JP2006256902A - Automatic heat controlling, color tone matching and light shielding glass, and its producing method - Google Patents
Automatic heat controlling, color tone matching and light shielding glass, and its producing method Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/10165—Functional features of the laminated safety glass or glazing
- B32B17/10174—Coatings of a metallic or dielectric material on a constituent layer of glass or polymer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
- B32B17/10036—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising two outer glass sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/10165—Functional features of the laminated safety glass or glazing
- B32B17/10339—Specific parts of the laminated safety glass or glazing being colored or tinted
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/10165—Functional features of the laminated safety glass or glazing
- B32B17/10431—Specific parts for the modulation of light incorporated into the laminated safety glass or glazing
- B32B17/10467—Variable transmission
- B32B17/10477—Variable transmission thermochromic
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
- C03C17/008—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character comprising a mixture of materials covered by two or more of the groups C03C17/02, C03C17/06, C03C17/22 and C03C17/28
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
- C03C17/3417—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials all coatings being oxide coatings
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
Abstract
Description
本発明は、自動調熱色調調和遮光ガラス及び製造方法に関するものであり、更に詳しくは、可視光透過率が７０％以下で、遮光性に優れ、環境温度に応じて赤外線の透過率が自動的に調節でき、更に、透過色など、色調を好みや建築物、移動体の外装に応じて自由に色調調和できることにより、建築物の窓や自動車など移動体の窓ガラスとして使用でき、省エネルギー、健康快適、プライバシー保護等の機能を有し、環境に優しい新規製品としてその応用及び波及が大いに期待される新しい自動調熱色調調和遮光ガラスを提供するものである。本発明は、これまで実用化に壁があった二酸化バナジウム系の調光調熱ガラスを、特に、その基材ガラスが強い固有の黄色に着色する問題を根本的に解決して、その色調を任意の色調に調和することが可能な新しい色調調和機能を有する自動調熱色調調和遮光ガラスを提供するものである。 The present invention relates to an automatic heat-adjusting color-harmonic light-shielding glass and a manufacturing method. More specifically, the visible light transmittance is 70% or less, the light-shielding property is excellent, and the infrared transmittance automatically depends on the environmental temperature. In addition, it can be used as a window glass for mobile objects such as windows for buildings and automobiles because it can be adjusted freely according to preference, building, and exterior of mobile objects. The present invention provides a new automatic heat-adjusting color-harmonic shading glass that has functions such as comfort and privacy protection and is expected to be applied and spread as a new environmentally friendly product. The present invention fundamentally solves the problem of the vanadium dioxide-based light control and heat control glass, which has been impeded in practical use, in particular, the problem that the base glass is colored with a strong inherent yellow color. It is an object of the present invention to provide an automatic thermal color tone light-shielding glass having a new color tone harmony function capable of being harmonized with an arbitrary color tone.
従来の調光可能な省エネルギー窓ガラスとして、自動的に調光を行うガラス、例えば、エレクトロクロミック（ＥＣ：電圧の印加により可逆的に着色と消色を繰り返す）ガラスやガスクロミック（ＧＣ：水素ガスの導入により着色と消色を繰り返す）ガラスが研究されている。しかし、それらの窓ガラスは、高い調光能力を持つものの、構造が複雑であり、また、調光するためには追加の設備（電圧印加系やガス導入系）が必要であるため、コストが高くなるという欠点があった。 As a conventional energy-saving window glass capable of dimming, glass that automatically dims, for example, electrochromic (EC: reversibly coloring and decoloring by applying voltage) glass or gas chromic (GC: hydrogen gas) (Repeating coloring and decoloring with the introduction of) has been studied. However, although these window glasses have high dimming capability, the structure is complicated and additional equipment (voltage application system and gas introduction system) is necessary for dimming. There was a drawback of becoming higher.
一方、二酸化バナジウム（ＶＯ２）結晶は、６８℃で半導体・金属相転移によりサーモクロミック（温度による光特性の可逆的な変化）特性を示し、また、タングステン（Ｗ）など金属元素の添加で転移温度を室温好適まで下げることができることが周知となっている（非特許文献１、及び特許文献１、２）。その光学特性の温度変化を利用して、環境温度のみで自律的に太陽光を調節できる窓コーティング材料が研究されている（非特許文献１）。二酸化バナジウム系調光ガラスについては、構造が非常に簡単な上、環境温度の変化によって自然に且つ自動的に調光を行うため、余分な設備を必要としない。 On the other hand, vanadium dioxide (VO 2 ) crystals show thermochromic properties (reversible changes in optical properties with temperature) due to semiconductor-metal phase transition at 68 ° C, and transition with addition of metallic elements such as tungsten (W). It is well known that the temperature can be lowered to room temperature (Non-Patent Document 1, and Patent Documents 1 and 2). A window coating material that can autonomously adjust sunlight only by the environmental temperature using the temperature change of its optical characteristics has been studied (Non-Patent Document 1). The vanadium dioxide light control glass has a very simple structure and adjusts light naturally and automatically according to changes in environmental temperature, so that no extra equipment is required.
二酸化バナジウムによるサーモクロミック調光ガラスの研究に関して、例えば、それらの製造法（特許文献３、４）、サーモクロミック体及びその製造方法（特許文献５）、及びその他（特許文献１，２，６、７）、等により、その製造法や転移温度制御のための元素添加法などが公開されている。 Regarding research on thermochromic light control glass using vanadium dioxide, for example, their production method (Patent Documents 3 and 4), thermochromic body and its production method (Patent Document 5), and others (Patent Documents 1, 2, 6, 7), etc., the manufacturing method and element addition method for controlling the transition temperature are disclosed.
しかし、以上のように、従来型の二酸化バナジウム系サーモクロミック調光材料では、（１）もともと、可視光を含め短波長での強い吸収により、可視光透過率が小さいこと、（２）常温輻射熱に対する反射率が小さく、断熱性に乏しいこと、（３）バナジウム酸素系の相図が非常に複雑であり、二酸化バナジウム単一相薄膜の形成が非常に難しく、特に、単一相大面積且つ光学的均一被膜の形成が極めて困難であること、（４）工業生産に適切な二酸化バナジウム薄膜の形成法、特に、効率の高いＤＣスパッタ法による工業生産が確立されていないこと、（５）更に、二酸化バナジウム系薄膜の固有吸収による強い黄色に着色する問題があること、などの理由により、実用化には高い障害があった。 However, as described above, conventional vanadium dioxide-based thermochromic light-modulating materials (1) originally have low visible light transmittance due to strong absorption at short wavelengths including visible light, and (2) room temperature radiant heat. (3) Vanadium oxygen-based phase diagram is very complicated, and it is very difficult to form a vanadium dioxide single-phase thin film. (4) The production method of the vanadium dioxide thin film suitable for industrial production, in particular, the industrial production by the highly efficient DC sputtering method has not been established, (5) There was a high obstacle to practical use because of the problem of strong yellow coloring due to intrinsic absorption of the vanadium dioxide thin film.
本発明者は、長年にわたって、二酸化バナジウム系薄膜による自動調光ガラスの研究を絶えずに励行してきた結果、以上の問題点のいくつかを解決することができた。例えば、新しい複層構造を創出することにより、可視光透過率を大きく向上させると同時に、紫外線完全カット、熱線反射機能の強化、光触媒効果等の複数の機能の追加による付加価値の高いガラスを開発している（特許文献８、９）。また、二酸化バナジウム系薄膜の形成困難性については、構造テンプレート設計により断熱効果を飛躍的に向上させるとともに、二酸化バナジウム系調光膜を今までになく低い基板温度で大面積、且つ光学的均一的に形成する有効な製造方法等を開発している（特許文献９）。 The present inventor has been continuously researching the automatic light control glass using the vanadium dioxide thin film for many years, and as a result, has been able to solve some of the above problems. For example, by creating a new multi-layer structure, the visible light transmittance will be greatly improved, and at the same time, high value-added glass will be developed by adding multiple functions such as full UV cut, enhanced heat ray reflection function, and photocatalytic effect. (Patent Documents 8 and 9). In addition, regarding the difficulty of forming vanadium dioxide thin films, the structural template design dramatically improves the heat insulation effect, and the vanadium dioxide dimming films have a large area and optically uniform characteristics at a lower substrate temperature than ever before. The effective manufacturing method etc. which are formed in this are developed (patent document 9).
しかし、これまでの本発明者の発明を含む研究や発明による大きな進歩にもかかわらず、（１）可視光透過率が低い、（２）二酸化バナジウム系調光膜の強い黄色、その消去や色調調和、（３）工業生産にも適切な製造方法、及び（４）最も適切な使い道、すなわち、製品、などの課題は、依然として解決しておらず、当材料の実用化に大きな障害があった。 However, in spite of research and inventions including the invention of the present inventor so far, (1) low visible light transmittance, (2) strong yellow of vanadium dioxide based light control film, erasure and color tone Issues such as harmony, (3) manufacturing methods suitable for industrial production, and (4) the most appropriate usage, ie products, have not been solved yet, and there was a major obstacle to the practical application of this material .
また、自動的ではないが、常に可視光が透過するが赤外線（日射の一部や輻射熱）を反射する低放射ガラス（Ｌｏｗ−Ｅガラス）、或いは主に日射熱を遮断する熱線反射ガラスなど、太陽光熱を選択的に制御するガラスがある（非特許文献２）。このガラスは、優れた光学特性と比較的に低コストで普及が広がっているが、いずれも、固定した光学特性で熱線を反射するのみで、冬夏など季節や環境の変化に応じて日射や熱輻射を調節する機能、すなわち、環境温度に応じて自動的に調光遮熱する機能はない。 In addition, although not automatically, low radiation glass (Low-E glass) that always transmits visible light but reflects infrared rays (part of solar radiation and radiant heat), or heat ray reflective glass that mainly blocks solar heat, etc. There is glass that selectively controls solar heat (Non-Patent Document 2). This glass is spreading widely due to its excellent optical properties and relatively low cost, but all of them only reflect heat rays with fixed optical properties. There is no function to adjust the radiation, that is, the function of automatically adjusting and shielding the light according to the environmental temperature.
近年、冷房負荷を減らすととともに、室内物品の劣化や肌焼け防止、遮光、プライバシー保護など、省エネで快適さを追求する紫外線カット、赤外線カットガラスが急増している。例えば、自動車の後部座席など、プライバシー保護を目的とする濃色着色ガラス、又はプライバシー保護と同時に紫外線や赤外線カット機能を持つガラス、などが開発されている（特許文献１０〜１５）。こういった強い着色のガラスは、紫外線や赤外線の防止、プライバシー保護などを目的として開発されているが、これまで、環境温度によって自動的に調熱機能を持つ濃色着色ガラスは見つかっていない。 In recent years, there has been a rapid increase in UV-cutting and infrared-cutting glasses that reduce energy consumption and pursue comfort by reducing indoor loads, preventing deterioration of indoor items, preventing skin burn, shading, and protecting privacy. For example, dark colored glass for the purpose of privacy protection, such as a rear seat of an automobile, or glass having an ultraviolet ray or infrared ray cut function simultaneously with privacy protection has been developed (Patent Documents 10 to 15). Such strongly colored glass has been developed for the purpose of preventing ultraviolet rays and infrared rays, protecting privacy, etc., but no dark colored glass having a function of automatically adjusting the temperature depending on the environmental temperature has been found so far.
また、顕著な太陽光遮蔽特性を有する多層薄膜による被覆ガラスが提案されている（特許文献１６）。しかし、それは、選択性について、視感透過率が日射取得率（或いは、ソーラファクター）より大きいとして定義し、主に顕著な日射遮蔽特性を求めるものであり、環境温度による自動調熱機能や多彩な色調調和機能は期待できない。更に、安全、強化、防犯などを目的とする合わせガラスが市販されている。しかし、そういった商品にも、環境温度による自動調熱機能を持つものやその発想は全く見当たらない。 Moreover, the coating glass by the multilayer thin film which has a remarkable sunlight shielding characteristic is proposed (patent document 16). However, in terms of selectivity, the luminous transmittance is defined as being greater than the solar radiation acquisition rate (or solar factor), which mainly requires significant solar radiation shielding characteristics. It is not possible to expect a good color harmony function. Furthermore, laminated glass for the purpose of safety, strengthening, crime prevention and the like is commercially available. However, there is no such product that has an automatic temperature control function depending on the environmental temperature or its idea.
このような状況の中で、本発明者は、上記従来技術に鑑みて、上記従来技術の諸問題を解決して二酸化バナジウム薄膜の実用化を可能とする新技術を開発することを目標として、長年にわたって、二酸化バナジウム調光薄膜に関し、鋭意研究や実験を行った結果及び窓ガラスに関する知識から、市販建築物や自動車等の遮光やプライバシー保護するための濃色遮光ガラスに鑑み、従来のサーモクロミック調光ガラスの弱点、すなわち、可視光透過率が低いという特徴を優れた遮光特性として発想を逆転させて利用し、更に、今まで解決されなかった、二酸化バナジウム薄膜の最大の問題である強い固有の黄色を、補色原理に基づいて着色物質や着色基材を活用することによって所期の目的を達成できることを見出し、本発明を完成するに至った。 In such a situation, the present inventor, in view of the above-mentioned conventional technology, with the goal of developing a new technology that enables the practical use of vanadium dioxide thin film by solving the problems of the above-mentioned conventional technology, From the result of earnest research and experiment on vanadium dioxide light control thin film over many years and knowledge about window glass, in view of dark shade glass for shading and privacy protection of commercial buildings and cars etc., conventional thermochromic Utilizing the weakness of light control glass, that is, the characteristic of low visible light transmittance as an excellent light-shielding property, by reversing the idea, and further, the strong problem inherent in the vanadium dioxide thin film that has not been solved so far Was found that the intended purpose can be achieved by utilizing colored substances and colored base materials based on the complementary color principle, and the present invention has been completed. .
すなわち、本発明は、ガラスの色調を自由に調和できるようにしたこと、夏には過剰の日射熱の遮蔽、冬には日射熱の導入ができること、その機能を環境温度により自動的に行うことができること、また、好みや環境の外装によって色調が自由に選べること、更に、多数の機能を追加できることを実現する自動調熱色調調和遮光ガラス及びその製造方法を提供することを目的とするものである。また、本発明は、新しい機能性ガラス、すなわち、自動調熱、色調調和、紫外線カット、断熱、快適照度、プライバシー保護等の多彩な機能を持ち合わせたガラス、特に、その可視光透過率が７０％以下と低く、建築物、車両その他移動体の窓ガラスに、省エネルギー、健康快適、プライバシー保護、色調調和等の機能を付与できる全く新規なガラス製品及びその製造法を提供することを目的とするものである。 That is, according to the present invention, the color tone of the glass can be freely harmonized, the excessive solar heat can be shielded in summer, the solar heat can be introduced in winter, and the function is automatically performed according to the environmental temperature. In addition, it is intended to provide a self-adjusting color-harmoniced light-shielding glass and a method for manufacturing the same that can be freely selected according to taste and the exterior of the environment, and that many functions can be added. is there. In addition, the present invention is a new functional glass, that is, a glass having various functions such as automatic heat adjustment, color harmony, ultraviolet ray cut, heat insulation, comfortable illumination, privacy protection, etc., and particularly has a visible light transmittance of 70%. The purpose of the present invention is to provide a completely new glass product that can provide functions such as energy saving, health and comfort, privacy protection, and color harmony to the window glass of buildings, vehicles, and other moving objects, and its manufacturing method. It is.
上記課題を達成するための本発明は、以下の技術的手段から構成される。
（１）二酸化バナジウム系自動調熱ガラスにおいて、基材に、二酸化バナジウム系自動調熱膜と、調色膜が、被覆されていることを特徴とする自動調熱色調調和ガラス。
（２）二酸化バナジウム系自動調熱ガラスにおいて、基材に、二酸化バナジウム系自動調熱膜と、調色膜、及び機能膜が、被覆されていることを特徴とする自動調熱色調調和ガラス。
（３）自動調熱膜の固有色が、補色原理に基づき調色膜又は調色膜と機能膜との組み合わせで任意に調節することにより、所定の色調に制御されている前記（１）又は（２）に記載の自動調熱色調調和ガラス。
（４）自動調熱膜の固有色が、補色原理に基づき基材ガラスを着色することにより、所定の色調に制御されている前記（１）又は（２）に記載の自動調熱色調調和ガラス。
（５）自動調熱膜の固有色が、補色原理に基づき着色フィルムを基材ガラスに貼る又は２枚以上の板ガラスで挟む、又は着色樹脂で２枚以上のガラスを接着することにより、所定の色調に制御されている前記（１）又は（２）に記載の自動調熱色調調和ガラス。
（６）自動調熱膜の固有色が、補色原理に基づき着色材を基材ガラスに塗布することにより、所定の色調に制御されている前記（１）又は（２）に記載の自動調熱色調調和ガラス。
（７）二酸化バナジウム系自動調熱ガラスにおいて、二酸化バナジウム系自動調熱材料と、調色材料、及び任意に機能材料が、プラスチックや合成樹脂フィルムに塗布又は分散されて、自動調熱材料の固有色が、補色原理に基づき上記調色材料によって、所定の色調に制御されていることを特徴とする自動調熱色調調和フィルム又はそのフィルムを使用した自動調熱色調調和ガラス。
（８）建築物、又は移動体の窓ガラス用のガラスである前記（１）から（７）のいずれかに記載の自動調熱色調調和ガラス。
（９）可視光透過率が７０％以下で、遮光性に優れ、同時に色調が調節された自動調熱色調調和遮光プライバシーガラスである前記（１）から（８）のいずれかに記載の自動調熱色調調和ガラス。
（１０）調色膜が、着色機能を持つ遷移金属及び／又はその化合物、希土金属及び／又はその化合物、又は上記物質の単独或いは２種以上を任意に組み合わせた複合体からなる膜である前記（１）から（７）のいずれかに記載の自動調熱色調調和ガラス。
（１１）調色膜が、着色機能を持つ遷移金属及び／又はその化合物、希土金属及び／又はその化合物、又は上記物質の単独或いは２種以上を任意に組み合わせた複合体を、透明物質マトリックスに塗布又は分散させて形成された前記（１）から（７）のいずれかに記載の自動調熱色調調和ガラス。
（１２）調色膜の着色材が、着色機能を持つ無機物質、又は有機物質、又は無機物質と有機物質の混合物、又はそれらの分散系である前記（１）から（７）のいずれかに記載の自動調熱色調調和ガラス。
（１３）透明物質マトリックスが、ルチル結晶構造を有する結晶物質の単独又は２種以上の任意的組み合わせからなる前記（１１）に記載の自動調熱色調調和ガラス。
（１４）透明物質マトリックスが、ルチル結晶構造以外の酸化物、窒化物、フッ化物、硫化物等透明誘電体物質又は透明導電体物質の単独又は２種以上の任意的組み合わせからなる前記（１１）に記載の自動調熱色調調和遮光ガラス。
（１５）透明物質マトリックスが、透明ないし透光性プラスチックフィルム、合成樹脂又はそのフィルムである前記（１１）に記載の自動調熱色調調和ガラス。
（１６）着色フィルムや着色樹脂を、２枚以上の板ガラスで挟む、又は２枚以上のガラスを接着することにより、可視光透過率を７０％以下に低く抑えて、適切な照度とプライバシー保護ガラスとした前記（９）に記載の自動調熱色調調和ガラス。
（１７）色調調和のために、自動調熱膜に、遷移金属及び／又はその化合物、希土金属及び／又はその化合物、又は上記物質の単独或いは２種以上を任意に組み合わせた複合体が添加された前記（１）から（７）のいずれかに記載の自動調熱色調調和ガラス。
（１８）色調調和のために、基材ガラスに、着色機能を持つ遷移金属及び／又はその化合物、希土金属及び／又はその化合物、又は上記物質の単独或いは２種以上を任意に組み合わせた複合体を混入して、二酸化バナジウム系膜の強い固有色を色調調和できるように着色された前記（１）から（７）のいずれかに記載の自動調熱色調調和ガラス。
（１９）色調調和のために、基材ガラスに、着色機能を持つ次の着色物質：１）Ｎｄ及びその化合物、その質量百分率表示のＮｄ２Ｏ３基準含有量が０．１％以上であること、２）Ｃｏ及びその化合物、その質量百分率表示のＣｏＯ基準含有量が１ｐｐｍ以上であること、３）Ｎｄ及びＣｏを１）と２）の条件で同時に含有すること、により青色着色することにより、二酸化バナジウム系膜の強い固有の黄色が中性色の近くに調和された前記（１）から（７）のいずれかに記載の自動調熱色調調和ガラス。
（２０）自動調熱膜、調色膜、及び任意に機能膜が、任意に組み合わせてガラスの同一側に設置された、又はガラスの両側に分けて設置された、又は複数枚のガラスに分離して設置された前記（１）から（７）のいずれかに記載の自動調熱色調調和ガラス。
（２１）自動調熱膜が、次のいずれかの方法、１）主成分がバナジウム酸化物Ｖ２Ｏ５、又は組成がＶＯｘ（２＜ｘ＜２.５）を有するバナジウム酸化物、又はその混合物に、バナジウム金属を混合、成形又は焼結した導電性ターゲットを不活性ガス又は酸素含有不活性ガス中でスパッタする、２）主成分が二酸化バナジウムＶＯ２からなる化合物ターゲットを相転移温度以上に加熱し、金属相への相転移による導電性ターゲットを不活性ガス又は酸素含有不活性ガス中でスパッタする、３）自動調熱膜は、主成分が二酸化バナジウムからなる化合物ターゲットをＲＦスパッタさせ、ターゲットの温度が相転移温度以上に上昇させてから、金属相による導電性ターゲットを不活性ガス又は酸素含有不活性ガス中でスパッタする、によるＤＣ（パルスＤＣを含む）マグネトロンスパッタ法により形成されている前記（１）から（７）のいずれかに記載の自動調熱色調調和ガラス。
（２２） ターゲットが、転移温度降下のための微量元素の添加を含む前記（２１）に記載の自動調熱色調調和ガラス。
（２３）自動調熱膜、調色膜、及び任意の機能膜の少なくとも一つ以上が、フロートガラス製造ライン上におけるフロートバス又は徐冷窯の内部の熱環境を利用し、ガラス表面が高温のまま、常圧又は減圧で汎用薄膜形成法により、単独又は連続に形成されている前記（１）から（７）のいずれかに記載の自動調熱色調調和ガラス。
（２４）自動調熱膜、調色膜、及び任意の機能膜の少なくとも一つ以上が、ガラスの強化や曲げ加工プロセスの熱環境を利用し、所定の温度範囲で、常圧又は減圧で汎用薄膜形成法により単独又は連続に形成されている前記（１）から（７）のいずれかに記載の自動調熱色調調和ガラス。
（２５）自動調熱膜、調色膜、及び任意の機能膜の少なくとも一つ以上が、汎用薄膜形成法により室温を含む低温で形成した後、ガラスの強化や曲げ加工プロセスの熱環境を利用し、所定の温度範囲で、熱処理によって形成されている前記（１）から（７）のいずれかに記載の自動調熱色調調和ガラス。
In order to achieve the above object, the present invention comprises the following technical means.
(1) An automatic heat-adjusting color-harmonic glass characterized in that a vanadium dioxide-based automatic heat-adjusting glass is coated with a vanadium dioxide-based automatic heat-adjusting film and a color-adjusting film.
(2) A vanadium dioxide-based automatic temperature-adjusting glass, wherein the substrate is coated with a vanadium dioxide-based automatic heat-adjusting film, a color-adjusting film, and a functional film.
(3) The inherent color of the automatic heat-adjusting film is controlled to a predetermined color tone by arbitrarily adjusting the intrinsic color of the automatic heat-adjusting film by a toning film or a combination of a toning film and a functional film based on the complementary color principle (2) The automatic heat-adjusting color-harmonic glass.
(4) The self-adjusting color-tone glass according to (1) or (2), wherein the intrinsic color of the automatic heat-adjusting film is controlled to a predetermined color tone by coloring the base glass based on the complementary color principle. .
(5) The intrinsic color of the self-adjusting film is determined by pasting a colored film on the base glass or sandwiching it between two or more plate glasses based on the complementary color principle, or by adhering two or more glasses with a colored resin. The automatic heat-adjusting color-harmonic glass according to (1) or (2), which is controlled by color tone.
(6) The automatic heat control according to (1) or (2), wherein the inherent color of the automatic heat control film is controlled to a predetermined color tone by applying a coloring material to the base glass based on the complementary color principle. Color harmony glass.
(7) In vanadium dioxide-based self-adjusting glass, vanadium dioxide-based self-adjusting material, toning material, and optionally functional material are applied or dispersed on plastic or synthetic resin film, so An automatic heat-adjusting color-harmonic film or an automatic heat-adjusting color-adjusting glass using the film, wherein the color is controlled to a predetermined color tone by the color-adjusting material based on the complementary color principle.
(8) The automatic heat-adjusting color-harmonic glass according to any one of (1) to (7), which is a glass for a window of a building or a moving body.
(9) The automatic adjustment according to any one of (1) to (8) above, wherein the visible light transmittance is 70% or less, the light-shielding property is excellent, and the self-adjusting color-harmonic light-shielding privacy glass is adjusted at the same time. Thermal color harmony glass.
(10) The toning film is a film made of a transition metal having a coloring function and / or a compound thereof, a rare earth metal and / or a compound thereof, or a composite obtained by arbitrarily combining two or more of the above substances. The automatic heat-adjusting color-harmonic glass according to any one of (1) to (7).
(11) A transparent material matrix in which the toning film is a transition metal having a coloring function and / or a compound thereof, a rare earth metal and / or a compound thereof, or a composite in which any one of the above substances is arbitrarily combined. The self-adjusting and color-harmonizing glass according to any one of (1) to (7), which is formed by being applied or dispersed in the glass.
(12) The colorant of the toning film is an inorganic substance having a coloring function, an organic substance, a mixture of an inorganic substance and an organic substance, or a dispersion system thereof (1) to (7) The automatic heat-adjusting color-harmonic glass described.
(13) The automatic heat-adjusting color-harmonic glass according to (11), wherein the transparent material matrix is composed of a crystal material having a rutile crystal structure, or an arbitrary combination of two or more thereof.
(14) The transparent material matrix (11) comprising a transparent dielectric material such as an oxide, nitride, fluoride, or sulfide other than the rutile crystal structure, or a transparent conductor material alone or in any combination of two or more. The self-adjusting color tone-shading glass described in 1.
(15) The self-adjusting color-tone glass according to (11), wherein the transparent material matrix is a transparent or translucent plastic film, a synthetic resin, or a film thereof.
(16) By sandwiching a colored film or colored resin between two or more plate glasses, or by bonding two or more glasses, the visible light transmittance is suppressed to 70% or less, and appropriate illuminance and privacy protection glass. The self-adjusting color-harmonic glass described in (9) above.
(17) Addition of transition metal and / or compound thereof, rare earth metal and / or compound thereof, or a combination of two or more of the above substances to the automatic heat control film for color harmony The self-adjusting color-tone glass according to any one of (1) to (7).
(18) In order to harmonize color tone, a transition glass having a coloring function and / or a compound thereof, a rare earth metal and / or a compound thereof, or a composite obtained by arbitrarily combining two or more of the above substances with a base glass. The self-adjusting color-tone glass according to any one of the above (1) to (7), which is colored so that the body can be mixed and the strong intrinsic color of the vanadium dioxide film can be harmonized.
(19) In order to harmonize the color tone, the following colored substance having a coloring function on the base glass: 1) Nd and its compounds, and the Nd 2 O 3 standard content in mass percentage display is 0.1% or more. 2) Co and its compounds, CoO standard content of mass percentage display is 1 ppm or more, 3) By containing Nd and Co simultaneously under the conditions of 1) and 2), by coloring blue The automatic heat-adjusting color harmony glass according to any one of (1) to (7), wherein the strong intrinsic yellow color of the vanadium dioxide film is harmonized near a neutral color.
(20) An automatic heat-adjusting film, a toning film, and optionally a functional film are arbitrarily combined and installed on the same side of the glass, or are installed separately on both sides of the glass, or separated into a plurality of glasses The automatic heat-adjusting color-harmonic glass according to any one of (1) to (7).
(21) The automatic heat control film is any one of the following methods, 1) the main component is vanadium oxide V 2 O 5 , or the composition is VO x (2 <x <2.5), or Sputter a conductive target obtained by mixing, molding or sintering vanadium metal into the mixture in an inert gas or an oxygen-containing inert gas. 2) A compound target whose main component is vanadium dioxide VO 2 is above the phase transition temperature. 3) Sputter the conductive target by the phase transition to the metal phase in an inert gas or an oxygen-containing inert gas. 3) The automatic heat control film RF-sputters a compound target whose main component is vanadium dioxide. After the temperature of the target is raised above the phase transition temperature, the conductive target based on the metal phase is sputtered in an inert gas or an oxygen-containing inert gas. (Including pulsed DC) self-heat hue conditioner glass according to any one of the is formed by magnetron sputtering from (1) (7).
(22) The automatic heat-adjusting color-harmonic glass according to (21), wherein the target includes addition of a trace element for lowering the transition temperature.
(23) At least one of the automatic heat-adjusting film, the color-adjusting film, and the optional functional film uses the thermal environment inside the float bath or annealing furnace on the float glass production line, and the glass surface has a high temperature. The automatic heat-adjusting color-harmonic glass according to any one of (1) to (7), which is formed alone or continuously by a general-purpose thin film forming method at normal pressure or reduced pressure.
(24) At least one or more of an automatic heat-adjusting film, a color-adjusting film, and an arbitrary functional film is used at a normal temperature or a reduced pressure within a predetermined temperature range using a thermal environment of glass strengthening or bending process. The automatic heat-adjusting color-harmonic glass according to any one of (1) to (7), which is formed alone or continuously by a thin film forming method.
(25) After at least one of an automatic heat-adjusting film, a color-adjusting film, and an arbitrary functional film is formed at a low temperature including room temperature by a general-purpose thin film forming method, use the thermal environment of glass strengthening or bending process And the automatic heat-adjusting color-harmonic glass according to any one of (1) to (7), which is formed by heat treatment in a predetermined temperature range.
次に、本発明について更に詳細に説明する。
本発明は、二酸化バナジウム系物質の６８℃付近に発生する半導体・金属相転移、及びその相転移温度が元素添加等によって室温付近好適温度に設定できる特性を利用し、冬などの低温時に日射熱を透過させるが、夏などの高温時に過剰の日射や輻射熱を遮蔽する、また、これらを環境温度の変化だけで自動的に行うことのできるガラスの自動調熱膜を構成した点を特徴とするものである。また、本発明は、従来の二酸化バナジウム系薄膜の弱点である透過率が低いことを、逆転の発想により可視光透過率が７０％以下で、遮光を目的とする多機能ガラスに転じたこと、また、積極的に着色材料を利用し、補色原理を使って、中性又は目的に応じて色調を自由に調和できること、それによって、遮光性を更に向上すると同時に、従来の二酸化バナジウムが強い固有の黄色を呈するという大きな問題点を解決したこと、に特徴を有するものである。
Next, the present invention will be described in more detail.
The present invention utilizes the characteristics of a semiconductor / metal phase transition that occurs near 68 ° C. in a vanadium dioxide-based material and its phase transition temperature can be set to a suitable temperature near room temperature by adding elements, etc. It features a glass self-adjusting film that shields excessive solar radiation and radiant heat at high temperatures such as in summer, and can automatically perform these only by changes in environmental temperature. Is. In addition, the present invention has a low transmittance which is a weak point of the conventional vanadium dioxide thin film, the visible light transmittance is 70% or less due to the idea of reversal, and has turned into a multifunctional glass intended for light shielding, In addition, by using coloring materials positively and using the complementary color principle, it is possible to freely harmonize the color tone according to neutrality or purpose, thereby further improving the light shielding property and at the same time, the conventional vanadium dioxide has a strong inherent characteristic. It is characterized by solving the big problem of yellow.
本発明では、二酸化バナジウム系自動調熱膜Ａと、調色膜Ｂ、機能膜Ｃを、少なくともＡとＢの２層以上組み合わせで被覆し、系の色調は、自動調熱膜Ａの固有色を、調色原理に基づき調色膜Ｂ又は調色膜Ｂと機能膜Ｃとの組み合わせで任意に調節し、所定の透過色等色調を自由に制御できるようにすることができる。二酸化バナジウム系薄膜Ａには、二酸化バナジウム単一化合物、又は周知の知識により、例えば、転移温度制御のための金属元素、非金属元素、又はその任意の組み合わせによるものが含まれる［１）S.M. Babulanam, T.S. Eriksson, G.A. Niklasson and C.G. Granqvist: Solar Energy Matrials, 16(1987)347、２）特開昭５０−５０２９４号公報、３）特表２００２−５１６８１３号公報、等により添加元素の種類など知られている。］。 In the present invention, the vanadium dioxide-based automatic heat-adjusting film A, the toning film B, and the functional film C are coated with a combination of at least two layers of A and B. Can be arbitrarily adjusted by the toning film B or the combination of the toning film B and the functional film C on the basis of the toning principle, so that a predetermined color tone such as a transmission color can be freely controlled. The vanadium dioxide-based thin film A includes a vanadium dioxide single compound or, based on a well-known knowledge, for example, a metal element for controlling the transition temperature, a non-metal element, or any combination thereof [1) SM Babulanam , TS Eriksson, GA Niklasson and CG Granqvist: Solar Energy Matrials, 16 (1987) 347, 2) Japanese Patent Laid-Open No. 50-50294, 3) Japanese Translation of PCT International Publication No. 2002-516813, etc. ing. ].
本発明で最も重要なポイントの一つは、二酸化バナジウム系薄膜の系に、色調調和のための調色材料又は調色膜を導入することである。すなわち、調色膜Ｂには、遷移金属（Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｚｒ、Ｎｂ、Ｍｏ、Ｔｃ、Ｒｕ、Ｒｈ、Ｐｄ、Ａｇ、Ｈｆ、Ｔａ、Ｗ、Ｒｅ、Ｏｓ、Ｉｒ、Ｐｒ、Ａｕ）及び／又はその化合物、好適には、ガラスの着色によく使われるＣｏ、Ｍｎ、Ｃｒ、Ｃｕ、Ｎｉ、Ｆｅ、Ｍｏ、Ｗ、Ａｇ、Ａｕ、Ｔｉ及び／又はその化合物、又は希土金属（Ｓｃ、Ｙ、Ｌａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ、Ｌｕ）及び／又はその化合物、好適には、ガラスの着色に有効なＮｄ、Ｅｒ、Ｃｅ、Ｐｒ及び／又はその化合物、更に、上述の添加物の単独、或いは２種以上を任意に組み合わせた複合着色物質を含むことができる。 One of the most important points in the present invention is to introduce a toning material or a toning film for color tone harmony into the vanadium dioxide thin film system. That is, the toning film B includes transition metals (Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Hf, Ta, W, Re, Os, Ir, Pr, Au) and / or compounds thereof, preferably Co, Mn, Cr, Cu, Ni, Fe, Mo, W, Ag, Au, Ti and / or those often used for coloring glass Or a rare earth metal (Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) and / or a compound thereof, preferably Further, Nd, Er, Ce, Pr and / or a compound thereof effective for coloring the glass, and further, a composite coloring material obtained by combining any one of the above-mentioned additives or two or more of them may be included.
調色膜Ｂには、着色物質が、酸化バナジウムの本来の黄褐色の補色である青系を中心とするガラスの着色物質、例えば、酸化コバルト、酸化銅、酸化クロム、酸化ニッケル、酸化マンガン、酸化ネオジウム、酸化エルビウム、酸化プラセオジウム、酸化セリウム、酸化鉄などが、中性色を得るのに好適であるが、色調調節により多彩の色調が得られる限り、それらに制限されるものではない。特に、コバルトイオンＣｏ２＋が、６５０ｎｍ付近の可視光吸収により青色を呈することで、二酸化バナジウムの黄色の補色となり、それを中和することにより中性色を得るのに有効である。 In the toning film B, the coloring substance is a glass coloring substance centering on blue which is a complementary yellow-brown color of vanadium oxide, for example, cobalt oxide, copper oxide, chromium oxide, nickel oxide, manganese oxide, Neodymium oxide, erbium oxide, praseodymium oxide, cerium oxide, iron oxide, and the like are suitable for obtaining a neutral color, but are not limited thereto as long as various color tones are obtained by color tone adjustment. In particular, the cobalt ion Co 2+ exhibits a blue color due to visible light absorption near 650 nm, thereby becoming a yellow complementary color of vanadium dioxide, and is effective in obtaining a neutral color by neutralizing it.
また、本発明では、調色膜Ｂの着色材は、色素、蛍光体、染料、着色等の機能を持つ有機又は無機物質であってもよい。また、着色膜Ｂには、着色物質による単独の膜以外に、着色物質を透明物質マトリックスに塗布又は分散させてもよい。例えば、色調調節のために、通常の透明や透光性プラスチックフィルムや樹脂からなる着色フィルムをガラスに貼る、又はその物質で２枚以上の板ガラスを接着するなど、所定の透過色等の色調を自由に制御することが可能である。その場合、合わせガラスの製造プロセスと一致させるために、安全、防犯や強化など目的とする合せガラスに、自動調熱、遮光、色調調和等の機能を持ち合わせるようにすることができる。 In the present invention, the colorant of the toning film B may be an organic or inorganic substance having functions such as a pigment, a phosphor, a dye, and coloring. Further, in the colored film B, in addition to a single film made of a colored substance, a colored substance may be applied or dispersed in a transparent substance matrix. For example, in order to adjust the color tone, a normal transparent or translucent plastic film or a colored film made of a resin is attached to glass, or two or more plate glasses are adhered with the substance, and the color tone of a predetermined transmission color is adjusted. It can be freely controlled. In that case, in order to match the laminated glass manufacturing process, the laminated glass intended for safety, crime prevention and strengthening can have functions such as automatic heat adjustment, light shielding, and color harmony.
着色物質を直接にガラス等透明基材に添加すること、或いはガラス基材に塗布することによる着色ガラス等の基材の使用も、系の色調を調和できる。それは、最も簡単で有効な方法の一つであるが、二酸化バナジウム系膜の強い固有の黄色を調和するために、従来の着色ガラスと比べ、比較的に強く着色力と鮮明な着色の特殊なガラス基材が要求される。二酸化バナジウム系膜の強い固有の黄色を補色原理により中性色近くに色調調和するためには、やや強く青色に着色したガラス基材が望ましい。例えば、ガラスに青色着色剤として使われているＮｄ及びその化合物、Ｃｏ及びその化合物が好適である。 Addition of a coloring substance directly to a transparent substrate such as glass or use of a substrate such as colored glass by applying it to the glass substrate can also harmonize the color tone of the system. It is one of the simplest and most effective methods, but in order to harmonize the strong inherent yellow color of vanadium dioxide-based films, it has a relatively strong coloring power and special coloring with vivid coloring compared to conventional colored glass. A glass substrate is required. In order to harmonize the strong intrinsic yellow color of the vanadium dioxide-based film near the neutral color by the complementary color principle, a glass substrate that is slightly intensely colored in blue is desirable. For example, Nd and its compounds, Co and its compounds, which are used as blue colorants in glass, are suitable.
従来、Ｎｄ及びその化合物、Ｃｏ及びその化合物による淡青色板ガラス（特開２００４−１１５３５９号公報（Ｎｄ）、特開２０００−１４３２８３号公報（Ｃｏ））があるが、淡青色を得るために、その添加量が少量（質量百分率：Ｎｄ２Ｏ３、０．１％以下、ＣｏＯ、１ｐｐｍ以下）に限定されている。従って、二酸化バナジウム系膜の強い固有の黄色を補色原理により中性色近くに色調調和するためには、やや強い青色着色ガラス基材が望ましく、その添加元素及び量を、質量百分率でＮｄ２Ｏ３、０．１％以上、ＣｏＯ、１ｐｐｍ以上、と限定することが好ましい。 Conventionally, there are Nd and its compounds, Co and its pale blue plate glass (JP 2004-115359 (Nd), JP 2000-143283 (Co)). The addition amount is limited to a small amount (mass percentage: Nd 2 O 3 , 0.1% or less, CoO, 1 ppm or less). Therefore, in order to harmonize the strong intrinsic yellow color of the vanadium dioxide-based film close to the neutral color by the complementary color principle, a slightly strong blue-colored glass substrate is desirable, and its additive elements and amounts are expressed in terms of mass percentage as Nd 2 O. 3 , preferably 0.1% or more, CoO, 1 ppm or more.
以上の色調調和の方法をいくつか例示したが、二酸化バナジウム自動調熱膜の固有の色を、調色原理に基づき調色材料の使用によって、所定の透過色など色調が制御できる限り、それらの例に限られるものではない。また、本発明のガラスの系には、更に、機能膜Ｃを単層又は複数層で導入することができる。機能性膜Ｃとは、本発明のガラスに、自動調熱や色調調和以外の機能の追加ができる薄膜層を指す。例えば、可視光透過率反射率制御のための反射防止膜、二酸化バナジウム薄膜の結晶成長を有利にするための構造テンプレート膜、系の機械的特性等を強化するための保護膜、セルフクリーニング効果などを持たせるための光触媒薄膜、ガラスからの不純物の拡散を防ぐためのバリア膜、及び熱反射特性や断熱性を強化するための透明導電性膜などが挙げられる。 Several examples of the above-described color harmony methods have been exemplified. It is not limited to examples. Moreover, the functional film C can be further introduced into the glass system of the present invention in a single layer or a plurality of layers. The functional film C refers to a thin film layer capable of adding functions other than automatic heat adjustment and color harmony to the glass of the present invention. For example, antireflection film for visible light transmittance reflectance control, structural template film for advantageous crystal growth of vanadium dioxide thin film, protective film for enhancing mechanical properties of system, self-cleaning effect, etc. For example, a photocatalytic thin film for imparting heat, a barrier film for preventing diffusion of impurities from the glass, and a transparent conductive film for enhancing heat reflection characteristics and heat insulation.
その目的を達成するために使う物質群が、酸化物、窒化物、酸窒化物、炭化物、酸炭化物、炭素（ＤＬＣ）、フッ化物、硫化物等からなる透明絶縁体、誘電体、半導体、或いはその任意的組み合わせたものがよい。例えば、基材ガラスから順番に、構造テンプレート層（ＴｉＯ２、ＳｎＯ２等のルチル相の薄膜）、その上に二酸化バナジウム層、更に、その上に光触媒となる酸化チタン層を蒸着することにより本発明のガラスを構成する例が挙げられる。本発明では、色調調和のために着色ガラスを使ってもよく、また、着色剤を任意の層に混入してもよく、色調調和である限り制限されるものではない。 The substance group used to achieve the purpose is a transparent insulator, dielectric, semiconductor, or oxide, nitride, oxynitride, carbide, oxycarbide, carbon (DLC), fluoride, sulfide, etc. Any combination thereof is preferable. For example, in order from the base glass, a structural template layer (a thin film of a rutile phase such as TiO 2 , SnO 2 ), a vanadium dioxide layer thereon, and a titanium oxide layer serving as a photocatalyst thereon are deposited. An example of constituting the glass of the invention is given. In the present invention, colored glass may be used for color tone harmonization, and a colorant may be mixed in an arbitrary layer, and is not limited as long as color tone harmony is achieved.
二酸化バナジウム自動調熱膜は、好適には、例えば、スパッタ法によって作製される。スパッタ法により作製する場合、特に、効率の高い工業生産の場合、ＤＣマグネトロンスパッタ法が望ましい。従来、バナジウム金属を酸素含む雰囲気にＤＣマグネトロン反応性スパッタすることが知られているが、化学量論的にＶＯ２結晶質膜を得るため、プロセスの制御が非常に難しい。化学量論的にＶＯ２に近い組成を得るためには、ＶＯ２化合物ターゲットをスパッタすればよいが、従来、酸化物のスパッタは効率が悪く、更に、ＶＯ２化合物は常温では導電性が弱くＲＦスパッタしか使えないため、成膜速度が更に小さくなる。従って、本発明では、より組成が制御しやすく、なおかつ効率の高いＤＣマグネトロンスパッタする方法が好適に使用される。 The vanadium dioxide automatic heat control film is preferably manufactured by, for example, a sputtering method. In the case of producing by sputtering, DC magnetron sputtering is desirable particularly for highly efficient industrial production. Conventionally, it has been known that DC magnetron reactive sputtering is performed in an atmosphere containing vanadium metal in oxygen. However, since the VO 2 crystalline film is obtained stoichiometrically, it is very difficult to control the process. In order to obtain a composition close to VO 2 stoichiometrically, a VO 2 compound target may be sputtered. Conventionally, sputtering of oxide is inefficient, and VO 2 compound has low conductivity at room temperature. Since only RF sputtering can be used, the deposition rate is further reduced. Therefore, in the present invention, a method of DC magnetron sputtering that is easy to control the composition and that has high efficiency is preferably used.
すなわち、従来の導電性の悪い二酸化バナジウム化合物ターゲットに替えて、主成分がバナジウム酸化物（Ｖ２Ｏ５）とバナジウム金属Ｖ（転移温度制御のための添加元素を含む）となる化学量論的にＶＯ２に近い導電性粉末の混合物、又はそのプレス成形体又は焼結体からなる導電性ターゲットを、不活性ガス中、或いは少量の酸素を含む混合ガス雰囲気中でＤＣマグネトロンスパッタすることによって、二酸化バナジウム自動調熱膜が高効率で作製される。また、添加物を含む主成分が二酸化バナジウムからなる化合物ターゲットを使用する場合、常温では二酸化バナジウムが半導体であるため導電性が弱いが、そのターゲットを相転移温度以上、好適には７０℃以上に加熱することで、金属相へ相転移することにより形成される導電性ターゲットを、不活性ガス中、或いは少量の酸素を含む混合ガス雰囲気中でＤＣマグネトロンスパッタすることによって、二酸化バナジウム自動調熱膜が高効率で作製される。 That is, in place of the conventional vanadium dioxide compound target having poor conductivity, the main components are vanadium oxide (V 2 O 5 ) and vanadium metal V (including an additive element for controlling the transition temperature). to a mixture of conductive powder close to VO 2, or a conductive target made of the pressed bodies or sintered bodies in an inert gas, or by DC magnetron sputtering in a mixed gas atmosphere containing a small amount of oxygen, Vanadium dioxide self-regulating membrane is produced with high efficiency. Also, when using a compound target whose main component containing the additive is vanadium dioxide, the conductivity is weak because vanadium dioxide is a semiconductor at room temperature, but the target is above the phase transition temperature, preferably above 70 ° C. A vanadium dioxide self-adjusting film by conducting DC magnetron sputtering of a conductive target formed by a phase transition to a metal phase by heating in an inert gas or a mixed gas atmosphere containing a small amount of oxygen Is produced with high efficiency.
また、添加物を含む主成分が二酸化バナジウムからなる化合物ターゲットを、まず、ＲＦスパッタさせ、プラズマ発生によるイオン衝撃により、表面温度を上昇させ、ターゲットの温度を相転移温度以上に上昇させてから、金属相による導電性ターゲットを不活性ガス中、或いは少量の酸素を含む混合ガス雰囲気中でＤＣマグネトロンスパッタすることによって、二酸化バナジウム自動調熱膜が高効率で作製される。 In addition, a compound target whose main component including the additive is vanadium dioxide is first RF-sputtered, and the surface temperature is increased by ion bombardment by plasma generation, and the temperature of the target is increased to a phase transition temperature or higher. By performing DC magnetron sputtering of a conductive target made of a metal phase in an inert gas or in a mixed gas atmosphere containing a small amount of oxygen, a vanadium dioxide automatic heat control film is produced with high efficiency.
以上、スパッタ法について説明したが、スパッタ法以外にも、例えば、真空蒸着などＰＶＤに分類される物理蒸着法（例えば、朝倉書店発行、「ガラス工学ハンドブック」第４２３−４２８頁）、スプレー法やＣＶＤ法（パイロゾロ法含む）に分類される熱分解法（同上、第４２８−４３２頁）、及びゾルゲル法（同上、第４３２−４３８頁）など、汎用被膜法の一つ又は複数の手法で当該ガラスを被膜できることはいうまでもない。本発明のガラスへの薄膜形成、特に、二酸化バナジウム調熱膜の形成には、通常、基板を１００〜７００℃に加熱することが不可欠である。工業生産には、わざわざ基板を加熱して被膜することは設備やコストの問題点から、通常、望ましくない。 As described above, the sputtering method has been described. In addition to the sputtering method, for example, physical vapor deposition methods classified into PVD such as vacuum vapor deposition (for example, published by Asakura Shoten, “Glass Engineering Handbook”, pages 423-428), spray methods, One or a plurality of general-purpose coating methods such as thermal decomposition methods (including the pyrozolo method) (same as above, pages 428-432) and sol-gel methods (same as above, pages 432-438). Needless to say, glass can be coated. In order to form a thin film on the glass of the present invention, in particular, to form a vanadium dioxide heat-regulating film, it is usually essential to heat the substrate to 100 to 700 ° C. For industrial production, it is usually not desirable to bother heating and coating a substrate because of facilities and cost problems.
しかし、フロートガラス製造ライン上における熱処理プロセスの熱環境をそのまま利用する、いわゆるオンラインスプレー法やオンラインＣＶＤ法（朝倉書店発行、「ガラス工学ハンドブック」第４２８−４３２頁）などが開発されている。従来、これらの手法は、元素をドープした酸化スズなどの透明導電体膜、ＴｉＯ２膜、ＳｉＯ２膜などの生産にオンラインコーティングの手法として使われているが、近年、ＶＯ２薄膜の形成法としても報告されている〔例えば、１）Troy D. Manning, Ivan P. Parkin: Polyhedron, 23 (2004) 3087-3095、２）D. Vernardou, M.E.Pemble, D.W.Sheel: Surface & Coatings Technology, 188-189(2004)250-254〕。 However, a so-called online spray method and an online CVD method (published by Asakura Shoten, “Glass Engineering Handbook”, pages 428-432) that use the thermal environment of the heat treatment process on the float glass production line as they are developed. Traditionally, these techniques, a transparent conductive film such as tin oxide doped with elements, TiO 2 film, have been used in the production of such SiO 2 film as a method for online coating, in recent years, VO 2 thin film forming method [For example, 1) Troy D. Manning, Ivan P. Parkin: Polyhedron, 23 (2004) 3087-3095, 2) D. Vernardou, MEPemble, DWSheel: Surface & Coatings Technology, 188-189 ( 2004) 250-254].
従って、本発明では、成膜プロセスを従来の板ガラスの形成や加工に不可欠な熱処理段階に組み込むことで、基板加熱が難しい問題を解決することができる。すなわち、自動調熱膜Ａ、調色膜Ｂ、機能膜Ｃなど、本発明のガラスの構造の薄膜群の少なくとも一つ以上は、フロートガラス製造ライン上におけるフロートバス又は徐冷窯の内部の熱環境を利用し、ガラス表面温度が１００〜７００℃の高温のまま、常圧又は減圧で汎用薄膜形成法により、単独又は連続に形成される。 Therefore, in the present invention, it is possible to solve the problem that it is difficult to heat the substrate by incorporating the film forming process into the heat treatment stage essential for the formation and processing of the conventional plate glass. That is, at least one of the thin film groups having the glass structure of the present invention, such as the automatic heat-adjusting film A, the toning film B, and the functional film C, is heated in the float bath or the annealing furnace on the float glass production line. Using the environment, the glass surface temperature is formed at a high temperature of 100 to 700 ° C. alone or continuously by a general-purpose thin film forming method at normal pressure or reduced pressure.
以上の方法で、オンラインコーティングによって二酸化バナジウム薄膜を単独に形成することが可能であるが、構造テンプレートや機能膜など、本発明のガラスの構造の薄膜群の適切な薄膜と連続してオンラインコーティングすることが最も好適である。たとえば、構造テンプレートや熱線反射機能のある酸化スズ系薄膜のあと、ＶＯ２調熱薄膜を連続でオンラインコーティング形成することは最も望ましい。 By the above method, it is possible to form a vanadium dioxide thin film independently by on-line coating. However, on-line coating is continuously performed with an appropriate thin film of the thin film group of the glass structure of the present invention, such as a structural template or a functional film. Is most preferred. For example, it is most desirable to continuously form a VO 2 heat control thin film on-line after a structural template or a tin oxide thin film having a heat ray reflecting function.
上述と同じく、自動調熱膜Ａ、調色膜Ｂ、機能膜Ｃの少なくとも一つ以上が、ガラスの強化や曲げ加工プロセスの熱処理における熱環境を利用し、ガラス表面温度が1００〜７５０℃の範囲で、常圧又は減圧で汎用薄膜形成法により単独又は連続に形成される。また、自動調熱膜Ａ、調色膜Ｂ、機能膜Ｃの少なくとも一つ以上が、汎用薄膜形成法により室温を含む低温で形成した後、ガラスの強化や曲げ加工プロセスの熱環境を利用し、1００〜７５０℃の範囲で５秒〜１時間熱処理によって形成される。 As described above, at least one of the automatic heat-adjusting film A, the toning film B, and the functional film C uses a thermal environment in the heat treatment of glass strengthening or bending process, and the glass surface temperature is 10 to 750 ° C. In the range, it is formed alone or continuously by a general-purpose thin film forming method at normal pressure or reduced pressure. In addition, after at least one of the automatic heat-adjusting film A, the toning film B, and the functional film C is formed at a low temperature including room temperature by a general-purpose thin film forming method, the thermal environment of the glass strengthening or bending process is used. It is formed by heat treatment in the range of 10 to 750 ° C. for 5 seconds to 1 hour.
自動調熱膜Ａ、調色膜Ｂ、機能膜Ｃを、任意的組み合わせてガラスの同一側に設置する、又は必要に応じてガラスの両側に分けて設置する、又は複数枚のガラスに分離して設置する、又は複数のガラスで挟む、又は複数のガラスを接着する、などにより、自動調熱色調調和遮光ガラスが形成される。形成されたガラスは、建築物、移動体（車、船舶、列車、飛行機等）の窓ガラスを目的として使用することができる。これらは、特に、可視光透過率が７０％以下で遮光性に優れ、同時に色調が自由に調節できることを特徴とする自動調熱色調調和遮光プライバシーガラスとして使用される。 Automatic heating film A, toning film B, and functional film C can be installed on the same side of the glass in any combination, or can be installed separately on both sides of the glass as necessary, or separated into multiple sheets of glass Are installed, or are sandwiched between a plurality of glasses, or a plurality of glasses are bonded together. The formed glass can be used for the window glass of a building or a moving body (car, ship, train, airplane, etc.). In particular, they are used as a self-adjusting color tone light-shielding privacy glass characterized in that the visible light transmittance is 70% or less and excellent in light-shielding properties, and at the same time the color tone can be freely adjusted.
また、形成されたガラスは、建築物、移動体（車、船舶、列車、飛行機等）の窓ガラス、特に、調色膜や、着色フィルム又は着色樹脂等を２枚以上の板ガラスで挟む、又は２枚以上のガラスを接着することにより、従来の安全、強化、防犯機能に加え、可視光透過率が７０％以下で、遮光性に優れるため、適切の照度とプライバシー保護ガラスを目的として好適に使用することができる自動調熱色調調和遮光合わせガラスとして使用される。 The formed glass is a window glass of a building or a moving body (car, ship, train, airplane, etc.), in particular, a toning film, a colored film or a colored resin is sandwiched between two or more plate glasses, or By adhering two or more glasses, in addition to the conventional safety, strengthening, and crime prevention functions, the visible light transmittance is 70% or less and excellent in light shielding properties. It can be used as an automatic heat-adjusting color harmony light-shielding laminated glass.
本発明により、（１）自動調熱で快適さが達成とともに、冷暖房負荷の同時低減、色調調和、紫外線カット、遮光、プライバシー保護等の多彩な機能を持ち合わせたガラスで、建築物、車両その他の移動体用の新規窓ガラス、及びその製造方法を提供することができる、（２）ガラス等の透明又は透光性基材に、可視光が常に透過するが、主に赤外線が環境温度の変化に応じて自動的に透過率を調節できる、二酸化バナジウム系自動調熱膜を提供できる、（３）調色膜や着色基材、及び他の機能性膜との適切な組み合わせで、従来型の二酸化バナジウム系調光ガラスを、その可視光透過率が低いという欠点を、逆転の発想により、遮光ガラスとして有効利用に転じることができる、（４）更に、補色原理を活用した独自の色調調和法を提供できる、（５）建築や移動体の外装に合うように自由に色調調和ができる自動調熱色調調和遮光ガラス及び製造方法を提供できる、という効果が奏される。 According to the present invention, (1) glass is equipped with various functions such as simultaneous reduction of heating and cooling load, harmony of color tone, UV protection, shading, privacy protection, etc. A new window glass for a moving body and a method for manufacturing the same can be provided. (2) Visible light is always transmitted to a transparent or translucent base material such as glass, but mainly infrared light changes in environmental temperature. It is possible to provide a vanadium dioxide-based automatic heat-adjusting film that can automatically adjust the transmittance in accordance with (3) an appropriate combination with a toning film, a colored base material, and other functional films. Vanadium dioxide based light control glass can be converted to effective use as a light-shielding glass by the idea of reversing the disadvantage of low visible light transmittance. (4) In addition, a unique color harmony method utilizing the complementary color principle Provide in That, (5) self-heat hue conditioner shielding glass and a manufacturing method which can freely tone conditioner to match the exterior of the building and the mobile can provide an effect is exhibited that.
次に、実施例を示して本発明を具体的に説明するが、本発明は、これらに限定されるものではない。 Next, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.
（１）自動調熱多層構造の形成
１．構造テンプレート膜の形成
本実施例では、薄膜の作製に汎用型マグネトロンスパッタ装置を用いた。当該装置は、１）カソード３基まで配置することができる、２）それぞれに高周波電源又は直流電源で任意に電力制御することができる、３）この装置では、基板が回転可能であり、基板温度を室温から８００℃までの範囲で精密に設定することができる、という機能を有する。
(1) Formation of automatic heat control multilayer structure Formation of Structural Template Film In this example, a general-purpose magnetron sputtering apparatus was used for the production of a thin film. The apparatus can be arranged 1) up to 3 cathodes, 2) each can be arbitrarily controlled by a high frequency power supply or a DC power supply, and 3) In this apparatus, the substrate can be rotated and the substrate temperature Can be precisely set in a range from room temperature to 800 ° C.
二酸化バナジウムと同じルチル構造を有するＴｉＯ２及びＳｎＯ２を構造テンプレート薄膜とした。この構造テンプレート膜は、ＴｉＯ２化合物ターゲット（直径５０ｍｍ、厚さ５ｍｍ、純度９９．９％）、又はＳｎＯ２（Ｓｂドップ）化合物ターゲット（直径５０ｍｍ、厚さ５ｍｍ、純度９９．９％）をＲＦスパッタすることにより形成した。すなわち、バックグランド真空度２×１０−６Ｐａ、アルゴン流量３０ｓｃｃｍ、全圧０．６Ｐａ、基板温度２００−６００℃、ＲＦ電力１２０Ｗの条件で、石英ガラス、耐熱ガラス、シリコン単結晶及びサファイア単結晶基板上に５−２００ｎｍの厚さで構造テンプレート膜を形成した。 TiO 2 and SnO 2 having the same rutile structure as vanadium dioxide were used as the structural template thin film. This structural template film is obtained by using a TiO 2 compound target (diameter 50 mm, thickness 5 mm, purity 99.9%) or a SnO 2 (Sb Dop) compound target (diameter 50 mm, thickness 5 mm, purity 99.9%) as RF. It was formed by sputtering. That is, quartz glass, heat-resistant glass, silicon single crystal and sapphire single crystal under the conditions of a background vacuum of 2 × 10 −6 Pa, an argon flow rate of 30 sccm, a total pressure of 0.6 Pa, a substrate temperature of 200 to 600 ° C., and an RF power of 120 W. A structural template film having a thickness of 5-200 nm was formed on the substrate.
２．二酸化バナジウム系薄膜の形成
上述の構造テンプレートを形成した後、その上に、継続的に、二酸化バナジウム系薄膜を次の方法によって形成した。
１）市販のバナジウムターゲットによるスパッタ
市販のバナジウムターゲット（Ｖ、直径５０ｍｍ、厚さ５ｍｍ、純度９９．９％）、又は市販のバナジウム・タングステン合金ターゲット（Ｖ：Ｗ＝１．６ａｔ％）を、酸素とアルゴンの混合ガスの中、ＲＦ、或いはＤＣスパッタすることによって、二酸化バナジウム系薄膜の形成を行った。主なスパッタ条件は、次の通りである。すなわち、バックグランド真空度２×１０−６Ｐａ、アルゴン流量３０ｓｃｃｍ、酸素流量０〜３．００ｓｃｃｍ、全圧０．６Ｐａ、基板温度４００〜６００℃、ＲＦ電力２００Ｗ、又はＤＣ電圧２００〜４００Ｖ、電流０．１０〜０．３０Ａの条件で、基板としては、石英ガラス、耐熱ガラス、シリコン単結晶及びサファイア単結晶を用いた。
2. Formation of Vanadium Dioxide-Based Thin Film After the above-described structural template was formed, a vanadium dioxide-based thin film was continuously formed thereon by the following method.
1) Sputtering with a commercially available vanadium target A commercially available vanadium target (V, diameter 50 mm, thickness 5 mm, purity 99.9%) or a commercially available vanadium-tungsten alloy target (V: W = 1.6 at%) is oxygenated. A vanadium dioxide thin film was formed by RF or DC sputtering in a mixed gas of argon and argon. The main sputtering conditions are as follows. That is, background vacuum degree 2 × 10 −6 Pa, argon flow rate 30 sccm, oxygen flow rate 0 to 3.00 sccm, total pressure 0.6 Pa, substrate temperature 400 to 600 ° C., RF power 200 W, or DC voltage 200 to 400 V, current Quartz glass, heat-resistant glass, silicon single crystal, and sapphire single crystal were used as the substrate under conditions of 0.10 to 0.30 A.
以上の条件で、反応性スパッタによって、二酸化バナジウム単一相薄膜を形成する際に、特に、酸素流量を精密に所定に制御することが最も重要であり、非常に狭い酸素流量の範囲でしか二酸化バナジウム単一相薄膜が形成されないとの結果が得られた。一方、ＴｉＯ２やＳｎＯ２のような構造テンプレートを予め基板上に形成したあと、続けて二酸化バナジウム薄膜を形成すると、二酸化バナジウム単一相薄膜の形成がほぼ確実であることを突き止めた。しかし、以上のような反応性スパッタ法による二酸化バナジウム単一相薄膜の形成には、酸素流量などプロセスの精密な制御が厳しく要求され、また、一旦見つかった条件も、ターゲットの消耗などにより変動しやすいため、大量生産には困難であった。従って、以下の諸方法を考え、開発した。 Under the above conditions, when forming a vanadium dioxide single-phase thin film by reactive sputtering, it is most important to precisely control the oxygen flow rate to a predetermined level, and only in a very narrow range of oxygen flow rate. The result that the vanadium single phase thin film was not formed was obtained. On the other hand, when a structural template such as TiO 2 or SnO 2 was previously formed on the substrate and then a vanadium dioxide thin film was formed, it was found that the formation of the vanadium dioxide single-phase thin film was almost certain. However, the formation of a vanadium dioxide single-phase thin film by reactive sputtering as described above requires strict control of the process, such as the oxygen flow rate, and the conditions once found vary depending on target consumption. Because it was easy, it was difficult for mass production. Therefore, the following methods were considered and developed.
２）二酸化バナジウム化合物ターゲットによるスパッタ
二酸化バナジウム粉末（ＶＯ２純度９９．５％）に、酸化タングステン粉末（ＷＯ３、９９．９９％）を１．０％モル比で混合し、自動乳鉢で１〜３時間混合・粉砕してからプレス成形及び熱処理により、直径５０ｍｍ、厚さ約５ｍｍの円盤にしたものをターゲットとして、二酸化バナジウム系薄膜の形成を行った、すなわち、バックグランド真空度２×１０−６Ｐａ、アルゴン流量３０ｓｃｃｍ、酸素流量０〜０．５ｓｃｃｍ、全圧０．６Ｐａ、基板温度４００〜６００℃、ＲＦ電力１００Ｗの条件でスパッタし、石英ガラス、耐熱ガラス、シリコン単結晶及びサファイア単結晶基板上に二酸化バナジウム薄膜を形成した。
2) Sputtering with vanadium dioxide compound target Tungsten oxide powder (WO 3 , 99.99%) was mixed with vanadium dioxide powder (VO 2 purity 99.5%) at a 1.0% molar ratio, and 1 to A vanadium dioxide-based thin film was formed by mixing and pulverizing for 3 hours and then forming a disk having a diameter of 50 mm and a thickness of about 5 mm by press molding and heat treatment, that is, a background vacuum degree of 2 × 10 − Sputtered under conditions of 6 Pa, argon flow rate 30 sccm, oxygen flow rate 0-0.5 sccm, total pressure 0.6 Pa, substrate temperature 400-600 ° C., RF power 100 W, quartz glass, heat-resistant glass, silicon single crystal and sapphire single crystal A vanadium dioxide thin film was formed on the substrate.
バナジウム金属ターゲットを使った反応性スパッタ法より、安定した二酸化バナジウム薄膜が形成されたが、ＲＦスパッタの場合、成膜速度が遅い欠点があった。二酸化バナジウム系化合物ターゲットでは、常温では半導体相で導電性があまり示されない。従って、効率の悪いＲＦスパッタが必要である。しかし、本発明者は、次の手法によってターゲットに導電性を持たせ、ＤＣでもスパッタできるようにすることに成功した。すなわち、最初のみＲＦスパッタをし、ターゲット表面の温度が、二酸化バナジウムの相転移温度以上まで上昇し、金属相となるところで、効率のよいＤＣスパッタに切り替えた。 A stable vanadium dioxide thin film was formed by the reactive sputtering method using a vanadium metal target. However, in the case of RF sputtering, there was a drawback that the film forming rate was slow. The vanadium dioxide compound target does not exhibit much conductivity in the semiconductor phase at room temperature. Therefore, inefficient RF sputtering is required. However, the present inventor has succeeded in making the target conductive by the following technique so that sputtering can be performed even with DC. That is, RF sputtering was performed only at the beginning, and the temperature of the target surface was raised to a temperature higher than the phase transition temperature of vanadium dioxide and switched to efficient DC sputtering when it became a metal phase.
３）導電性ターゲットによるスパッタ
更に進化した方法として、次の手法で導電性ターゲットを形成してＤＣスパッタによって、二酸化バナジウム薄膜を形成した。すなわち、五酸化バナジウム（Ｖ２Ｏ５、９９．９％）粉末に、バナジウム金属（Ｖ、９９．９％）を０．２５モル比で混入し、更に、ＷＯ３を１％モル比で加え、総組成を（Ｖ＋Ｗ）：Ｏ＝１：２とした。それを混合・粉砕してからプレス成形又は熱処理により、直径５０ｍｍ、厚さ約５ｍｍの円盤にしたものをターゲットとした。混合物からなるターゲットが、金属バナジウムにより導電性を持つため、ＤＣスパッタにより二酸化バナジウム薄膜を形成した。
3) Sputtering with a conductive target As a further advanced method, a conductive target was formed by the following method, and a vanadium dioxide thin film was formed by DC sputtering. That is, vanadium pentoxide (V 2 O 5 , 99.9%) powder was mixed with vanadium metal (V, 99.9%) at a 0.25 molar ratio, and WO 3 was added at a 1% molar ratio. The total composition was (V + W): O = 1: 2. This was mixed and pulverized, and then the target was a disk having a diameter of 50 mm and a thickness of about 5 mm by press molding or heat treatment. Since the target made of the mixture has conductivity due to metal vanadium, a vanadium dioxide thin film was formed by DC sputtering.
以上の１）〜３）の方法により、基板を加熱せずに二酸化バナジウム組成となるアモルファス薄膜を形成した後、４００℃／３０分、空気中でアニールすることで、結晶性のよい二酸化バナジウム薄膜を得た。本発明では、上述の基板上に形成した構造テンプレート及び酸化バナジウム薄膜の表面に、更に、任意の機能性膜を形成することができる。 By forming an amorphous thin film having a vanadium dioxide composition without heating the substrate by the above methods 1) to 3), annealing is performed in the air at 400 ° C. for 30 minutes, so that the vanadium dioxide thin film having good crystallinity is obtained. Got. In the present invention, an arbitrary functional film can be further formed on the surface of the structural template and the vanadium oxide thin film formed on the substrate.
３．機能性膜の形成
基板上に形成した構造テンプレート及び酸化バナジウム薄膜の表面に、更に、反射防止や光触媒となるＴｉＯ２機能膜を適切の厚さで被覆した。形成した構造テンプレート薄膜、酸化バナジウム薄膜、及び酸化チタン薄膜を含む自動調熱多層構造について、分光光度計等により典型的透過特性及び色調特性を調べた。その例は、次の通りである：
（サンプル１）
石英ガラス基板上に、厚さ５０ｎｍのＶＯ２系調熱膜、可視光透過率５８％、色度座標：ｘ＝０．３７６、ｙ＝０．３９８、主波長が５７１ｎｍ、刺激純度が４５．３％で、強い黄色透過を呈した。
（サンプル２）
石英ガラス基板上に、厚さ７０ｎｍのＶＯ２系調熱膜、可視光透過率４０％、色度座標：ｘ＝０．４００、ｙ＝０．４１０、主波長が５７５ｎｍ、刺激純度が５０％で、強い黄色透過を呈した。
3. Formation of Functional Film The surface of the structural template and vanadium oxide thin film formed on the substrate was further coated with a TiO 2 functional film serving as an antireflection or photocatalyst with an appropriate thickness. A typical transmission characteristic and color characteristic of the self-adjusting multilayer structure including the formed structural template thin film, vanadium oxide thin film, and titanium oxide thin film were examined by a spectrophotometer or the like. An example is as follows:
(Sample 1)
On a quartz glass substrate, a 50 nm thick VO 2 heat control film, visible light transmittance 58%, chromaticity coordinates: x = 0.376, y = 0.398, dominant wavelength 571 nm, stimulation purity 45. 3% showed strong yellow transmission.
(Sample 2)
On a quartz glass substrate, a VO 2 heat control film having a thickness of 70 nm, visible light transmittance of 40%, chromaticity coordinates: x = 0.400, y = 0.410, dominant wavelength of 575 nm, and excitation purity of 50% And exhibited strong yellow transmission.
（２）着色膜等による二酸化バナジウム系薄膜の色調調和
１．二酸化バナジウム色調調和の概略
補色原理により、補色による二酸化バナジウム系薄膜色調の変化を調べた。すなわち、ＲＧＢ３原色をもとに、加法混色で１２色相を持つカラーシートを作成した。透過率を適切に調節して、サンプル１又はサンプル２と重ね合わせ、バックライトに白色光源を透過して、透過色の変化を写真に取り、色調調和の効果を確認した。その結果を図１にまとめて示す。図１から分かるように、二酸化バナジウム系薄膜の固有の強い黄色を、補色原理を活用することによって、好み又は建築や移動体の外装に調和した色調に任意に変えることができることが分かった。特に、９番（Ｎｏ．９）の青色に近い補色を使えば、中性色に近い透過色が得られることが確認された。
(2) Color harmony of vanadium dioxide thin film by colored film, etc. Outline of vanadium dioxide color harmony The change in vanadium dioxide thin film color tone due to complementary colors was investigated using the complementary color principle. That is, based on the RGB three primary colors, a color sheet having 12 hues by additive color mixture was created. The transmittance was appropriately adjusted and superimposed with Sample 1 or Sample 2, the white light source was transmitted through the backlight, the change in transmitted color was photographed, and the effect of color harmony was confirmed. The results are summarized in FIG. As can be seen from FIG. 1, it was found that the inherent strong yellow color of the vanadium dioxide-based thin film can be arbitrarily changed to a color tone that matches the taste or the exterior of the building or the moving body by utilizing the complementary color principle. In particular, it was confirmed that a transmission color close to a neutral color can be obtained if a complementary color close to blue of No. 9 (No. 9) is used.
すなわち、二酸化バナジウム調熱薄膜にとって、その応用へ最も障害となる二酸化バナジウム系薄膜の固有の強い黄色着色を、補色原理により中性色を含む、任意の色調に設定することができた。補色設計により可視光透過率が更に低くなるが、本発明の目的、すなわち、遮光ガラスやプライバシー保護ガラスなどとは全く矛盾がなく、本発明により、むしろ逆転の発想で、不利因子を有利因子にすることが可能となった。 That is, for the vanadium dioxide heat-adjusting thin film, the inherent strong yellow coloring of the vanadium dioxide-based thin film, which is the most obstacle to its application, could be set to any color tone including neutral colors by the complementary color principle. Although the visible light transmittance is further reduced by the complementary color design, there is no contradiction with the purpose of the present invention, i.e., the light-shielding glass or the privacy protection glass, and the present invention makes the disadvantageous factor an advantageous factor rather than the idea of reversal. It became possible to do.
２．調色膜による二酸化バナジウム色調調和
（色調調和例１）
可視光透過率が４２％、ＸＹＺ表色系における色度座標値：ｘ＝０．２５８、ｙ＝０．２５３、主波長４７９ｎｍ、刺激純度が２４％で、やや強い青色透過の着色フィルム（Ｓ１）を作製した。Ｓ１を、石英ガラス基板上に厚さ５０ｎｍのＶＯ２系調熱膜（サンプル１）及びもう一枚の石英ガラス板に挟み、加熱加圧することによって固定した。その構造の概略を図２に示す。
2. Vanadium dioxide color tone harmonization by color-coating film (Color tone harmony example 1)
Colored film (S1) having a visible light transmittance of 42%, chromaticity coordinate values in the XYZ color system: x = 0.258, y = 0.253, main wavelength 479 nm, stimulus purity 24%, and slightly strong blue transmission ) Was produced. S1 was sandwiched between a 50 nm thick VO 2 heat control film (sample 1) and another quartz glass plate on a quartz glass substrate, and fixed by heating and pressing. An outline of the structure is shown in FIG.
図２の構造の分光透過率を分光光度計により測定した。測定した分光透過率によりＣＩＥ表色系における視感透過率や色度座標値などを算出した。その結果は、次の通りである。すなわち、視感透過率２２％、色度座標値：ｘ＝０．３００、ｙ＝０．３５６、主波長５３０ｎｍ、刺激純度が１１％で、わずかの緑を呈した。本発明の一部となる、着色フィルムを挟む形で色調調節を行う手法は、合わせガラス技術との組み合わせによって、更に、安全性、防犯性等を附加することが可能である。 The spectral transmittance of the structure of FIG. 2 was measured with a spectrophotometer. Luminous transmittance and chromaticity coordinate values in the CIE color system were calculated from the measured spectral transmittance. The results are as follows. That is, the luminous transmittance was 22%, the chromaticity coordinate values: x = 0.300, y = 0.356, the dominant wavelength was 530 nm, the stimulation purity was 11%, and a slight green color was exhibited. The technique for adjusting the color tone with a colored film sandwiched as a part of the present invention can be added with safety, crime prevention and the like by combination with laminated glass technology.
（色調調和例２）
可視光透過率が１６％、ＸＹＺ表色系における色度座標値：ｘ＝０．１９８、ｙ＝０．１６７、主波長４６８ｎｍ、刺激純度が５７％で、非常に強い青色透過の着色フィルム（Ｓ２）を作製した。すなわち、厚さ７０ｎｍのＶＯ２系調色膜で被覆した石英ガラス（サンプル２）を上述の非常に強い青色透過の着色フィルム（Ｓ２）で被覆し、系の分光透過率を分光光度計により測定した。また、調熱特性を調べるために、系を２０℃（ＶＯ２系調熱膜が低温半導体相である）及び８０℃（同金属相）に温度を変えながら光学特性を測定した。系は、次の光学色学特性を示した。低温相：透過率６％、色度座標値：ｘ＝０．２６１、ｙ＝０．２８６、主波長４８６ｎｍ、刺激純度が２０％で、暗青色を呈した。高温相：透過率５％、色度座標値：ｘ＝０．２９８、ｙ＝０．３３５、主波長５２０ｎｍ、刺激純度が８％で、暗青色を呈した。
(Tone example 2)
Visible light transmittance of 16%, chromaticity coordinate value in XYZ color system: x = 0.198, y = 0.167, dominant wavelength of 468 nm, stimulus purity of 57%, very strong blue transmission colored film ( S2) was prepared. That is, quartz glass (sample 2) covered with a VO 2 toning film having a thickness of 70 nm is covered with the above-mentioned very strong blue transmitting colored film (S2), and the spectral transmittance of the system is measured with a spectrophotometer. did. Further, in order to examine the heat control characteristics, the optical characteristics were measured while changing the temperature of the system to 20 ° C. (VO 2 system heat control film is a low-temperature semiconductor phase) and 80 ° C. (same metal phase). The system exhibited the following optical color characteristics. Low-temperature phase: transmittance 6%, chromaticity coordinate values: x = 0.261, y = 0.286, dominant wavelength 486 nm, stimulation purity 20%, and dark blue color. High-temperature phase: transmittance 5%, chromaticity coordinate values: x = 0.298, y = 0.335, dominant wavelength 520 nm, stimulation purity 8%, and dark blue color.
３．自動調熱の効果
厚さ７０ｎｍのＶＯ２系調色膜で被覆した石英ガラス（サンプル２）を上述の非常に強い青色透過の着色フィルム（Ｓ２）で被覆し、系を２０℃（半導体相）及び８０℃（金属相）状態において、温度を変化して分光透過特性率の変化、すなわち、自動調熱の効果を測定した。その結果を図３に示す。低温及び高温時において、透過率、特に、７８０ｎｍより波長の長い赤外線の透過率に大きな差が確認され、非常によい調熱効果を示した。
3. Effect of automatic heat control Quartz glass (sample 2) covered with a VO 2 toning film having a thickness of 70 nm is covered with the above-mentioned very strong blue-transmitting colored film (S2), and the system is 20 ° C. (semiconductor phase) At 80 ° C. (metal phase), the temperature was changed to change the spectral transmission characteristic ratio, that is, the effect of automatic heat control. The result is shown in FIG. At low and high temperatures, a large difference was observed in the transmittance, particularly the transmittance of infrared rays having a wavelength longer than 780 nm, indicating a very good heat-control effect.
以上のように、本発明の、可視光が適切に透過し、赤外光が温度変化に応じて大きな変化を示す自動調熱色調調和遮光ガラスの実施例を示したが、本発明によって、二酸化バナジウム系自動調熱膜、及び着色膜又は着色機能を持つ他の機能性膜や基材を組み合わせることで、例えば、可視光透過率を７０％以下に押さえ、建築や移動体の外装に合うように着色を自由に調節できる、自動調熱、自動調光、色調調和、紫外線カット、断熱、快適照度、プライバシー保護等の多彩な機能を持ち合わせた自動調熱色調調和遮光ガラス及び製造方法を提供することが可能である。 As described above, examples of the automatic heat-adjusting color harmony light-shielding glass according to the present invention in which visible light is appropriately transmitted and infrared light exhibits a large change according to a temperature change are shown. By combining a vanadium-based automatic heat control film and a colored film or other functional film having a coloring function or a base material, for example, the visible light transmittance is suppressed to 70% or less, so that it fits the exterior of a building or a moving body. To provide automatic heat control, color control, light control, color control, UV control, heat insulation, comfortable illumination, privacy protection, etc. It is possible.
比較例
石英ガラス基板上に、構造テンプレート薄膜、酸化バナジウム薄膜（７０ｎｍ）、及び酸化チタン薄膜を含む自動調熱多層構造を作製し、分光光度計等により２０℃及び８０℃における透過特性及び色調特性を調べた。その結果は、次の通りである。すなわち、低温及び高温時において、透過率、特に、７８０ｎｍより波長の長い赤外線の透過率に大きな差が確認され、非常によい調熱効果を示すが、色調特性に関しては、可視光透過率４０％、色度座標値：ｘ＝０．４００、ｙ＝０．４１０、主波長が５７５ｎｍ、刺激純度が５０％であり、色調調節をしない限り、二酸化バナジウム固有の強い黄色透過のみを呈した。
Comparative Example A self-adjusting multilayer structure including a structural template thin film, a vanadium oxide thin film (70 nm), and a titanium oxide thin film is fabricated on a quartz glass substrate, and transmission characteristics and color characteristics at 20 ° C. and 80 ° C. using a spectrophotometer or the like. I investigated. The results are as follows. That is, at low and high temperatures, a large difference was confirmed in the transmittance, particularly the transmittance of infrared rays having a wavelength longer than 780 nm, and a very good heat adjustment effect was exhibited. Chromaticity coordinate values: x = 0.400, y = 0.410, the dominant wavelength was 575 nm, the excitation purity was 50%, and only strong yellow transmission specific to vanadium dioxide was exhibited unless the color tone was adjusted.
以上詳述したように、本発明は、自動調熱色調調和遮光ガラス及びその製造方法に係るものであり、本発明により、例えば、可視光透過率が７０％以下で、遮光性に優れ、環境温度に応じて赤外線の透過率が自動的に調節でき、更に、透過色の色調を自由に色調調和することが可能な新しい自動調熱色調調和遮光ガラス及び製造方法を提供することができる。本発明は、ガラスなどの透明基材に、可視光が透過するが、赤外光が温度変化に応じて大きな変化を示す二酸化バナジウム系自動調熱膜を使用することは従来通りであるが、系の構造に新たに濃色着色膜を加え、二酸化バナジウム薄膜の固有の黄色と補色原理に基づく設計で、中性色化又は好みや建築物、移動体の外装に色調調和された自動調熱色調調和遮光ガラスを開発し、提供するものである。本発明は、従来の二酸化バナジウム可視光透過率が低いという弱点を発想を逆転して有効利用し、可視光透過率を７０％以下と低く押さえ、自動調熱、遮光調光、色調調和、紫外線カット、断熱、快適照度、プライバシー保護等の多彩な機能を持ち合わせた自動調熱色調調和遮光ガラス及び製造方法を提供することを可能とするものである。本発明は、例えば、建築物や自動車など移動体のガラスとして好適な、省エネルギー、健康快適、環境に優しい新しいガラスを提供するものとして、建築産業その他産業界への応用が大いに期待できるものである。 As described above in detail, the present invention relates to an automatic heat-adjusting color-harmoniced light-shielding glass and a method for producing the same. According to the present invention, for example, the visible light transmittance is 70% or less, the light-shielding property is excellent, and the environment It is possible to provide a new automatic heat-adjusting color tone-shading glass and manufacturing method that can automatically adjust the infrared transmittance according to the temperature and can freely adjust the color tone of the transmitted color. Although the present invention uses a vanadium dioxide-based automatic heat control film in which visible light is transmitted through a transparent substrate such as glass, but infrared light exhibits a large change in response to a temperature change, A new dark colored film is added to the structure of the system, and the design is based on the inherent yellow and complementary color principle of vanadium dioxide thin film. We develop and provide color-tone light-shielding glass. The present invention effectively utilizes the weakness of the conventional low vanadium dioxide visible light transmittance by reversing the idea and keeps the visible light transmittance as low as 70% or less, automatic heat control, shading light control, color harmony, ultraviolet light The present invention makes it possible to provide an automatic heat-adjusting color-harmoniced light-shielding glass having various functions such as cutting, heat insulation, comfortable illumination, and privacy protection, and a manufacturing method. INDUSTRIAL APPLICABILITY The present invention can be expected to be applied to the construction industry and other industries as a new energy-saving, healthy, comfortable, and environmentally friendly glass suitable as a glass for moving objects such as buildings and automobiles. .
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| PCT/JP2006/305457 WO2006098451A1 (en) | 2005-03-17 | 2006-03-17 | Automatic heat conditioning color tone conditioning light shielding glass and method for producing the same |
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| WO2006098451A1 (en) | 2006-09-21 |
| JP5147034B2 (en) | 2013-02-20 |
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