JPWO2011024740A1 - Light reflector comprising heat-resistant silver alloy light reflector - Google Patents
Light reflector comprising heat-resistant silver alloy light reflector Download PDFInfo
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/08—Mirrors
- G02B5/0816—Multilayer mirrors, i.e. having two or more reflecting layers
- G02B5/085—Multilayer mirrors, i.e. having two or more reflecting layers at least one of the reflecting layers comprising metal
- G02B5/0858—Multilayer mirrors, i.e. having two or more reflecting layers at least one of the reflecting layers comprising metal the reflecting layers comprising a single metallic layer with one or more dielectric layers
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/08—Mirrors
- G02B5/0808—Mirrors having a single reflecting layer
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/208—Filters for use with infrared or ultraviolet radiation, e.g. for separating visible light from infrared and/or ultraviolet radiation
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- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Catalysts (AREA)
- Laminated Bodies (AREA)
- Optical Elements Other Than Lenses (AREA)
- Optical Record Carriers And Manufacture Thereof (AREA)
Abstract
Ａｇ膜利用の場合に匹敵する光学特性を有し、かつ、光触媒材料として代表的なアナターゼＴｉＯ２の形成に必要な熱処理を経ても光学特性の劣化が少ない、耐熱性銀合金光反射材を含む光反射体を提供する。Ｓｂを１〜７ｗｔ％含有し、残部がＡｇおよび不可避的不純物からなる耐熱性Ａｇ合金光反射材を含む光反射層と、ＩＴＯ、ＳｉＯ２、ＳｎＯ２、Ｔａ２Ｏ５、Ｎｂ２Ｏ５、Ａｌ２Ｏ３から選択される金属酸化物を主成分とする付加層とを具備することを特徴とする赤外光等の光反射体。Light containing a heat-resistant silver alloy light reflecting material that has optical characteristics comparable to the case of using an Ag film and has little deterioration in optical characteristics even after a heat treatment necessary for forming a typical anatase TiO2 as a photocatalytic material Provide a reflector. A light-reflecting layer containing a heat-resistant Ag alloy light-reflecting material containing 1 to 7 wt% of Sb, the balance being Ag and inevitable impurities, and a metal oxide selected from ITO, SiO2, SnO2, Ta2O5, Nb2O5, and Al2O3 A light reflector such as infrared light, characterized by comprising an additional layer containing as a main component.
Description
本発明は、ガラスなどの基材上に膜として形成され得る、耐熱性銀合金光反射材を含む光反射層と、特定の金属酸化物を主成分とする付加層とを含む耐熱性光反射体、及び、該耐熱性光反射体等を透光性基材上に積層した日射熱反射シートに関する。 The present invention relates to a heat-resistant light reflection comprising a light-reflective layer containing a heat-resistant silver alloy light-reflecting material and an additional layer mainly composed of a specific metal oxide, which can be formed as a film on a substrate such as glass. The present invention relates to a solar heat reflective sheet in which a body, the heat-resistant light reflector and the like are laminated on a light-transmitting substrate.
銀（Ａｇ）は、高い光反射率を有し、かつ導電性も高いので、光反射膜および導電性膜として幅広く利用されている。しかし、加熱によりＡｇ膜の光学特性や電気特性が劣化することが問題であり、耐熱性の向上が求められている。 Silver (Ag) is widely used as a light reflection film and a conductive film because it has high light reflectivity and high conductivity. However, there is a problem that the optical characteristics and electrical characteristics of the Ag film are deteriorated by heating, and improvement in heat resistance is required.
Ａｇ膜の優れた光学特性を維持しつつ力学的および熱的性質を改善するためには合金化が有望と考えられている。特許文献１〜５に見られるように、これまでも、耐食性などが改善されたＡｇ合金薄膜形成用スパッタリングターゲット材、および、このスパッタリングターゲット材を用いて形成された薄膜などについて多くの発明がなされた。耐熱性および耐食性の向上を意図したＡｇの合金化では、Ａｕ、Ｐｔ、Ｐｄ、Ｒｕ、Ｎｉ、Ｍｇ、Ｉｎ、Ｓｎ、Ｐ、Ｚｎ、Ｙ、Ｎｄ、Ｓｂ、Ａｌなど多種の元素の添加が提案されている。 Alloying is considered promising to improve the mechanical and thermal properties while maintaining the excellent optical properties of Ag films. As seen in Patent Documents 1 to 5, many inventions have been made so far about a sputtering target material for forming an Ag alloy thin film with improved corrosion resistance, and a thin film formed using this sputtering target material. It was. In the alloying of Ag intended to improve heat resistance and corrosion resistance, the addition of various elements such as Au, Pt, Pd, Ru, Ni, Mg, In, Sn, P, Zn, Y, Nd, Sb, and Al is proposed. Has been.
特許文献１に記載の技術では、導電性を低下させずに耐熱性を高めたＡｇ合金としてＡｇにＹを０．０５〜５ｗｔ％添加することを基本とし、この基本合金にＺｎまたはＳｂを補助的に添加したＡｇ合金を報告している。実施例によれば、最適な組成はＡｇ-１ｗｔ％Ｙ-０．５ｗｔ％ＳｂまたはＡｇ-１ｗｔ％Ｙ-０．５ｗｔ％Ｚｎとされる。 The technique described in Patent Document 1 is based on adding 0.05 to 5 wt% of Y to Ag as an Ag alloy having improved heat resistance without reducing conductivity, and supplementing Zn or Sb to this basic alloy. Added Ag alloys are reported. According to the examples, the optimum composition is Ag-1 wt% Y-0.5 wt% Sb or Ag-1 wt% Y-0.5 wt% Zn.
特許文献２に記載のＡｇ合金は、スパッタリングターゲット材について、高い反射率を維持しながら耐ハロゲン性、耐酸化性、耐硫化性の改善を意図したもので、Ａｇに、Ｇｅ、Ｇａ、Ｓｂの少なくとも１種の金属０．１〜４．９ｗｔ％、および、Ａｕ、Ｐｄ、Ｐｔの少なくとも１種の金属０．１〜４．９ｗｔ％を添加した組成である。 The Ag alloy described in Patent Document 2 is intended to improve halogen resistance, oxidation resistance, and sulfidation resistance while maintaining high reflectivity for the sputtering target material. Ag, Ge, Ga, and Sb are included in Ag. It is a composition in which 0.1 to 4.9 wt% of at least one metal and 0.1 to 4.9 wt% of at least one metal of Au, Pd, and Pt are added.
特許文献３に記載のＡｇ合金は、高熱伝導率・高反射率・高耐久性を有する光情報記録媒体用の利用を意図したもので、ＡｇにＢｉまたはＳｂを合計で０．００５〜０．４０ｗｔ％添加した組成である。 The Ag alloy described in Patent Document 3 is intended for use in an optical information recording medium having high thermal conductivity, high reflectance, and high durability, and 0.005 to 0.005 in total of Bi or Sb in Ag. The composition is 40 wt% added.
特許文献４に記載のＡｇ合金は、液晶表示素子の光反射電極または光反射膜としての利用を意図したもので、ＡｇにＢｉまたはＳｂを合計で０．０１〜４原子％添加した組成である。 The Ag alloy described in Patent Document 4 is intended for use as a light reflecting electrode or a light reflecting film of a liquid crystal display element, and has a composition in which Bi or Sb is added to Ag in a total amount of 0.01 to 4 atomic%. .
特許文献５には、光ディスクのレーザーマーキングに適した低熱伝導率・低溶融温度・高耐食性・耐熱性を実現する合金として、ＢｉまたはＳｂを合計で０．０１〜３原子％含有し、かつ、ＣｕまたはＧｅまたはＭｇまたはＺｎを合計で３〜４２原子％含有することを特徴とする光情報記録Ａｇ合金反射膜が記載されている。 Patent Document 5 contains a total of 0.01 to 3 atomic percent of Bi or Sb as an alloy that realizes low thermal conductivity, low melting temperature, high corrosion resistance, and heat resistance suitable for laser marking of optical disks, and An optical information recording Ag alloy reflective film containing a total of 3 to 42 atomic% of Cu, Ge, Mg or Zn is described.
しかしながら、特許文献１に記載のＡｇ合金は、接点材料に関するもので、硬さ、強度、伸び、結晶粗大化、導電率で示される耐熱性については検討されているものの、反射材料やその耐熱性については、全く検討されていないし、Ｓｂ単独添加の場合の耐熱性についても検討されていない。
また、特許文献２では、上記スパッタリングターゲット材を用いて形成された薄膜の反射率、耐候性、耐硫化性等は検討されているものの、Ａｇ合金や形成薄膜の耐熱性については検討されていないし、Ｓｂ単独添加についても検討されていない。
これらの公知技術の中で、特許文献３〜５の技術は高い光反射率の維持と耐熱性向上を主眼としており、本発明と同様の光反射膜の応用分野を想定している。しかしながら、特許文献３〜５の実施例では耐久性試験乃至環境試験として、温度８０℃、湿度９０％RHの試験結果による耐久性が示されていることから、この技術が想定する耐熱温度は８０℃前後と推測される。However, the Ag alloy described in Patent Document 1 relates to a contact material, and although the heat resistance indicated by hardness, strength, elongation, crystal coarsening, and conductivity has been studied, the reflective material and its heat resistance are studied. No consideration has been made at all, and the heat resistance when Sb alone is added has not been studied.
In Patent Document 2, although the reflectance, weather resistance, sulfidation resistance and the like of the thin film formed using the sputtering target material are studied, the heat resistance of the Ag alloy and the formed thin film is not studied. Further, addition of Sb alone has not been studied.
Among these known techniques, the techniques of Patent Documents 3 to 5 focus on maintaining high light reflectivity and improving heat resistance, and assume the same application fields of light reflecting films as those of the present invention. However, in Examples of Patent Documents 3 to 5, durability is shown as a durability test or an environmental test based on a test result of a temperature of 80 ° C. and a humidity of 90% RH. Presumed to be around ° C.
このような反射膜については、一方で、機能層を積層し、高機能化することが検討されている。本発明者らは、独自に反射膜にアナターゼＴｉＯ２膜等を付加することにより高機能化することを検討した。このような膜の高機能化では、機能の発現にとって熱処理が好ましい場合がしばしばあり、反射膜のＡｇ合金は、そのような熱処理に耐える耐熱性を必要とすることが予想された。例えば、アナターゼＴｉＯ２膜の形成に関し、非特許文献１には、光触媒機能を有するアナターゼＴｉＯ２膜の形成にはおよそ２００℃の熱処理を要することが記載されている。それ故、ＴｉＯ２の光触媒活性を高めるには、２００℃の熱処理が必要であるが、熱処理すると、従来のＡｇ合金反射膜では光学特性が劣化してしまうことが予見されていた。実際、光触媒機能を有するアナターゼＴｉＯ２膜を具備するＡｇ合金反射膜は、従来には全く存在しなかった。
加えて、反射型液晶パネルや反射型プロジェクター、ディスプレイ用バックライト、光ディスク等においても高耐熱性のＡｇ合金反射膜が求められている。現在、耐熱性が必要のためにアルミニウムやその合金の反射膜が使用されているが、これを耐熱性Ａｇ合金反射材に代替することにより低い光吸収と高反射率を活かして光機能物品としての高性能化を図ることができる。
かくして、光反射膜を内部に含む光機能物品の高性能化や高機能化には、Ａｇ合金の耐熱温度を前記公知技術の８０℃よりもはるかに高くする必要性が認識された。Regarding such a reflective film, on the other hand, it has been studied to increase the functionality by laminating functional layers. The inventors of the present invention independently examined the enhancement of functionality by adding an anatase TiO 2 film or the like to the reflective film. In the enhancement of the function of such a film, heat treatment is often preferable for the expression of the function, and the Ag alloy of the reflective film is expected to require heat resistance that can withstand such heat treatment. For example, regarding the formation of an anatase TiO 2 film, Non-Patent Document 1 describes that the formation of an anatase TiO 2 film having a photocatalytic function requires a heat treatment at about 200 ° C. Therefore, in order to increase the photocatalytic activity of TiO 2 , a heat treatment at 200 ° C. is necessary. However, it has been predicted that the optical properties of the conventional Ag alloy reflective film will deteriorate when the heat treatment is performed. Actually, there has never been an Ag alloy reflective film having an anatase TiO 2 film having a photocatalytic function.
In addition, a highly heat-resistant Ag alloy reflective film is also required for reflective liquid crystal panels, reflective projectors, display backlights, optical disks, and the like. Currently, aluminum and its alloy reflective films are used because of their heat resistance, but they can be replaced with heat-resistant Ag alloy reflectors to make use of low light absorption and high reflectivity as optical functional articles. High performance can be achieved.
Thus, it has been recognized that it is necessary to make the heat resistance temperature of the Ag alloy much higher than 80 ° C. of the above-mentioned known technique in order to improve the performance and functionality of the optical functional article including the light reflecting film.
非特許文献２および非特許文献３には、従来技術におけるＡｇ合金組成、Ａｇ二元系合金の状態図、Ａｇ合金の融点、冷却過程での相分離、Ａｇを主成分とする金属間化合物等について記載されているが、Ａｇ合金を８０℃よりもはるかに高い耐熱温度にすることについては全く記載されていない。
特許文献６には、Ａｇ合金の凝集や硫化による反射性の低下を防止するため、Ａｇ合金薄膜層のＡｇ合金をＡｕ、Ｐｔ、Ｐｄ、Ｂｉ、希土類元素から選ばれる１種以上の元素を含む耐凝集性の良い組成にするとともに、大気中のハロゲンイオンや水分が浸入してＡｇの凝集や変色が生じないように、Ｓｉ、Ａｌ、Ｔｉから選ばれる１種以上の金属の酸化膜或いは酸窒化膜の層と、有機シリコン重合体膜の層を前記Ａｇ合金薄膜層に積層すること、実施例として、Ａｇ−Ｂｉ−Ｎｄ合金薄膜、Ｓｉ酸化膜、及び有機シリコンプラズマ重合体膜からなる反射膜は、１６０℃の恒温装置に入れても表面に全く変化がなかったこと等が記載されている。しかしながら、このような反射膜は高コストであるし、また、アナターゼＴｉＯ２膜の形成に必要なおよそ２００℃の耐熱性を実現することについての教示は全くなされていない。Non-Patent Document 2 and Non-Patent Document 3 include a conventional Ag alloy composition, a phase diagram of an Ag binary alloy, a melting point of the Ag alloy, a phase separation in the cooling process, an intermetallic compound mainly composed of Ag, and the like. However, there is no description about bringing the Ag alloy to a heat resistance temperature much higher than 80 ° C.
Patent Document 6 includes one or more elements selected from Au, Pt, Pd, Bi, and rare earth elements in the Ag alloy thin film layer in order to prevent a decrease in reflectivity due to aggregation and sulfurization of the Ag alloy. An oxide film or acid of one or more metals selected from Si, Al, and Ti so that the composition has good aggregation resistance and does not cause aggregation or discoloration of Ag due to entry of halogen ions or moisture in the atmosphere. A nitride film layer and an organic silicon polymer film layer are laminated on the Ag alloy thin film layer, and as an example, a reflection made of an Ag-Bi-Nd alloy thin film, a Si oxide film, and an organic silicon plasma polymer film. It is described that there was no change in the surface of the film even when it was placed in a thermostatic device at 160 ° C. However, such a reflective film is expensive, and there is no teaching about achieving the heat resistance of approximately 200 ° C. necessary for forming an anatase TiO 2 film.
以上のような従来技術を背景として、本発明では、Ａｇ膜に代替できる耐熱性のＡｇ合金光反射材を含み、該耐熱性Ａｇ合金よりもさらに高い耐熱性を有する光反射体を得ることを課題とした。より具体的には、本発明では上記のような目的の耐熱性Ａｇ合金反射材を含む光反射層と、耐熱性を向上する特定の酸化物を主成分とする付加層とを含む光反射体により少なくとも１５０℃以上、好ましくは２００℃の耐熱温度を目標とした。 Against the background of the prior art as described above, the present invention provides a light reflector that includes a heat-resistant Ag alloy light reflecting material that can be substituted for an Ag film, and that has higher heat resistance than the heat-resistant Ag alloy. It was an issue. More specifically, in the present invention, a light reflector including a light reflecting layer including a heat-resistant Ag alloy reflector for the purpose as described above, and an additional layer mainly composed of a specific oxide that improves heat resistance. Therefore, a heat resistant temperature of at least 150 ° C. or more, preferably 200 ° C. was targeted.
金属材料では合金化による析出硬化、すなわち、合金母相内に他の結晶構造の相を析出させて硬度を高める方法が知られている。本発明者らは、硬化と耐熱性向上には共通の要素が多いと考え、析出硬化の手法をＡｇの耐熱性向上に応用し得る可能性について検討した。具体的には、金属間化合物を内部に析出させることにより耐熱性を向上することを検討した。非特許文献２および非特許文献３によれば、Ａｇとの金属間化合物形成が報告された元素は、Ｃｅ、Ｄｙ、Ｅｒ、Ｅｕ、Ｇｄ、Ｇａ、Ｌａ、Ｉｎ、Ｎｄ、Ｐｒ、Ｓｂ、Ｓｎ、Ｓｒ、Ｔｂ、Ｔｉなど多数ある。Ａｇの優れた光学的性質をできるだけ維持するためには、Ａｇに対してより少ない原子比で金属間化合物が形成される組み合わせが好ましいことが想定された。そこで、これら元素の中から、Ａｇ：Ｓｂの原子比＝11.5：1での金属間化合物が報告されているＳｂが望ましいと考えた。 For metal materials, there is known a precipitation hardening by alloying, that is, a method of increasing the hardness by precipitating a phase of another crystal structure in the alloy matrix. The present inventors considered that there are many common elements for improving curing and heat resistance, and examined the possibility of applying the precipitation hardening technique to improving the heat resistance of Ag. Specifically, investigation was made to improve heat resistance by precipitating intermetallic compounds inside. According to Non-Patent Document 2 and Non-Patent Document 3, elements reported to form intermetallic compounds with Ag are Ce, Dy, Er, Eu, Gd, Ga, La, In, Nd, Pr, Sb, Sn , Sr, Tb, Ti, etc. In order to maintain the excellent optical properties of Ag as much as possible, it was assumed that a combination in which an intermetallic compound was formed with a smaller atomic ratio than Ag was preferable. Therefore, among these elements, Sb, which is reported to be an intermetallic compound with an Ag: Sb atomic ratio = 11.5: 1, was considered desirable.
一般に、金属間化合物は硬さの利点と脆さの欠点を併せ持つので、金属間化合物の利用では硬さと脆さのバランスを図った材料組成とする必要がある。応用上好ましいのは母体金属内部に金属間化合物が析出した状態と考えられる。本発明では、Ａｇ：Ｓｂ＝11.5：1の金属間化合物の析出を意図しており、Ｓｂの含有量がその比率未満でも前記金属間化合物が析出すると考えられる。Ｓｂが低濃度の場合には析出する金属間化合物の密度は低いものの、ランダムな空間分布を期待できるのでパーコレーションの観点からは１ｗｔ％程度から効果を見込める。一方、Ｓｂの濃度が高くなると金属間化合物の欠点である脆さの問題が現れると予測され、１〜７ｗｔ％のＳｂ添加が効果的であると推測した。そのような推測は、試作した参考例や実施例から確認することができ、さらに、最適値は３〜５ｗｔ％であることが分かった。具体的には、Ｓｂが５ｗｔ％を越えると可視光の吸収が大きくなり、７ｗｔ％を越えると反射膜表面にひび割れが発生する傾向が見られた。このひび割れは金属間化合物の欠点である脆さが原因と考えられる。
このような１〜７ｗｔ％（好ましくは３〜５ｗｔ％）のＳｂ添加したＡｇ合金は、従来の耐熱性Ａｇ合金よりもかなり高い１５０℃程度の耐熱性を示すことを本発明者は確認したが、光触媒機能層を設けるには、耐熱性が必ずしもまだ充分ではないことも明らかになった。そこで、本発明者は、この耐熱性Ａｇ合金を超える高耐熱性を得るべく、さらに試行錯誤を重ねた試験研究過程で、この耐熱性Ａｇ合金反射材を含む光反射層を含む光反射体に、ＩＴＯ、ＳｉＯ２、ＳｎＯ２、Ｔａ２Ｏ５、Ｎｂ２Ｏ５、Ａｌ２Ｏ３から選択される金属酸化物を主成分とする付加層を設けることにより、耐熱性Ａｇ合金を大きく超える耐熱性が得られることを見出した。In general, since intermetallic compounds have both the advantage of hardness and the disadvantage of brittleness, the use of intermetallic compounds requires a material composition that balances hardness and brittleness. From the viewpoint of application, it is considered that an intermetallic compound is precipitated inside the base metal. In the present invention, precipitation of an intermetallic compound of Ag: Sb = 11.5: 1 is intended, and it is considered that the intermetallic compound is precipitated even if the Sb content is less than the ratio. When the concentration of Sb is low, the density of the intermetallic compound to be deposited is low, but a random spatial distribution can be expected, so that an effect can be expected from about 1 wt% from the viewpoint of percolation. On the other hand, when the concentration of Sb increases, it is predicted that the problem of brittleness, which is a defect of the intermetallic compound, appears, and it is estimated that 1 to 7 wt% of Sb addition is effective. Such a guess can be confirmed from the reference examples and examples that were prototyped, and the optimum value was found to be 3 to 5 wt%. Specifically, when Sb exceeds 5 wt%, the absorption of visible light increases, and when it exceeds 7 wt%, a tendency that cracks occur on the surface of the reflective film is observed. This crack is thought to be caused by brittleness, which is a defect of intermetallic compounds.
Although the present inventors have confirmed that such an Ag alloy added with 1 to 7 wt% (preferably 3 to 5 wt%) of Sb exhibits a heat resistance of about 150 ° C., which is considerably higher than a conventional heat resistant Ag alloy. It has also been clarified that the heat resistance is not yet sufficient for providing the photocatalytic functional layer. Therefore, the present inventor has obtained a light reflector including the light reflecting layer including the heat resistant Ag alloy reflector in a test and research process in which trial and error are repeated in order to obtain a high heat resistance exceeding that of the heat resistant Ag alloy. By providing an additional layer mainly composed of a metal oxide selected from ITO, SiO 2 , SnO 2 , Ta 2 O 5 , Nb 2 O 5 , and Al 2 O 3 , the heat resistance greatly exceeds that of the heat-resistant Ag alloy. It was found that sex can be obtained.
本発明は、以上のような金属学的考察やその考察を裏付けるべくなされた試験研究で得られた知見に基づいてなされたもので、以下のことを特徴としている。
１．Ｓｂを１〜７ｗｔ％含有し、残部がＡｇおよび不可避的不純物からなるＡｇ合金光反射材を含む光反射層と、ＩＴＯ、ＳｉＯ２、ＳｎＯ２、Ｔａ２Ｏ５、Ｎｂ２Ｏ５、Ａｌ２Ｏ３から選択される金属酸化物を主成分とする付加層とを具備することを特徴とする光反射体。
２．前記光反射層に隣接して前記付加層としてのＳｉＯ２を主成分とする層が設けられたことを特徴とする上記１に記載の光反射体。
３．前記光反射層と前記ＳｉＯ２を主成分とする層とを交互に各２層以上具備することを特徴とする上記２に記載の光反射体。
４．前記Ａｇ合金光反射材が膜状であり、前記光反射層が該膜状のＡｇ合金反射材からなることを特徴とする上記１〜３のいずれか１項に記載の光反射体。
５．前記Ａｇ合金光反射材が微粒子状であり、前記光反射層が該微粒子状のＡｇ合金反射材を練り込んだ樹脂シートからなることを特徴とする上記１〜３のいずれか１項に記載の光反射体。
６．前記Ａｇ合金光反射材が微粒子状であり、前記光反射層が該微粒子状のＡｇ合金反射材を４ｗｔ％以上含有する塗料の塗布膜からなることを特徴とする上記１〜３のいずれか１項に記載の光反射体。
７．前記Ａｇ合金光反射材は、Ｓｂの含有量が３〜５ｗｔ％であることを特徴とする上記１〜６のいずれか１項に記載の光反射体。
８．前記光反射層が可視光半透過性で赤外光反射性である上記１〜７のいずれか１項に記載の光反射体。
９．上記８に記載の光反射体、および、光触媒機能を有するアナターゼ型ＴｉＯ２を主成分とする層を透光性基材上に積層したシートであって、最外層が該ＴｉＯ２を主成分とする層となるように構成したことを特徴とする可視光透過性日射熱反射シート。The present invention has been made on the basis of the metallurgical considerations as described above and the knowledge obtained through the test research to support the considerations, and has the following features.
1. A light reflecting layer containing an Ag alloy light reflecting material containing 1 to 7 wt% of Sb and the balance of Ag and inevitable impurities, ITO, SiO 2 , SnO 2 , Ta 2 O 5 , Nb 2 O 5 , Al 2 A light reflector comprising an additional layer mainly composed of a metal oxide selected from O 3 .
2. 2. The light reflector according to 1 above, wherein a layer mainly composed of SiO 2 as the additional layer is provided adjacent to the light reflection layer.
3. 3. The light reflector as described in 2 above, further comprising two or more layers of the light reflection layer and the SiO 2 as a main component alternately.
4). 4. The light reflector according to any one of the above items 1 to 3, wherein the Ag alloy light reflecting material is in the form of a film, and the light reflecting layer is made of the film-shaped Ag alloy reflecting material.
5. The said Ag alloy light reflection material is a particulate form, The said light reflection layer consists of a resin sheet which knead | mixed this particulate Ag alloy reflection material, The said any one of 1-3 characterized by the above-mentioned. Light reflector.
6). Any one of the above 1 to 3, wherein the Ag alloy light reflecting material is in the form of fine particles, and the light reflecting layer is made of a coating film of a paint containing 4 wt% or more of the fine particle Ag alloy reflecting material. The light reflector according to Item.
7). 7. The light reflector according to any one of 1 to 6, wherein the Ag alloy light reflecting material has an Sb content of 3 to 5 wt%.
8). 8. The light reflector according to any one of 1 to 7, wherein the light reflecting layer is visible light semi-transmissive and infrared light reflective.
9. 9. A sheet obtained by laminating a light reflector as described in 8 above and a layer mainly composed of anatase TiO 2 having a photocatalytic function on a translucent substrate, and the outermost layer is composed mainly of the TiO 2. A visible light transmissive solar heat reflective sheet, characterized in that the layer is configured to be a layer to be used.
本発明に係る耐熱性Ａｇ合金反射材を含む光反射層と、特定の酸化物を主成分とする付加層とを具備する光反射体は、該耐熱性Ａｇ合金を大きく上回る耐熱性の向上を達成しており、次のような効果をもたらす。
（１）Ａｇ膜形成プロセスにおいてしばしば必要だった冷却が不要となるので、製造プロセスがより簡便になり製造コスト低減効果を有する。
（２）耐熱性、耐久性に優れ、かつ、光に対して損失が少ない光反射膜としてＡｇ膜よりも高い温度まで利用可能である。
（３）日射熱反射膜への応用において、炎天下など比較的高温な環境にて耐久性に優れる。
（４）熱処理を経ても光学特性の劣化が少ないので、光機能膜の高性能化に有用である。例えば、日射熱反射膜形成後に、熱処理を伴うプロセスによりアナターゼＴｉＯ２等の光触媒機能層を付加することが可能になる。この場合、透光性基材のＡｇ合金反射材が形成された同じ片面上に光触媒機能層をＡｇ合金反射材と近接して設けることもできる。
（５）アルミニウムやその合金による光反射膜を代替すると、低い光吸収と高反射率を活かして光機能物品としての高性能化を図ることができる。
（６）１０ｎｍ前後の薄膜とすると、高導電性と可視光透過を両立するので、透明伝導膜の代替として利用可能である。The light reflector comprising the light reflecting layer containing the heat resistant Ag alloy reflecting material according to the present invention and the additional layer containing a specific oxide as a main component has improved heat resistance greatly exceeding that of the heat resistant Ag alloy. Has achieved the following effects:
(1) Since the cooling often required in the Ag film forming process is unnecessary, the manufacturing process becomes simpler and the manufacturing cost can be reduced.
(2) It can be used up to a temperature higher than that of the Ag film as a light reflecting film that is excellent in heat resistance and durability and has little loss with respect to light.
(3) In application to a solar heat reflective film, it is excellent in durability in a relatively high temperature environment such as under a hot sun.
(4) Since optical characteristics are hardly deteriorated even after heat treatment, it is useful for improving the performance of optical functional films. For example, it becomes possible to add a photocatalytic functional layer such as anatase TiO 2 by a process involving heat treatment after the formation of the solar heat reflective film. In this case, the photocatalytic functional layer can be provided close to the Ag alloy reflector on the same surface on which the Ag alloy reflector of the translucent substrate is formed.
(5) If a light reflection film made of aluminum or an alloy thereof is substituted, it is possible to achieve high performance as an optical functional article utilizing low light absorption and high reflectance.
(6) When a thin film of about 10 nm is used, both high conductivity and visible light transmission are compatible, and therefore it can be used as an alternative to a transparent conductive film.
本発明に係る光反射体を構成するＡｇ合金光反射材のＡｇ合金は、Ａｇの優れた光学的性質をできるだけ維持するとともに、高耐熱性とするために、Ｓｂを１〜７ｗｔ％含有し、残部がＡｇと不可避的不純物で、それ以外の成分を含有しない。
本発明に係る光反射体を構成するＡｇ合金光反射材において、Ｓｂ添加量は、Ａｇの優れた光学的性質、耐熱性、及び、強度の観点から、１〜７ｗｔ％が適当であり、好ましくは３〜５ｗｔ％であることを実験から得た。Ｓｂが７ｗｔ％を越えるとひび割れが生じやすくなるが、その原因はＡｇ−Ｓｂ金属間化合物の占める割合が高まるためと考えられる。The Ag alloy of the Ag alloy light reflecting material constituting the light reflector according to the present invention contains 1 to 7 wt% of Sb in order to maintain the excellent optical properties of Ag as much as possible and to have high heat resistance. The balance is Ag and inevitable impurities and does not contain other components.
In the Ag alloy light reflecting material constituting the light reflector according to the present invention, the amount of Sb added is suitably 1 to 7 wt% from the viewpoint of excellent optical properties, heat resistance, and strength of Ag. Was obtained from experiments to be 3-5 wt%. If Sb exceeds 7 wt%, cracks are likely to occur, but the cause is considered to be a higher proportion of the Ag-Sb intermetallic compound.
本発明に係る光反射体を構成するＡｇ合金光反射材は、各種の形状、構造をとることができるが、望ましい形状、構造としては、例えば、膜状、微粒子状等が挙げられる。
膜状のＡｇ合金光反射材は、スパッタ法、真空蒸着法、電子ビーム蒸着法、レーザ蒸着法、ＣＶＤ法、塗布法、スプレー法などの公知の膜形成技術を利用して、透光性基材上に形成することができる。塗布法やスプレー法では、後述のような耐熱性Ａｇ合金の微粒子を内部に分散した分散液を用いて微粒子の被膜を形成した後、該被膜を熱処理し焼結して膜状とする。
膜状のＡｇ合金光反射材の膜厚は、限定するものではないが、通常、５〜２００ｎｍが適当である。透光性の高い半透過光反射膜とする場合は、膜厚を薄くするが、通常、５〜２０ｎｍ程度が適当であり、また、低透光性の反射膜とする場合は、５０〜２００ｎｍが適当である。
膜状のＡｇ合金光反射材が形成される透光性基材としては、ガラス基板、プラスチック基板等が挙げられる。そのような基材の用途としては、窓ガラス、自動車用ガラス、レンズ、サングラス等が挙げられる。
このような透光性基材面上に膜状のＡｇ合金光反射材が形成された光反射体においては、日射熱、赤外光等の光は膜側から入射させて膜表面を反射面とすることができるし、また、光を透光性基材側から入射させて基材と膜の界面を反射面として利用することもできる。The Ag alloy light reflecting material constituting the light reflector according to the present invention can take various shapes and structures. Examples of desirable shapes and structures include film shapes and fine particle shapes.
The film-like Ag alloy light reflecting material is formed by using a known film forming technique such as sputtering, vacuum vapor deposition, electron beam vapor deposition, laser vapor deposition, CVD, coating, spraying, etc. It can be formed on a material. In a coating method or a spray method, a coating film of fine particles is formed using a dispersion liquid in which fine particles of a heat-resistant Ag alloy as described later are dispersed, and then the coating film is heat-treated and sintered to form a film.
The film thickness of the film-like Ag alloy light reflecting material is not limited, but is usually 5 to 200 nm. In the case of a translucent light reflecting film having a high translucency, the film thickness is made thin, but usually about 5 to 20 nm is appropriate, and in the case of a low translucent reflecting film, it is 50 to 200 nm. Is appropriate.
Examples of the translucent substrate on which the film-shaped Ag alloy light reflecting material is formed include a glass substrate and a plastic substrate. Examples of the use of such a substrate include window glass, glass for automobiles, lenses, and sunglasses.
In such a light reflector in which a film-like Ag alloy light reflecting material is formed on the surface of the translucent substrate, light such as solar heat and infrared light is incident from the film side to reflect the film surface. It is also possible to make light incident from the translucent substrate side and use the interface between the substrate and the film as a reflecting surface.
微粒子状のＡｇ合金光反射材は、球状、扁平状等、その形状は限定されない。このような微粒子状のＡｇ合金光反射材は、水溶液中の銀イオンとアンチモンイオンの同時還元、不活性雰囲気下での遠心噴霧法等の公知の製法により製造することができる。その寸法は、限定するものではないが、動的光散乱法粒子分布測定装置(サブミクロン粒子アナライザー)で測定される平均有効径は、一般的には、５〜５００ｎｍ程度であり、半透過性乃至可視光透過性とする場合は、５〜２０ｎｍが適当である。
微粒子状のＡｇ合金光反射材は、高光反射性の顔料、充填剤等として、塗料やプラスチック材料中に練り込み等により含有させて、可視光透過性を有する、または、可視光透過性を有さない光反射塗装膜や光反射プラスチック製品等の光反射層とすることができる。微粒子状のＡｇ合金光反射材を塗料やプラスチック材料に含有させる場合の含有量は、一般的には４ｗｔ％以上であり、好ましくは、６〜５０ｗｔ％である。塗膜層やプラスチック製品を可視光透過性とするには、微粒子状のＡｇ合金光反射材の含有量を４〜１０ｗｔ％程度に少なくするとともに、塗膜層やプラスチック製品の厚さを薄くする必要がある。The shape of the particulate Ag alloy light reflecting material is not limited to a spherical shape or a flat shape. Such a particulate Ag alloy light reflecting material can be produced by a known production method such as simultaneous reduction of silver ions and antimony ions in an aqueous solution, or centrifugal spraying in an inert atmosphere. Although the size is not limited, the average effective diameter measured by a dynamic light scattering particle distribution measuring device (submicron particle analyzer) is generally about 5 to 500 nm, and is semi-transparent. Or when it is set as visible-light transmittance, 5-20 nm is suitable.
The particulate Ag alloy light reflecting material has a visible light transmission property or a visible light transmission property by being incorporated into a paint or plastic material as a highly light reflective pigment, filler, etc. by kneading. It can be used as a light reflecting layer such as a light reflecting coating film or a light reflecting plastic product. The content in the case where the particulate Ag alloy light reflecting material is contained in the paint or plastic material is generally 4 wt% or more, and preferably 6 to 50 wt%. In order to make the coating layer and the plastic product transparent to light, the content of the particulate Ag alloy light reflecting material is reduced to about 4 to 10 wt%, and the thickness of the coating layer and the plastic product is reduced. There is a need.
前記耐熱性Ａｇ合金光反射材を含む光反射層を具備する光反射体は、その耐熱性向上のために、その反射面に、ＩＴＯ、ＳｉＯ２、ＳｎＯ２、Ｔａ２Ｏ５、Ｎｂ２Ｏ５、Ａｌ２Ｏ３から選択される金属酸化物を主成分とする付加層を具備する。耐熱性Ａｇ合金光反射材を含む光反射体の耐熱性向上は、前記金属酸化物を主成分とする付加層であれば得ることができるが、特に、付加層がＳｉＯ２である場合に著しい。このような付加層の厚さは、適宜調整できるが、通常、１０〜２００ｎｍが適当である。耐熱性Ａｇ合金光反射材を含む光反射層と該付加層とは、透光性基材上に各１層、または、交互に各２層以上形成することができる。なお、前記金属酸化物を主成分とする付加層は、可視光透過性を維持したままでの反射率向上効果や反射面の保護効果も奏し得る。In order to improve the heat resistance, the light reflector having the light reflecting layer containing the heat resistant Ag alloy light reflecting material has ITO, SiO 2 , SnO 2 , Ta 2 O 5 , Nb 2 O on its reflecting surface. 5 and an additional layer mainly composed of a metal oxide selected from Al 2 O 3 . The improvement in heat resistance of the light reflector including the heat-resistant Ag alloy light reflecting material can be obtained if it is an additional layer containing the metal oxide as a main component, and is particularly remarkable when the additional layer is made of SiO 2. . The thickness of such an additional layer can be adjusted as appropriate, but usually 10 to 200 nm is appropriate. The light reflecting layer containing the heat-resistant Ag alloy light reflecting material and the additional layer can be formed on the light-transmitting substrate in one layer each, or alternately two or more layers. In addition, the additional layer which has the said metal oxide as a main component can also show the reflectance improvement effect and protective effect of a reflective surface, maintaining visible light transmittance | permeability.
前記耐熱性Ａｇ合金光反射材を含む光反射体は、その反射面に、前記付加層を介して、光触媒機能を有する公知のアナターゼ型ＴｉＯ２等の機能層を形成することができる。機能層の厚さは、機能層の種類によって適宜調整されるが、アナターゼ型ＴｉＯ２の場合、通常、１０〜２００ｎｍである。前記耐熱性Ａｇ合金光反射材を含む光反射体の反射面に、前記付加層を介して前記機能層を形成する場合、耐熱性Ａｇ合金光反射材を含む光反射層と該付加層とは、透光性基材上に各１層、または、交互に各２層以上形成することができる。
また、前記耐熱性Ａｇ合金光反射材を含む光反射層は、透光性基材上に、ＩＴＯ、ＳｉＯ２、ＳｎＯ２、Ｔａ２Ｏ５、Ｎｂ２Ｏ５、Ａｌ２Ｏ３から選択される金属酸化物を主成分とする付加層の１種又は複数種の基材側付加層を介して形成することもできる。このような透光性基材と耐熱性Ａｇ合金反射材を含む光反射層との間の基材側付加層は通常１０〜２００ｎｍである。この場合、耐熱性Ａｇ合金反射材を含む光反射層は、基材側付加層との界面を反射面とすることもできるし、形成された耐熱性Ａｇ合金反射材の表面を反射面とし、前述のような金属酸化物を主成分とする付加層及び機能層を該表面上に形成することができる。The light reflector including the heat-resistant Ag alloy light reflecting material can form a functional layer such as a known anatase TiO 2 having a photocatalytic function on the reflection surface via the additional layer. The thickness of the functional layer is suitably adjusted depending on the kind of the functional layer, when the anatase type TiO 2, usually 10 to 200 nm. When the functional layer is formed on the reflecting surface of the light reflector including the heat resistant Ag alloy light reflecting material via the additional layer, the light reflecting layer including the heat resistant Ag alloy light reflecting material and the additional layer are: Each layer can be formed on the translucent substrate, or two or more layers can be alternately formed.
The light reflecting layer including the heat-resistant Ag alloy light reflecting material is selected from ITO, SiO 2 , SnO 2 , Ta 2 O 5 , Nb 2 O 5 , and Al 2 O 3 on the translucent substrate. It can also be formed through one or a plurality of types of base layer side additional layers of the additional layer mainly composed of a metal oxide. The base material side additional layer between such a translucent base material and the light reflection layer containing the heat-resistant Ag alloy reflector is usually 10 to 200 nm. In this case, the light reflection layer containing the heat-resistant Ag alloy reflective material can have the interface with the base material side additional layer as a reflective surface, or the surface of the formed heat-resistant Ag alloy reflective material as the reflective surface. An additional layer and a functional layer mainly composed of the metal oxide as described above can be formed on the surface.
本発明に係る耐熱性Ａｇ合金光反射材を含む光反射体について、以下、参考例、実施例に基づき図面を参照しつつさらに具体的に説明するが、本発明はこの参考例や実施例によって何ら限定されるものではない。
なお、光学薄膜における耐熱性の問題は、加熱による反射率低下として現れるため、以下の参考例や実施例では、試作した半透過反射膜の反射特性を加熱前後で比較することにより本発明に係るＡｇ合金光反射膜や該Ａｇ合金光反射膜を含む光反射体を評価した。The light reflector including the heat-resistant Ag alloy light reflecting material according to the present invention will be described more specifically below with reference to the drawings based on reference examples and examples. It is not limited at all.
In addition, since the problem of heat resistance in the optical thin film appears as a decrease in reflectance due to heating, the following reference examples and examples are related to the present invention by comparing the reflection characteristics of the semitransparent reflective film that was produced before and after the heating. An Ag alloy light reflecting film and a light reflector including the Ag alloy light reflecting film were evaluated.
（参考例１）
パルスレーザ蒸着法によりガラス基板上に、Ａｇ合金（Ａｇ−１ｗｔ％Ｓｂ）を厚さ約１６ｎｍ堆積し、図１（ａ）に示すような構造の半透過反射膜を具備する半透過反射体を形成した。光を膜側から入射させて膜表面からの鏡面反射条件での反射率を熱処理前後で測定したところ、図１（ｂ）に示すように、大気中１５０℃１時間の熱処理を経ても反射率特性が維持された。(Reference Example 1)
A semi-transmissive reflector including a semi-transmissive reflective film having a structure as shown in FIG. 1A is formed by depositing an Ag alloy (Ag-1 wt% Sb) to a thickness of about 16 nm on a glass substrate by a pulse laser deposition method. Formed. When light was incident from the film side and the reflectance under the specular reflection condition from the film surface was measured before and after the heat treatment, as shown in FIG. Characteristics were maintained.
比較のために、半透過反射膜の材料を従来のＡｇとした以外は参考例１と同様の条件とした結果を図１（ｃ）に示す。大気中１５０℃１時間の熱処理により、Ａｇの半透過反射膜では図に示すように大きく反射率が低下した。これらの実験結果から、Ａｇ膜と比較して１ｗｔ％Ｓｂ添加のＡｇ合金光反射膜における耐熱性向上を確認した。 For comparison, FIG. 1C shows the results obtained under the same conditions as in Reference Example 1 except that the material of the transflective film is conventional Ag. As a result of the heat treatment at 150 ° C. for 1 hour in the atmosphere, the reflectance of the Ag transflective film was greatly reduced as shown in the figure. From these experimental results, it was confirmed that the heat resistance of the Ag alloy light reflecting film added with 1 wt% Sb was improved as compared with the Ag film.
（参考例２）
パルスレーザ蒸着法によりガラス基板上に、Ａｇ合金（Ａｇ−３ｗｔ％Ｓｂ）を厚さ約１６ｎｍ堆積し、図２（ａ）に示すような構造の半透過反射膜を具備する半透過反射体を形成した。光を膜側から入射させて膜表面からの鏡面反射条件での反射率を熱処理前後で測定したところ、図２（ｂ）に示すように、大気中１５０℃１時間の熱処理後も反射率がほぼ維持された。(Reference Example 2)
A semi-transmissive reflector including a semi-transmissive reflective film having a structure as shown in FIG. 2A is formed by depositing an Ag alloy (Ag-3 wt% Sb) to a thickness of about 16 nm on a glass substrate by a pulse laser deposition method. Formed. When light was incident from the film side and the reflectance under the specular reflection condition from the film surface was measured before and after the heat treatment, as shown in FIG. Almost maintained.
（参考例３）
パルスレーザ蒸着法によりガラス基板上に、Ａｇ合金（Ａｇ−７ｗｔ％Ｓｂ）を厚さ約１６ｎｍ堆積し、図３（ａ）に示すような構造の反射膜を具備する反射体を形成した。光を膜側から入射させて膜表面からの鏡面反射条件での反射率を熱処理前後で測定したところ、図３（ｂ）に示す反射率特性から分かるように、真空中１５０℃１時間の熱処理後も反射率はほぼ維持された。真空中２００℃１時間の熱処理により反射率が７割程度に低下したが、従来のＡｇ膜よりも遥かに高い耐熱性を示した。ここで、熱処理を真空中としたのは、ＴｉＯ２膜などを真空中の膜形成プロセスにより付加する場合を想定して耐熱性を評価するためである。(Reference Example 3)
An Ag alloy (Ag-7 wt% Sb) was deposited to a thickness of about 16 nm on a glass substrate by a pulsed laser deposition method to form a reflector having a reflective film having a structure as shown in FIG. When light was incident from the film side and the reflectivity under the specular reflection condition from the film surface was measured before and after the heat treatment, as can be seen from the reflectance characteristics shown in FIG. After that, the reflectance was almost maintained. Although the reflectance decreased to about 70% by heat treatment at 200 ° C. for 1 hour in vacuum, the heat resistance was much higher than that of the conventional Ag film. Here, the reason why the heat treatment is performed in a vacuum is to evaluate heat resistance on the assumption that a TiO 2 film or the like is added by a film formation process in a vacuum.
（実施例１）
パルスレーザ蒸着法によりガラス基板上に、Ａｇ合金（Ａｇ−４ｗｔ％Ｓｂ）層、ＩＴＯ（Ｉｎ２Ｏ３−５ｗｔ％ＳｎＯ２）層の順に積層し、図４（ａ）に示すような構造の２層膜を具備する反射体を形成した。２５０℃１時間の熱処理後、光を膜側から入射させて膜表面からの鏡面反射条件での反射率を測定した結果を図４（ｂ）の実線で示す。比較のために、金属膜部分の材料のみを従来のＡｇとした以外は実施例１と同じ条件とした結果を図４（ｂ）の破線で示す。なお、熱処理を真空中としたのは、ＴｉＯ２膜などを付加する真空中成膜プロセスの条件に準じたためである。実施例１のＡｇ合金光反射膜は、２５０℃１時間の熱処理後も高い反射率を維持しており、アナターゼ型ＴｉＯ２の形成に十分な耐熱性を有することを確認した。一方、従来技術による反射膜は、特性が２５０℃１時間の熱処理により破線に示すように大きく劣化した。この実施例１のＡｇ合金光反射膜は、参考例１〜３よりも高い耐熱性を有しており、このような耐熱性の向上は、参考例１〜３との比較から見て、ＩＴＯの付加層を形成したためと考えられる。Example 1
An Ag alloy (Ag-4 wt% Sb) layer and an ITO (In 2 O 3 -5 wt% SnO 2 ) layer are laminated in this order on a glass substrate by a pulse laser deposition method, and the structure as shown in FIG. A reflector having a two-layer film was formed. The solid line in FIG. 4B shows the result of measuring the reflectance under the condition of specular reflection from the film surface by making light incident from the film side after heat treatment at 250 ° C. for 1 hour. For comparison, the result of the same conditions as in Example 1 except that only the material of the metal film portion is changed to conventional Ag is shown by a broken line in FIG. The reason why the heat treatment was performed in a vacuum was that it conformed to the conditions of the vacuum film formation process for adding a TiO 2 film or the like. It was confirmed that the Ag alloy light reflecting film of Example 1 maintained high reflectance even after heat treatment at 250 ° C. for 1 hour, and had sufficient heat resistance for the formation of anatase TiO 2 . On the other hand, the reflective film according to the prior art has greatly deteriorated in characteristics as shown by the broken line by heat treatment at 250 ° C. for 1 hour. The Ag alloy light reflecting film of Example 1 has higher heat resistance than those of Reference Examples 1 to 3, and such an improvement in heat resistance is seen from a comparison with Reference Examples 1 to 3 by ITO. This is thought to be because the additional layer was formed.
（実施例２）
実施例２として、光触媒機能を有する日射熱反射シートへの応用例を図５に示す。図５（ａ）はその基本構造であり、透光性基板上に、Ａｇ合金、ＳｉＯ２、アナターゼ型ＴｉＯ２を順次積層することにより成る。各層の適当な厚さはＡｇ合金が９〜２０ｎｍ、ＳｉＯ２が１０〜２００ｎｍ、アナターゼ型ＴｉＯ２が１０〜２００ｎｍである。アナターゼ型ＴｉＯ２の形成には通常熱処理を必要とするが、実施例１の結果から本実施例の日射熱反射特性は熱処理後も維持できると見込まれる。
図５（ｂ）は日射熱反射特性を向上させるためにＡｇ合金、ＳｉＯ２、Ａｇ合金、ＳｉＯ２、アナターゼ型ＴｉＯ２を順次積層した５層膜とした例である。各層の厚さとしては、Ａｇ合金が７〜１２ｎｍ、ＳｉＯ２が１０〜２００ｎｍ、アナターゼ型ＴｉＯ２が１０〜２００ｎｍとなるように積層するのが適当である。多層膜化の利点は、可視光透過と日射熱反射の遷移特性を急峻にできることである。特性を最適化するための各層の膜厚については日射熱反射膜の設計指針をそのまま利用できる。(Example 2)
As Example 2, an application example to a solar heat reflecting sheet having a photocatalytic function is shown in FIG. FIG. 5A shows its basic structure, which is formed by sequentially laminating an Ag alloy, SiO 2 , and anatase TiO 2 on a translucent substrate. The appropriate thickness of each layer is 9 to 20 nm for Ag alloy, 10 to 200 nm for SiO 2, and 10 to 200 nm for anatase TiO 2 . The formation of anatase TiO 2 usually requires heat treatment, but from the results of Example 1, it is expected that the solar heat reflection characteristics of this example can be maintained after heat treatment.
FIG. 5B shows an example of a five-layer film in which Ag alloy, SiO 2 , Ag alloy, SiO 2 , and anatase TiO 2 are sequentially laminated in order to improve solar heat reflection characteristics. The thickness of each layer is suitably laminated so that the Ag alloy is 7 to 12 nm, the SiO 2 is 10 to 200 nm, and the anatase TiO 2 is 10 to 200 nm. The advantage of using a multilayer film is that the transition characteristics between visible light transmission and solar heat reflection can be sharpened. For the film thickness of each layer for optimizing the characteristics, the design guideline of the solar heat reflecting film can be used as it is.
（実施例３）
実施例３は、本発明による耐熱性銀合金光反射材を含む光反射体の応用として、光触媒機能を有する日射熱反射シートを試作した例である。図６（ａ）に示す基本構造に沿って板ガラス（１ｍｍ厚）上に、ＳｉＯ２、ＴｉＯ２、ＳｉＯ２、Ａｇ合金（Ａｇ−２ｗｔ％Ｓｂ）、ＳｉＯ２、アナターゼ型ＴｉＯ２を順次積層することにより成る。これら材料の積層にはスパッタリング法を用い、表面がアナターゼ型ＴｉＯ２となるようにプロセス中適宜加熱を施した。アナターゼ型ＴｉＯ２の形成はＸ線回折測定により確認し、Ａｇ合金の耐熱性も考慮しつつ基板温度２００℃など最適なプロセス条件を定めた。光触媒機能については、水に対する接触角の紫外光照射による変化から評価した。図６（ｂ）に示す実験結果のように、紫外光照射（波長３６５ｎｍ、強度２ｍＷ／ｃｍ２）により接触角は１０度以下に低下し、試料表面が明確な親水性を示すことを確認した。観測された接触角の初期値（約８０度）は文献等で報告された値（３５度前後）よりかなり大きいが、この差異の原因は試料表面への吸着物や汚れの影響が大きいと考えられる。日射熱反射機能については透過率および反射率の分光測定により評価し、図６（ｃ）に示すように可視光透過と近赤外光反射の特性を確認した。日射熱反射にとって重要な波長８００ｎｍにて従来材料を用いた場合の反射率と比較したところ、従来材料では１２％程度であった反射率を約７０％に改善できた。本実施例の光反射体は、アナターゼ型ＴｉＯ２形成時の約２００℃の温度だけでなく、スパッタリングによる厳しい環境にも晒されたにも拘わらず、このように高い耐熱性を示しており、参考例１〜３や実施例１を併せ考慮すると、この高耐熱性は、Ｓｂ添加Ａｇ合金反射層と付加層との組み合わせによるものと考えられる。この例のように多層膜において日射熱反射機能と光触媒機能を融合するためには日射熱反射膜の耐熱性が必要となるため、本発明による耐熱性銀合金光反射材を含む光反射体の利用が最善と考えられる。(Example 3)
Example 3 is an example in which a solar heat reflecting sheet having a photocatalytic function was experimentally manufactured as an application of a light reflector including a heat-resistant silver alloy light reflecting material according to the present invention. In accordance with the basic structure shown in FIG. 6A, SiO 2 , TiO 2 , SiO 2 , Ag alloy (Ag-2 wt% Sb), SiO 2 , and anatase TiO 2 are sequentially laminated on a sheet glass (1 mm thick). It consists of Lamination of these materials was performed using a sputtering method and appropriately heated during the process so that the surface became anatase TiO 2 . The formation of anatase TiO 2 was confirmed by X-ray diffraction measurement, and optimum process conditions such as a substrate temperature of 200 ° C. were determined in consideration of the heat resistance of the Ag alloy. About the photocatalytic function, it evaluated from the change by the ultraviolet light irradiation of the contact angle with respect to water. As shown in the experimental results shown in FIG. 6 (b), it was confirmed that the contact angle decreased to 10 degrees or less by ultraviolet light irradiation (wavelength 365 nm, intensity 2 mW / cm 2 ), and the sample surface showed clear hydrophilicity. . The observed initial value of contact angle (approximately 80 degrees) is considerably larger than the value reported in the literature (around 35 degrees), but the reason for this difference is thought to be the effect of adsorbate and dirt on the sample surface. It is done. The solar heat reflection function was evaluated by spectroscopic measurement of transmittance and reflectance, and the characteristics of visible light transmission and near-infrared light reflection were confirmed as shown in FIG. When compared with the reflectance when the conventional material is used at a wavelength of 800 nm which is important for solar heat reflection, the reflectance which was about 12% with the conventional material can be improved to about 70%. The light reflector of this example shows such a high heat resistance in spite of being exposed not only to a temperature of about 200 ° C. during the formation of anatase TiO 2 but also to a severe environment by sputtering, Considering Reference Examples 1 to 3 and Example 1 together, this high heat resistance is considered to be due to the combination of the Sb-added Ag alloy reflective layer and the additional layer. As shown in this example, in order to fuse the solar heat reflection function and the photocatalytic function in the multilayer film, the heat resistance of the solar heat reflection film is required. Therefore, the light reflector including the heat resistant silver alloy light reflection material according to the present invention is used. Use is considered the best.
（実施例４）
実施例４は、本発明による耐熱性銀合金光反射材を含む光反射体を用いて光触媒機能を有する日射熱反射シートを試作した例である。図７（ａ）に示す基本構造に沿って板ガラス（１ｍｍ厚）上に、ＳｉＯ２、ＴｉＯ２、ＳｉＯ２、Ａｇ合金（Ａｇ−２ｗｔ％Ｓｂ）、ＳｉＯ２、アナターゼ型ＴｉＯ２を順次積層することにより成る。これら材料の積層にはスパッタリング法を用い、表面がアナターゼ型ＴｉＯ２となるようにプロセス中適宜加熱を施した。アナターゼ型ＴｉＯ２の形成はＸ線回折測定により確認し、Ａｇ合金の耐熱性も考慮しつつ基板温度２００℃など最適なプロセス条件を定めた。光触媒機能については、水に対する接触角の紫外光照射による変化から評価した。図７（ｂ）に示す実験結果のように、紫外光照射（波長３６５ｎｍ、強度２ｍＷ／ｃｍ２）により接触角は１０度以下に低下し、試料表面が明確な親水性を示すことを確認した。観測された接触角の初期値（約８０度）は文献等で報告された値（３５度前後）よりかなり大きいが、この差異の原因は試料表面への吸着物や汚れの影響が大きいと考えられる。日射熱反射機能については透過率および反射率の分光測定により評価した。図７（ｃ）に示すように、可視光透過と近赤外光反射の特性を確認した。以上の結果から本実施例４が光触媒機能を有する日射熱反射シートであることが示された。Example 4
Example 4 is an example in which a solar heat reflecting sheet having a photocatalytic function was experimentally manufactured using a light reflector including a heat-resistant silver alloy light reflecting material according to the present invention. In accordance with the basic structure shown in FIG. 7A, SiO 2 , TiO 2 , SiO 2 , Ag alloy (Ag-2 wt% Sb), SiO 2 , and anatase TiO 2 are sequentially laminated on a sheet glass (1 mm thick). It consists of Lamination of these materials was performed using a sputtering method and appropriately heated during the process so that the surface became anatase TiO 2 . The formation of anatase TiO 2 was confirmed by X-ray diffraction measurement, and optimum process conditions such as a substrate temperature of 200 ° C. were determined in consideration of the heat resistance of the Ag alloy. About the photocatalytic function, it evaluated from the change by the ultraviolet light irradiation of the contact angle with respect to water. As shown in the experimental results shown in FIG. 7B, the contact angle was reduced to 10 degrees or less by ultraviolet light irradiation (wavelength 365 nm, intensity 2 mW / cm 2 ), and it was confirmed that the sample surface showed clear hydrophilicity. . The observed initial value of contact angle (approximately 80 degrees) is considerably larger than the value reported in the literature (around 35 degrees), but the reason for this difference is thought to be the effect of adsorbate and dirt on the sample surface. It is done. The solar heat reflection function was evaluated by spectroscopic measurement of transmittance and reflectance. As shown in FIG. 7C, the characteristics of visible light transmission and near-infrared light reflection were confirmed. From the above results, it was shown that Example 4 is a solar heat reflective sheet having a photocatalytic function.
（実施例５）
実施例５は、本発明による耐熱性銀合金光反射材を含む光反射体を用いて光触媒機能を有する日射熱反射シートを試作した例である。図８（ａ）に示す基本構造に沿って板ガラス（１ｍｍ厚）上に、ＳｉＯ２、ＴｉＯ２、ＳｉＯ２、Ａｇ合金（Ａｇ−３ｗｔ％Ｓｂ）、ＳｉＯ２、アナターゼ型ＴｉＯ２を順次積層することにより成る。これら材料の積層にはスパッタリング法を用い、表面がアナターゼ型ＴｉＯ２となるようにプロセス中適宜加熱を施した。アナターゼ型ＴｉＯ２の形成はＸ線回折測定により確認し、Ａｇ合金の耐熱性も考慮しつつ基板温度２００℃など最適なプロセス条件を定めた。光触媒機能については、水に対する接触角の紫外光照射による変化から評価した。図８（ｂ）に示す実験結果のように、紫外光照射（波長３６５ｎｍ、強度２ｍＷ／ｃｍ２）により接触角は１０度以下に低下し、試料表面が明確な親水性を示すことを確認した。観測された接触角の初期値（約８０度）は文献等で報告された値（３５度前後）よりかなり大きいが、この差異の原因は試料表面への吸着物や汚れの影響が大きいと考えられる。日射熱反射機能については透過率および反射率の分光測定により評価し、図８（ｃ）に示すように可視光透過と近赤外光反射を確認した。以上の結果から本実施例５が光触媒機能を有する日射熱反射シートであることが示された。(Example 5)
Example 5 is an example in which a solar heat reflecting sheet having a photocatalytic function was experimentally manufactured using a light reflector including a heat-resistant silver alloy light reflecting material according to the present invention. In accordance with the basic structure shown in FIG. 8A, SiO 2 , TiO 2 , SiO 2 , Ag alloy (Ag-3 wt% Sb), SiO 2 , and anatase TiO 2 are sequentially laminated on a plate glass (1 mm thick). It consists of Lamination of these materials was performed using a sputtering method and appropriately heated during the process so that the surface became anatase TiO 2 . The formation of anatase TiO 2 was confirmed by X-ray diffraction measurement, and optimum process conditions such as a substrate temperature of 200 ° C. were determined in consideration of the heat resistance of the Ag alloy. About the photocatalytic function, it evaluated from the change by the ultraviolet light irradiation of the contact angle with respect to water. As shown in the experimental results shown in FIG. 8B, the contact angle was reduced to 10 degrees or less by ultraviolet light irradiation (wavelength 365 nm, intensity 2 mW / cm 2 ), and it was confirmed that the sample surface showed clear hydrophilicity. . The observed initial value of contact angle (approximately 80 degrees) is considerably larger than the value reported in the literature (around 35 degrees), but the reason for this difference is thought to be the effect of adsorbate and dirt on the sample surface. It is done. The solar heat reflection function was evaluated by spectroscopic measurement of transmittance and reflectance, and visible light transmission and near-infrared light reflection were confirmed as shown in FIG. From the above results, it was shown that Example 5 is a solar heat reflective sheet having a photocatalytic function.
本発明に係る耐熱性Ａｇ合金光反射材を含む光反射層と所定の金属酸化物を主成分とする付加層とを具備する光反射体は、優れた光学特性と高耐熱性を有しているので光反射膜または半透過反射膜として極めて有用である。産業上の特に重要な利用分野は光触媒機能を有する日射熱反射シートへの応用である。Ａｇ並みの低い光吸収特性を維持したままアナターゼ型ＴｉＯ２形成に十分な耐熱性を達成したので、本発明に係る合金膜利用の日射熱反射膜に後プロセスでアナターゼ型ＴｉＯ２による光触媒機能を付加することが初めて可能となった。実施例３〜５は光触媒機能を有する日射熱反射シートへの具体的な応用例である。これら試作結果によれば、高い近赤外光反射率および十分な可視光透過率、並びに紫外光照射による高い親水性を得ており、産業上の利用可能性は高い。
次に重要な利用分野は、反射型液晶パネルや反射型プロジェクター、バックライト等における反射膜としての利用である。耐熱性の要請から現在はアルミニウムやその合金の薄膜が用いられているが、本発明に係る耐熱性Ａｇ合金光反射材に代替することにより低い光吸収と高反射率を活かして低消費電力化と演色性の向上を図ることができる。
また、添加したＳｂの熱伝導率（２４Ｗ/ｍＫ）はＡｇの熱伝導率（４２９Ｗ/ｍＫ）よりも遥かに低いので、得られた合金膜もＡｇ膜より熱伝導率が低いと推定される。このように優れた光反射特性、耐熱性、および、低熱伝導率を有するので、本発明に係る耐熱性Ａｇ合金光反射材を含む光反射体はＤＶＤなど光情報記録用の反射膜として適当である。
The light reflector comprising the light reflecting layer containing the heat resistant Ag alloy light reflecting material according to the present invention and the additional layer mainly composed of a predetermined metal oxide has excellent optical characteristics and high heat resistance. Therefore, it is extremely useful as a light reflecting film or a semi-transmissive reflecting film. A particularly important field of application in industry is application to solar heat reflecting sheets having a photocatalytic function. Since sufficient heat resistance was achieved for the formation of anatase TiO 2 while maintaining light absorption characteristics as low as Ag, the photocatalytic function of anatase TiO 2 in the post-process was applied to the solar heat reflective film using the alloy film according to the present invention. It became possible for the first time to add. Examples 3 to 5 are specific application examples to a solar heat reflecting sheet having a photocatalytic function. According to these prototype results, high near-infrared light reflectivity, sufficient visible light transmittance, and high hydrophilicity by ultraviolet light irradiation are obtained, and industrial applicability is high.
The next important field of application is the use as a reflective film in reflective liquid crystal panels, reflective projectors, backlights and the like. Currently, thin films of aluminum and its alloys are used due to the demand for heat resistance, but by replacing the heat-resistant Ag alloy light reflecting material according to the present invention, low power consumption and low power consumption can be achieved. And color rendering can be improved.
Further, since the thermal conductivity (24 W / mK) of the added Sb is much lower than the thermal conductivity (429 W / mK) of Ag, it is estimated that the obtained alloy film also has a lower thermal conductivity than the Ag film. . Since it has such excellent light reflection characteristics, heat resistance, and low thermal conductivity, the light reflector containing the heat resistant Ag alloy light reflecting material according to the present invention is suitable as a reflection film for optical information recording such as DVD. is there.
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| JP2009196264 | 2009-08-27 | ||
| JP2009196264 | 2009-08-27 | ||
| PCT/JP2010/064144 WO2011024740A1 (en) | 2009-08-27 | 2010-08-23 | Light reflector comprising heat-resistant silver alloy light-reflecting material |
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| JP2008158120A (en) * | 2006-12-22 | 2008-07-10 | Nakai Kogyo Kk | Film for pasting window |
| JP2008164768A (en) * | 2006-12-27 | 2008-07-17 | Asahi Glass Co Ltd | Reflection mirror |
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2010
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| JP2002162510A (en) * | 2000-11-22 | 2002-06-07 | Murakami Corp | Translucent high reflection film |
| JP2004126497A (en) * | 2002-08-08 | 2004-04-22 | Kobe Steel Ltd | Light reflection film, liquid crystal display element using the same, and sputtering target for light reflection film |
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