WO2018181220A1

WO2018181220A1 - Light-transmissive substrate for reflecting heat rays, and heat-ray-reflecting window

Info

Publication number: WO2018181220A1
Application number: PCT/JP2018/012217
Authority: WO
Inventors: 陽介中西; 恵梨上田; 広宣待永; 大森　裕
Original assignee: 日東電工株式会社
Priority date: 2017-03-31
Filing date: 2018-03-26
Publication date: 2018-10-04
Also published as: KR20240019407A

Abstract

Provided is a light-transmissive substrate for reflecting heat rays, the light-transmissive substrate having: a light-transmissive substrate; a hard coat layer disposed on one surface of the light-transmissive substrate; and a transparent electroconductive oxide layer containing a transparent electroconductive oxide, the transparent electroconductive oxide layer being disposed on the hard coat layer.

Description

Heat ray reflective translucent substrate, heat ray reflective window

The present invention relates to a heat ray reflective translucent substrate and a heat ray reflection window.

Conventionally, a heat ray reflective translucent substrate having a layer having a function of reflecting heat rays on a translucent substrate such as glass or resin is known.

As a heat ray reflective translucent base material, a part of visible light such as sunlight and near infrared rays are reflected, so that the near infrared rays are prevented from entering the room and the inside of the vehicle, and the heat shielding property is suppressed to suppress the temperature rise. What has been prepared has been studied. Further, in recent years, studies are also being conducted on heat ray reflective translucent substrates having reduced emissivity and heat insulation.

For example, Patent Document 1 discloses a transparent substrate, a transparent conductive layer and a film thickness of 10 nm on the transparent substrate for the purpose of providing a transparent substrate with a laminated film that has excellent durability in addition to high heat shielding and color rendering. A transparent substrate with a laminated film having a laminated film in which a super nitrogen-containing light absorbing layer is laminated is disclosed.

Japanese Unexamined Patent Publication No. 2016-79051

By the way, the heat ray reflective translucent base material is used as a translucent base material of a lighting part such as a window or affixed to a translucent base material of a lighting part such as a window because of its function. There are many opportunities to touch hands and objects. For this reason, even when a human hand or an object moves while causing friction in a state where pressure is applied to the surface of the heat ray reflective translucent base material, the transparent constituting the heat ray reflective translucent base material It has been demanded to prevent the functional layer such as the conductive layer from being peeled off or scratched to deteriorate the function or impair the appearance. That is, a heat ray reflective translucent base material excellent in scratch resistance has been demanded.

However, the scratch resistance of the transparent substrate with a laminated film disclosed in Patent Document 1 has not been sufficiently studied.

Therefore, in view of the above-described problems of the prior art, an object of one aspect of the present invention is to provide a heat ray reflective translucent substrate having excellent scratch resistance.

In order to solve the above problems, in one aspect of the present invention, a translucent substrate,
A hard coat layer disposed on one surface of the translucent substrate;
Provided is a heat ray reflective translucent substrate having a transparent conductive oxide layer containing a transparent conductive oxide disposed on the hard coat layer.

According to one aspect of the present invention, a heat ray reflective translucent substrate having excellent scratch resistance can be provided.

It is sectional drawing of the heat ray reflective translucent base material of the example of 1 structure which concerns on embodiment of this invention. It is sectional drawing of the heat ray reflective translucent base material of the other structural example which concerns on embodiment of this invention. It is sectional drawing of the heat ray reflective translucent base material of the other structural example which concerns on embodiment of this invention. It is sectional drawing of the heat ray reflective window of the one structural example which concerns on embodiment of this invention.

Hereinafter, an embodiment of the present disclosure (hereinafter referred to as “the present embodiment”) will be described in detail, but the present embodiment is not limited thereto.
[Heat ray reflective translucent substrate]
One structural example of the heat ray reflective translucent substrate of the present embodiment will be described below.

The heat ray reflective translucent substrate of the present embodiment includes a translucent substrate, a hard coat layer disposed on one surface of the translucent substrate, and a transparent conductive layer disposed on the hard coat layer. And a transparent conductive oxide layer containing an oxide.

The inventor of the present invention has intensively studied to reduce the emissivity and to make the heat ray reflective translucent substrate having heat insulating property a heat ray reflective translucent substrate excellent in scratch resistance.

As a result, firstly, it has been found that by having a transparent conductive oxide layer containing a transparent conductive oxide, a heat ray reflective translucent substrate having heat insulating properties can be obtained. This is presumably because far-infrared rays can be reflected using the carriers of the transparent conductive oxide contained in the transparent conductive oxide layer.

However, when only the transparent conductive oxide layer is disposed on the translucent base material, for example, when a hand or an object is moved against the transparent conductive oxide layer while causing friction in a pressed state. In addition, the transparent conductive oxide layer may be deformed, and scratches or peeling may occur in the transparent conductive oxide layer. If the transparent conductive oxide layer is scratched or peeled off, the function of the transparent conductive oxide layer may be deteriorated or the appearance may be impaired.

Therefore, by disposing a hard coat layer on the translucent substrate, even when the transparent conductive oxide layer is pressed and rubbed, the deformation of the transparent conductive oxide layer is reduced, and scratches, peeling, etc. The inventors have found that generation can be suppressed, that is, scratch resistance can be improved, and the present invention has been completed.

Here, the structural example of the heat ray reflective translucent base material of this embodiment is shown in FIG. FIG. 1 schematically shows a cross-sectional view of the heat ray reflective translucent substrate of the present embodiment on a plane parallel to the lamination direction of the translucent substrate, hard coat layer, and transparent conductive oxide layer. ing.

As shown in FIG. 1, the heat ray reflective translucent substrate 10 of the present embodiment has a hard coat layer 12 and a transparent disposed on the hard coat layer 12 on one surface of the translucent substrate 11. A structure in which the conductive oxide layer 13 is stacked can be provided. Each layer will be described below.

As the translucent substrate 11, various translucent substrates that can transmit visible light can be preferably used. As the translucent substrate 11, a substrate having a visible light transmittance of 10% or more can be used more preferably. In this specification, the visible light transmittance is measured according to JIS A5759-2008 (architectural window glass film).

As the translucent substrate 11, a glass plate, a translucent resin substrate, or the like can be preferably used. The heat ray reflective translucent base material of this embodiment can suppress a deformation | transformation of a transparent conductive oxide layer and can improve abrasion resistance by providing a hard-coat layer. And when a translucent base material is especially easy to deform | transform like a translucent resin base material, the effect can be exhibited especially. For this reason, as for the translucent base material of the heat ray reflective translucent base material of this embodiment, it is more preferable that it is a translucent resin base material.

As a material of the translucent resin base material, any material that can transmit visible light as described above can be preferably used. However, when forming each layer on the translucent base material 11, a heat treatment or the like is performed. Since it may be performed, a resin having heat resistance can be preferably used. As the resin material constituting the translucent resin base material, for example, one or more selected from polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyetheretherketone (PEEK), polycarbonate (PC) and the like are preferable. Can be used.

The heat ray reflective translucent base material of the present embodiment can be used by being fitted into a window frame or the like as a translucent base material of a lighting part such as a window. It can also be used by pasting together. For this reason, the translucent base material 11 can select the thickness and material according to a use etc. The thickness of the translucent substrate 11 can be, for example, 10 μm or more and 10 mm or less.

For example, when the heat ray reflective translucent substrate of the present embodiment is used as a translucent substrate of a daylighting unit such as a window, the thickness or material of the translucent substrate 11 is sufficient so as to have sufficient strength. Is preferably selected.

In addition, when the heat ray reflective translucent base material of the present embodiment is used by being bonded to a light transmissible base material of a lighting part such as a window, the productivity of the heat ray reflective substrate is increased and the light transmissivity of the window or the like is increased. It is preferable to select a thickness and a material so that the translucent substrate 11 is flexible so that it can be easily bonded to the substrate. When it is set as the translucent base material which has flexibility, a translucent resin base material is used suitably as a translucent base material. When a translucent resin substrate is used as the flexible translucent substrate, the thickness is preferably in the range of about 10 μm to 300 μm.

In addition, although the translucent base material 11 can also be comprised from one translucent base material, it can also be used, for example, combining two or more translucent base materials by bonding etc. When two or more translucent substrates are used in combination by bonding or the like, it is preferable that the total thickness satisfies, for example, a range of suitable thicknesses of the above-described translucent substrate.

The hard coat layer 12 supports the transparent conductive oxide layer 13 and can suppress deformation of the transparent conductive oxide layer 13 when pressed or the like.

The hard coat layer 12 can be formed using a resin, for example, and can be a resin hard coat layer. The material of the hard coat layer is not particularly limited. For example, one or more kinds of resins selected from acrylic resins, silicone resins, urethane resins and the like can be preferably used.

Also, by incorporating inorganic particles in the hard coat layer, an improvement in adhesion between the hard coat layer and the transparent conductive layer can be expected. The material of the inorganic particles is not particularly limited, but for example, one or more kinds of inorganic particles selected from silica, alumina, zirconia and the like can be preferably used.

The hard coat layer 12 can be formed by, for example, applying a resin on one surface of the translucent substrate 11 and curing the resin.

The thickness of the hard coat layer 12 is not particularly limited, and can be arbitrarily selected according to the material of the hard coat layer 12, the required visible light transmittance, the degree of scratch resistance, and the like. For example, the thickness of the hard coat layer 12 is preferably 0.5 μm or more and 10 μm or less, and more preferably 0.7 μm or more and 5 μm or less.

This is because, by setting the thickness of the hard coat layer 12 to 0.5 μm or more, a hard coat layer having sufficient strength can be obtained, and deformation of the transparent conductive oxide layer 13 can be particularly suppressed. It is. Moreover, it is because the internal stress which arises by shrinkage | contraction of a hard-coat layer can be suppressed because the thickness of the hard-coat layer 12 shall be 10 micrometers or less.

The transparent conductive oxide layer 13 is a layer containing a transparent conductive oxide, and may be a layer made of a transparent conductive oxide. According to the study of the inventors of the present invention, far infrared rays can be reflected by the carrier contained in the transparent conductive oxide. For this reason, the heat ray reflective translucent base material of this embodiment can be made into the heat ray reflective translucent base material excellent in heat insulation by providing a transparent conductive oxide layer.

The transparent conductive oxide contained in the transparent conductive oxide layer is not particularly limited, and various transparent conductive oxides can be used as long as they can reflect far infrared rays. However, as described above, since far infrared rays are reflected by the carrier, the transparent conductive oxide is doped with, for example, one or more selected from tin, titanium, tungsten, molybdenum, zinc, and hydrogen. Indium oxide, tin oxide doped with one or more selected from antimony, indium, tantalum, chlorine and fluorine, and one or more selected from indium, aluminum, tin, gallium, fluorine and boron It is preferable to contain at least one selected from doped zinc oxide.

The transparent conductive oxide is more preferably indium oxide doped with one or more selected from tin, titanium, tungsten, molybdenum, zinc, and hydrogen, and one or more selected from tin and zinc Is more preferably doped indium oxide.

The thickness of the transparent conductive oxide layer is not particularly limited, and can be arbitrarily selected according to required heat insulating properties. For example, the thickness of the transparent conductive oxide layer is preferably 30 nm or more and 500 nm or less, and more preferably 35 nm or more and 400 nm or less.

This is because by setting the thickness of the transparent conductive oxide layer to 30 nm or more, particularly far infrared rays can be reflected and the heat insulation performance can be improved. Moreover, it is because visible light transmittance can be maintained sufficiently high by setting the thickness of the transparent conductive oxide layer to 500 nm or less.

The film forming method of the transparent conductive oxide layer is not particularly limited, but a film forming method by any one or more dry processes selected from, for example, a sputtering method, a vacuum evaporation method, a CVD method, and an electron beam evaporation method is preferable. Can be used. In addition, it is preferable to increase the crystallinity by performing a heat treatment after the film formation.

The heat ray reflective translucent base material of the present embodiment is not limited to the translucent base material, hard coat layer, and transparent conductive oxide layer described so far, and may further have an arbitrary layer.

For example, undercoat layers such as an optical adjustment layer, a gas barrier layer, and an adhesion improving layer can be provided between the hard coat layer and the transparent conductive oxide layer. The optical adjustment layer can improve the color and transparency, the gas barrier layer can improve the crystallization speed of the transparent conductive oxide, and the adhesion improving layer can prevent delamination and resistance. It is possible to improve durability such as cracks.

The specific configuration of the underlayer is not particularly limited, and examples of the adhesion improving layer and the gas barrier layer include a layer containing alumina (Al ₂ O ₃ ). Examples of the optical adjustment layer include a layer containing zirconia (ZrO ₂ ) and a layer containing hollow particles.

For example, the heat ray reflective translucent substrate of the present embodiment is the same as the heat ray reflective translucent substrate 20 shown in FIG. The pressure-sensitive adhesive layer 21 can also be provided on the other surface 11b opposite to the one surface 11a on which the layer 13 is provided.

As described above, the heat ray reflective translucent substrate of the present embodiment can be used by being attached to a translucent substrate of a daylighting unit such as a window. Therefore, by providing the pressure-sensitive adhesive layer 21 as described above, it can be easily attached to a light-transmitting substrate of a daylighting unit such as a window.

The material of the pressure-sensitive adhesive layer is not particularly limited, but it is preferable to use a material having a high visible light transmittance. As a material for the pressure-sensitive adhesive layer, for example, an acrylic pressure-sensitive adhesive, a rubber-based pressure-sensitive adhesive, a silicone-based pressure-sensitive adhesive, or the like can be used. Among them, the acrylic pressure-sensitive adhesive mainly composed of an acrylic polymer is excellent in optical transparency, exhibits appropriate wettability, cohesion and adhesion, and is excellent in weather resistance, heat resistance, etc. It is suitable as a material.

The pressure-sensitive adhesive layer preferably has a high visible light transmittance and a low ultraviolet transmittance. By reducing the ultraviolet transmittance of the pressure-sensitive adhesive layer, it is possible to suppress deterioration of the translucent substrate, the hard coat layer, and the transparent conductive oxide layer caused by ultraviolet rays such as sunlight. From the viewpoint of reducing the ultraviolet transmittance of the pressure-sensitive adhesive layer, the pressure-sensitive adhesive layer can also contain an ultraviolet absorber. In addition, degradation of the transparent conductive oxide layer etc. resulting from the ultraviolet-ray from the outdoors can be suppressed also by using the translucent base material etc. which contain a ultraviolet absorber. The exposed surface of the pressure-sensitive adhesive layer is preferably covered with a release paper for the purpose of preventing contamination of the exposed surface until the heat ray reflective / translucent substrate is put to practical use. Thereby, the contamination by the contact with the exterior of the exposed surface of an adhesive layer can be prevented in the usual handling state.

In addition, when the heat ray reflective translucent base material of this embodiment is fitted into a window frame or the like and used as a translucent base material of a daylighting part such as a window, it is necessary to stick to another translucent base material. Therefore, it is preferable not to have an adhesive layer.

Moreover, the heat ray reflective translucent base material of this embodiment may further have a surface protective layer 31 on the transparent conductive oxide layer 13 like the heat ray reflective translucent base material 30 shown in FIG. it can. In addition, the heat ray reflective translucent base material 30 can have the hard-coat layer 12 and the translucent base material 11 under the transparent conductive oxide layer 13, as shown in FIG.

By providing the surface protective layer 31, it is possible to suppress the transparent conductive oxide layer 13 from directly touching a human hand or the like, so that the scratch resistance can be particularly improved.

The thickness of the surface protective layer is preferably 5 nm or more and 1 μm or less, and more preferably 5 nm or more and 500 nm or less. This is because by setting the thickness of the surface protective layer to 5 nm or more, the transparent conductive oxide layer 13 can be sufficiently protected and the scratch resistance can be particularly improved. Further, even if the thickness of the surface protective layer is made thicker than 1 μm, there is no significant difference in the effect. Rather, there is a possibility that the emissivity may be increased by far-infrared absorption, so that the thickness is preferably 1 μm or less.

The material of the surface protective layer 31 is preferably a material having high visible light transmittance and excellent mechanical strength and chemical strength. From the viewpoint of enhancing scratch prevention and chemical protection for the transparent conductive oxide layer, organic materials and inorganic materials are preferred. Examples of organic materials include fluorine, acrylic, urethane, ester, epoxy, silicone, and olefin actinic ray curable or thermosetting organic materials, and organic and inorganic components chemically bonded. The organic / inorganic hybrid material is preferably used.

In addition, examples of the inorganic material include transparent oxide containing at least one selected from silicon, aluminum, zinc, titanium, zirconium, and tin as a main component, diamond-like carbon, and the like.

When an organic material is used as the surface protective layer 31, a crosslinked structure is preferably introduced into the organic material. By forming the crosslinked structure, the mechanical strength and chemical strength of the surface protective layer are increased, and the protective function for the transparent conductive oxide layer and the like is increased. Among these, it is preferable that a crosslinked structure derived from an ester compound having an acidic group and a polymerizable functional group in the same molecule is introduced.

Examples of ester compounds having an acidic group and a polymerizable functional group in the same molecule include polyvalent acids such as phosphoric acid, sulfuric acid, oxalic acid, succinic acid, phthalic acid, fumaric acid, and maleic acid; And an ester of a compound having a polymerizable functional group such as a group, silanol group or epoxy group and a hydroxyl group in the molecule. The ester compound may be a polyester such as a diester or triester, but it is preferable that at least one acidic group of the polyvalent acid is not esterified.

When the surface protective layer 31 has a cross-linked structure derived from the above ester compound, the mechanical strength and chemical strength of the surface protective layer are increased, and between the surface protective layer 31 and the transparent conductive oxide layer 13. Adhesion is enhanced and the durability of the transparent conductive oxide layer is particularly enhanced. Among the ester compounds, an ester compound (phosphate ester compound) of phosphoric acid and an organic acid having a polymerizable functional group is excellent in adhesion to the transparent conductive oxide layer. In particular, the surface protective layer having a cross-linked structure derived from a phosphate ester compound is excellent in adhesion with the transparent conductive oxide layer.

From the viewpoint of increasing the mechanical strength and chemical strength of the surface protective layer 31, the ester compound preferably contains a (meth) acryloyl group as a polymerizable functional group. From the viewpoint of facilitating introduction of a crosslinked structure, the ester compound may have a plurality of polymerizable functional groups in the molecule. As the ester compound, for example, a phosphoric acid monoester compound or a phosphoric acid diester compound represented by the following formula (1) is preferably used. In addition, phosphoric acid monoester and phosphoric acid diester can also be used together.

In the formula, X represents a hydrogen atom or a methyl group, and (Y) represents an —OCO (CH ₂ ) ₅ — group. n is 0 or 1, and p is 1 or 2.

The content of the structure derived from the ester compound in the surface protective layer 31 is preferably 1 to 20% by mass, more preferably 1.5 to 17.5% by mass, and more preferably 2 to 15% by mass. More preferably, it is more preferably 2.5% by mass or more and 12.5% by mass or less. If the content of the ester compound-derived structure is excessively small, the effect of improving strength and adhesion may not be sufficiently obtained. On the other hand, if the content of the ester compound-derived structure is excessively large, the curing rate at the time of forming the surface protective layer is reduced and the hardness is lowered, or the slipping property of the surface protective layer surface is lowered and the scratch resistance is lowered. There is a case. Content of the structure derived from the ester compound in a surface protective layer can be made into a desired range by adjusting content of the said ester compound in a composition at the time of surface protective layer formation.

The method for forming the surface protective layer 31 is not particularly limited. The surface protective layer is prepared, for example, by dissolving an organic material, or a curable monomer or oligomer of the organic material, and the ester compound in a solvent, and applying the solution on the transparent conductive oxide layer 13. After drying, it is preferably formed by a method of curing by irradiating with ultraviolet rays or electron beams or applying thermal energy.

When an inorganic material is used as the material of the surface protective layer 31, the film can be formed by any one or more dry processes selected from, for example, a sputtering method, a vacuum evaporation method, a CVD method, and an electron beam evaporation method. .

In addition to the organic materials and inorganic materials described above, the surface protective layer 31 is made of a coupling agent such as a silane coupling agent or a titanium coupling agent, a leveling agent, an ultraviolet absorber, an antioxidant, or a heat stabilizer. Additives such as lubricants, plasticizers, anti-coloring agents, flame retardants and antistatic agents may be included.

Furthermore, the surface protective layer 31 may be composed of a plurality of layers having different materials, such as laminating an inorganic material and an organic material.

Although the characteristic requested | required of the heat ray reflective translucent base material of this embodiment is not specifically limited, It is preferable that the emissivity measured from the transparent conductive oxide layer side is 0.60 or less, and 0.50 or less It is more preferable that it is 0.40 or less.

It is because it can be set as the heat ray reflective translucent base material provided with sufficient heat insulation by making emissivity 0.60 or less, and it is preferable. The lower limit of the emissivity is not particularly limited, but is preferably smaller than 0 because it is preferably smaller.

As described above, the heat ray reflective translucent substrate of the present embodiment includes a translucent substrate, a hard coat layer, and a transparent conductive oxide layer. And the emissivity measured from the side of the transparent conductive oxide layer is the surface of the heat ray reflective translucent substrate, from the surface on the side close to the transparent conductive oxide layer in the three layers, It means the emissivity measured by irradiating infrared rays on the transparent conductive oxide layer.
[Heat ray reflection window]
Next, a configuration example of the heat ray reflective window of this embodiment will be described. As shown in FIG. 4, the heat ray reflective window 40 of the present embodiment includes a window translucent base material 41 and the heat ray reflective translucent member described above disposed on one surface 41 a of the window translucent base material 41. It can have an optical substrate 42.

The translucent base material 41 for windows is a translucent base material disposed in, for example, a daylighting portion of a window, and for example, a glass material or a translucent resin base material can be used.

And the heat ray reflective translucent base material 42 described above can be disposed on one surface of the translucent base material 41 for windows. The method for fixing the heat ray reflective translucent substrate 42 on the window translucent substrate 41 is not particularly limited. For example, the window light translucent substrate 41 of the heat ray reflective translucent substrate 42 is used. The pressure-sensitive adhesive layer described with reference to FIG. 2 can be disposed and fixed on the side facing the surface 42b.

When fixing the heat ray reflective translucent substrate 42 on the window translucent substrate 41, it is preferable that the transparent conductive oxide layer is positioned indoors or inside the vehicle. That is, the heat ray reflective translucent base material 42 is preferably fixed so that the transparent conductive oxide layer is located indoors or inside the vehicle, rather than the light translucent base material of the heat ray reflective translucent base material 42. .

Usually, the heat ray reflective translucent base material 42 is disposed on the indoor side of the translucent base material 41 for windows. Therefore, in the example shown in FIG. 4, the heat ray reflective translucent substrate 42 is transparent on the other surface 42 a side opposite to the one surface 42 b facing the translucent substrate 41 for windows. It is preferable to fix so that the conductive oxide layer is located.

This is because the transparent conductive oxide layer has a function of reflecting far-infrared rays, so that the far-infrared rays generated in the room or the like are radiated to the outside by being arranged in the direction of the room or the like. This is because it can be suppressed.

According to the heat ray reflective window of the present embodiment, the heat ray reflective translucent substrate described above is provided. For this reason, far infrared rays can be reflected and it can have a heat insulation function. Moreover, it can be set as the heat ray reflective window excellent in abrasion resistance.

Specific examples will be described below, but the present invention is not limited to these examples.
(1) Visible Light Transmittance Visible light transmittance was determined according to JIS A5759-2008 (architectural window glass film) using a spectrophotometer (product name “U-4100” manufactured by Hitachi High-Tech).
(2) Emissivity Emissivity is measured using a Fourier transform infrared spectroscopic (FT-IR) device (manufactured by Varian) equipped with a variable angle reflection accessory, and infrared rays in the wavelength range of 5 μm to 25 μm from the surface protective layer side. The regular reflectance when irradiated was measured and determined according to JIS R3106-2008 (Testing method for transmittance, reflectance, emissivity, and solar heat gain of plate glass).
(3) Scratch resistance A sample obtained by bonding a surface of a heat ray reflective translucent substrate cut to 15 cm × 5 cm to a 1.5 mm glass through a 25 μm thick adhesive layer. Used as. Using a 10-point pen tester, while applying a load of 1 kg with steel wool (Bonster # 0000), the range of 10 cm length of the exposed surface of the heat ray reflective translucent substrate fixed on the glass is 10 Rubbed back and forth.
Note that the exposed surface of the heat ray reflective translucent substrate is the surface protective layer surface in Examples 1 to 9, Example 11 to Example 13, Comparative Example 1 and Comparative Example 2, and Example 10 is transparent. It becomes the surface of the conductive oxide layer.

The sample after the test was visually evaluated for scratches and peeling of the transparent conductive oxide layer, and evaluated according to the following evaluation criteria.

◯: Scratch or peeling is not confirmed on the transparent conductive oxide layer △: Scratch or peeling can be confirmed partially on the transparent conductive oxide layer ×: Scratch or peeling on the transparent conductive oxide layer [Example 1]
The heat ray reflective translucent base material which has the structure shown in Table 1 was produced and evaluated.

As shown in Table 1, a heat ray reflective translucent substrate having a translucent substrate, a hard coat layer, a transparent conductive oxide layer, and a surface protective layer was produced.

A polyethylene terephthalate (PET) film having a thickness of 50 μm (trade name: T602E50, manufactured by Mitsubishi Plastics, Inc.) was used as the light-transmitting substrate.

The thickness shown in Table 1 is obtained by applying a resin solution on one surface of a light-transmitting substrate using spin coating, drying, and then curing by ultraviolet (UV) irradiation (300 mJ / cm ² ) in a nitrogen atmosphere. A hard coat layer was formed.

For the resin solution, an optical polymerization initiator (trade name: Irgacure 184, manufactured by BASF) is mixed with a UV curable urethane acrylate hard coat resin solution (trade name: ENS1068, manufactured by DIC Corporation) so that the resin equivalent is 3 wt%. Produced.

An ITO film (Indium Tin Oxide film, indium tin oxide film) was formed as a transparent conductive oxide layer on the hard coat layer. Specifically, the thickness shown in Table 1 is obtained by DC magnetron sputtering using a composite oxide target having a SnO ₂ content of 10 wt% with respect to the total amount of In ₂ O ₃ and SnO _2. Then, the film was formed by heat treatment at 150 ° C. for 30 minutes.

The sputtering gas was a mixed gas of argon and a small amount of oxygen, and film formation was performed under a process pressure of 0.2 Pa.

A surface protective layer was formed on the transparent conductive oxide layer. Specifically, an acrylic hard coat resin solution (manufactured by JSR Corporation, trade name: Opster Z7535) was mixed with an optical polymerization initiator (trade name: Irgacure 127, manufactured by BASF Corporation) so as to have a resin equivalent of 3 wt%. A mixed solution was prepared. Then, the mixed solution was coated on the transparent conductive oxide layer by spin coating so that the thickness after drying became the thickness shown in Table 1. After drying, UV irradiation (300 mJ / cm ² ) was performed in a nitrogen atmosphere to cure.

The above-mentioned evaluation was performed about the obtained heat ray reflective translucent base material. The results are shown in Table 1.
[Examples 2 and 3]
Except for the point that the transparent conductive oxide layer had the thickness shown in Table 1, a heat ray reflective translucent substrate was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.
[Example 4]
Except for the point that the surface protective layer had the thickness shown in Table 1, a heat ray reflective translucent substrate was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.
[Example 5]
A heat ray reflective translucent base material was produced and evaluated in the same manner as in Example 1 except that the surface protective layer was configured as follows. The results are shown in Table 1.

An oxide film (described as “SXO” in Table 1) containing Si and Zr was formed as a surface protective layer on the transparent conductive oxide layer. Specifically, using an alloy target having a Zr content of 30 wt% with respect to the total amount of metal Si and Zr, a film was formed by DC magnetron sputtering so as to have a thickness shown in Table 1.

As a sputtering gas, a mixed gas of argon / oxygen = 85/15 (volume ratio) was used, and film formation was performed under a process gas pressure of 0.2 Pa.

The evaluation results are shown in Table 1.
[Example 6]
Except for the point that the surface protective layer was formed to have the thickness shown in Table 1, a heat ray reflective translucent substrate was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.
[Example 7]
As a transparent conductive oxide layer, instead of the ITO film, an IZO film (Indium Zinc Oxide film, indium zinc oxide film) was formed in the same manner as in Example 1 except that the film was formed to a thickness of 400 nm. A reflective translucent substrate was prepared and evaluated. The results are shown in Table 1.

The IZO film was formed to a thickness of 400 nm by DC magnetron sputtering using a complex oxide target having a ZnO content of 10 wt% with respect to the total amount of In ₂ O ₃ and ZnO.

The evaluation results are shown in Table 1.
[Example 8]
A heat ray reflective translucent substrate was prepared and evaluated in the same manner as in Example 3 except that the hard coat layer was formed to have a thickness shown in Table 1. The results are shown in Table 1.
[Example 9]
Except for the point that the hard coat layer was formed to have the thickness shown in Table 1, a heat ray reflective translucent substrate was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.
[Example 10]
Except for the point that blue plate glass (manufactured by Matsunami Glass Co., Ltd.) having a thickness of 3 mm was used as the translucent substrate and the surface protective layer was not provided, the heat ray reflective translucent light was conducted in the same manner as in Example 1. A porous substrate was prepared and evaluated. The results are shown in Table 1.
[Example 11]
Except for the point that the transparent conductive oxide layer was formed to have the thickness shown in Table 1, a heat ray reflective translucent substrate was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.
[Example 12]
Except for the point that the surface protective layer was formed to have the thickness shown in Table 1, a heat ray reflective translucent substrate was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.
[Example 13]
A heat ray reflective translucent substrate was prepared and evaluated in the same manner as in Example 1 except that a base layer was formed between the hard coat layer and the transparent conductive oxide layer.

On the hard coat layer, an Al oxide film as an adhesion improving layer, that is, an alumina film (described as “Al ₂ O ₃ ” in Table 1) was formed as a base layer. Specifically, an underlayer was formed on the hard coat layer using a metal Al target so as to have the thickness shown in Table 1 by DC magnetron sputtering.

After forming the underlayer, a transparent conductive oxide layer and a surface protective layer were formed on the underlayer in the same manner as in Example 1 to obtain a heat ray reflective translucent substrate.

The evaluation results are shown in Table 1.
[Comparative Example 1]
Except that the hard coat layer was not provided, a heat ray reflective translucent substrate was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.
[Comparative Example 2]
Instead of the transparent conductive oxide layer, a heat ray reflective translucent substrate was prepared and evaluated in the same manner as in Example 1 except that a SiO ₂ film was formed. The results are shown in Table 1.

The SiO ₂ layer was formed to a thickness of 80 nm by a DC magnetron sputtering method using a metal Si target. A mixed gas of argon / oxygen = 85/15 (volume ratio) was used as the sputtering gas, and the process was performed under a process pressure of 0.2 Pa.

Evaluation results are shown in Table 1.

According to the results shown in Table 1, when Examples 1 to 13 and Comparative Example 1 are compared, a heat ray reflective translucent substrate having excellent scratch resistance can be obtained by providing a hard coat layer. I was able to confirm. This is considered to be because by providing the hard coat layer, it is possible to suppress deformation even when the transparent conductive oxide layer is pressed and the like, and it is possible to suppress the occurrence of scratches or peeling cracks due to friction.

Further, when Examples 1 to 13 are compared with Comparative Example 2 that does not have a transparent conductive oxide layer, the emissivity is significantly reduced in Examples 1 to 13 compared to Comparative Example 2. It was also confirmed that heat insulation can be exhibited by providing a transparent conductive oxide layer.

Although the heat ray reflective translucent base material and the heat ray reflection window have been described above in the embodiments and examples, the present invention is not limited to the above embodiments and examples. Various modifications and changes are possible within the scope of the gist of the present invention described in the claims.

This application is based on Japanese Patent Application No. 2017-073174 filed with the Japan Patent Office on March 31, 2017, and Japanese Patent Application No. 2018-049516 filed with the Japan Patent Office on March 16, 2018. The contents of Japanese Patent Application No. 2017-073174 and Japanese Patent Application No. 2018-049516 are incorporated herein by reference.

10, 20, 30, 42 Heat ray reflective translucent base material 11 Translucent base material 12 Hard coat layer 13 Transparent conductive oxide layer 21 Adhesive layer 31 Surface protective layer 40 Heat ray reflective window 41 Translucent group for window Material

Claims

A translucent substrate;
A hard coat layer disposed on one surface of the translucent substrate;
The heat ray reflective translucent base material which has a transparent conductive oxide layer containing the transparent conductive oxide arrange | positioned on the said hard-coat layer.
The transparent conductive oxide layer, as the transparent conductive oxide,
Indium oxide doped with one or more selected from tin, titanium, tungsten, molybdenum, zinc, and hydrogen;
Tin oxide doped with one or more selected from antimony, indium, tantalum, chlorine, and fluorine;
The heat ray reflective translucent substrate according to claim 1, comprising one or more selected from zinc oxide doped with one or more selected from indium, aluminum, tin, gallium, fluorine, and boron. .
The heat ray reflective translucent substrate according to claim 1 or 2, wherein the transparent conductive oxide layer has a thickness of 30 nm to 500 nm.
The heat ray reflective translucent substrate according to any one of claims 1 to 3, wherein the thickness of the hard coat layer is 0.5 µm or more and 10 µm or less.
The heat ray reflective translucent substrate according to any one of claims 1 to 4, further comprising a surface protective layer on the transparent conductive oxide layer.
The heat ray reflective translucent substrate according to claim 5, wherein the thickness of the surface protective layer is 5 nm or more and 1 µm or less.
The heat ray reflective translucent substrate according to any one of claims 1 to 6, further comprising an adhesive layer on a surface opposite to the one surface of the translucent substrate.
The heat ray reflective translucent substrate according to any one of claims 1 to 7, wherein an emissivity measured from the transparent conductive oxide layer side is 0.60 or less.
A translucent substrate for windows;
A heat ray reflective window having the heat ray reflective translucent substrate according to any one of claims 1 to 8, which is disposed on one surface of the window translucent substrate.