JP2002146228A - Method for treating fine indium-tin oxide particle for forming sunshine-screening film and sunshine-screening film - Google Patents
Method for treating fine indium-tin oxide particle for forming sunshine-screening film and sunshine-screening filmInfo
- Publication number
- JP2002146228A JP2002146228A JP2000343692A JP2000343692A JP2002146228A JP 2002146228 A JP2002146228 A JP 2002146228A JP 2000343692 A JP2000343692 A JP 2000343692A JP 2000343692 A JP2000343692 A JP 2000343692A JP 2002146228 A JP2002146228 A JP 2002146228A
- Authority
- JP
- Japan
- Prior art keywords
- tin oxide
- fine particles
- sunshine
- indium tin
- oxide fine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
Landscapes
- Surface Treatment Of Glass (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Paints Or Removers (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は車両、ビル、事務
所、一般住宅などの窓、電話ボックス、ショーウインド
ー、照明用ランプ、透明ケースなど、ガラス、プラスチ
ックスその他の日射遮蔽機能を必要とする透明基材に用
いる日射遮蔽膜形成用インジウム錫酸化物微粒子の処理
方法と日射遮蔽膜に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transparent material such as a vehicle, a building, an office, a general house, such as a window, a telephone box, a show window, a lighting lamp, and a transparent case, which require glass, plastics and other solar radiation shielding functions. The present invention relates to a method for treating indium tin oxide fine particles for forming a solar shading film used for a substrate and a solar shading film.
【０００２】[0002]
【従来の技術】従来、太陽光や電球などの外部光源から
熱成分を除去・減少する方法として、ガラス表面に可視
・赤外域の波長を反射する材料を利用して熱線反射ガラ
スとすることが行われていた。その材料にはＦｅＯｘ、
ＣｏＯｘ、ＣｒＯｘ、ＴｉＯｘなどの金属酸化物やＡ
ｇ、Ａｕ、Ｃｕ、Ｎｉ、Ａｌなどの自由電子を多量にも
つ金属材料が選択されてきた。しかし、これらの材料で
は熱効果に大きく寄与する近赤外線以外に、可視光も同
時に反射もしくは吸収する性質があるために可視光透過
率が低下する問題があった。2. Description of the Related Art Conventionally, as a method of removing or reducing a heat component from an external light source such as sunlight or a light bulb, a heat ray reflecting glass using a material which reflects a visible / infrared wavelength on a glass surface is used. It was done. The material is FeOx,
Metal oxides such as CoOx, CrOx, TiOx, and A
Metal materials having a large amount of free electrons, such as g, Au, Cu, Ni, and Al, have been selected. However, these materials have the property of simultaneously reflecting or absorbing visible light, in addition to near infrared rays, which greatly contribute to the thermal effect, and thus have a problem in that the visible light transmittance is reduced.
【０００３】建材、乗り物、電話ボックスなどに用いら
れる透明基材では可視光領域の高い透過率が必要とされ
ることから、前記材料を利用する場合は膜厚を非常に薄
くしなければならない。従ってスプレー焼付けやＣＶＤ
法、あるいはスパッタ法や真空蒸着法などの物理成膜法
を用いて１０ｎｍレベルの薄膜に成膜して用いられるこ
とが通常行われてきた。[0003] Transparent substrates used for building materials, vehicles, telephone boxes, and the like require a high transmittance in the visible light region. Therefore, when using the above materials, the film thickness must be extremely thin. Therefore spray baking and CVD
It has been generally practiced to form a thin film having a thickness of 10 nm using a physical film forming method such as a sputtering method or a vacuum evaporation method.
【０００４】しかしこれらの成膜方法は大がかりな装置
や真空設備を必要とし、また生産性や大面積化に問題が
あるために膜の製造コストが高いといった欠点がある。
これら膜の膜厚を薄くして透過率を高くしようとすると
日射遮蔽特性が低下し、逆に膜厚を厚くして日射遮蔽特
性を高くすると膜が暗くなってしまうという問題もあ
る。またこれらの材料で日射遮蔽特性を高くしようとす
ると、可視光領域の反射率も同時に高くなってしまう傾
向があり、鏡のようなギラギラした外観を与えて美観を
損ねてしまう。[0004] However, these film forming methods have disadvantages such as requiring large-scale equipment and vacuum equipment, and having high productivity due to problems in productivity and large area.
There is also a problem that when the transmittance is increased by reducing the thickness of these films, the solar shading characteristics are reduced, and when the solar shading characteristics are increased by increasing the film thickness, the films become dark. In addition, when trying to enhance the solar shading characteristics with these materials, the reflectance in the visible light region also tends to increase at the same time, giving a glare-like appearance like a mirror and impairing the aesthetic appearance.
【０００５】さらにこれらの材料では膜の導電性が高く
なるものが多く、膜の導電性が高いと携帯電話やＴＶ、
ラジオなどの電波を反射して受信不能になったり、周辺
地域に電波障害を引き起こすなどの欠点があった。Further, in many of these materials, the conductivity of the film is high, and when the conductivity of the film is high, a cellular phone, a TV,
There are drawbacks such as the reception of radio waves from a radio or the like becoming unreceivable and the occurrence of radio interference in surrounding areas.
【０００６】このような上記従来の欠点を改善するため
には、膜の物理特性として可視光領域の光の反射率が低
くて赤外線領域の反射率が高く、かつ膜の導電性が概ね
１０ ６Ω／口以上に制御可能な膜を形成する必要があっ
た。しかしながら従来にはこのような膜、あるいはこの
ような膜を形成する材料は知られていなかった。[0006] In order to improve the above-mentioned conventional disadvantages,
Has a low reflectance of light in the visible light region as a physical property of the film.
High reflectivity in the infrared region and the conductivity of the film is generally
10 6It is necessary to form a controllable film above
Was. However, conventionally, such a film or this
A material for forming such a film has not been known.
【０００７】可視光透過率が高く、かつ日射遮蔽機能を
持つ材料としてはアンチモン含有酸化錫（ＡＴＯ）や、
錫含有酸化インジウム（ＩＴＯ）が知られている。これ
らの材料は可視光反射率が比較的低くギラギラした外観
を与えることはないが、プラズマ波長が近赤外域の比較
的長波長側にあり、可視光に近い近赤外域におけるこれ
らの膜の反射・吸収効果が十分でなかった。As a material having a high visible light transmittance and having a solar shading function, antimony-containing tin oxide (ATO),
Tin-containing indium oxide (ITO) is known. Although these materials have a relatively low visible light reflectance and do not give a glare-like appearance, the plasma wavelength is on the relatively long wavelength side of the near-infrared region, and the reflection of these films in the near-infrared region close to visible light.・ The absorption effect was not sufficient.
【０００８】そこで上記問題点を解消するため、例えば
加圧不活性ガス中で加熱処理する方法（特開平７−７０
４８１号公報参照）、アルコール含有窒素ガス中で加熱
処理する方法（特開平８−４１４４１号公報参照）、不
活性ガスあるいは還元性ガス中で加熱処理する方法（特
開平１０−１２０９４６号公報参照）等が提案されてい
る。しかしこれらの方法ではいずれも処理温度が３００
℃を超えるためインジウム錫酸化物微粒子の凝集・焼結
が避けられず、膜の可視光透過率が８０％以上でへイズ
値が１％未満の機能を発揮するような材料は実現できな
かった。へイズ値は全光線透過光に対する拡散透過光の
割合であり、この値が高いと曇って見える。したがって
透明性を要求される窓材、特により透明性を必要とする
車両用途では１％を下回るヘイズ値の膜が望まれてい
た。加えて従来提案されていた方法は、処理時間が数時
間と長く、処理効率が悪いという欠点もあった。In order to solve the above problem, for example, a method of performing a heat treatment in a pressurized inert gas (Japanese Patent Laid-Open No. 7-70)
481), a method of performing heat treatment in an alcohol-containing nitrogen gas (see JP-A-8-41441), a method of performing a heat treatment in an inert gas or a reducing gas (see JP-A-10-120946). Etc. have been proposed. However, in any of these methods, the processing temperature is 300
Since the temperature exceeds ℃, aggregation and sintering of indium tin oxide fine particles are unavoidable, and a material exhibiting a function of a film having a visible light transmittance of 80% or more and a haze value of less than 1% could not be realized. . The haze value is the ratio of the diffuse transmitted light to the total light transmitted light, and when this value is high, it looks cloudy. Therefore, a film having a haze value of less than 1% has been desired for window materials that require transparency, particularly for vehicles that require more transparency. In addition, the conventionally proposed method has the disadvantage that the processing time is long, several hours, and the processing efficiency is poor.
【０００９】[0009]
【発明が解決しようとする課題】本発明は上記従来技術
の問題点を解消し、可視光透過率が高くて日射透過率が
より低く、しかもへイズ値が低い日射遮蔽膜形成用イン
ジウム錫酸化物微粒子の高効率的な処理方法と、この微
粒子を用いた日射遮蔽膜とを提供することを目的とする
ものである。SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems of the prior art, and has a high visible light transmittance, a lower solar transmittance, and a low haze value. It is an object of the present invention to provide a highly efficient method for treating substance fine particles and a solar shading film using the fine particles.
【００１０】[0010]
【課題を解決するための手段】上記目的を達成するため
に、本発明者らはインジウム錫酸化物微粒子と周期律表
の１Ａ族群から選択された１種の金属源とを混合するこ
とによって、微粒子の凝集・焼結が生じない１５０〜３
００℃といった低い温度でも、短い処理時間で近赤外域
における反射・吸収特性が改善されること、また塩素イ
オン、硝酸イオン、硫酸イオンからなる残留不純物量を
少なくしたインジウム錫酸化物微粒子と周期律表の１Ａ
族群から選択された１種の金属源の混合によって前記効
果が一層増すこと、さらにこれを分散した膜の作製によ
って可視光領域に透過率の極大を持つとともに可視光領
域に近い近赤外域に強いプラズマ吸収を発現して透過率
の極小を持ち、かつヘイズ値が極めて低くなるという現
象を見出し、本発明を完成するに至った。Means for Solving the Problems In order to achieve the above object, the present inventors mixed indium tin oxide fine particles with one kind of metal source selected from the group 1A group of the periodic table. 150 to 3 without aggregation and sintering of fine particles
Even at a low temperature such as 00 ° C, the reflection and absorption characteristics in the near infrared region can be improved in a short processing time. In addition, the indium tin oxide fine particles having a reduced amount of residual impurities composed of chloride ions, nitrate ions, and sulfate ions can be used in combination with periodic rules. 1A in the table
The effect is further enhanced by mixing one kind of metal source selected from the group of metals, and furthermore, by producing a film in which the above-mentioned metal source is dispersed, the film has a transmittance maximum in the visible light region and is strong in the near infrared region near the visible light region. The inventors have found that a phenomenon in which plasma absorption is exhibited to minimize the transmittance and the haze value is extremely low has been achieved, and the present invention has been completed.
【００１１】すなわち本発明に係る日射遮蔽膜形成用イ
ンジウム錫酸化物微粒子の処理方法は、平均粒径が１０
０ｎｍ以下のインジウム錫酸化物微粒子と周期律表の１
Ａ族群から選択された少なくとも１種の金属源とを混合
した後、不活性ガス、あるいはアルコールを含む不活性
ガス、もしくは還元性ガスと不活性ガスとの混合ガス雰
囲気下１５０〜３００℃の温度で処理することを特徴と
する。また本発明は、平均粒径が１００ｎｍ以下のイン
ジウム錫酸化物微粒子を、塩素イオン、硝酸イオン、硫
酸イオンからなる残留不純物量を０．６％以下とした
後、周期律表の１Ａ族群から選択された少なくとも１種
の金属源と混合し、つぎに不活性ガス、あるいはアルコ
ールを含む不活性ガス、もしくは還元性ガスと不活性ガ
スとの混合ガス雰囲気下１５０〜３００℃の温度で処理
することを特徴とする。さらに本発明の日射遮蔽膜は、
前記のような処理を施したインジウム錫酸化物微粒子か
らなり、可視光透過率８０％以上のときの波長域３００
〜２１００ｎｍにおける日射透過率が７０％未満で、へ
イズ値が１％未満であることを特徴とする。That is, in the method for treating indium tin oxide fine particles for forming a solar shading film according to the present invention, the average particle diameter is 10%.
Indium tin oxide fine particles of 0 nm or less and 1 in the periodic table
After mixing with at least one metal source selected from the group A group, a temperature of 150 to 300 ° C. in an atmosphere of an inert gas, an inert gas containing alcohol, or a mixed gas of a reducing gas and an inert gas. The process is characterized by In the present invention, the indium tin oxide fine particles having an average particle diameter of 100 nm or less are selected from the group 1A group of the periodic table after the amount of residual impurities composed of chloride ions, nitrate ions, and sulfate ions is reduced to 0.6% or less. Mixed with at least one metal source, and then treated at a temperature of 150 to 300 ° C. in an atmosphere of an inert gas, an inert gas containing alcohol, or a mixed gas of a reducing gas and an inert gas. It is characterized by. Furthermore, the solar shading film of the present invention,
A wavelength region 300 made of indium tin oxide fine particles treated as described above and having a visible light transmittance of 80% or more.
It is characterized by having a solar transmittance of less than 70% at a wavelength of ｎｍ2100 nm and a haze value of less than 1%.
【００１２】[0012]
【発明の実施の形態】本発明において、処理を施すイン
ジウム錫酸化物微粒子は、元素換算での錫含有量は１〜
１５重量％が好ましい。すなわち、１重量％未満では錫
の添加効果が見られず、他方、１５重量％を超えると錫
の固溶が不十分となるからである。またインジウム錫酸
化物微粒子の平均粒径は１００ｎｍ以下とする。その理
由は、１００ｎｍを超えると光散乱源となって膜に曇り
（へイズ）を生じたり、可視光透過率が減少する原因と
なるので好ましくないからである。なおここでは粒子の
大きさを平均粒径で表しているが、特に１００ｎｍを超
えるような粗粉の割合が少なく粒度分布の狭い微粉が好
ましく、かつ経済的に入手可能な最低の粒径は２ｎｍ程
度の微粒子であるが下限をこれに限定するものではな
い。酸化物換算での周期律表の１Ａ族群の金属源とイン
ジウム錫酸化物微粒子との混合割合は、処理効率と光学
特性の観点から０．０１：９９．９９〜１０：９０、好
ましくは０．１：９９．９〜５：９５である。なお混合
方法は均一に混合できれば特に限定されず、公知の方法
を採用できる。また、１Ａ族群の金属源は特に限定され
ず、勿論２種以上の金属源を混合してもよい。DETAILED DESCRIPTION OF THE INVENTION In the present invention, the indium tin oxide fine particles to be treated have a tin content of 1 to 1 in terms of element.
15% by weight is preferred. That is, when the content is less than 1% by weight, the effect of adding tin is not seen, and when it exceeds 15% by weight, the solid solution of tin becomes insufficient. The average particle size of the indium tin oxide fine particles is 100 nm or less. The reason for this is that if the thickness exceeds 100 nm, it becomes a light scattering source, causing fogging (haze) in the film and causing a decrease in visible light transmittance, which is not preferable. Although the size of the particles is represented by an average particle size here, a fine powder having a small ratio of coarse powder exceeding 100 nm and a narrow particle size distribution is particularly preferable, and the lowest economically available particle size is 2 nm. Although the fine particles are of the order of magnitude, the lower limit is not limited to this. The mixing ratio of the metal source of the group 1A group of the periodic table and the indium tin oxide fine particles in terms of oxide is 0.01: 99.99 to 10:90, preferably 0.1 to 9:90, from the viewpoint of processing efficiency and optical characteristics. 1: 99.9-5: 95. The mixing method is not particularly limited as long as it can be uniformly mixed, and a known method can be employed. Further, the metal source of the group 1A group is not particularly limited, and of course, two or more metal sources may be mixed.
【００１３】インジウム錫酸化物微粒子の処理は、不活
性ガス単独、あるいはアルコールを含む不活性ガス、も
しくは不活性ガスと還元性ガスの混合ガス雰囲気で行う
が、不活性ガスとしては、窒素、アルゴン、へリウムガ
スなどが、また還元性ガスとしては、水素や一酸化炭素
などが用いられる。これらのガスは、単独でも混合して
用いてもよい。用いるアルコールは特に限定されるもの
ではないが、揮発性とコス卜の観点からメタノール、エ
タノール、プロパノールなどが好ましい。不活性ガス中
のアルコール、水素、一酸化炭素の各濃度やフィード量
は、処理効率や所望とする光学特性が得られるように適
宜選択すればよい。The indium tin oxide fine particles are treated in an inert gas alone, in an inert gas containing alcohol, or in a mixed gas atmosphere of an inert gas and a reducing gas. , Helium gas and the like, and as the reducing gas, hydrogen and carbon monoxide are used. These gases may be used alone or as a mixture. The alcohol used is not particularly limited, but methanol, ethanol, propanol and the like are preferable from the viewpoint of volatility and cost. The concentrations and feed amounts of alcohol, hydrogen, and carbon monoxide in the inert gas may be appropriately selected so as to obtain processing efficiency and desired optical characteristics.
【００１４】処理温度は１５０〜３００℃の範囲とする
が、その理由は３００℃を超えると凝集・焼結が起こり
易く、他方、１５０℃未満では所望とする光学特性が得
られないからである。また還元時間は温度に応じて適宜
選択すればよいが、本発明では１時間以内で十分であ
る。The processing temperature is in the range of 150 to 300 ° C., because if it exceeds 300 ° C., aggregation and sintering tend to occur, while if it is lower than 150 ° C., desired optical characteristics cannot be obtained. . The reduction time may be appropriately selected according to the temperature, but in the present invention, one hour or less is sufficient.
【００１５】インジウム錫酸化物微粒子中に残留する塩
素イオン、硝酸イオン、硫酸イオンなどの不純物は還元
阻害因子となるため、洗浄によって０．６％以下、好ま
しくは０．３％以下とする。Impurities such as chloride ions, nitrate ions, and sulfate ions remaining in the indium tin oxide fine particles serve as reduction inhibiting factors, and thus are reduced to 0.6% or less, preferably 0.3% or less by washing.
【００１６】上記のインジウム錫酸化物微粒子を用いて
日射遮蔽膜を形成するには、インジウム錫酸化物微粒子
を溶媒中に分散し、塗布液とし、スピンコート法、バー
コート法、スプレーコート法、ディップコー卜法、スク
リーン印刷法、ロ−ルコート法、流し塗りなどの方法を
用いればよい。In order to form a solar shading film using the above-described indium tin oxide fine particles, the indium tin oxide fine particles are dispersed in a solvent to form a coating solution, which is then subjected to spin coating, bar coating, spray coating, or the like. Dip coating, screen printing, roll coating, flow coating, and the like may be used.
【００１７】溶媒は特に限定されるものではなく、塗布
条件、塗布環境、および無機バインダーや樹脂バインダ
ーを含有させたときはバインダーに合わせて適宜選択す
る。例えば水やエタノール、プロパノール、ブタノー
ル、イソプロピルアルコール、イソブチルアルコール、
ジアセトンアルコールなどのアルコ一ル類、メチルエー
テル、エチルエーテル、プロピルエーテルなどのエーテ
ル類、エステル類、アセトン、メチルエチルケトン、ジ
エチルケトン、シクロヘキサノン、イソブチルケトンな
どのケトン類といった各種の有機溶媒が使用可能であ
り、また必要に応じて酸やアルカリを添加してｐＨ調整
してもよい。The solvent is not particularly limited, and is appropriately selected according to the coating conditions, the coating environment, and when an inorganic binder or a resin binder is contained, according to the binder. For example, water, ethanol, propanol, butanol, isopropyl alcohol, isobutyl alcohol,
Various organic solvents such as alcohols such as diacetone alcohol, ethers such as methyl ether, ethyl ether and propyl ether, esters, ketones such as acetone, methyl ethyl ketone, diethyl ketone, cyclohexanone and isobutyl ketone can be used. Yes, and if necessary, acid or alkali may be added to adjust the pH.
【００１８】さらに塗布液中の微粒子の分散安定性を一
層向上させるためには、各種の界面活性剤、カップリン
グ剤などの添加も勿論可能である。Further, in order to further improve the dispersion stability of the fine particles in the coating liquid, it is of course possible to add various surfactants and coupling agents.
【００１９】無機バインダーや樹脂バインダーの種類は
特に限定されるものではないが、無機バインダーとして
は、珪素、ジルコニウム、チタンもしくはアルミニウム
の金属アルコキシドやこれらの部分加水分解縮重合物あ
るいはオルガノシラザンが、樹脂バインダーとしてはア
クリル樹脂などの熱可塑性樹脂、エポキシ樹脂などの熱
硬化性樹脂などが利用できる。The kind of the inorganic binder or the resin binder is not particularly limited. Examples of the inorganic binder include metal alkoxides of silicon, zirconium, titanium or aluminum, partially hydrolyzed polycondensates thereof, and organosilazanes. As the binder, a thermoplastic resin such as an acrylic resin or a thermosetting resin such as an epoxy resin can be used.
【００２０】インジウム錫酸化物微粒子の分散方法は塗
布液中に均一に分散する方法であれば特に限定されず、
例えばビーズミル、ボールミル、サンドミル、ペイント
シェーカー、超音波ホモジナイザーなどが挙げられる。The method for dispersing the fine particles of indium tin oxide is not particularly limited as long as it is a method of uniformly dispersing in the coating solution.
Examples include a bead mill, a ball mill, a sand mill, a paint shaker, an ultrasonic homogenizer, and the like.
【００２１】日射遮蔽膜のさらなる紫外線遮蔽機能を付
与させるため、無機系の酸化チタンや酸化亜鉛、酸化セ
リウムなどの微粒子や、有機系のベンゾフェノンやベン
ゾトリアゾールなどの１種もしくは２種以上を添加して
もよい。In order to provide a further ultraviolet shielding function of the solar shading film, one or more of inorganic fine particles such as titanium oxide, zinc oxide and cerium oxide and one or more of organic benzophenone and benzotriazole are added. You may.
【００２２】インジウム錫酸化物微粒子は無機材料であ
るので有機材料と比べて耐候性は非常に高く、例えば太
陽光線（紫外線）の当たる部位に使用しても色や諸機能
の劣化はほとんど生じない。Since indium tin oxide fine particles are inorganic materials, they have extremely high weather resistance compared to organic materials. For example, even if they are used in a portion exposed to sunlight (ultraviolet rays), color and various functions are hardly deteriorated. .
【００２３】[0023]
【実施例】以下、本発明を実施例および比較例とともに
さらに詳細に説明する。ただし、本発明は下記実施例に
限定されるものでない。なお、得られた膜の可視光透過
率や日射透過率は日立製作所（株）製の分光光度計Ｕ−
４０００を用いて測定した。またヘイズ値は村上色彩技
術研究所（株）製ＨＲ−２００を用いて測定した。膜評
価においては線径の異なる３種のバーコーターで成膜
し、これらにより得られる膜厚の異なる３種類の膜の可
視光透過率、日射透過率、へイズ値をそれぞれ測定し、
これらの３点プロットからの内挿値として、可視光透過
率８６％のときの日射透過率およびへイズ値を求めた。
各実施例の結果は表１にまとめて示した。The present invention will be described below in more detail with reference to examples and comparative examples. However, the present invention is not limited to the following examples. In addition, the visible light transmittance and the solar transmittance of the obtained film were measured by a spectrophotometer U-manufactured by Hitachi, Ltd.
It measured using 4000. The haze value was measured using HR-200 manufactured by Murakami Color Research Laboratory. In the film evaluation, the film was formed with three types of bar coaters having different wire diameters, and the visible light transmittance, the solar radiation transmittance, and the haze value of the three types of films obtained with these different thicknesses were measured.
As the interpolated values from these three-point plots, the solar radiation transmittance and the haze value when the visible light transmittance was 86% were determined.
The results of each example are summarized in Table 1.
【００２４】実施例１ 錫含有量１０重量％、残留不純物量０．７％、平均粒径
０．０３μｍのインジウム錫酸化物微粒子（住友金属鉱
山（株）製）と酸化物換算での炭酸カリウムとの混合割
合を９８：２とし、３０分混合した。これを５００ｍｌ
のセパラブルフラスコに入れ、撹拌しながらメタノール
含有窒素キャリアガスをフィードして加熱し、３００℃
の温度で３０分処理してカリウム添加インジウム錫酸化
物微粒子を得た。続いて、該微粒子２０重量％、メチル
イソブチルケトン６３．３重量％、分散剤１６．７重量
％、および充填率６３％相当の０．３ｍｍジルコニアビ
ーズをペイントシェーカーで２４時間分散した。つぎに
該分散液６７．５重量％、バインダーとしてメチルイソ
ブチルケトンに溶解したアクリル樹脂溶液２７．５重量
％および硬化剤５重量％からなる塗布液を、番手４０、
２４、６のバーでそれぞれ１００ｍｍ×１００ｍｍ×３
ｍｍのソーダライムガラス基板に塗布した後、１８０℃
で１時間焼成して膜ａを得た。表１から分かる通り、日
射透過率およびへイズ値はそれぞれ６５．５％、０．４
％であった。Example 1 Indium tin oxide fine particles (manufactured by Sumitomo Metal Mining Co., Ltd.) having a tin content of 10% by weight, a residual impurity amount of 0.7% and an average particle size of 0.03 μm, and potassium carbonate in terms of oxides Was set to 98: 2 and mixed for 30 minutes. 500 ml of this
And heated while feeding a nitrogen-containing nitrogen carrier gas with stirring.
For 30 minutes to obtain potassium-added indium tin oxide fine particles. Subsequently, 20% by weight of the fine particles, 63.3% by weight of methyl isobutyl ketone, 16.7% by weight of a dispersant, and 0.3 mm zirconia beads corresponding to a filling rate of 63% were dispersed by a paint shaker for 24 hours. Next, a coating liquid consisting of 67.5% by weight of the dispersion, 27.5% by weight of an acrylic resin solution dissolved in methyl isobutyl ketone as a binder, and 5% by weight of a curing agent was used as a 40-counter.
100 mm x 100 mm x 3 with 24 and 6 bars
mm on soda lime glass substrate
For 1 hour to obtain a film a. As can be seen from Table 1, the solar radiation transmittance and the haze value were 65.5% and 0.4, respectively.
%Met.
【００２５】実施例２、実施例３ 処理時間を７分とした以外は実施例１と同様にして膜ｂ
（実施例２）を、４５分とした以外は実施例１と同様に
して膜ｃ（実施例３）を得た。表１から分かる通り、実
施例２の日射透過率およびへイズ値はそれぞれ６６．１
％、０．５％であり、実施例３の日射透過率およびヘイ
ズ値はそれぞれ６７．５％、０．６％であった。Examples 2 and 3 The film b was prepared in the same manner as in Example 1 except that the processing time was changed to 7 minutes.
A film c (Example 3) was obtained in the same manner as in Example 1 except that (Example 2) was changed to 45 minutes. As can be seen from Table 1, the solar radiation transmittance and the haze value of Example 2 were respectively 66.1.
% And 0.5%, and the solar radiation transmittance and the haze value of Example 3 were 67.5% and 0.6%, respectively.
【００２６】実施例４ インジウム錫酸化物微粒子と酸化物換算での炭酸カリウ
ムとの混合割合を９９．６：０．４とした以外は実施例
１と同様にして膜ｄ（実施例４）を得た。表１から分か
る通り、実施例４の日射透過率およびへイズ値はそれぞ
れ６６．１％、０．５％であった。Example 4 A film d (Example 4) was prepared in the same manner as in Example 1 except that the mixing ratio of indium tin oxide fine particles and potassium carbonate in terms of oxide was 99.6: 0.4. Obtained. As can be seen from Table 1, the solar radiation transmittance and the haze value of Example 4 were 66.1% and 0.5%, respectively.
【００２７】実施例５〜実施例７ 炭酸カリウムに代えて、炭酸リチウムとした以外は実施
例４と同様にして膜ｅ（実施例５）を、炭酸ナトリウム
とした以外は実施例４と同様にして膜ｆ（実施例６）
を、炭酸水素カリウムとした以外は実施例４と同様にし
て膜ｇ（実施例７）を得た。表１から分かる通り、実施
例５の日射透過率およびへイズ値はそれぞれ６６．３
％、０．６％、実施例６の日射透過率およびヘイズ値は
それぞれ６６．５％、０．６％、実施例７の日射透過率
およびへイズ値はそれぞれ６６．８％、０．６％であっ
た。Examples 5 to 7 A film e (Example 5) was prepared in the same manner as in Example 4 except that lithium carbonate was used instead of potassium carbonate. Film f (Example 6)
Was changed to potassium hydrogen carbonate, and a film g (Example 7) was obtained in the same manner as in Example 4. As can be seen from Table 1, the solar radiation transmittance and the haze value of Example 5 were each 66.3.
%, 0.6%, the solar transmittance and haze value of Example 6 were 66.5% and 0.6%, respectively, and the solar transmittance and haze value of Example 7 were 66.8% and 0.6, respectively. %Met.
【００２８】実施例８ インジウム錫酸化物微粒子と酸化物換算での炭酸カリウ
ムとの混合割合を９６：４とし、処理時間を７分とした
以外は実施例１と同様にして膜ｈ（実施例８）を得た。
表１から分かる通り、実施例４の日射透過率およひヘイ
ズ値はそれぞれ６６．４％、０．５％であった。Example 8 A film h (Example 1) was prepared in the same manner as in Example 1 except that the mixing ratio of indium tin oxide fine particles to potassium carbonate in terms of oxide was 96: 4 and the treatment time was 7 minutes. 8) was obtained.
As can be seen from Table 1, the solar radiation transmittance and the haze value of Example 4 were 66.4% and 0.5%, respectively.
【００２９】実施例９ インジウム錫酸化物微粒子と酸化物換算での炭酸カリウ
ムとの混合割合を９６：４とし、１０％水素バランス窒
素からなる混合ガスで処理時間を２０分とした以外は実
施例１と同様にして膜ｉ（実施例９）を得た。表１から
分かる通り、実施例８の日射透過率およびへイズ値はそ
れぞれ６６．５％、０．５％であった。Example 9 Example 9 was repeated except that the mixing ratio of indium tin oxide fine particles to potassium carbonate in terms of oxide was 96: 4, and the treatment time was 20 minutes with a mixed gas comprising 10% hydrogen balance nitrogen. In the same manner as in Example 1, a film i (Example 9) was obtained. As can be seen from Table 1, the solar radiation transmittance and the haze value of Example 8 were 66.5% and 0.5%, respectively.
【００３０】実施例１０ ２．８％ＮＨ４ＯＨで洗浄した後、６００ｍｌのイオン
交換水で６回水洗処理を施した錫含有量１０重量％、残
留不純物量０．１％、平均粒径０．０３μｍのインジウ
ム錫酸化物微粒子（住友金属鉱山（株）製）と酸化物換
算での炭酸カリウムとの混合割合を９６：４とし、２３
０℃で４０分処理した以外は実施例１と同様にして膜ｊ
（実施例１０）を得た。表１から分かる通り、日射透過
率およびへイズ値はそれぞれ６６．５％、０．６％であ
った。Example 10 After washing with 2.8% NH 4 OH, water was washed six times with 600 ml of ion-exchanged water. Tin content 10% by weight, residual impurity amount 0.1%, average particle size 0 The mixing ratio of 0.03 μm indium tin oxide fine particles (manufactured by Sumitomo Metal Mining Co., Ltd.) and potassium carbonate in terms of oxide was 96: 4, and 23
A film j was prepared in the same manner as in Example 1 except that the treatment was performed at 0 ° C. for 40 minutes.
(Example 10) was obtained. As can be seen from Table 1, the solar radiation transmittance and the haze value were 66.5% and 0.6%, respectively.
【００３１】実施例１１ ２．８％ＮＨ４ＯＨで洗浄したあと、６００ｍｌのイオ
ン交換水で６回水洗処理を施した錫含有量１０重量％、
残留不純物量０．１％、平均粒径０．０３μｍのインジ
ウム錫酸化物微粒子（住友金属鉱山（株）製）と酸化物
換算での炭酸カリウムとの混合割合を９６：４とし、窒
素ガス単独で２８０℃で４０分処理した以外は実施例１
と同様にして膜ｋ（実施例１１）を得た。表１から分か
る通り、日射透過率およびへイズ値はそれぞれ６７．１
％、０．５％であった。Example 11 After washing with 2.8% NH 4 OH, the resultant was washed with 600 ml of ion-exchanged water six times. The tin content was 10% by weight.
The mixing ratio of indium tin oxide fine particles (manufactured by Sumitomo Metal Mining Co., Ltd.) having a residual impurity amount of 0.1% and an average particle size of 0.03 μm to potassium carbonate in terms of oxide was set to 96: 4, and nitrogen gas alone was used. Example 1 except that the treatment was performed at 280 ° C. for 40 minutes.
In the same manner as in the above, a film k (Example 11) was obtained. As can be seen from Table 1, the solar radiation transmittance and the haze value were each 67.1.
% And 0.5%.
【００３２】比較例１ 錫含有量１０重量％、平均粒径０．０３μｍのインジウ
ム錫酸化物微粒子（住友金属鉱山（株）製）の還元処理
を施さなかった以外は、実施例１と同様にして膜ｉ（比
較例１）を得た。評価結果を表１に併せて示す。表１か
ら分かる通り、得られた膜ｉは日射透過率が７０％を超
え、かつへイズ値も１％を超えるもので、本発明法で得
られたものより劣るものであった。Comparative Example 1 The procedure of Example 1 was repeated except that the indium tin oxide fine particles having a tin content of 10% by weight and an average particle size of 0.03 μm (manufactured by Sumitomo Metal Mining Co., Ltd.) were not subjected to a reduction treatment. Thus, a film i (Comparative Example 1) was obtained. The evaluation results are also shown in Table 1. As can be seen from Table 1, the obtained film i had a solar transmittance of more than 70% and a haze value of more than 1%, which was inferior to that obtained by the method of the present invention.
【００３３】比較例２ 炭酸カリウムを添加せず、インジウム錫酸化物微粒子を
３００℃で１８０分処理した以外は、実施例１と同様に
して膜ｍ（比較例２）を得た。評価結果を表１に併せて
示す。表１から分かる通り、得られた膜ｍの日射透過率
およびへイズ値は実施例１とほぼ同レベルであったが、
処理時間が１８０分と長時間要した。Comparative Example 2 A film m (Comparative Example 2) was obtained in the same manner as in Example 1 except that potassium carbonate was not added and indium tin oxide fine particles were treated at 300 ° C. for 180 minutes. The evaluation results are also shown in Table 1. As can be seen from Table 1, the solar radiation transmittance and haze value of the obtained film m were almost the same level as in Example 1,
Processing time required a long time of 180 minutes.
【００３４】[0034]
【表１】 [Table 1]
【００３５】[0035]
【発明の効果】以上説明したごとく、本発明は可視光透
過率が高くて日射透過率およびヘイズ値が低い膜形成用
インジウム錫酸化物微粒子の高効率的な処理方法を提供
できることから、工業的有用性が極めて高い。As described above, the present invention provides a highly efficient method for treating indium tin oxide fine particles for film formation having a high visible light transmittance and a low solar transmittance and a low haze value. Very useful.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０９Ｄ 5/00 Ｃ０９Ｄ 5/00 Ｚ Ｆターム(参考） 4G059 AA01 AC06 EA02 EA03 EB09 4J037 AA08 CA01 CA10 CA16 CB04 DD05 DD20 DD27 EE19 EE25 FF02 FF13 FF30 4J038 AA011 CG001 DB001 DL031 DM001 HA211 HA431 KA06 NA19 PB02 PB05 PB07 PC03 PC08 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) C09D 5/00 C09D 5/00 Z F Term (Reference) 4G059 AA01 AC06 EA02 EA03 EB09 4J037 AA08 CA01 CA10 CA16 CB04 DD05 DD20 DD27 EE19 EE25 FF02 FF13 FF30 4J038 AA011 CG001 DB001 DL031 DM001 HA211 HA431 KA06 NA19 PB02 PB05 PB07 PC03 PC08
Claims (3)
錫酸化物微粒子と周期律表の１Ａ族群から選択された少
なくとも１種の金属源とを混合した後、不活性ガス、あ
るいはアルコールを含む不活性ガス、もしくは還元性ガ
スと不活性ガスとの混合ガス雰囲気下１５０〜３００℃
の温度で処理することを特徴とする日射遮蔽膜形成用イ
ンジウム錫酸化物微粒子の処理方法。An inactive gas or an inert gas containing an alcohol after mixing indium tin oxide fine particles having an average particle size of 100 nm or less with at least one metal source selected from the group 1A group of the periodic table. 150-300 ° C in a mixed gas atmosphere of gas or reducing gas and inert gas
A method for treating indium tin oxide fine particles for forming a solar shading film, characterized in that the treatment is performed at a temperature of:
錫酸化物微粒子中に含有する塩素イオン、硝酸イオン、
硫酸イオンからなる残留不純物量を０．６％以下とした
後、周期律表の１Ａ族群から選択された少なくとも１種
の金属源と混合し、つぎに不活性ガス、あるいはアルコ
ールを含む不活性ガス、もしくは還元性ガスと不活性ガ
スとの混合ガス雰囲気下１５０℃〜３００℃の温度で処
理してインジウム錫酸化物微粒子とすることを特徴とす
る日射遮蔽膜形成用インジウム錫酸化物微粒子の処理方
法。2. Chloride ions, nitrate ions contained in indium tin oxide fine particles having an average particle diameter of 100 nm or less,
After reducing the amount of residual impurities composed of sulfate ions to 0.6% or less, it is mixed with at least one metal source selected from Group 1A of the periodic table, and then inert gas or inert gas containing alcohol. Or a treatment at a temperature of 150 ° C. to 300 ° C. in a mixed gas atmosphere of a reducing gas and an inert gas to obtain indium tin oxide fine particles, the treatment of indium tin oxide fine particles for forming a solar shading film. Method.
用インジウム錫酸化物微粒子からなり、可視光透過率８
０％以上のときの波長域３００〜２１００ｎｍにおける
日射透過率が７０％未満で、へイズ値が１％未満である
ことを特徴とする日射遮蔽膜。3. A visible light transmittance of 8 comprising the indium tin oxide fine particles for forming a solar shading film according to claim 1 or 2.
A solar shading film characterized by having a solar transmittance of less than 70% and a haze value of less than 1% in a wavelength range of 300 to 2100 nm at 0% or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000343692A JP2002146228A (en) | 2000-11-10 | 2000-11-10 | Method for treating fine indium-tin oxide particle for forming sunshine-screening film and sunshine-screening film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000343692A JP2002146228A (en) | 2000-11-10 | 2000-11-10 | Method for treating fine indium-tin oxide particle for forming sunshine-screening film and sunshine-screening film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2002146228A true JP2002146228A (en) | 2002-05-22 |
Family
ID=18818019
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000343692A Pending JP2002146228A (en) | 2000-11-10 | 2000-11-10 | Method for treating fine indium-tin oxide particle for forming sunshine-screening film and sunshine-screening film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2002146228A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004046057A1 (en) * | 2002-11-21 | 2004-06-03 | Nippon Sheet Glass Company, Limited | Thermal shielding plate and method for manufacture thereof, and fluid composition for use therein |
| WO2004060807A1 (en) * | 2002-12-27 | 2004-07-22 | Sumitomo Metal Mining Co., Ltd. | FINE In4Sn3O12 COMPOSITE OXIDE PARTICLE FOR SOLAR RADIATION SHIELDING, PROCESS FOR PRODUCING THE SAME, COATING FLUID FOR FORMING SOLAR RADIATION SHIELDING FILM, SOLAR RADIATION SHIELDING FILM, AND SUBSTRATE FOR SOLAR RADIATION SHIELDING |
| EP1477465A1 (en) * | 2003-05-14 | 2004-11-17 | Nippon Sheet Glass Company, Limited | Substrate with film containing functional particles |
-
2000
- 2000-11-10 JP JP2000343692A patent/JP2002146228A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004046057A1 (en) * | 2002-11-21 | 2004-06-03 | Nippon Sheet Glass Company, Limited | Thermal shielding plate and method for manufacture thereof, and fluid composition for use therein |
| WO2004060807A1 (en) * | 2002-12-27 | 2004-07-22 | Sumitomo Metal Mining Co., Ltd. | FINE In4Sn3O12 COMPOSITE OXIDE PARTICLE FOR SOLAR RADIATION SHIELDING, PROCESS FOR PRODUCING THE SAME, COATING FLUID FOR FORMING SOLAR RADIATION SHIELDING FILM, SOLAR RADIATION SHIELDING FILM, AND SUBSTRATE FOR SOLAR RADIATION SHIELDING |
| EP1477465A1 (en) * | 2003-05-14 | 2004-11-17 | Nippon Sheet Glass Company, Limited | Substrate with film containing functional particles |
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