JP5953592B2 - Transparent heat ray reflective laminate - Google Patents

Transparent heat ray reflective laminate Download PDF

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JP5953592B2
JP5953592B2 JP2012147023A JP2012147023A JP5953592B2 JP 5953592 B2 JP5953592 B2 JP 5953592B2 JP 2012147023 A JP2012147023 A JP 2012147023A JP 2012147023 A JP2012147023 A JP 2012147023A JP 5953592 B2 JP5953592 B2 JP 5953592B2
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heat ray
metal layer
ray reflective
transparent heat
oxide
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JP2014008681A (en
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健 古田
健 古田
近藤 康雄
康雄 近藤
憲親 古市
憲親 古市
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Kitagawa Industries Co Ltd
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Description

本発明は、住宅、ビル、車両等の窓として使用されるか、あるいは窓に貼り付けて使用され、可視光線透過率が高く透明性に優れるとともに、日射の反射率が高く熱線を遮蔽する効果に優れる透明熱線反射積層体に関する。   INDUSTRIAL APPLICABILITY The present invention is used as a window of a house, a building, a vehicle, or the like, or is used by being attached to a window, and has a high visible light transmittance and excellent transparency, and also has a high solar reflectance and an effect of shielding heat rays. It is related with the transparent heat ray reflective laminated body which is excellent in.

従来、この種の透明熱線反射積層体としては、例えば、透明なガラス板や樹脂板を基材として、その基材上に薄膜状の酸化物層や金属層を積層したものや、透明な樹脂フィルムを基材として、その基材上に薄膜状の酸化物層や金属層を積層したものなどが知られている(例えば、特許文献1参照。)。   Conventionally, as this type of transparent heat ray reflective laminate, for example, a transparent glass plate or resin plate as a base material, a thin oxide layer or a metal layer laminated on the base material, or a transparent resin A film having a film as a base material and a thin oxide layer or a metal layer laminated on the base material is known (for example, see Patent Document 1).

これらのうち、ガラス板や樹脂板を基材とする積層体は、積層体そのものが建物や車両の窓材として利用され、樹脂フィルムを基材とする積層体は、積層体を窓ガラスに貼って利用される。このような積層体を利用すれば、可視光を十分に透過させつつ、熱線の透過を抑制することができ、熱線の透過先における温度上昇を抑制し、例えば、冷房効率の改善など、省エネルギーに寄与することができる。   Among these, the laminates based on glass plates and resin plates are used as window materials for buildings and vehicles, and the laminates based on resin films are laminated on window glass. Used. By using such a laminate, it is possible to suppress the transmission of heat rays while sufficiently transmitting visible light, suppress the temperature rise at the transmission destination of the heat rays, and save energy, for example, improve the cooling efficiency. Can contribute.

また、特許文献1には、金属層として銀やパラジウムを利用する例、酸化物層としてニオブの酸化物を利用する例について言及されている(例えば、特許文献1の請求項3,5参照。)。   Patent Document 1 mentions an example of using silver or palladium as a metal layer and an example of using niobium oxide as an oxide layer (see, for example, claims 3 and 5 of Patent Document 1). ).

国際公開第2008/065962号International Publication No. 2008/065962

しかしながら、上記のような従来の透明熱線反射積層体においては、例えばスパッタリングのような物理的気相成長法によって金属層や酸化物層を順次成膜する際に、金属層の酸化を招くことがあり、これが原因で熱線反射性能が低下することがあった。また、このような熱線反射性能の低下を補うために金属層を厚くすると透明性が低下してしまうという問題もあった。   However, in the conventional transparent heat ray reflective laminate as described above, when a metal layer or an oxide layer is sequentially formed by a physical vapor deposition method such as sputtering, the metal layer may be oxidized. There was a case where the heat ray reflection performance deteriorated due to this. Further, when the metal layer is thickened to compensate for such a decrease in the heat ray reflection performance, there is a problem that the transparency is lowered.

これらの諸問題に対し、本件発明者らは、高い透明性を確保したまま、高い熱線反射効果を得るべく鋭意検討を重ねた。その結果、金属層を挟む両側に特定の金属酸化物からなる酸化物層を形成するとともに、その金属酸化物中に含まれる酸素量を最適化することで、高い透明性と高い熱線反射効果を両立させて得られることを見いだした。   With respect to these problems, the present inventors have conducted intensive studies to obtain a high heat ray reflection effect while ensuring high transparency. As a result, by forming an oxide layer made of a specific metal oxide on both sides of the metal layer and optimizing the amount of oxygen contained in the metal oxide, high transparency and a high heat ray reflection effect are achieved. I found out that it is possible to achieve both.

本発明は、上記のような知見に基づいて完成されたものであり、その目的は、高い透明性と高い熱線反射効果を兼ね備えた透明熱線反射積層体を提供することにある。   This invention is completed based on the above knowledge, The objective is to provide the transparent heat ray reflective laminated body which has high transparency and the high heat ray reflective effect.

以下、本発明において採用した構成について説明する。
本発明の透明熱線反射積層体は、透明な基材と、銀又は銀合金を主成分として含む金属層と、組成式NbOx(ただし式中のxは1.6≦x≦1.7)で表されるニオブ酸化物を主成分として含む酸化物層とを有し、一層の前記金属層が二層の前記酸化物層によって挟まれてなる三層構造部分を少なくとも含む複数の層が、前記基材上に積層された構造とされていることを特徴とする。
Hereinafter, the configuration employed in the present invention will be described.
The transparent heat ray reflective laminate of the present invention comprises a transparent substrate, a metal layer containing silver or a silver alloy as a main component, and a composition formula NbO x (where x is 1.6 ≦ x ≦ 1.7). And a plurality of layers including at least a three-layer structure portion in which one metal layer is sandwiched between two oxide layers, The structure is laminated on the base material.

本発明の透明熱線反射積層体において、基材としては、板状のものやフィルム状のものを利用することができ、板状のものであれば、透明熱線反射積層体そのものを建物や車両の窓材として利用することができる。また、フィルム状のものであれば、透明熱線反射積層体を窓ガラスに貼って利用することができる。   In the transparent heat ray reflective laminate of the present invention, a plate-like or film-like material can be used as the substrate, and if it is plate-like, the transparent heat ray reflective laminate itself is used for buildings or vehicles. It can be used as a window material. Moreover, if it is a film form, a transparent heat ray reflective laminated body can be affixed on a window glass, and can be utilized.

また、基材を構成する材料としては、必要とする透明性を確保できれば、透明なガラスや透明な樹脂などを任意に採用できる。透明な樹脂の代表例としては、例えば、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレートなどのポリエステル樹脂を挙げることができる。また、透明性が確保されていれば、ポリエステル樹脂以外でもよく、例えば、ポリエチレン、ポリプロピレンなどのポリオレフィン樹脂、ナイロン6、ナイロン12などのポリアミド樹脂、ポリビニルアルコールやエチレン−ビニルアルコール共重合体などのビニルアルコール樹脂、ポリスチレン、トリアセチルセルロース、アクリル、ポリ塩化ビニル、ポリカーボネート、ポリイミド、ポリエーテルサルホン、環状ポリオレフィンなどを用いることができる。   Moreover, as a material which comprises a base material, if the required transparency can be ensured, transparent glass, transparent resin, etc. can be employ | adopted arbitrarily. Typical examples of the transparent resin include polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate. Moreover, as long as transparency is ensured, it may be other than polyester resin, for example, polyolefin resin such as polyethylene and polypropylene, polyamide resin such as nylon 6 and nylon 12, vinyl such as polyvinyl alcohol and ethylene-vinyl alcohol copolymer. Alcohol resin, polystyrene, triacetyl cellulose, acrylic, polyvinyl chloride, polycarbonate, polyimide, polyethersulfone, cyclic polyolefin, and the like can be used.

これら中でも、基材をフィルム状とする場合には、透明性が高く、機械的強度も高く、寸法安定性にも優れる点で、ポリエチレンテレフタレートフィルムを採用すると好ましい。フィルム状とする場合、基材の厚さは、用途によっても変わり得るが、実用上一般的と考えられる厚さとしては、25〜188μm程度とされていると好適である。   Among these, when making a base material into a film form, it is preferable to employ | adopt a polyethylene terephthalate film at the point which is highly transparent, has high mechanical strength, and is excellent also in dimensional stability. In the case of a film shape, the thickness of the substrate may vary depending on the use, but it is preferable that the thickness is considered to be about 25 to 188 μm as a practically considered thickness.

金属層は、可視光領域で吸収が少なく日射の反射率が高い銀又は銀を主成分とする銀合金が好ましい。ちなみに、銀は、熱に対して耐性が低く、特定の温度では銀が拡散して反射率が変化してしまうことがあり、また、直接銀が大気に触れると大気中の湿気を吸収して黄色化し反射率が損なわれることもあるなど、安定性に乏しい面を持っている。   The metal layer is preferably silver or a silver alloy containing silver as a main component, which has low absorption in the visible light region and high solar reflectance. By the way, silver has low resistance to heat, and silver may diffuse and reflectivity may change at a certain temperature. Also, when silver directly touches the atmosphere, it absorbs moisture in the atmosphere. It has a surface with poor stability, such as yellowing and loss of reflectance.

ただし、本発明の透明熱線反射積層体の場合は、金属層が二層の酸化物層によって挟まれており、金属層中に銀が含まれていても、その銀が大気に直接触れるわけではないため、反射率の変化を抑制できる。また、銀を主成分として、パラジウム、銅、ビスマス、金、白金等の金属元素を少なくとも一種以上含んだ銀合金で金属層を形成すれば、熱や湿気に対する安定性をより一層高めることができる。   However, in the case of the transparent heat ray reflective laminate of the present invention, the metal layer is sandwiched between two oxide layers, and even if the metal layer contains silver, the silver does not directly touch the atmosphere. Therefore, the change in reflectance can be suppressed. Further, if the metal layer is formed of a silver alloy containing silver as a main component and containing at least one metal element such as palladium, copper, bismuth, gold, platinum, etc., the stability to heat and moisture can be further enhanced. .

酸化物層は、組成式NbOx(ただし式中のxは1.6≦x≦1.7)で表されるニオブ酸化物を主成分として含む層である。上記組成式中の酸素量xは、例えば、物理的気相成長法によって酸化物層を成膜する際に、系内に導入される酸素の流量を増減することでコントロールすることができる。 The oxide layer is a layer containing, as a main component, a niobium oxide represented by a composition formula NbO x (where x is 1.6 ≦ x ≦ 1.7). The amount of oxygen x in the composition formula can be controlled by increasing or decreasing the flow rate of oxygen introduced into the system, for example, when an oxide layer is formed by physical vapor deposition.

この酸素量が1.6を下回る場合には、積層膜の可視光線透過率が70%より低下しやすく、透明性が損なわれることになる。一方、酸素量が1.7を上回る場合には、金属層が劣化しやすく、日射反射率が30%を下回り、熱線の遮蔽効果が低下する。   When this amount of oxygen is less than 1.6, the visible light transmittance of the laminated film tends to be lower than 70%, and the transparency is impaired. On the other hand, when the amount of oxygen exceeds 1.7, the metal layer easily deteriorates, the solar reflectance is less than 30%, and the heat ray shielding effect is lowered.

これらの金属層及び酸化物層は、一層の金属層が二層の酸化物層によって挟まれてなる三層構造とされる。ただし、このような三層構造部分を少なくとも含んでいれば、更に他の層が積層されて四層以上の層が基材上に積層されていてもよい。他の層の例としては、例えば、基材の片面又は両面に施されたハードコート層、層間の接着性を高めるための易接着層、透明熱線反射積層体を他の材に貼り付けるための粘着層、その他、透明熱線反射積層体の最外面に設けられる保護層などを挙げることができる。   These metal layers and oxide layers have a three-layer structure in which one metal layer is sandwiched between two oxide layers. However, as long as at least such a three-layer structure portion is included, other layers may be laminated and four or more layers may be laminated on the substrate. Examples of other layers include, for example, a hard coat layer applied to one or both sides of a base material, an easy-adhesion layer for enhancing adhesion between layers, and a transparent heat ray reflective laminate for attaching to other materials. Examples thereof include an adhesive layer and other protective layers provided on the outermost surface of the transparent heat ray reflective laminate.

以上のように構成された透明熱線反射積層体によれば、上述のような金属層及び酸化物層を備え、特に、酸化物層は、組成式NbOx(ただし式中のxは1.6≦x≦1.7)で表されるニオブ酸化物を主成分として含む層とされている。このような金属層及び酸化物層を形成すれば、発明者らが実験的に確認したところ、成膜時に金属層の酸化が発生するのを効果的に抑制することができる。 According to the transparent heat ray reflective laminate configured as described above, the metal layer and the oxide layer as described above are provided. In particular, the oxide layer has a composition formula NbO x (wherein x is 1.6). ≦ x ≦ 1.7) is a layer containing niobium oxide as a main component. When such a metal layer and an oxide layer are formed, the inventors have experimentally confirmed that oxidation of the metal layer can be effectively suppressed during film formation.

そのため、このような構成を採用すれば、透明性が十分に高くなる程度まで金属層の膜厚を薄くしても、金属層による熱線反射効果を十分に高くすることができるようになり、高い透明性と高い熱線反射効果を兼ね備えた透明熱線反射積層体とすることができる。   Therefore, if such a configuration is adopted, even if the thickness of the metal layer is reduced to such an extent that the transparency is sufficiently high, the heat ray reflection effect by the metal layer can be sufficiently increased, which is high. It can be set as the transparent heat ray reflective laminated body which has transparency and a high heat ray reflective effect.

ところで、本発明の透明熱線反射積層体において、どの程度まで透明性を高めるかは用途によっても変わり得るが、例えば、十分に高い透明性が要求される自動車のフロントガラスなどは、道路運送車両法により可視光線透過率が70%以上と定められているので、自動車用ガラスとして利用する場合、あるいはそれに準じた透明性が要求される用途である場合には、可視光線透過率が70%以上とされていると好ましい。   By the way, in the transparent heat ray reflective laminate of the present invention, to what extent the transparency is increased may vary depending on the application. For example, a windshield of an automobile that requires sufficiently high transparency is a road transport vehicle method. The visible light transmittance is determined to be 70% or more by the above, so that the visible light transmittance is 70% or more when used as glass for automobiles, or when it is an application requiring transparency corresponding thereto. Preferably.

また、本発明の透明熱線反射積層体は、日射反射率についても任意に設定し得るが、目安としては、例えば、日射反射率が30%以上のフィルム状透明熱線反射積層体であれば、透明なガラスに貼り付けることで、JIS A 5759(建築ガラス用フィルム)において規定される熱線遮蔽係数を0.6以下にまで低下させることができるので、建物の窓に貼り付ける熱線反射フィルムとして有用なものとなる。なお、ここでいう熱線遮蔽係数とは、3mmの透明板ガラスの透過、及び再放射による室内流入熱量を1.00として、これに対する比で太陽光線の流入熱量を表す数値であり、遮蔽係数の数値が小さくなるほど日射熱をよく遮ることを意味する。   In addition, the transparent heat ray reflective laminate of the present invention can be arbitrarily set with respect to solar reflectance, but as a guideline, for example, if it is a film-like transparent heat ray reflective laminate having a solar reflectance of 30% or more, it is transparent. By sticking to a glass, the heat ray shielding coefficient defined in JIS A 5759 (architectural glass film) can be reduced to 0.6 or less, which is useful as a heat ray reflective film to be attached to a building window. It will be a thing. The heat ray shielding coefficient referred to here is a numerical value representing the amount of inflowing heat of solar rays in a ratio with respect to the amount of heat inflowing into the room due to the transmission and re-radiation of 3 mm transparent plate glass, and the numerical value of the shielding coefficient. The smaller the value, the better the solar heat is blocked.

本発明の実施形態として例示した透明熱線反射積層体の断面図。Sectional drawing of the transparent heat ray reflective laminated body illustrated as embodiment of this invention.

次に、本発明の実施形態について一例を挙げて説明する。
[透明熱線反射積層体の構造例]
図1に例示する透明熱線反射積層体1は、基材2と、酸化物層3と、金属層4と、酸化物層5とを、この順序で積層した構造とされている。
Next, an embodiment of the present invention will be described with an example.
[Structural example of transparent heat ray reflective laminate]
The transparent heat ray reflective laminate 1 illustrated in FIG. 1 has a structure in which a base material 2, an oxide layer 3, a metal layer 4, and an oxide layer 5 are laminated in this order.

本実施形態において、基材2は、厚さ50μmのPETフィルムとされている。
また、酸化物層3,5は、スパッタリングによって形成された薄膜で、組成式NbOx(ただし式中のxは1.6≦x≦1.7)で表されるニオブ酸化物を主成分とする層とされている。このニオブ酸化物中に含まれる酸素量xは、スパッタリングによる成膜の際に、系内に導入される酸素の流量を増減することでコントロールすることができる。なお、具体的な成膜の例と、その酸素量の測定例については後述する。なお、本実施形態において、酸化物層3,5の膜厚は、30〜41nm程度とされている。
In the present embodiment, the substrate 2 is a PET film having a thickness of 50 μm.
The oxide layers 3 and 5 are thin films formed by sputtering, and are mainly composed of niobium oxide represented by the composition formula NbO x (where x is 1.6 ≦ x ≦ 1.7). It is supposed to be a layer. The amount of oxygen x contained in the niobium oxide can be controlled by increasing or decreasing the flow rate of oxygen introduced into the system during film formation by sputtering. A specific example of film formation and an example of measuring the amount of oxygen will be described later. In the present embodiment, the oxide layers 3 and 5 have a thickness of about 30 to 41 nm.

金属層4も、スパッタリングによって形成された薄膜で、この金属層4は、銀パラジウム合金を主成分とする層とされている。なお、本実施形態において、金属層4の膜厚は、16〜21nm程度とされている。酸化物層3,5及び金属層4の膜厚は、目標とする可視光線透過率及び日射反射率に応じて適宜調節される。   The metal layer 4 is also a thin film formed by sputtering, and the metal layer 4 is a layer mainly composed of a silver palladium alloy. In the present embodiment, the thickness of the metal layer 4 is about 16 to 21 nm. The film thicknesses of the oxide layers 3 and 5 and the metal layer 4 are appropriately adjusted according to the target visible light transmittance and solar reflectance.

[透明熱線反射積層体の製造例]
次に、透明熱線反射積層体の製造例について説明する。
本実施形態において、酸化物層3,5及び金属層4の成膜には、Roll to Roll方式のマグネトロンスパッタリング装置を用いた。
[Production example of transparent heat ray reflective laminate]
Next, a production example of the transparent heat ray reflective laminate will be described.
In the present embodiment, a Roll to Roll system magnetron sputtering apparatus was used for forming the oxide layers 3 and 5 and the metal layer 4.

具体的には、スパッタリング設備のチャンバー内にフィルム状の基材2を取り付け、チャンバー内に複数設置されているカソードのうち、その一つにニオブ酸化物ターゲットを配置し、その隣のカソードに銀パラジウム合金ターゲットを配置し、更にその隣のカソードにニオブ酸化物ターゲットを配置した。   Specifically, a film-like substrate 2 is attached in a chamber of a sputtering facility, a niobium oxide target is placed on one of a plurality of cathodes installed in the chamber, and silver is placed on the adjacent cathode. A palladium alloy target was placed, and a niobium oxide target was placed on the cathode next to it.

そして、チャンバー内を真空排気し、チャンバー内の圧力を1×10-3Pa〜1×10-5Pa程度とした。次に、ニオブ酸化物ターゲットを設置したカソードにはアルゴン(Ar)と酸素(O2)との混合ガスを導入し、銀パラジウム合金ターゲットを配置したカソードにはアルゴン(Ar)ガスを導入した。このとき、それぞれのカソードの圧力を0.2〜0.8Paに調整した。また、ニオブ酸化物ターゲットを設置したカソードのアルゴンに対する酸素の割合(アルゴン流量に対する酸素流量の比率)は2〜6%とした。 And the inside of a chamber was evacuated and the pressure in a chamber was made into about 1 * 10 < -3 > Pa-1 * 10 < -5 > Pa. Next, a mixed gas of argon (Ar) and oxygen (O 2 ) was introduced into the cathode on which the niobium oxide target was placed, and argon (Ar) gas was introduced into the cathode on which the silver palladium alloy target was placed. At this time, the pressure of each cathode was adjusted to 0.2 to 0.8 Pa. In addition, the ratio of oxygen to argon (ratio of oxygen flow rate to argon flow rate) in the cathode on which the niobium oxide target was installed was 2 to 6%.

次に、フィルム状の基材2を任意の速度で搬送しながら、それぞれのカソードに接続した電源(直流パルス電源RPG−100:日本MKS社製)にてカソードに電力を供給しスパッタリング成膜を行った。   Next, while transporting the film-like substrate 2 at an arbitrary speed, sputtering is performed by supplying power to the cathode with a power source (DC pulse power supply RPG-100: manufactured by MKS Japan) connected to each cathode. went.

このとき各カソードに投入する電力は所定の膜厚になるように調整して成膜を実施した。これにより、ニオブ酸化物からなる酸化物層3、銀パラジウム合金からなる金属層4、ニオブ酸化物からなる酸化物層5が積層され、基材2上には三層構造の積層膜が形成された。   At this time, the power applied to each cathode was adjusted so as to have a predetermined film thickness, and the film was formed. As a result, the oxide layer 3 made of niobium oxide, the metal layer 4 made of silver palladium alloy, and the oxide layer 5 made of niobium oxide are laminated, and a laminated film having a three-layer structure is formed on the substrate 2. It was.

なお、以上説明した製法においては、基材2の搬送を一回実施する中で、酸化物層3,5及び金属層4の三層を形成していたが、基材2を一回搬送するたびに一層分ずつの成膜を行い、計3回の搬送で三層分の成膜を行ってもよい。   In addition, in the manufacturing method demonstrated above, in carrying out conveyance of the base material 2 once, three layers of the oxide layers 3 and 5 and the metal layer 4 were formed, However, The base material 2 is conveyed once. Each time, one layer of film formation may be performed, and three layers of film formation may be performed by a total of three conveyances.

[性能測定]
上述のような製法で、酸素流量を変更しながら、いくつかの透明熱線反射積層体1を試作し、その性能を以下のような方法で測定した。
[Performance measurement]
Several transparent heat ray reflective laminates 1 were manufactured by changing the oxygen flow rate by the manufacturing method as described above, and the performance was measured by the following method.

(1)可視光線透過率
可視光線透過率については、JIS A 5759 6.3項に準拠して評価した。評価設備としては、分光光度計(U4100、日立ハイテク社製)を利用した。
(1) Visible light transmittance The visible light transmittance was evaluated in accordance with JIS A 5759 6.3. As the evaluation equipment, a spectrophotometer (U4100, manufactured by Hitachi High-Tech) was used.

(2)日射反射率
日射反射率については、JIS A 5759 6.4.5項に準拠して評価した。評価設備として分光光度計(U4100、日立ハイテク社製))を利用した。
(2) Solar reflectance The solar reflectance was evaluated according to JIS A 5759 6.4.5. A spectrophotometer (U4100, manufactured by Hitachi High-Tech) was used as an evaluation facility.

(3)膜厚
酸化物層3,5及び金属層4それぞれを複数の膜厚で基材2上へ形成し、段差計(DEKTAKIIA、SLOAN社製)を用いて膜厚の計測を行った。これらの膜厚を測定したサンプルを蛍光X線分析装置(ZSX−100e、リガク社製)の検量線標準サンプルとして登録し、未知試料の膜厚を蛍光X線の検量線を用いた定量分析により測定した。
(3) Film thickness Each of the oxide layers 3 and 5 and the metal layer 4 was formed on the substrate 2 with a plurality of film thicknesses, and the film thickness was measured using a step gauge (DEKTAKIIA, manufactured by SLOAN). Samples for which these film thicknesses were measured were registered as calibration curve standard samples for a fluorescent X-ray analyzer (ZSX-100e, manufactured by Rigaku Corporation), and the film thickness of an unknown sample was determined by quantitative analysis using a fluorescent X-ray calibration curve. It was measured.

(4)酸素量x
測定装置としてX線光電子分光分析(ESCA5400、ULVAC−PHl社製)を用い、同装置に附属のArイオン銃でサンプルの表面をエッチングし、表面の自然酸化層を取り除いた(エッチング条件:加速電圧3kV、エミッション電流25mA、圧力10mPa、エッチング面積30mm×30mm、エッチング時間5分)。
(4) Oxygen amount x
X-ray photoelectron spectroscopic analysis (ESCA5400, manufactured by ULVAC-PHI) was used as a measuring device, the surface of the sample was etched with an Ar ion gun attached to the same device, and the natural oxide layer on the surface was removed (etching condition: acceleration voltage) 3 kV, emission current 25 mA, pressure 10 mPa, etching area 30 mm × 30 mm, etching time 5 minutes).

その後、X線源としてMgアノード(出力300W、管電圧14kV)を用い、直径0.8mmの測定範囲で、Nb:3d、O:1sの結合エネルギー(Binding Energy)に相当するピークが現れる範囲で測定を実施した。得られた測定結果は、ESCA装置に附属のソフトウェア(MultiPak、ULVAC−PHl社製)にて解析を行った。このとき、各ピークに対し、Shirley background除去を行い、ピーク面積に各元素の感度係数補正を行い、原子数比を求める。得られた原子数比について、Nb原子数を1とし、O原子数を計算した。1サンプルにつき3点測定し、平均値を酸素量xとして採用した。   After that, using an Mg anode (output 300 W, tube voltage 14 kV) as an X-ray source, a peak corresponding to Nb: 3d, O: 1s binding energy (Binding Energy) appears in a measurement range with a diameter of 0.8 mm. Measurements were performed. The obtained measurement results were analyzed by software attached to the ESCA apparatus (MultiPak, manufactured by ULVAC-PHl). At this time, Shirley background removal is performed on each peak, sensitivity coefficient correction of each element is performed on the peak area, and the atomic ratio is obtained. With respect to the obtained atomic ratio, the number of O atoms was calculated by setting the number of Nb atoms to 1. Three points were measured per sample, and the average value was adopted as the oxygen amount x.

(5)表面抵抗値
JIS K 7194に準拠して評価した。評価設備としては抵抗率計(ロレスタEP、三菱化学社製)を用いた。
(5) Surface resistance value It evaluated based on JISK7194. As an evaluation facility, a resistivity meter (Loresta EP, manufactured by Mitsubishi Chemical Corporation) was used.

(6)体積抵抗率
以下の数式により、体積抵抗率を算出した。
体積抵抗率(Ω・cm)=表面抵抗値(Ω/□)×膜厚(nm)×10,000,000(単位換算)
各試料の測定結果を表1に示す。
(6) Volume resistivity The volume resistivity was calculated by the following formula.
Volume resistivity (Ω · cm) = Surface resistance (Ω / □) x film thickness (nm) x 10,000,000 (unit conversion)
Table 1 shows the measurement results of each sample.

Figure 0005953592
Figure 0005953592

以上の測定結果から、酸化物層3,5を形成するニオブ酸化物NbOxの酸素量xを、1.6≦x≦1.7の範囲内に調節することにより、可視光線透過率が70%以上、且つ、日射反射率が30%以上の積層体を得られることがわかる(表1中の試料No.3〜9参照。)。 From the above measurement results, the visible light transmittance is 70 by adjusting the oxygen amount x of the niobium oxide NbO x forming the oxide layers 3 and 5 within the range of 1.6 ≦ x ≦ 1.7. It can be seen that a laminate having a solar reflectance of 30% or more can be obtained (see Sample Nos. 3-9 in Table 1).

一方、ニオブ酸化物NbOxの酸素量xが1.6を下回る場合(表1中の試料No.1,2参照。)、日射反射率は30%を上回るものの、可視光透過率が70%を下回り、透明性がやや劣る結果となる。また、ニオブ酸化物NbOxの酸素量xが1.7を上回る場合(表1中の試料No.10参照。)、日射反射率が30%を下回るとともに、可視光透過率も70%を下回り、熱線遮蔽効果・透明性ともにやや劣る結果となることがわかる。この領域では、酸素量xが増加するほど日射反射率は低下する傾向がある。これは、金属層4に含まれるAgが成膜時の酸素ダメージを受けるため、その特性が低下し、反射率が低下するからではないかと考えられる。酸素量xと体積抵抗率の関係を見ても、酸素量xが大きくなるとAgの体積抵抗が上昇する傾向があるので、この点からも金属層4(Ag)の特性低下(酸化)が起こっているものと推察できる。 On the other hand, when the oxygen content x of the niobium oxide NbO x is less than 1.6 (see Sample Nos. 1 and 2 in Table 1), the solar reflectance is higher than 30%, but the visible light transmittance is 70%. The result is slightly inferior in transparency. Further, when the oxygen amount x of the niobium oxide NbO x exceeds 1.7 (see sample No. 10 in Table 1), the solar reflectance is less than 30% and the visible light transmittance is also less than 70%. It can be seen that the heat ray shielding effect and transparency are slightly inferior. In this region, the solar reflectance tends to decrease as the oxygen amount x increases. This is presumably because Ag contained in the metal layer 4 is subjected to oxygen damage during film formation, so that its characteristics are lowered and the reflectance is lowered. Even if the relationship between the oxygen amount x and the volume resistivity is seen, there is a tendency that the volume resistivity of Ag increases as the oxygen amount x increases. From this point, the characteristics of the metal layer 4 (Ag) deteriorate (oxidation) Can be inferred.

[その他の実施形態]
以上、本発明の実施形態について説明したが、本発明は上記の具体的な一実施形態に限定されず、この他にも種々の形態で実施することができる。
[Other Embodiments]
As mentioned above, although embodiment of this invention was described, this invention is not limited to said specific one Embodiment, In addition, it can implement with a various form.

例えば、上記実施形態では、基材2としてフィルム材を例示したが、ガラス板のような板状体を基材として採用してもよい。また、基材2を構成する材料については、必要とする透明性を確保できれば、透明なガラスや透明な樹脂などを任意に採用できる。透明な樹脂としては、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレートなどのポリエステル樹脂を利用することができる。また、透明性が確保されていれば、ポリエステル樹脂以外でもよく、例えば、ポリエチレン、ポリプロピレンなどのポリオレフィン樹脂、ナイロン6、ナイロン12などのポリアミド樹脂、ポリビニルアルコールやエチレン−ビニルアルコール共重合体などのビニルアルコール樹脂、ポリスチレン、トリアセチルセルロース、アクリル、ポリ塩化ビニル、ポリカーボネート、ポリイミド、ポリエーテルサルホン、環状ポリオレフィンなどを利用することができる。   For example, in the said embodiment, although the film material was illustrated as the base material 2, you may employ | adopt a plate-like body like a glass plate as a base material. Moreover, about the material which comprises the base material 2, if the required transparency is ensured, transparent glass, transparent resin, etc. can be employ | adopted arbitrarily. As the transparent resin, polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate can be used. Moreover, as long as transparency is ensured, it may be other than polyester resin, for example, polyolefin resin such as polyethylene and polypropylene, polyamide resin such as nylon 6 and nylon 12, vinyl such as polyvinyl alcohol and ethylene-vinyl alcohol copolymer. Alcohol resin, polystyrene, triacetyl cellulose, acrylic, polyvinyl chloride, polycarbonate, polyimide, polyethersulfone, cyclic polyolefin, and the like can be used.

また、上記実施形態では、銀パラジウム合金を主成分とする金属層4を例示したが、銀を主成分とする金属層、あるいは、他の銀合金を主成分とする金属層を設けてもよく、例えば、銅、ビスマス、金、白金等の金属元素を少なくとも一種以上含んだ銀合金を利用して金属層を形成してもよい。   Moreover, in the said embodiment, although the metal layer 4 which has a silver palladium alloy as a main component was illustrated, the metal layer which has silver as a main component, or the metal layer which has another silver alloy as a main component may be provided. For example, the metal layer may be formed using a silver alloy containing at least one or more metal elements such as copper, bismuth, gold, and platinum.

また、上記実施形態では、酸化物層3、金属層4、及び酸化物層5の三層を基材2の上に積層する例を示したが、これら各層の機能を阻害しない限り、これら以外の層が更に積層されていてもよい。例えば、基材2の表裏のうち、酸化物層3とは反対側となる面に粘着層を設けてもよい。あるいは、酸化物層5を保護するための保護膜を積層してもよいし、層間の接着性を高めるための易接着層を層間に設けてあってもよい。   Moreover, in the said embodiment, although the example which laminates | stacks the oxide layer 3, the metal layer 4, and the oxide layer 5 on the base material 2 was shown, as long as the function of these each layer is not inhibited, other than these These layers may be further laminated. For example, an adhesive layer may be provided on the surface opposite to the oxide layer 3 of the front and back surfaces of the substrate 2. Or the protective film for protecting the oxide layer 5 may be laminated | stacked, and the easily bonding layer for improving the adhesiveness of an interlayer may be provided in the interlayer.

1・・・透明熱線反射積層体、2・・・基材、3,5・・・酸化物層、4・・・金属層。   DESCRIPTION OF SYMBOLS 1 ... Transparent heat ray reflective laminated body, 2 ... Base material, 3, 5 ... Oxide layer, 4 ... Metal layer.

Claims (3)

透明な基材と、
銀又は銀合金を主成分として含む金属層と、
組成式NbOx(ただし式中のxは1.6≦x≦1.7)で表されるニオブ酸化物を主
成分として含む酸化物層と
を有し、
一層の前記金属層が二層の前記酸化物層によって挟まれてなる三層構造部分を少なくとも含む複数の層が、前記基材上に積層された構造とされ
可視光線透過率が70%以上とされている
ことを特徴とする透明熱線反射積層体。
A transparent substrate,
A metal layer containing silver or a silver alloy as a main component;
An oxide layer containing as a main component a niobium oxide represented by a composition formula NbO x (where x is 1.6 ≦ x ≦ 1.7),
A plurality of layers including at least a three-layer structure part in which one metal layer is sandwiched between two oxide layers are stacked on the base material ,
A transparent heat ray reflective laminate having a visible light transmittance of 70% or more .
日射反射率が30%以上とされている
ことを特徴とする請求項1に記載の透明熱線反射積層体。
The solar radiation reflectance is 30% or more. The transparent heat ray reflective laminate according to claim 1, wherein the solar radiation reflectance is 30% or more.
前記金属層は、銀パラジウム合金を主成分として含む
ことを特徴とする請求項1又は請求項2に記載の透明熱線反射積層体。
The metal layer, a transparent heat ray reflective laminate according to claim 1 or claim 2, characterized in that it comprises a silver-palladium alloy as the main component.
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