of the layer [E] tends to increase), the optical characteristics are simplified while simplifying the configuration of the far-infrared reflective substrate. It becomes easy to obtain an excellent one.

  In addition, adjusting the refractive index and film thickness of the layer [E] according to the refractive index and film thickness of the other layers constituting the far-infrared reflective substrate makes it possible to adjust the visible light transmittance and infrared reflection of the far-infrared reflective substrate. It is an effective means for adjusting the performance. In order to obtain stable corrosion resistance and good adhesion between the layer [E] and the layer [D], the thickness of the layer [E] is preferably 1 nm or more, and preferably 5 nm or more. More preferably, it is 10 nm or more. Further, from the viewpoint of productivity and ease of adjustment of optical characteristics, the film thickness of the layer [E] is preferably 500 nm or less, more preferably 200 nm or less, and further preferably 100 nm or less. .

  In addition, the refractive index of the layer [E] being 1.6 or more is preferable because the visible light transmittance of the far-infrared reflective substrate can be easily adjusted by the film thickness of the layer [E]. is there. When the refractive index of the layer [E] is 1.7 or more, the effect of suppressing the interface reflection of the far-infrared reflective substrate is increased, so that a good visible light transmittance can be obtained without using the layer [F] described later. This is a more preferable embodiment because it is easy to obtain.

  The far-infrared reflective substrate of the present invention may include a layer [I] in addition to the layer [E]. And as a concrete example of this far-infrared reflective board, layer [E], layer [D], layer in order from base [A] side between base [A] and layer [G] A far-infrared reflective substrate having [C], a layer [H] and a layer [I], in which the layer [H] and the layer [I] are in direct contact can be exemplified (specifically, Substrate [A] / layer [E] / layer [D] / layer [C] / layer [H] / layer [I] / layer [G]). In the far-infrared reflective substrate having the above configuration, the corrosion resistance of the far-infrared reflective substrate can be further improved. Although the reason is not clear, it is assumed that it is possible to suppress the occurrence of defects in the interface structure between the layer [H] and the layer [I]. In addition, about the composition and thickness of layer [I], the description about the composition and thickness of said layer [E] is employ | adopted as it is. The layer [I] may have the same configuration as the layer [E] or may have a different configuration.

  Further, the layer [E] and / or the layer [I] have two or more constituent layers having different compositions from each other, and characteristics such as adhesion and optical characteristics between the constituent layers of the far-infrared reflective substrate. It is preferable for the reason that it is easy to adjust. Here, for the composition of each constituent layer, the description of the composition of the layer [E] is applied as it is.

  In addition, for example, the layer [E] includes two or more constituent layers (the constituent layers directly contacting the layer [D] among these constituent layers are referred to as constituent layers [J], and constituent layers other than the constituent layers [J] In the case of having the constituent layer [K]), the constituent layer [K] can be used because the visible light transmittance of the far-infrared reflective substrate can be excellent without using the layer [F] described later. ] Contains tin and zinc, and the constituent layer [J] contains silicon for the reason that the adhesion of the far-infrared reflective substrate can be excellent. preferable. That is, the far-infrared reflective substrate having this configuration has excellent visible light transmittance without providing a separate layer [F], as in the case of the far-infrared reflective substrate of Example 5 described later, and further has excellent adhesion. It will have. In order to achieve both good adhesion between the layer [E] and the layer [D] and good visible light transmittance of the far-infrared reflective substrate, in the layer [E] having two or more constituent layers, In one preferred embodiment, the oxygen content of the constituent layer [J] is less than the oxygen content of the constituent layer [K].

(Layer [F])
The far-infrared reflecting substrate of the present invention has a refractive index of 1.7 or more between at least one of the base [A] and the layer [C] and between the layer [C] and the layer [G]. The formation of a layer [F] having a composition different from that of [D] and the layer [E] is preferable in order to suppress the reflection of visible light at the interface between the layer [C] and another layer, and the substrate [ It is more preferable to have a layer [F] between A] and the layer [C], and between both the layer [C] and the layer [G].

  Examples of the material of the layer [F] include titanium oxide, zirconium oxide, yttrium oxide, niobium oxide, tantalum oxide, zinc oxide, tin-doped indium oxide (ITO), oxides such as tin oxide and bismuth oxide, and silicon nitride. A nitride, a mixture thereof, or a metal-doped carbon such as aluminum or copper, or a carbon-doped carbon may be appropriately selected and used. Depending on the refractive index and thickness of the layer [F], it is possible to adjust the interface tone of the far-infrared reflective substrate and the color tone of reflected or transmitted light. The higher the refractive index of the layer [F], 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 layer [F] uses various metal and metalloid / semiconductor elements and alloys, their oxides, nitrides, suboxides, subnitrides, oxynitrides, oxynitrides and the like, A method for obtaining a thin film by a sputtering process that reacts with a gas such as oxygen or nitrogen as required, a method for obtaining a thin film by a CVD process in which a vaporized organometallic compound and a gas such as oxygen or nitrogen are reacted with plasma, etc. It can be formed by a method of obtaining a thin film by a wet coating process in which a diluted organometallic compound is dried and cured. In the case where the layer [C] is formed by the sputtering process, it is preferable to form the layer [F] by the sputtering process because it is advantageous for forming the layer [C] continuously.

  In order to control the visible light transmission performance and infrared reflection performance of the entire far-infrared reflective substrate, for example, a layer [F] such as (layer [F]) m (/ layer [C] / layer [F]) n is used. And a plurality of layers [C] are laminated (where m is 0 or 1 and n is an integer of 1 or more). Here, adjusting the number of repetitive n and the refractive index and film thickness of the layer [F] and the layer [C] adjust the visible light transmittance and infrared reflection performance of the far-infrared reflective substrate. It is an effective means.

  Further, the far-infrared reflecting substrate of the present invention has excellent infrared reflecting performance and visible light transmitting performance as long as the number “n” of (/ layer [C] / layer [F]) is 1 or more. Can be obtained. Furthermore, it is preferable that the number “n” of (/ layer [C] / layer [F]) is 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 (/ layer [C] / layer [F]) is not particularly limited, but from the viewpoint of balance between the complexity of the manufacturing process and the obtained infrared reflection performance and visible light transmission performance. 3 or less is preferable.

  On the other hand, in order to make the far-infrared reflective substrate more excellent in weather resistance, the layer [F] can be adjacent to the substrate [A], the layer [C], the layer [D], and the layer [E]. Or a layer [G] or a layer [B] to be described later is 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 atomic percentage of tin contained in the layer [F] to 10 atomic% or more and 90 atoms with respect to the sum of the metal elements, metalloid elements and semiconductor elements contained in the layer [F]. The atomic percentage of zinc contained in the layer [F] is 10 atomic% or more and 90 atoms with respect to the sum of the metal elements, metalloid elements and semiconductor elements contained in the layer [F]. Furthermore, the base [A], the layer [C], the layer [D], the layer [E], or the layer [G], which will be described later, B] is directly laminated on at least one of the above, so that the visible light transmittance of the far-infrared reflective substrate is not deteriorated, and adhesion between the layer [F] and a layer that can be adjacent to the layer [F] or far-infrared rays The weather resistance of the reflective substrate can be improved, and its form is preferable. 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 forming the layer [F] as described above, the layer [F] is formed during film formation. It is thought that this is because distortion and damage to the substrate [A], the layer [C], the layer [D], the layer [E], and the layer [B] to be described later are reduced. Further, it is presumed that the strain generated in the layer [E] and the layer [G] and the damage given to the layer [F] are reduced when the layer [E] and the layer [G] are formed.

  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.

(Layer [B])
The layer [B] is to suppress damage to each interface between the substrate [A] and the layer [G], the layer [C], the layer [D], the layer [E], or the layer [F]. It is a layer to be provided. In the far-infrared reflective substrate of the present invention, the layer [B] is interposed between the base [A] and the layer [G], the layer [C], the layer [D], the layer [E], or the layer [F]. It is preferable to provide it. 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 layer [B]. The thickness of the layer [B] 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 layer [B] is a far-infrared reflective substrate according to the combination of the base material [A], the layer [G], the layer [C], the layer [D], the layer [E], and the layer [F]. In order to prevent stress concentration at the inside of each layer or the interface between layers, the far-infrared reflecting performance or visible light transmitting performance of the far-infrared reflecting substrate, or the layer [C], the layer [D], the layer [E], And it can select suitably from viewpoints, such as the adhesive force of layer [F] and layer [B]. 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 layer [B] is an organic film mainly composed of a crosslinkable resin such as acrylic, urethane, or melamine. Depending on the type and amount, it is preferable because the film characteristics can be adjusted relatively easily. 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. Further, modifying the layer [B] by adding at least one kind selected from the group consisting of a polyester resin, a polyurethane resin, a polyester urethane resin, and a silicone resin to the layer [B], It is preferable for improving the adhesion between the layer [C] or the layer [F] and the layer [B]. In particular, when an acrylic cross-linked resin is used as the layer [B], it is preferable to use a silicone resin as the additive resin because of excellent compatibility between the cross-linked resin and its solvent and the additive resin. The addition amount 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 layer [B], the layer [B] 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.

  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 surface of these particles, a cross-linking reaction occurs between the cross-linkable resin and the surface of the particles, thereby improving the properties of the layer [B]. . 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 layer [B] is an inorganic film mainly composed of a metal, a semi-metal, or a semiconductor element such as silica, alumina, zirconia, diamond-like carbon (DLC), oxygen, nitrogen, carbon, or the like. The layer [C] and the layer [F] have good affinity and can be continuously processed by a dry coating process such as sputtering. When the layer [B] is an inorganic film, it is easy to obtain a dense film, and thus has an advantage such as high hardness. It may be difficult, and there may be restrictions on the design such as the strain applied to the far-infrared reflective substrate tends 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 layer [B] by a sputtering process in which it is reacted with a gas such as oxygen or nitrogen as required.

  As the layer [B], 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 for obtaining layer [B] by a process, a method for obtaining layer [B] 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 layer [B]. To suppress distortion such as curling due to stress generated during the formation of the layer [B], the layer [B] Since it is preferable to reduce the thickness of B], the thickness of the layer [B] is preferably 0.1 μm to 10 μm, more preferably 0.2 μm to 5 μm, and 0.4 μm to 3 μm. More preferably.

  When the layer [B] is an organic film having a crosslinkable resin as a main component, the flexibility of the layer [B] is increased and the followability to deformation is improved, but the film hardness is reduced, so the layer [B ] Is required to be adjusted to 0.4 μm or more, more preferably 0.5 μm or more, and further preferably 1 μm to 3 μm.

(Layer [G])
As the layer [G] used in the present invention, an inorganic layer, an organic layer, or a combination of an inorganic layer and an organic layer can be employed. The layer [G] is provided to protect the far-infrared reflecting substrate from defects such as scratches and corrosion due to chemicals, etc., but the far-infrared reflecting performance deteriorates because the layer [G] absorbs far-infrared rays. Therefore, in order to obtain a good far-infrared reflection performance, it is necessary to make the layer [G] sufficiently thin. Accordingly, when a hard film such as glass or acrylic hard coat resin is used for the layer [G], the thickness of the layer [G] is preferably 5 μm or less, more preferably 2 μm or less, and 0.5 μm or less. More preferably. In addition, in order to prevent the change in the thickness of the layer [G] and the change in the observation angle from being easily observed as a change in the color of the transmitted light or reflected light of the visible light, the thickness of the layer [G] is 0. It is preferably 2 μm or less, more preferably 0.1 μm or less, and even 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 layer [G] is preferably as thick as possible. In order to obtain a continuous and uniform layer [G], the thickness of the layer [G] is preferably 2 nm or more, more preferably 5 nm or more, and further preferably 10 nm or more.

  In order to obtain a hard layer [G] with a thinner film thickness, the layer [G] is at least one selected from the group consisting of silicon oxide, aluminum oxide, silicon nitride, and aluminum nitride. It is a preferred embodiment that the inorganic layer [G1] contains 50 atomic% or more of the oxynitride of [G1]. For the purpose of obtaining a dense and high hardness protective film, it is preferable that silicon oxide or the like is contained in the inorganic layer [G1] in an amount of 70 atomic% or more, and 90 atomic%. It is more preferable that it is contained above. Here, the atomic percentage of at least one oxynitride selected from the group consisting of silicon oxide, aluminum oxide, silicon nitride, and aluminum nitride is the entire inorganic layer [G1]. Is the sum of atomic percentages of silicon, aluminum, oxygen, and nitrogen.

Further, in order to obtain more uniform characteristics against penetration of moisture and the like, an organic system containing a resin having a resin skeleton in which the layer [G] is made of — (CH ₂ ) — or — (CF ₂ ) — The layer [G2] 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 layer [G2] with respect to water is preferably 60 ° or more, and more preferably 80 ° or more. More preferably, the angle is 100 ° or more. It is assumed that the organic layer [G2] contains a fluororesin or a silicone resin as a component, and that the organic layer [G2] is the outermost layer of the far-infrared reflective substrate, with respect to the water of the organic layer [G2] This is a preferred embodiment for increasing the contact angle. Further, in addition to the above, the above-described aspect is that when the adhesive is removed from the far-infrared reflective substrate in which an adhesive such as a tape is attached on the surface of the organic layer [G2]. This is also a preferred embodiment because the layer formed on the material [A] is prevented from peeling off. The layer formed on the substrate [A] is prevented from being peeled off because the adhesive force between the organic layer [G2] and the adhesive is, for example, an inorganic layer [G1]. This is considered to be because the adhesive strength between the adhesive and the adhesive is low.

  In addition, as a method for modifying the surface hardness and optical properties of the organic layer [G2], inorganic or organic particles or a combination thereof may be used to combine one or more particles into the organic layer [G2]. It can be added and 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 crosslinking reaction occurs between the crosslinkable resin and the particle surface, thereby modifying the characteristics of the organic layer [G2]. 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. .

  In order to protect the far-infrared reflective substrate from defects such as scratches and corrosion due to chemicals, it is a preferred embodiment to have both the inorganic layer [G1] and the organic layer [G2].

(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, as described above, the film thickness of the layer [G] can be reduced.

  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. By adjusting the components, film quality and film thickness of the substrate [A], layer [G], layer [C], layer [F], layer [B], surface protective film and other constituent layers 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 substrate whose determination by an evaluation method is B or more.

(Use)
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, the constituent films such as the layer [G] described above are formed on the surface of the base [A] described above, for example, as shown in the brief description paragraph of the drawings. It is manufactured by stacking.

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 solution (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 for 7 hours in a 23 ° C. environment sealed with a petri dish containing water.
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 layer [C] progresses slightly, a discoloration point appears as it progresses, and further, when the corrosion of the layer [C] progresses greatly, surface peeling occurs. 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.

  The discoloration point is a spot having a color tone different from that of the surroundings, which is observed on the surface of the far-infrared reflective substrate on the layer [G] side when the far-infrared reflective substrate is observed from the layer [G] side, or This refers to a spot having a color tone different from the surrounding and having a crack. And said surface peeling means the location where either of the layers arrange | positioned on the layer [G] side rather than the base material [A] in the far-infrared reflective substrate has dropped from the far-infrared reflective substrate.

  In addition, when corrosion or delamination occurs in the far-infrared reflective substrate, defects such as corrosion and delamination tend to expand further from the starting point, and as the use period of the far-infrared reflective substrate becomes longer, the far-infrared reflective substrate tends to expand. Deterioration of the appearance of the infrared reflective substrate and a decrease in infrared reflective performance tend to progress.

(2) Corrosion resistance 2
An evaluation solution (dissolved in 2.5 g of lactic acid and 5 g of NaCl in 50 ml of water) was dropped onto the surface of the prepared test specimen for evaluation, and the exposure was performed for 3 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 gap spacer for cross-cutting (Cortech Co., Ltd .: Model No. 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: Partial peeling occurred in a lattice of 1 square or more out of 25 squares.
C: Separation of the entire lattice occurred in a lattice of 1 square or more in 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 layer [G], layer [C], layer [D], layer [E], layer [F] STEM (Scanning Transmission) observed using a field emission electron microscope (JEM2100F manufactured by JEOL Ltd.) The thickness was measured from an Electron Microscope 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) Atomic% of Layer [C], Layer [D], Layer [E], Layer [F], and Layer [G], Content Ratio The atomic number% was calculated using X-ray photoelectron spectroscopy. 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 layer [D] is x, the content ratio of nitrogen (N) to silicon (Si) in layer [D] is y, and the content ratio of silicon (Si) in layer [D] is relative to silicon (Si). X and y used for calculation of the value of x + y when the content ratio of the other element (M) is z and the element content ratio of the layer [D] is expressed as SiOxNyMz were obtained from the following equations.
x = “number of oxygen atoms obtained” / “number of silicon atoms%”
y = “number of nitrogen atoms obtained” / “number of silicon atoms%”
Observation element: Li to U
-Number of measurement n: 1.

(8) 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.

(9) 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 a layer [B] having a thickness of 2.5 μm.
On the layer [B] of the film, using a metal oxide target in which tin is 50 atomic% and zinc is 50 atomic% with respect to the sum of metal elements, metalloid elements, and semiconductor elements, argon is used. Sputtering was performed under film forming gas conditions with a / oxygen pressure ratio of 90% / 10% to form a first layer [F] having a thickness of 15 nm. The refractive index of the first layer [F] was 2.0.

  Subsequently, using a Si target, sputtering was performed under a film forming gas condition in which the pressure ratio of argon / nitrogen was 50% / 50%, thereby forming a layer [E] having a thickness of 10 nm. In the layer [E], Si was 44 atomic%, nitrogen was 39 atomic%, and oxygen was 17 atomic%.

Subsequently, using a Si target, sputtering was performed under a film forming gas condition of 100% argon to form a layer [D] having a thickness of 4 nm. In the layer [D], Si was 95 atomic% and oxygen was 5 atomic%.
Subsequently, using a metal target in which silver (Ag) is 97 atomic%, gold is 2 atomic%, and copper is 1 atomic% with respect to the sum of the metal element, metalloid element, and semiconductor element, argon 100 Sputtering was performed under a film forming gas condition of% to form a layer [C] having a thickness of 13 nm.

  Subsequently, using a metal oxide target in which tin is 50 atomic% and zinc is 50 atomic%, the argon / oxygen pressure ratio is 95% with respect to the sum of metal elements, metalloid elements, and semiconductor elements. After forming the second layer [F] having a thickness of 5 nm by performing sputtering under a film forming gas condition of / 5%, a film forming gas condition in which the argon / oxygen pressure ratio is 90% / 10% is formed. Sputtering was performed to form a second layer [F] having a total thickness of 35 nm. The refractive index of the second layer [F] was 2.0.

Further, using an Si target, sputtering was performed under a film forming gas condition in which the pressure ratio of argon / oxygen / nitrogen was 50% / 35% / 15%, and an inorganic layer [G1] having a thickness of 20 nm was formed. The far-infrared reflective substrate was obtained.
Table 1 shows the configuration of the far-infrared reflective substrate of Example 1, and Table 2 shows the evaluation results.

[Example 2]
After forming the substrate [A], the layer [B], the first layer [F], the layer [E], the layer [D], and the layer [C] as in Example 1, the Si target was used to form argon. Sputtering was performed under a film forming gas condition of 100% to form a layer [H] having a thickness of 4 nm.

  Subsequently, using a metal oxide target in which tin is 50 atomic% and zinc is 50 atomic%, the argon / oxygen pressure ratio is 90% with respect to the sum of metal elements, metalloid elements, and semiconductor elements. Sputtering was performed under a film forming gas condition of / 10% to form a second layer [F] having a thickness of 30 nm.

Subsequently, as in Example 1, an inorganic layer [G1] was formed to obtain a far-infrared reflective substrate.
Table 1 shows the configuration of the far-infrared reflective substrate of Example 2, and Table 2 shows the evaluation results.

[Example 3]
After forming the substrate [A], the layer [B], the first layer [F], the layer [E], the layer [D], the layer [C], and the layer [H] as in Example 2, the Si target Was used to form a layer [I] having a thickness of 10 nm by performing sputtering under a film forming gas condition with an argon / nitrogen pressure ratio of 50% / 50%.

Subsequently, using a metal oxide target in which tin is 50 atomic% and zinc is 50 atomic%, the argon / oxygen pressure ratio is 90% with respect to the sum of metal elements, metalloid elements, and semiconductor elements. Sputtering was performed under a film forming gas condition of / 10% to form a second layer [F] having a thickness of 15 nm.
Subsequently, as in Example 1, an inorganic layer [G1] was 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]
A hard coat film (Toughtop (registered trademark) THS: manufactured by Toray Film Processing Co., Ltd.) was used as the substrate [A] having a layer [B] having a thickness of 2.5 μm.
On the layer [B] of the film, using a metal oxide target in which tin is 50 atomic% and zinc is 50 atomic% with respect to the sum of metal elements, metalloid elements, and semiconductor elements, argon is used. Sputtering was performed under a film forming gas condition in which the pressure ratio of / nitrogen was 50% / 50% to form a layer [E] having a thickness of 30 nm. Layer [E] was 28 atomic percent tin, 25 atomic percent zinc, 43 atomic percent oxygen, and 4 atomic percent nitrogen.

  Subsequently, as in Example 2, layer [D], layer [C], and layer [H] were formed.

  Subsequently, using a metal oxide target in which tin is 50 atomic% and zinc is 50 atomic%, the argon / nitrogen pressure ratio is 50% with respect to the sum of metal elements, metalloid elements, and semiconductor elements. Sputtering was performed under a film forming gas condition of / 50% to form a layer [I] having a thickness of 30 nm.

Subsequently, as in Example 1, an inorganic layer [G1] was formed to obtain a far-infrared reflective substrate.
Table 1 shows the configuration of the far-infrared reflective substrate of Example 4, and Table 2 shows the evaluation results.

[Example 5]
A hard coat film (Toughtop (registered trademark) THS: manufactured by Toray Film Processing Co., Ltd.) was used as the substrate [A] having a layer [B] having a thickness of 2.5 μm.
On the layer [B] of the film, using a metal oxide target in which tin is 50 atomic% and zinc is 50 atomic% with respect to the sum of metal elements, metalloid elements, and semiconductor elements, argon is used. Sputtering was performed under a film forming gas condition in which the pressure ratio of nitrogen / nitrogen was 50% / 50% to form a constituent layer [K] having a thickness of 15 nm.

  Subsequently, using a Si target, sputtering was performed under a film forming gas condition with an argon / nitrogen pressure ratio of 50% / 50%, thereby forming a constituent layer [J] having a thickness of 10 nm.

Subsequently, as in Example 4, the layer [D], the layer [C], the layer [H], the layer [I], and the inorganic layer [G1] 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]
Similarly to Example 2, the substrate [A], the layer [B], the first layer [F], the layer [E], the layer [D], the layer [C], the layer [H], and the second layer [F] ], After forming the inorganic layer [G1]
On the inorganic layer [G1], Novec 1720 (manufactured by 3M, active ingredient 0.1 wt%) was applied using a bar coater (counter No. 3), dried at 80 ° C. for 3 minutes, and the organic layer [ G2] was formed to obtain a far-infrared reflective substrate. The contact angle of water on the surface of the organic layer [G2] was 107 °.
Table 3 shows the configuration of the far-infrared reflective substrate of Example 6, and Table 4 shows the evaluation results.

[Example 7]
As in Example 3, the substrate [A], layer [B], first layer [F], layer [E], layer [D], layer [C], layer [H], layer [I], first After forming the second layer [F] and the inorganic layer [G1], the organic layer [G2] is formed on the inorganic layer [G1] in the same manner as in Example 6, and the far-infrared reflective substrate is formed. Obtained.
Table 3 shows the configuration of the far-infrared reflective substrate of Example 7, and Table 4 shows the evaluation results.

[Example 8]
As in Example 5, the substrate [A], the layer [B], the layer [D] (the constituent layer [K] and the constituent layer [J]), the layer [D], the layer [C], the layer [H], After forming the layer [I] and the inorganic layer [G1], the organic layer [G2] was formed on the inorganic layer [G1] in the same manner as in Example 6 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.

[Comparative Example 1]
A hard coat film (Toughtop (registered trademark) THS: manufactured by Toray Film Processing Co., Ltd.) was used as the substrate [A] having a layer [B] having a thickness of 2.5 μm.
On the layer [B] of the film, using a metal oxide target in which tin is 50 atomic% and zinc is 50 atomic% with respect to the sum of metal elements, metalloid elements, and semiconductor elements, argon is used. Sputtering was performed under film forming gas conditions with a / oxygen pressure ratio of 90% / 10% to form a first layer [F] having a thickness of 30 nm. In the first layer [F], tin was 25 atomic%, zinc was 24 atomic%, and oxygen was 51 atomic%.
Subsequently, a sputtering process was performed using a Si target under a film forming gas condition of 100% argon to form a layer [D] having a thickness of 4 nm.
Subsequently, as in Example 1, the layer [C], the second layer [F], and the inorganic layer [G1] 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]
After forming the substrate [A], the layer [B], and the first layer [F] in the same manner as in Example 2,
Using a Si target, sputtering was performed under a film forming gas condition in which the pressure ratio of argon / oxygen / nitrogen was 50% / 40% / 10% to form a layer [E] having a thickness of 10 nm. In the layer [E], Si was 32 atomic% and oxygen was 68 atomic%.
Subsequently, the layer [D], the layer [C], the layer [H], the second layer [F], and the inorganic layer [G1] were formed in the same manner as in Example 2 to obtain a far-infrared reflective substrate.
Table 1 shows the configuration of the far-infrared reflective substrate of Comparative Example 2, and Table 2 shows the evaluation results.

[Comparative Example 3]
After forming the substrate [A], the layer [B], the first layer [F], and the layer [E] as in Example 2, without forming the layer [D], as in Example 2, Layer [C], layer [H], second layer [F], and inorganic layer [G1] 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.

[Comparative Example 4]
As in Comparative Example 1, the substrate [A], the layer [B], the first layer [F], the layer [D], the layer [C], the second layer [F], and the inorganic layer [G1] are formed. After forming
Similarly to Example 6, an organic layer [G2] was formed on the inorganic layer [G1] to obtain a far-infrared reflective substrate.
Table 3 shows the configuration of the far-infrared reflective substrate of Comparative Example 4, and Table 4 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: Layer [B]
3: First layer [F]
4: Layer [E]
5: Layer [D]
6: Layer [C]
7: Layer [H]
8: Layer [I]
9: Second layer [F]
10: Layer [G]
11: Inorganic layer [G1]
12: Organic layer [G2]
13: Component layer [J]
14: Component layer [K]

Claims (7)

Between the substrate [A] and the layer [G], the layer [C], the layer [D] directly in contact with the layer [C], and the layer [D] are in direct contact from the layer [G] side. The far-infrared reflective board | substrate which has layer [E], a far-infrared reflectance is 60% or more, and satisfies the following (1)-(4).
(1) The layer [C] has a layer made of one or more layers of metal, and contains 50 atomic% or more of silver with respect to the entire layer [C]. (2) The layer [D] contains silicon. Or silicon and carbon are contained, and the total content of silicon and carbon in the layer [D] with respect to the entire layer [D] is 40 atomic% or more. (3) Layer [E] contains nitrogen Or the nitrogen content of the layer [E] is 2 atomic% or more with respect to the whole layer [E], and the oxygen content of the layer [E] is the whole layer [E]. (4) The total content of nitrogen and oxygen in the layer [E] (number of atoms%) in the layer [E] is 0 to 45 atomic% relative to the total amount of nitrogen and oxygen in the layer [D]. Greater than the total content (atomic%) with respect to the entire layer [D] Furthermore, it has a layer [H] arranged between the layer [C] and the layer [G],
Layer [H] is in direct contact with layer [C],
The layer [H] contains silicon or contains silicon and carbon, and the total content of silicon and carbon in the layer [H] with respect to the entire layer [H] is 40 atomic% or more. The far-infrared reflective board of description. Furthermore, it has a layer [I] arranged between the layer [C] and the layer [G],
Layer [I] is in direct contact with layer [H],
The layer [I] contains nitrogen or contains nitrogen and oxygen, and the nitrogen content of the layer [I] is 2 atomic% or more with respect to the whole layer [I], and the oxygen of the layer [I] Content is 0-45 atomic% with respect to the whole layer [I],
The total content (atomic number%) of nitrogen and oxygen in layer [I] with respect to the entire layer [I] is the total content (atomic number%) of nitrogen and oxygen in layer [H] with respect to the entire layer [H]. The far-infrared reflective substrate according to claim 2, which is larger than that.   The far-infrared reflective substrate according to any one of claims 1 to 3, wherein the layer [E] has two or more constituent layers having different compositions.   The refractive index is 1.7 or more, the layer [F] has a layer [D] and a layer [F] having a composition different from that of the layer [E], and the layer [F] is between the substrate [A] and the layer [C]. 5. The far-infrared reflective substrate according to claim 1, wherein the far-infrared reflective substrate is formed on at least one of the layer [C] and the layer [G].   The layer [G] has an inorganic layer [G1], and the inorganic layer [G1] is selected from the group consisting of silicon oxide, silicon nitride, aluminum oxide and aluminum nitride. The far-infrared reflective substrate according to any one of claims 1 to 5, wherein the far-infrared reflective substrate contains 50% by mass or more based on the total amount of the inorganic layer [G1].   The layer [G] has an organic layer [G2], the far-infrared reflective substrate according to any one of claims 1 to 6.

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