JP2018205440A - Infrared reflection film, infrared reflection film with release film, window glass and production method of infrared reflection film - Google Patents

Abstract

To provide an infrared reflection film having high barrier property against permeation of ions, since permeation of ions such as chloride ions into an infrared reflection film might induce degradation of the infrared reflection film.SOLUTION: The infrared reflection film has a substrate and an infrared reflection part, in this order, wherein the infrared reflection part has a metal part and a metal oxide part, and the metal oxide part has, successively from the substrate side, a first metal oxide layer and a second metal oxide layer containing the same metal element as in the first metal oxide layer.SELECTED DRAWING: Figure 1

Description

  The present disclosure relates to an infrared reflective film.

For example, in order to insulate the window glass, an infrared reflecting film including an infrared reflecting portion having a metal layer and a metal oxide layer may be installed. As a method for forming the metal layer and the metal oxide layer, a sputtering method is generally used. For example, Patent document 1, by reactive sputtering to form a metal oxide layer (TiO _x), a method of forming a metal layer (Ag) is disclosed by sputtering. Patent Document 2 discloses an infrared reflective substrate including a first metal oxide layer, a second metal oxide layer, and a metal layer in this order on a transparent substrate.

JP 2017-053967 A Japanese Patent Laying-Open No. 2015-166141

  For example, when ions such as chloride ions penetrate into the infrared reflective film, the infrared reflective film may be deteriorated. The present disclosure has been made in view of the above circumstances, and a main object of the present disclosure is to provide an infrared reflective film having high barrier properties against ion penetration.

  In the present disclosure, the infrared reflection film having a base material and an infrared reflection part in this order, the infrared reflection part has a metal part and a metal oxide part, the metal oxide part is An infrared reflective film having a first metal oxide layer and a second metal oxide layer containing the same metal element as the first metal oxide layer in this order from the substrate side is provided.

  In the present disclosure, the above-described infrared reflective film, the adhesive layer positioned on the opposite side of the infrared reflective portion with respect to the substrate, and the opposite side of the substrate with respect to the adhesive layer. An infrared reflective film with a release film is provided.

  In the present disclosure, the above-described infrared reflective film, the adhesive layer positioned on the opposite side of the infrared reflective portion with respect to the substrate, and the opposite side of the substrate with respect to the adhesive layer. And a glass member.

  In this indication, it is a manufacturing method of the infrared reflective film which manufactures the infrared reflective film mentioned above, Comprising: The above-mentioned infrared reflective part is provided in the substrate preparation process which prepares the above-mentioned base material, and one surface side of the above-mentioned base material And forming the precursor layer of the first metal oxide layer by sputtering using a metal oxide oxygen defect as a target. The second metal oxide layer is formed by a precursor layer formation process and a reactive sputtering method using the oxygen deficient body as a target in an oxygen atmosphere, and the precursor layer is oxidized to form the first metal oxide. And a metal oxide layer forming process for forming a layer.

  The infrared reflective film of the present disclosure has an effect of high barrier properties against ion penetration.

It is a schematic sectional drawing which shows an example of the infrared reflective film of this indication. It is a schematic sectional drawing which shows an example of the infrared reflective film of this indication. It is a schematic sectional drawing which shows an example of the infrared reflective film with a peeling film of this indication. It is a schematic sectional drawing which shows an example of the window glass of this indication. It is a schematic plan view which shows an example of the window glass of this indication. It is a schematic sectional drawing which shows an example of the manufacturing method of the infrared reflective film of this indication.

A. Infrared Reflective Film FIG. 1 is a schematic cross-sectional view showing an example of the infrared reflective film of the present disclosure. The infrared reflective film 10 shown in FIG. 1 has the base material 1 and the infrared reflective part 4 in this order in the thickness direction. The infrared reflecting part 4 includes a metal part 2 and a metal oxide part 3 in this order from the substrate 1 side. Furthermore, the metal oxide part 3 has the 1st metal oxide layer 3x and the 2nd metal oxide layer 3y containing the same metal element as the 1st metal oxide layer 3x in order from the base material 1 side.

  According to this indication, since a metal oxide part has a 1st metal oxide layer and a 2nd metal oxide layer, it can be set as an infrared reflective film with high barrier property to penetration of ions. The reason why the barrier property is increased is presumed to be that a minute space is formed at the boundary between the first metal oxide layer and the second metal oxide layer, and ions are difficult to diffuse.

Typically, ions that degrade the infrared reflective film include chloride ions. When chloride ions react with the metal part, the infrared reflectivity decreases (salt damage) easily occurs. Since the infrared reflective film of this indication has a 1st metal oxide layer and a 2nd metal oxide layer, generation | occurrence | production of salt damage can be suppressed. Furthermore, as will be described later, when the oxygen deficiency rate of the first metal oxide layer is small, galvanic corrosion occurring between the metal part (metal layer) and the first metal oxide layer can be suppressed, and the occurrence of salt damage can be prevented. It can suppress more effectively.
Hereinafter, the infrared reflective film of the present disclosure will be described for each configuration.

1. Substrate The substrate is a member that holds an infrared reflecting portion described later. Although the material of a base material is not specifically limited, For example, resin is mentioned. Examples of the resin include polyesters such as polyethylene terephthalate, polyethylene naphthalate and polybutylene terephthalate, and polyolefins such as polyethylene and polypropylene, and polyester is preferred. Other examples of the resin include polycarbonate, polyamide, polyimide, polyamideimide and the like. Fluorine-containing resins such as polytetrafluoroethylene and tetrafluoroethylene / perfluoroalkyl vinyl ether copolymers may also be used. Moreover, it is preferable that a base material contains resin as a main component.

  The thickness of the base material is, for example, 10 μm or more and 200 μm or less, and may be 20 μm or more and 100 μm or less. If the thickness of the substrate is too small, the handling property may be deteriorated when forming the infrared reflecting portion, and if the thickness of the substrate is too large, the flexibility may be decreased.

  Although the manufacturing method of a base material is not specifically limited, For example, the method of shape | molding into a film form is mentioned by melt-extruding raw material resin to a film form, or solution extrusion. If necessary, the obtained film may be subjected to at least one of a stretching process, a heat setting process, and a heat relaxation process. The stretching process may be a process in the longitudinal direction, a process in the width direction, or a process in the longitudinal direction and the width direction.

2. Infrared reflective part An infrared reflective part has a metal part and a metal oxide part. Furthermore, a metal oxide part has a 1st metal oxide layer and the 2nd metal oxide layer containing the same metal element as a 1st metal oxide layer in an order from the base material side.

(1) Metal part A metal part is a layer which provides infrared reflectivity. The metal part may have a single layer structure or may have two or more multilayer structures. In the former case, the metal part corresponds to a metal layer, and in the latter case, the metal part has a plurality of metal layers. The material of the metal part is not particularly limited, and examples thereof include metals such as Ag, Al, Cu, Pd, Au, Pt, Ni, Bi, Ge, and Ga, and alloys containing at least one of these metals. It is done. Among these, silver, silver alloy, aluminum, aluminum alloy, copper, and copper alloy are preferable. Since these have high free electron density, even if it is a thin film, high infrared reflectivity can be obtained.

  The thickness of the metal part is, for example, 5 nm or more and 50 nm or less. If the thickness of the metal part is too small, the infrared reflectivity may be lowered, and if the thickness of the metal part is too large, the flexibility may be lowered.

  The metal part may be a layer having no opening (so-called solid layer). In this case, high infrared reflectivity can be obtained. On the other hand, the metal part may be a layer having a metal region and an opening region. By providing the opening region, radio wave transmission is improved. Each metal region may be electrically independent or may not be electrically independent, but the former is preferable. This is because radio wave permeability is improved. Moreover, a pattern is obtained by arrange | positioning the several metal area | region in the direction which cross | intersects the longitudinal direction of a metal area | region, respectively. Examples of the pattern shape composed of a plurality of metal regions include a stripe shape. Moreover, it is preferable that the width | variety of a metal area | region and the width | variety of an adjacent metal area | region are 10 micrometers or more and 5 mm or less, respectively.

  When the metal part has a metal region and an opening region, the opening ratio of the opening region is not particularly limited, but may be, for example, 0.5% or more and 30% or less, and 0.5% or more and 10% or less. It may be 0.7% or more and 2% or less. The aperture ratio refers to the area of the opening region relative to the area of the entire metal part including the area of the opening region.

(2) Metal oxide part A metal oxide part has a 1st metal oxide layer and the 2nd metal oxide layer containing the same metal element as a 1st metal oxide layer in an order from the base material side. The metal oxide portion may have only the first metal oxide layer and the second metal oxide layer, or may further have another metal oxide layer.

(I) First metal oxide layer The first metal oxide layer is preferably a layer having a refractive index higher than that of the metal portion. The material of the first metal oxide layer preferably has a refractive index of 1.4 or more with respect to light of 633 nm. This is because a good interference effect can be obtained. Examples of the material of the first metal oxide layer include, for example, oxides of metals such as Ti, Zr, Hf, Nb, Zn, Al, Ga, In, Tl, Ga, Sn, and Si, and at least of these metals. A composite oxide containing one kind can be given, among which TiO ₂ , ZnO and SiO ₂ are preferable.

The oxygen deficiency rate (%) of the metal oxide contained in the first metal oxide layer is not particularly limited,
For example, it may be 10% or less and may be 5% or less. When the oxygen deficiency rate of the first metal oxide layer is small, galvanic corrosion occurring between the metal part (metal layer) and the first metal oxide layer can be suppressed, and the occurrence of salt damage can be effectively suppressed. Note that the oxygen deficiency rate (%) refers to the ratio of oxygen deficiency to the stoichiometric metal oxide. For example, Ti (divalent) stoichiometrically forms a metal oxide called TiO ₂ . Therefore, for example, the oxygen deficiency rate of TiO _1.9 is (2-1.9) / 2 × 100 = 5 (%). Moreover, an oxygen deficiency rate (%) can be calculated | required, for example by TEM-EELS (Transmission electron microscope-electron energy loss spectroscopy).

  Although the thickness of a 1st metal oxide layer is not specifically limited, For example, it is 15 nm or less, may be 12 nm or less, and may be 10 nm or less. For example, when the thickness of the first metal oxide layer is 10 nm or less, the precursor layer can be sufficiently oxidized while forming the second metal oxide layer in the method for producing an infrared reflective film described later. And the formation of a highly insulating first metal oxide layer can be obtained. On the other hand, the thickness of the first metal oxide layer is, for example, 4 nm or more.

(Ii) Second metal oxide layer The second metal oxide layer contains the same metal element as the first metal oxide layer. The second metal oxide layer and the first metal oxide layer preferably contain the same metal oxide.

  Although the oxygen deficiency rate (%) of the metal oxide contained in the second metal oxide layer is not particularly limited, for example, it is 5% or less, and may be 3% or less.

  The thickness of the second metal oxide layer is preferably larger than the thickness of the first metal oxide layer. The difference between the thickness of the second metal oxide layer and the thickness of the first metal oxide layer is, for example, 5 nm or more, 10 nm or more, or 20 nm or more. Although the thickness of a 2nd metal oxide layer is not specifically limited, For example, they are 10 nm or more and 100 nm or less, and 20 nm or more and 90 nm or less may be sufficient.

(Iii) Metal oxide part A metal oxide part has a 1st metal oxide layer and a 2nd metal oxide layer in order from the base material side. The size of the metal oxide crystal grains contained in the first metal oxide layer is preferably substantially the same as the size of the metal oxide crystal grains contained in the second metal oxide layer. For example, when a precursor layer forming process and a metal oxide layer forming process, which will be described later, are continuously performed, the crystal grains of the metal oxide have substantially the same size.

(3) Infrared reflective part The infrared reflective part may have one or more metal parts, and may have one or more metal oxide parts. As an example of the infrared reflection part, as shown in FIG. 1, an infrared reflection part 4 having a metal part 2 and a metal oxide part 3 in order from the base material 1 side is mentioned. Moreover, as another example of an infrared reflective part, as shown in FIG. 2, the 1st metal part 2a, the 1st metal oxide part 3a, the 2nd metal part 2b, and the 2nd metal oxidation in order from the base material 1 side. Infrared reflective part 4 which has physical part 3b is mentioned.

  The infrared reflective film preferably has alternately metal parts and metal oxide parts. Between the base material and the metal part closest to the base material, it may have a metal oxide part or may not have a metal oxide part.

  As the configuration of the infrared reflecting portion, for example, in order from the base material, the configuration of the metal portion and the metal oxide portion, the configuration of the first metal oxide portion, the first metal portion and the second metal oxide portion, the first metal portion , First metal oxide part, second metal part and second metal oxide part configuration, first metal oxide part, first metal part, second metal oxide part, second metal part and third metal oxide The structure of a physical part, the structure of a 1st metal part, a 1st metal oxide part, a 2nd metal part, a 2nd metal oxide part, a 3rd metal part, a 3rd metal oxide part, etc. are mentioned. When the infrared reflection part has two or more metal oxide parts, it is sufficient that at least one metal oxide part has the first metal oxide layer and the second metal oxide layer described above.

3. Infrared reflective film An infrared reflective film has a base material and an infrared reflective part in this order. Furthermore, the infrared reflective film may or may not have a hard coat layer at a position on the substrate side with respect to the infrared reflective portion. Similarly, the infrared reflective film may or may not have a hard coat layer at a position opposite to the substrate with respect to the infrared reflective portion.

  The hard coat layer preferably has a surface hardness higher than that of the infrared reflecting portion (metal portion or metal oxide portion). The pencil hardness of JIS K5600-5-4 (1999) on the surface of the hard coat layer is, for example, F or more and may be H or more. The material of the hard coat layer may be any material that is generally used. For example, an ionizing radiation curable resin can be used. Examples of the ionizing radiation curable resin include acrylate resins, oxetane resins, silicone resins, and the like.

  The infrared reflective film preferably has a high visible light transmittance. This is because good visibility can be obtained. The visible light transmittance is, for example, 70% or more, preferably 80% or more, and more preferably 90% or more. The visible light transmittance can be measured based on JIS A 5759: 2008.

  The infrared reflective film preferably has a low visible light reflectance (regular reflectance). This is because glare can be suppressed. The visible light reflectance (regular reflectance) is, for example, 6% or less, preferably 5% or less, and more preferably 4% or less.

  The infrared reflective film preferably has a low shielding coefficient. This is because good heat shielding properties can be obtained. The shielding coefficient is, for example, 0.8 or less, and preferably 0.7 or less.

The infrared reflective film preferably has a low thermal conductivity. This is because good heat insulating properties can be obtained. The thermal conductivity is, for example, 4.5 W / m ² · K or less, and preferably 4.0 W / m ² · K or less. In addition, the visible light transmittance, visible light reflectance (regular reflectance), shielding coefficient, and thermal conductivity described above can be measured based on JIS A 5759: 2008.

  The infrared reflective film preferably has a high infrared reflectance. The infrared reflectance is, for example, 60% or more, preferably 70% or more, and more preferably 80% or more. The infrared reflectance is specified as an average value of the reflectance at each wavelength when measured at a measurement wavelength of 500 nm or more and 2200 nm or less.

  The infrared reflective film preferably has radio wave transparency. The radio wave shielding coefficient of the infrared reflective film may be, for example, 10 dB or less, or 7 dB or less. The radio wave shielding coefficient is specified by measuring a frequency of 30 MHz to 1 GHz by the KEC method using an electromagnetic wave shielding effect evaluator TSES-KEC (manufactured by Technoscience Japan) and obtaining a numerical value (dB) at 1 GHz.

  The thickness of the infrared reflecting film is, for example, 3 mm or less, 1 mm or less, or 500 μm or less.

B. FIG. 3 is a schematic cross-sectional view showing an example of an infrared reflective film with a release film of the present disclosure. The infrared reflective film 20 with a release film shown in FIG. 3 is based on the infrared reflective film 10, the adhesive layer 11 located on the opposite side of the infrared reflective part 4 with respect to the substrate 1, and the adhesive layer 11 as a reference. It has a release film 12 located on the opposite side to the material 1.

  According to this indication, it can be set as an infrared reflective film with a peeling film with high barrier property to osmosis of ion by using the infrared reflective film mentioned above.

  The adhesive layer is a layer containing an adhesive. As an adhesive, acrylic resin is mentioned, for example. Specifically, it is represented by the formula A-B-A (wherein A and B represent different polymer blocks, A is composed of an alkyl ester unit of methacrylic acid, and B is composed of an alkyl ester unit of acrylic acid). An acrylic resin containing a triblock copolymer.

  The pressure-sensitive adhesive layer preferably has a peeling force with respect to a glass plate according to a 180-degree peeling test specified in JIS K6854-2, for example, 20 N / 25 mm width or more and 30 N / 25 mm width or less. Moreover, the thickness of the adhesion layer is 50 micrometers or more and 2000 micrometers or less, for example.

  A peeling film is a film for protecting an adhesion layer in the state (preservation state) before sticking an infrared reflective film to a glass member. Examples of the material of the release film include resin films such as polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene aphthalate, and polyolefin resins such as polypropylene and polymethylpentene. The thickness of the release film is, for example, 20 μm or more and 100 μm or less.

C. Window Glass FIG. 4 is a schematic cross-sectional view illustrating an example of the window glass of the present disclosure. The window glass 30 shown in FIG. 4 is based on the infrared reflective film 10 and the base material 1 of the infrared reflective film 10, the adhesive layer 11 located on the opposite side of the infrared reflective part 4, and the adhesive layer 11 as a reference. It has the glass member 13 located on the opposite side to the base material 1.

  According to the present disclosure, by using the above-described infrared reflective film, it is possible to obtain a window glass in which deterioration of the infrared reflective film due to ion permeation hardly occurs. In addition, about the adhesion layer, since it is the same as that of the content mentioned above, description here is abbreviate | omitted.

  Examples of the glass member include inorganic glass and organic glass. Examples of the inorganic glass material include silicon oxide. The inorganic glass is preferably glass containing silicon oxide as a main component, and specific examples include soda lime glass, borosilicate glass, alkali-free glass, aluminosilicate glass, and the like. On the other hand, the organic glass material typically includes a resin, specifically, a polycarbonate resin such as polydiethylene glycol bisallyl carbonate, an acrylic resin such as polymethyl methacrylate, and the like. The organic glass is preferably glass containing the above resin as a main component.

  Moreover, a glass member can be classified into plate glass and processed glass, for example. Examples of the plate glass include float plate glass, polished plate glass, mold plate glass, mesh-inserted plate glass, wire-inserted plate glass, and heat ray absorbing plate glass. The thickness of the plate glass is, for example, 2 mm or more and 12 mm or less. On the other hand, examples of the processed glass include laminated glass, heat-treated glass (for example, tempered glass and double-strength glass), chemically tempered glass, and the like. Laminated glass refers to glass in which two or more plate glasses are bonded with an intermediate film interposed therebetween.

  For example, as shown in FIG. 5, the window glass 30 may have a plurality of infrared reflective films 10. 5 corresponds to a plan view of the infrared reflective film 10 in FIG. 4 viewed from the indoor side. The longitudinal direction D of the infrared reflective film 10 is preferably parallel to the vertical direction. For example, when an infrared reflective film is pasted with water, the infrared reflective film has a property that water is difficult to escape compared to other films, so water stain is likely to occur, but the longitudinal direction of the infrared reflective film is perpendicular to the vertical direction. By being parallel, it becomes easy for water to come off by gravity, and the occurrence of water stain can be suppressed. Note that “parallel to the vertical direction” includes not only strict parallel but also a case where the angle with respect to the vertical direction is within ± 15 °.

  Further, for example, as shown in FIG. 5, when the window glass 30 has a plurality of infrared reflection films 10, the adhesive layer of the infrared reflection film is an infrared reflection film at a joint portion between two adjacent infrared reflection films 10. It is preferable to cover the end of the infrared reflecting portion. This is because the end of the infrared reflecting portion can be protected.

  A window glass is used for the opening part of a building and a vehicle, for example. As said vehicle, vehicles, such as a motor vehicle and a train, a ship, an aircraft, etc. are mentioned, for example. In this indication, it is a closure member used for an opening of a building or a vehicle, Comprising: The closure member which has the window glass mentioned above and a sash (window frame) can also be provided. In addition, by attaching an infrared reflecting sheet to an existing closing member that does not have an infrared reflecting sheet, a closing member having high infrared reflectivity can be obtained at low cost. Furthermore, in this indication, the building or vehicle which has the window glass mentioned above in an opening part can also be provided.

D. FIG. 6 is a schematic cross-sectional view illustrating an example of a method for producing an infrared reflective film of the present disclosure. In FIG. 6, first, the base material 1 is prepared (FIG. 6 (a)). Next, the metal part 2 is formed on one surface side of the base material 1 by a sputtering method (FIG. 6B). Next, the precursor layer 3α of the first metal oxide layer is formed on the side opposite to the base material 1 with the metal part 2 as a reference by sputtering using a metal oxide oxygen deficient body as a target (FIG. 6 (c)). Next, in an oxygen atmosphere, the second metal oxide layer 3y is formed by reactive sputtering using a metal oxide oxygen defect as a target, and the precursor layer 3α is oxidized to form the first metal oxide layer 3x. Is formed (FIG. 6D). Thereby, the infrared reflective film 10 which has the base material 1 and the infrared reflective part 4 in this order is obtained.

  According to the present disclosure, in the infrared reflecting portion forming step, the metal oxide portion having the first metal oxide layer and the second metal oxide layer is obtained by performing the precursor layer forming treatment and the metal oxide layer forming treatment. Can be formed. As a result, an infrared reflective film having a high barrier property against ion penetration can be obtained.

  As a general method for forming a metal oxide portion, a sputtering method is known. Among sputtering methods, a DC (direct current) sputtering method having a high film formation rate is preferable in terms of mass production, but an insulator (metal oxide) cannot be targeted by the DC sputtering method. In contrast, in the present disclosure, the precursor of the first metal oxide layer can be formed at a high production rate by using an oxygen-deficient body of the metal oxide as a target. In particular, there is an advantage that the oxidation of the base material or the metal part can be prevented by performing the precursor layer forming treatment in a non-oxygen atmosphere. In addition, the oxidation of a metal part becomes a cause which reduces infrared reflectivity.

  Furthermore, in the present disclosure, the precursor layer can be oxidized (formation of the first metal oxide layer) while forming the second metal oxide layer by the reactive sputtering method. Therefore, it is possible to reduce the oxygen deficiency rate of the first metal oxide layer. Here, when the oxygen vacancy rate of the first metal oxide layer is large and functions as a conductive layer, the metal part (metal layer) and the first metal oxide layer are in contact with different types of conductive layers. Galvanic corrosion is likely to occur. In contrast, in the present disclosure, since the oxygen deficiency rate of the first metal oxide layer can be reduced, galvanic corrosion that occurs between the metal part (metal layer) and the first metal oxide layer is prevented. It can suppress and generation | occurrence | production of salt damage can be suppressed effectively.

  Furthermore, in the precursor layer formation process, by using an oxygen-deficient body of metal oxide as a target, for example, it is easier to form a first metal oxide layer having a higher insulating property than when using a single metal as a target. There is an advantage. Furthermore, in the precursor layer forming process and the metal oxide layer forming process, there is an advantage that the production efficiency is high by using the same target.

1. Base material preparation process The base material preparation process is a process of preparing the base material used for an infrared reflective film. About a base material, since it is the same as that of the content described in said "A. infrared reflection film", description here is abbreviate | omitted.

2. Infrared reflecting portion forming step The infrared reflecting portion forming step is a step of forming an infrared reflecting portion on one surface side of the substrate. In the infrared reflecting portion forming step, the metal portion and the metal oxide portion are formed in accordance with the configuration of the target infrared reflecting portion.

  As a method for forming the metal part, for example, a vapor deposition method is exemplified. Examples of the vapor deposition method include a PVD method such as a sputtering method, a vacuum vapor deposition method, and an electron beam vapor deposition method, and a CVD method. Further, the metal part may be formed by an evaporation method using a mask. By using a mask, a metal part having a metal region and an opening region can be obtained.

  Examples of the method for forming the metal oxide portion include a vapor deposition method. Examples of the vapor deposition method include a PVD method such as a sputtering method, a vacuum vapor deposition method, and an electron beam vapor deposition method, and a CVD method. Moreover, it is preferable to perform the precursor layer formation process mentioned later and a metal oxide layer formation process in an infrared reflective part formation process.

(1) Precursor layer formation process A precursor layer formation process is a process which forms the precursor layer of a 1st metal oxide layer with the sputtering method which made the oxygen deficient body of the metal oxide the target.

  The oxygen deficiency rate (%) of the oxygen deficient body is, for example, 5% or more, and may be 10% or more. If the oxygen deficiency rate is too small, the conductivity is low, and for example, there is a possibility that the DC sputtering method cannot be used. On the other hand, the oxygen deficiency rate (%) is, for example, 80% or less, and may be 70% or less. If the oxygen deficiency rate is too high, the first metal oxide layer may not be sufficiently oxidized and corrosion of the metal layer may occur.

  Examples of the sputtering method include DC (direct current) sputtering. Further, the sputtering method is preferably performed in a non-oxygen atmosphere. This is because, for example, oxidation of the metal layer can be prevented. Note that the non-oxygen atmosphere includes an atmosphere in which a slight amount of oxygen exists so that the oxidation of the metal layer can be substantially prevented. In addition, examples of the non-oxygen atmosphere include a rare gas atmosphere such as an Ar atmosphere.

(2) Metal oxide layer formation treatment In an oxygen atmosphere, the second metal oxide layer is formed by reactive sputtering using the oxygen deficient body as a target, and the precursor layer is oxidized to form the first metal. This is a process for forming an oxide layer. Since the oxygen deficient body is the same as described above, description thereof is omitted here.

  Examples of the sputtering method include DC (direct current) sputtering. Further, the sputtering method is preferably performed in an oxygen atmosphere. This is because oxidation of the precursor layer (formation of the first metal oxide layer) can be performed while forming the second metal oxide layer. The oxygen concentration is preferably diluted with a rare gas such as Ar. In particular, in the present disclosure, it is preferable to perform the precursor layer forming process and the metal oxide layer forming process continuously. For example, both processes can be performed continuously by adjusting the amount of oxygen introduced.

3. Infrared Reflective Film The infrared reflective film obtained by the method for producing an infrared reflective film of the present disclosure is the same as the content described in “A.

  In addition, this indication is not limited to the said embodiment. The above-described embodiment is an exemplification, and the technical idea described in the claims of the present disclosure has substantially the same configuration and exhibits the same function and effect in any case. It is included in the technical scope of the disclosure.

  Hereinafter, more specific description will be given using examples.

[Example 1]
A biaxially oriented transparent PET film (manufactured by Toyobo Co., Ltd., A4100, thickness 50 μm, Tg 67 ° C.) was placed on a Canon Anelpa sputtering apparatus SPC-350UHV so as to be formed on the smooth surface side of the PET film. The target was Ti, and evacuation was performed until the pressure in the chamber became 2.0 × 10 ⁻³ Pa or less, and 10 sccm of Ar and 5 sccm of O ₂ were introduced. Thereafter, the pressure in the chamber was adjusted to 0.4 Pa, and a direct current sputtering method was performed. At this time, the discharge current was 0.3 A, and the temperature of the PET film was room temperature. Thereby, a metal oxide part (thickness 30 nm, titanium oxide layer (1)) was formed on the PET film.

Next, the target was changed to Ag, Pd, and Cu, and the chamber was evacuated until the pressure in the chamber became 2.0 × 10 ⁻³ Pa or less, and 25 sccm of Ar was introduced as a discharge gas. Thereafter, the pressure in the chamber was adjusted to 0.4 Pa, and a direct current sputtering method was performed. At this time, the discharge current was 0.2 A, and the PET film temperature was room temperature. Thereby, a metal part (thickness 18 nm, Ag alloy layer) was formed on the metal oxide part.

Next, the target was oxygen-deficient titanium oxide, and the chamber was evacuated until the pressure in the chamber became 2.0 × 10 ⁻³ Pa or less, and 8 sccm of Ar was introduced. Thereafter, the pressure in the chamber was adjusted to 0.4 Pa, and a direct current sputtering method was performed. At this time, the discharge current was 0.3 A, and the PET film temperature was room temperature. Thereby, the precursor layer of the 1st metal oxide layer was formed into a film on the metal part.

Next, using the same target, the chamber was evacuated until the pressure in the chamber became 2.0 × 10 ⁻³ Pa or less, and 8 sccm of Ar and ₂ sccm of O ₂ were introduced. Thereafter, the pressure in the chamber was adjusted to 0.4 Pa, and a direct current sputtering method was performed. At this time, the discharge current was 0.3 A, and the PET film temperature was room temperature. Thereby, a second metal oxide layer (thickness 30 nm, titanium oxide layer (3)) was formed on the precursor layer. At the same time, the precursor layer was oxidized to obtain a first metal oxide layer (thickness 4 nm, titanium oxide layer (2)). In this way, an infrared reflective film was obtained.

[Example 2]
An infrared reflective film was obtained in the same manner as in Example 1 except that the thickness of the first metal oxide layer was changed to 8 nm.

[Example 3]
An infrared reflective film was obtained in the same manner as in Example 1 except that the thickness of the first metal oxide layer was changed to 10 nm.

[Comparative Example 1]
First, in the same manner as in Example 1, a metal oxide part (thickness 30 nm, titanium oxide (1)) and a metal part (thickness 18 nm, Ag alloy) were formed on a PET film. Next, the target was oxygen-deficient titanium oxide, and the chamber was evacuated until the pressure in the chamber became 2.0 × 10 ⁻³ Pa or less, and 8 sccm of Ar and ₂ sccm of O ₂ were introduced. Thereafter, the pressure in the chamber was adjusted to 0.4 Pa, and a direct current sputtering method was performed. At this time, the discharge current was 0.3 A, and the PET film temperature was room temperature. Thereby, a metal oxide layer (thickness 30 nm, titanium oxide layer (3)) was formed on the metal part. In this way, an infrared reflective film was obtained.

[Comparative Example 2]
First, in the same manner as in Example 1, a metal oxide part (thickness 30 nm, titanium oxide (1)) and a metal part (thickness 18 nm, Ag alloy) were formed on a PET film. Next, the target was oxygen-deficient titanium oxide, and the chamber was evacuated until the pressure in the chamber became 2.0 × 10 ⁻³ Pa or less, and 8 sccm of Ar was introduced. Thereafter, the pressure in the chamber was adjusted to 0.4 Pa, and a direct current sputtering method was performed. At this time, the discharge current was 0.3 A, and the PET film temperature was room temperature. Thereby, a metal oxide layer (thickness 30 nm, titanium oxide layer (2)) was formed on the metal part.

[Evaluation]
(Evaluation of visible light characteristics, heat insulation and heat insulation)
Using the infrared reflective films obtained in Examples 1 to 3 and Comparative Examples 1 and 2, the visible light characteristics (visible light transmittance), the heat shielding property (shielding coefficient), and the heat insulating property (heat transmissivity) were evaluated. All of these measurements were performed based on JIS A 5759: 2008. Specifically, assuming the case where construction was performed on the building window from the indoor side, the visible light transmittance and the shielding factor were measured from the glass side (outdoor side) by bonding the film to 3 mm thick soda glass. . On the other hand, the heat transmissivity was measured from the film side (indoor side) in order to reflect the indoor heating effect. The visible light transmittance and the shielding coefficient were measured with a spectrophotometer (trade name: UV-2600 / 2700, manufactured by Shimadzu Corporation). The reflectance of far-infrared rays (having a wavelength of 5 μm or more and 25 μm or less) necessary for calculating the heat transmissivity was measured with an infrared spectrophotometer (trade name: FTS7000, manufactured by DigiLab). The results are shown in Table 1.

(Salt water test)
The infrared reflective films obtained in Examples 1 to 3 and Comparative Examples 1 and 2 were immersed in 5% strength brine and placed at room temperature (23 ° C.) for 14 days. The case where there was no change in the appearance and the decrease in the visible light transmittance was 3% or less was rated as ◯, and the case where there was a change in the appearance or the decrease in the visible light transmittance was 3% or more was marked as x. The results are shown in Table 1.

  As shown in Table 1, in Examples 1 to 3, the results of the salt water test were good, and infrared reflective films capable of suppressing the occurrence of salt damage were obtained. On the other hand, the results of the salt water test were not good in Comparative Examples 1 and 2. The reason is that the metal oxide portion is a single-layer titanium oxide layer (titanium oxide layer (2) or titanium oxide layer (3)) and the intrusion of chloride ions could not be effectively suppressed. Guessed. In Comparative Example 1, the Ag alloy layer was oxidized by oxygen plasma, the surface became rough, and the titanium oxide layer (3) formed on the Ag alloy layer also became a sparse layer, so corrosion may have occurred. There is also. Moreover, in the comparative example 2, it is estimated that the titanium oxide layer (2) functions as a conductive layer and corrosion has occurred.

  Moreover, the visible light transmittances of Examples 1 to 3 were higher than those of Comparative Examples 1 and 2. Moreover, the shielding coefficient of Examples 1-3 was low compared with Comparative Examples 1 and 2, and the heat shielding property was high. Moreover, the heat | fever transmissivity of Examples 1-3 and Comparative Example 2 was low compared with the comparative example 1, and heat insulation was high. Also from these viewpoints, it was confirmed that the infrared reflective sheets obtained in Examples 1 to 3 have excellent characteristics.

DESCRIPTION OF SYMBOLS 1 ... Base material 2 ... Metal part 3 ... Metal oxide part 4 ... Infrared reflective part 10 ... Infrared reflective film 11 ... Adhesive layer 12 ... Release film 13 ... Glass member 20 ... Infrared reflective film with release film 30 ... Window glass

Claims (6)

An infrared reflective film having a base material and an infrared reflective part in this order,
The infrared reflecting portion has a metal portion and a metal oxide portion,
The said metal oxide part is an infrared reflective film which has a 1st metal oxide layer and the 2nd metal oxide layer containing the same metal element as a said 1st metal oxide layer in an order from the said base material side.   The infrared reflective film according to claim 1, wherein a thickness of the second metal oxide layer is larger than a thickness of the first metal oxide layer.   The infrared reflective film according to claim 1 or 2, wherein the first metal oxide layer has a thickness of 10 nm or less. Infrared reflective film according to any one of claims 1 to 3,
With the base material as a reference, an adhesive layer located on the opposite side of the infrared reflecting portion,
Based on the adhesive layer, a release film located on the opposite side of the substrate,
An infrared reflective film with a release film. Infrared reflective film according to any one of claims 1 to 3,
With the base material as a reference, an adhesive layer located on the opposite side of the infrared reflecting portion,
Based on the adhesive layer, a glass member located on the opposite side of the substrate,
Having a window glass. An infrared reflective film manufacturing method for manufacturing the infrared reflective film according to any one of claims 1 to 3,
A substrate preparation step of preparing the substrate;
An infrared reflecting portion forming step of forming the infrared reflecting portion on one surface side of the base material;
Have
The infrared reflecting portion forming step includes
A precursor layer forming process for forming a precursor layer of the first metal oxide layer by a sputtering method using an oxygen deficient body of a metal oxide as a target;
A metal oxide that forms the first metal oxide layer by oxidizing the precursor layer and forming the second metal oxide layer by reactive sputtering using the oxygen deficient body as a target in an oxygen atmosphere Layer formation processing;
A method for producing an infrared reflective film, comprising:

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