JP3250125B2 - Infrared cutoff powder - Google Patents
Infrared cutoff powderInfo
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- JP3250125B2 JP3250125B2 JP26024893A JP26024893A JP3250125B2 JP 3250125 B2 JP3250125 B2 JP 3250125B2 JP 26024893 A JP26024893 A JP 26024893A JP 26024893 A JP26024893 A JP 26024893A JP 3250125 B2 JP3250125 B2 JP 3250125B2
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- infrared
- powder
- ito powder
- film
- ito
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Description
【０００１】[0001]
【産業上の利用分野】この発明は、従来のものより低波
長側から赤外線をカットオフすることができる粉末に関
する。より具体的には、1000 nm 以下、特に 700〜900
nmの範囲内のある波長から長波長側の赤外線を90％以上
カットオフする錫ドープ酸化インジウム粉末に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a powder capable of cutting off infrared rays from a lower wavelength side than conventional ones. More specifically, 1000 nm or less, especially 700-900
The present invention relates to a tin-doped indium oxide powder that cuts off infrared rays on a long wavelength side from a certain wavelength in the range of nm by 90% or more.
【０００２】本発明の粉末は、特に平均一次粒子径が0.
2 μｍ以下であると、塗料中に分散させて透明膜を形成
することができ、得られた透明膜に優れた赤外線カット
オフ効果を付与することができる。The powder of the present invention particularly has an average primary particle size of 0.1.
When it is 2 μm or less, a transparent film can be formed by dispersing in a paint, and an excellent infrared cutoff effect can be imparted to the obtained transparent film.
【０００３】この赤外線カットオフ効果を示す透明膜
は、近年多発しているカードや金券等の偽造に対する防
止手段として、あるいは冷暖房効率の改善に効果の高い
赤外線反射膜として利用することができる。特にハウジ
ングの一般窓、サンルームの屋根材、壁材、あるいは自
動車のガラス等に適用した場合、夏期の太陽光の赤外線
カットオフ効果により大幅な冷房用電力節減効果を発揮
し、また冬期は室内の保温効果の高い透明膜として利用
できる。A transparent film exhibiting the infrared cut-off effect can be used as a means for preventing counterfeiting of cards, cash vouchers, etc., which have frequently occurred in recent years, or as an infrared reflecting film which is highly effective in improving the cooling and heating efficiency. In particular, when applied to general windows of housings, roofing materials and walls of sunrooms, and glass of automobiles, the infrared ray cutoff effect of sunlight in the summer brings about a significant power saving effect for cooling and indoors in the winter. It can be used as a transparent film with high heat retention effect.
【０００４】[0004]
【従来の技術】可視領域の光に対して透明 (透過性) で
あって、赤外領域の光に対しては反射性である赤外線カ
ットオフ機能を有する透明膜として従来より知られてい
るのは、(a) ＩＴＯ (錫ドープ酸化インジウム) の薄膜
を物理蒸着、化学蒸着、またはスパッタリングによって
ガラス基板上に形成したもの、(b) フタロシアニン系、
アントラキノン系、ナフトキノン系、シアニン系、ナフ
タロシアニン系、高分子縮合アゾ系、ピロール系等の有
機色素型の近赤外吸収剤か、またはジチオール系、メル
カプトナフトール系などの有機金属錯塩を、有機溶媒と
有機バインダーとを用いてインク化して基板に塗工する
か、或いは樹脂に練り込んでフィルム化し、基板上にラ
ミネートしたものなどである。2. Description of the Related Art A transparent film having an infrared cutoff function, which is transparent (transmittable) to light in the visible region and reflective to light in the infrared region, is conventionally known. (A) a thin film of ITO (tin-doped indium oxide) formed on a glass substrate by physical vapor deposition, chemical vapor deposition, or sputtering, (b) phthalocyanine,
An anthraquinone-based, naphthoquinone-based, cyanine-based, naphthalocyanine-based, polymer-condensed azo-based, or pyrrole-based organic dye-type near-infrared absorber, or a dithiol-based or mercapton-naphthol-based organic metal complex salt, an organic solvent And an organic binder, and then applied to a substrate or kneaded with a resin to form a film and laminated on the substrate.
【０００５】しかし、(a) については、高真空や精度の
高い雰囲気制御が必要な装置を使用しなければならない
ため、コスト高になるばかりか、膜の大きさ、形状にも
限りがある。しかも、量産性が悪く、汎用性に乏しい等
の問題もある。However, in the case of (a), a device that requires high vacuum and high-precision atmosphere control must be used, which not only increases the cost but also limits the size and shape of the film. In addition, there are problems such as poor mass productivity and poor versatility.
【０００６】(b) については、(a) の問題点は解決され
るものの、可視領域の光の透過率が低く、暗褐色から暗
青色の濃厚な着色を有している上、多くは 690〜1000 n
m 程度の限られた近赤外領域の赤外線吸収であるため、
例えばハウジングの一般窓、サンルームの屋根材、壁材
等へ利用した場合には、窓やガラスを通した室内外の視
認性が悪く、色調から受ける美観性にも劣る上、室内の
冷暖房効果も不十分である等の問題点がある。As for (b), although the problem of (a) is solved, the transmittance of light in the visible region is low, the color is dark brown to dark blue, and most of the color is 690. ~ 1000 n
m because of the limited infrared absorption in the near infrared region
For example, when used for general windows in housings, roof materials for solar rooms, wall materials, etc., the visibility inside and outside of the room through windows and glass is poor, the aesthetics received from the color tone are poor, and the indoor cooling and heating effect Are also insufficient.
【０００７】[0007]
【発明が解決しようとする課題】本発明の目的は、従来
より低波長側から赤外線をカットオフすることができ、
可視光に対しては優れた透明性を示す膜を形成すること
ができる、赤外線カットオフ機能を有する無機粉末を提
供することである。SUMMARY OF THE INVENTION An object of the present invention is to cut off infrared rays from a lower wavelength side than before,
An object of the present invention is to provide an inorganic powder having an infrared cutoff function, which can form a film exhibiting excellent transparency to visible light.
【０００８】本発明のより具体的な目的は、1000 nm 以
下の赤外領域内またはその近傍のある波長から長波長側
の赤外線を全面的に90％以上カットオフする錫ドープ酸
化インジウム粉末を提供することである。A more specific object of the present invention is to provide a tin-doped indium oxide powder that cuts off at least 90% or more of infrared rays on a longer wavelength side from a certain wavelength in or near an infrared region of 1000 nm or less. It is to be.
【０００９】[0009]
【課題を解決するための手段】本発明者等は、錫ドープ
酸化インジウム (ＩＴＯ) が可視光に対して透明であ
り、かつ赤外線反射性を示すことに着目し、塗料化によ
り優れた赤外線カットオフ効果を持つ透明膜を形成でき
るＩＴＯ粉末を得るべく検討を重ねた。The present inventors have paid attention to the fact that tin-doped indium oxide (ITO) is transparent to visible light and exhibits infrared reflectivity. The study was repeated to obtain an ITO powder capable of forming a transparent film having an off-effect.
【００１０】ＩＴＯ粉末は、一般にInと少量のSnの水溶
塩を含む水溶液をアルカリと反応させてInとSnの水酸化
物を共沈させ、この共沈物を原料として、これを大気中
で加熱焼成して酸化物に変換させることにより製造され
る。こうして従来法により製造されたＩＴＯ粉末のスペ
クトル特性を調べたところ、例えば、図１に比較例２と
して示すように、可視領域での透過性に優れ、透明性は
良好であるが、赤外線カットオフ効果は、1000 nm 超、
たいていは1200 nm 以上の波長領域の赤外線しかカット
オフせず、1200 nm 以下、特に1000 nm 以下の領域の赤
外線のカットオフ効果が欠如ないし不足していることが
判明した。[0010] In general, ITO powder is prepared by co-precipitating In and Sn hydroxide by reacting an aqueous solution containing In and a small amount of a water-soluble salt of Sn with an alkali, and using the co-precipitate as a raw material. It is manufactured by heating and firing to convert it to an oxide. When the spectral characteristics of the ITO powder manufactured by the conventional method were examined in this manner, for example, as shown in FIG. 1 as Comparative Example 2, the transmittance in the visible region was excellent and the transparency was good, but the infrared cutoff was good. The effect is over 1000 nm,
In most cases, only infrared rays in the wavelength region of 1200 nm or more are cut off, and it has been found that the effect of cutting off infrared rays in the region of 1200 nm or less, particularly in the region of 1000 nm or less is lacking or insufficient.
【００１１】ＩＴＯ粉末に1000 nm 以下での赤外線カッ
トオフ機能を持たせるようにさらに検討した結果、ＩＴ
Ｏ粉末の原料を加圧不活性ガス中で焼成するか、或いは
大気中での焼成により得られたＩＴＯ粉末を加圧不活性
ガス中で熱処理すると、1000nm 以下、好ましくは 700
〜900 nmの範囲内のある波長から長波長側の赤外線を90
％以上カットオフするＩＴＯ粉末が得られることを見出
した。このようなＩＴＯ粉末の特性を調べたところ、粉
末の色調はｘｙ色度図上でｘ値 0.220〜0.295、ｙ値 0.
235〜0.325 の範囲内であり、かつ結晶の格子定数が10.
110〜10.160Åの範囲内にあることがわかった。[0011] As a result of further study to provide an infrared cutoff function at 1000 nm or less to the ITO powder,
When the raw material of the O powder is fired in a pressurized inert gas, or when the ITO powder obtained by firing in the air is heat-treated in a pressurized inert gas, it is 1000 nm or less, preferably 700 nm or less.
Infrared rays from a certain wavelength in the range of
% Of ITO powder was found to be obtained. When the characteristics of such an ITO powder were examined, the color tone of the powder was found to be 0.220 to 0.295 for the x value and 0.2 for the y value on the xy chromaticity diagram.
Is in the range of 235 to 0.325, and the lattice constant of the crystal is 10.
It was found to be in the range of 110-10.160Å.
【００１２】本発明は上記知見に基づいて完成したもの
であり、その要旨とするところは、ｘｙ色度図上でｘ値
0.220〜0.295 、ｙ値 0.235〜0.325 の色調を有し、格
子定数が10.110〜10.160Åであり、赤外領域またはその
近傍の最低カットオフ波長が1000 nm 以下であることを
特徴とする、赤外線カットオフ機能を有するＩＴＯ粉末
である。The present invention has been completed on the basis of the above findings, and the gist of the present invention is that the x value on the xy chromaticity diagram
It has a color tone of 0.220 to 0.295 and a y value of 0.235 to 0.325, has a lattice constant of 10.110 to 10.160 °, and has a minimum cutoff wavelength in or near the infrared region of 1000 nm or less. It is an ITO powder having an off function.
【００１３】格子定数とは結晶を特徴づける原子配列の
繰り返し最小単位の大きさと形を規定する結晶学的定数
であり、ここではその１辺の長さ (Å) を意味する。ま
た、最低カットオフ波長とは、赤外領域またはその近傍
(600 nm以上) において光のカットオフ率が少なくとも
90％となる最低の波長を意味する。これは、光透過スペ
クトルにおいて、長波長側方向に光透過率が10％以下と
なる波長領域における最低波長に相当する。好ましく
は、本発明のＩＴＯ粉末は、最低カットオフ波長が 700
〜900 nmの範囲内にあるが、それよりいくらか長波長側
(900〜1000 nm)または低波長側(600〜700 nm) にあって
もよい。The lattice constant is a crystallographic constant that defines the size and shape of the minimum repeating unit of the atomic arrangement that characterizes a crystal, and here means the length (Å) of one side thereof. In addition, the minimum cutoff wavelength is in the infrared region or in the vicinity thereof.
(> 600 nm)
It means the lowest wavelength of 90%. This corresponds to the lowest wavelength in the wavelength region where the light transmittance in the long wavelength direction becomes 10% or less in the light transmission spectrum. Preferably, the ITO powder of the present invention has a minimum cutoff wavelength of 700
In the range of ~ 900 nm, but somewhat longer
(900 to 1000 nm) or the lower wavelength side (600 to 700 nm).
【００１４】このＩＴＯ粉末の平均一次粒子径が0.2 μ
ｍ以下であると、この粉末を塗料化して膜を形成した時
に、可視光の透明性に優れた赤外線カットオフ膜が得ら
れる。従って、本発明のＩＴＯ粉末の平均粒子径は0.2
μｍ以下、特に0.1 μｍ以下であることが好ましい。た
だし、透明性をさほど要求されない用途に用いる場合
(例、屋根材や壁材の赤外線反射膜) には、ＩＴＯ粉末
の粒子径はこれより大きくてもよい。本発明のＩＴＯ粉
末のSnの組成比は、Sn/(Sn+In)のモル比で0.01〜0.15、
特に0.04〜0.12の範囲内が好ましい。The average primary particle diameter of the ITO powder is 0.2 μm.
When it is less than m, an infrared cutoff film having excellent transparency of visible light can be obtained when this powder is formed into a coating material to form a film. Therefore, the average particle size of the ITO powder of the present invention is 0.2
It is preferably at most μm, particularly preferably at most 0.1 μm. However, when used for applications where transparency is not so required
For example, the particle size of the ITO powder may be larger than this (for example, an infrared reflection film of a roof material or a wall material). The composition ratio of Sn of the ITO powder of the present invention is 0.01 / 0.15 in a molar ratio of Sn / (Sn + In),
Particularly, it is preferably in the range of 0.04 to 0.12.
【００１５】また、本発明のＩＴＯ粉末の赤外線カット
オフ効果は、上記範囲内のｘｙ値と格子定数の値の中
で、ｘ値、ｙ値が共に小さいほど良く、特にｙ値の値が
大きくなると効果が急激に低下する。ｘｙ色度の範囲が
上記条件を満足していても、格子定数の値が上記条件か
ら外れると、従来のＩＴＯ粉末と同程度のせいぜい1000
nm より長波長の赤外線カットオフ効果しか得られな
い。In addition, the infrared cutoff effect of the ITO powder of the present invention is better as the x value and the y value are smaller among the xy values and the lattice constant values within the above range, and particularly, the y value is larger. The effect drops sharply. Even if the range of xy chromaticity satisfies the above condition, if the value of the lattice constant deviates from the above condition, the same as that of the conventional ITO powder, at most 1000
Only an infrared cutoff effect with a wavelength longer than nm can be obtained.
【００１６】なお、ＩＴＯ粉末のｘｙ値は主に酸素欠陥
の発生やキャリア電子濃度に依存し、格子定数は主にド
ープ剤の含有量、酸素欠陥などによる結晶の歪みに依存
するので、製造条件を変化させることによりこれらの値
をある程度調整できる。The xy value of the ITO powder mainly depends on the occurrence of oxygen defects and the carrier electron concentration, and the lattice constant mainly depends on the content of the dopant and the crystal distortion due to oxygen defects. These values can be adjusted to some extent by changing.
【００１７】本発明のＩＴＯ粉末は、例えば、次に述べ
るように、加圧不活性ガス雰囲気中での焼成または熱処
理を特徴とする方法により製造することができる。もち
ろん、ＩＴＯ粉末の製造方法は下記の方法に限定される
ものではなく、上記範囲内のｘｙ色度値と格子定数を有
する限り、任意の方法で製造されたＩＴＯ粉末を本発明
において使用することができる。The ITO powder of the present invention can be produced, for example, by a method characterized by firing or heat treatment in a pressurized inert gas atmosphere as described below. Of course, the method of producing the ITO powder is not limited to the following method, and any method of producing the ITO powder may be used in the present invention as long as it has an xy chromaticity value and a lattice constant within the above ranges. Can be.
【００１８】ＩＴＯ粉末の原料は、従来法と同様に調製
すればよい。例えば、Sn/(Sn+In)のモル比が好ましくは
0.01〜0.15、特に0.02〜0.12となる割合でInとSnの水溶
性化合物 (例、塩化物、硝酸塩など) を水に溶解させた
水溶液を、アルカリ水溶液 (例、アルカリ金属またはア
ンモニウムの水酸化物、炭酸塩、炭酸水素塩などの水溶
液) と反応させて、各水溶性化合物を加水分解し、In−
Sn共沈水酸化物を析出させる。この時点で可及的に微細
な沈殿が析出するように、一方の水溶液を他方の水溶液
に攪拌下に滴下しながら反応を進めることが好ましい。The raw material of the ITO powder may be prepared in the same manner as in the conventional method. For example, the molar ratio of Sn / (Sn + In) is preferably
An aqueous solution in which a water-soluble compound of In and Sn (e.g., chloride, nitrate, etc.) is dissolved in water at a ratio of 0.01 to 0.15, particularly 0.02 to 0.12, is converted to an alkali aqueous solution (e.g., alkali metal or ammonium hydroxide) , Carbonate, bicarbonate, etc.) to hydrolyze each water-soluble compound,
Precipitate Sn coprecipitated hydroxide. At this point, it is preferable to proceed the reaction while dropping one aqueous solution into the other aqueous solution with stirring so that a fine precipitate is deposited as much as possible.
【００１９】こうして得た含水状態のIn−Sn共沈混合水
酸化物をそのまま、或いはこれを加熱乾燥して水分を除
去した無水の混合水酸化物、または脱水をさらに進め
て、少なくとも部分的に酸化物とした混合 (水) 酸化物
を原料として用いる。この時の加熱温度は、乾燥だけで
あれば200 ℃以下、特に150 ℃以下でよいが、酸化物に
変換するのであれば、より高温 (例、 200〜900 ℃) で
加熱することができる。得られた原料を、酸素を遮断し
た加圧不活性ガス雰囲気中で、完全に酸化物になるまで
焼成すると、本発明のＩＴＯ粉末が得られる。或いは、
原料を従来と同様に、例えば大気中で焼成してＩＴＯ粉
末を得た後、この粉末を加圧不活性ガス雰囲気中で熱処
理することによっても、本発明の上記ｘｙ色度値と格子
定数を有するＩＴＯ粉末を得ることができる。The water-containing In-Sn coprecipitated mixed hydroxide thus obtained is used as it is, or it is dried by heating to remove water, or an anhydrous mixed hydroxide obtained by further removing water, or at least partially dehydrated. Use mixed (water) oxides as oxides as raw materials. The heating temperature at this time may be 200 ° C. or less, particularly 150 ° C. or less if only drying is performed, but if it is converted to an oxide, it can be heated at a higher temperature (eg, 200 to 900 ° C.). When the obtained raw material is fired in a pressurized inert gas atmosphere in which oxygen is blocked until it is completely converted into an oxide, the ITO powder of the present invention is obtained. Or,
The xy chromaticity value and lattice constant of the present invention can also be obtained by calcining the raw material in the same manner as in the past, for example, to obtain an ITO powder by heat treatment in a pressurized inert gas atmosphere. The resulting ITO powder can be obtained.
【００２０】この焼成または熱処理 (以下、これらを加
熱処理と総称する) 時の不活性ガス雰囲気は、アルゴ
ン、ヘリウムなどの希ガス、窒素ガス、およびこれらの
混合ガスのいずれでもよい。不活性ガス雰囲気の圧力条
件は、室温下における全圧で２kgf/cm2 以上、特に５〜
60 kgf/cm2の範囲内が好ましい。The inert gas atmosphere during the firing or heat treatment (hereinafter collectively referred to as heat treatment) may be any of a rare gas such as argon and helium, a nitrogen gas, and a mixed gas thereof. The pressure condition of the inert gas atmosphere is 2 kgf / cm 2 or more at the total pressure at room temperature, especially 5 to 5 kgf / cm 2.
It is preferably within the range of 60 kgf / cm 2 .
【００２１】圧力が２kgf/cm2 未満では、赤外線カット
オフ効果は従来のＩＴＯ粉末と同程度であり、その改善
はほとんど得られないが、加熱処理温度が800 ℃を超え
るような高温の場合には、不活性ガス雰囲気の圧力が常
圧であっても、本発明の範囲内のｘｙ色度、格子定数お
よび赤外線カットオフ機能を有するＩＴＯ粉末が得られ
ることがある。圧力を60 kgf/cm2を超えて高くしても、
それ以上の効果の改善がわずかであるので、実用上はこ
れ以上の加圧は必要ない。不活性ガス雰囲気中の酸素分
圧は0.2 kgf/cm2 (150 Torr)以下、特に0.02 kgf/cm2
(15 Torr)以下に制限することが好ましい。When the pressure is less than 2 kgf / cm 2 , the infrared cutoff effect is almost the same as that of the conventional ITO powder, and the improvement is hardly obtained. However, when the heat treatment temperature is higher than 800 ° C. In some cases, an ITO powder having xy chromaticity, lattice constant, and infrared cutoff function within the range of the present invention may be obtained even when the pressure of the inert gas atmosphere is normal pressure. Also by increasing the pressure in excess of 60 kgf / cm 2,
Since further improvement of the effect is slight, no further pressurization is necessary in practical use. Oxygen partial pressure in an inert gas atmosphere is 0.2 kgf / cm 2 (150 Torr) or less, especially 0.02 kgf / cm 2
(15 Torr) or less.
【００２２】加熱処理温度は、一般に 350〜1000℃の範
囲内、好ましくは 400〜800 ℃の範囲内が効果的であ
る。処理温度が 350℃以下であると、微粒子化の効果は
高いが、赤外線カットオフ効果の改善はほとんど得られ
ない。一方、1000℃以上では粒子径が著しく成長してし
まうため、塗膜の透明性が要求される分野に使用する場
合には好ましくない。また、加熱処理時間については、
原料またはＩＴＯ粉末に均一な加熱処理が達成されれば
よく、その仕込量や温度によっても異なるが、一般には
１〜４時間の範囲内である。昇温、降温速度は特に制限
されない。The heat treatment temperature is generally in the range of 350 to 1000 ° C, preferably in the range of 400 to 800 ° C. When the treatment temperature is 350 ° C. or lower, the effect of atomization is high, but the infrared cutoff effect is hardly improved. On the other hand, if the temperature is higher than 1000 ° C., the particle size grows remarkably. For the heat treatment time,
It is sufficient that a uniform heat treatment is achieved on the raw material or the ITO powder, and it varies depending on the charged amount and the temperature, but is generally in the range of 1 to 4 hours. The rate of temperature rise and fall is not particularly limited.
【００２３】上記範囲内のｘｙ色度値と格子定数を有す
る本発明のＩＴＯ粉末は、前述したように、各種の透明
皮膜形成成分と共に塗料化することにより、ガラスなど
の基板上に赤外線反射性の透明膜を形成するのに用いる
ことができる。また、樹脂に練り込んでフィルム化する
ことにより、赤外線反射性透明フィルムを得ることもで
きる。得られた透明膜またはフィルムは、従来より低波
長側から赤外線をカットオフすることができるので、赤
外線カットオフ効果が高く、従って冷暖房効率改善等の
実用上効果も高い。The ITO powder of the present invention having an xy chromaticity value and a lattice constant within the above range is coated with various transparent film-forming components to form a coating on a substrate such as glass as described above. Can be used to form a transparent film. In addition, an infrared-reflective transparent film can be obtained by kneading the resin into a film. The obtained transparent film or film can cut off infrared rays from a lower wavelength side than before, and thus has a high infrared cutoff effect, and thus has a high practical effect such as improvement in cooling and heating efficiency.
【００２４】本発明の赤外線カットオフ効果を有するＩ
ＴＯ粉末は、例えば、窓ガラス、サンルーフ、光ファイ
バー、プリペイドカード、サンバイザー、ＰＥＴ（ポリ
エチレンテレフタレート）ボトル、包装用フィルム、メ
ガネなどの製品に適用して、製品に赤外線反射効果を付
与することができる。The I having an infrared cut-off effect of the present invention
The TO powder can be applied to products such as window glass, sunroofs, optical fibers, prepaid cards, sun visors, PET (polyethylene terephthalate) bottles, packaging films, glasses, and the like, to give the products infrared reflection effects. .
【００２５】窓ガラスに対しては、本発明のＩＴＯ粉末
を皮膜形成成分と共に塗料化し、この塗料を適当な塗布
手段（例、塗装、スプレー、浸漬など）でガラスに塗布
し、ＩＴＯ粉末を含有する透明膜をガラス上に形成する
ことができる。或いは、適当な軟質透明樹脂フィルム
（例、ＰＥＴフィルム）中にＩＴＯ粉末を練り込みによ
り混入させて得たＩＴＯ含有樹脂フィルムを窓ガラスに
張りつけるという手法で適用することもできる。こうし
て窓ガラスの表面に設けたＩＴＯ粉末を含有する透明膜
またはフィルムにより、太陽光線の赤外線を広い波長範
囲で反射することができ、室内の冷暖房効率が著しく改
善される。For a window glass, the ITO powder of the present invention is formed into a paint together with a film-forming component, and this paint is applied to the glass by a suitable coating means (eg, coating, spraying, dipping, etc.) to contain the ITO powder. Transparent film can be formed on glass. Alternatively, it can be applied by a method in which an ITO-containing resin film obtained by mixing an ITO powder into a suitable soft transparent resin film (eg, a PET film) by kneading is adhered to a window glass. Thus, the transparent film or film containing the ITO powder provided on the surface of the window glass can reflect infrared rays of sunlight in a wide wavelength range, thereby significantly improving the indoor cooling and heating efficiency.
【００２６】プリペイドカードに対しては、本発明のＩ
ＴＯ粉末を含有する透明塗料をプリペイドカードの所定
部分に塗布しておく。このプリペイドカードに赤外線を
照射し、反射光の有無を検査することにより偽造か否か
を判別することができる。For a prepaid card, the I of the present invention
A transparent paint containing TO powder is applied to a predetermined portion of the prepaid card. By irradiating the prepaid card with infrared rays and inspecting the presence or absence of reflected light, it is possible to determine whether or not the card is counterfeit.
【００２７】残りのサンルーフ、光ファイバー、サンバ
イザー、ＰＥＴボトル、包装用フィルム、メガネについ
ても、上記の窓ガラスと同様に、ＩＴＯ粉末を塗料化し
て製品表面に赤外線反射効果を有するＩＴＯ含有透明膜
を形成することができる。これらの製品の素材がプラス
チックスである場合には、塗布手段ではなく、素材のプ
ラスチックス中にＩＴＯ粉末を練り込みにより直接混入
することにより、製品に赤外線反射効果を付与すること
もできる。さらに、サンルーフのようにフィルムの張り
付けが可能な場合には、窓ガラスについて述べたよう
に、ＩＴＯ粉末を練り込んだ透明フィルムを製品に張り
つけることによっても、製品に赤外線反射性を付与でき
る。Regarding the remaining sunroof, optical fiber, sun visor, PET bottle, packaging film, and eyeglasses, similarly to the above-mentioned window glass, an ITO powder is made into a paint to form an ITO-containing transparent film having an infrared reflecting effect on the product surface. Can be formed. When the material of these products is plastics, an infrared reflection effect can be imparted to the products by directly mixing the ITO powder into the plastics of the material by kneading instead of the coating means. Further, when a film can be attached like a sunroof, infrared reflectiveness can be imparted to the product by attaching a transparent film into which ITO powder has been kneaded, as described for the window glass.
【００２８】本発明のＩＴＯ粉末を練り込むことができ
るプラスチックスの種類は特に制限されず、汎用樹脂か
ら、高強度樹脂（エンジニアリングプラスチックス）、
耐候性樹脂、耐熱性樹脂等の機能性樹脂までを含む各種
の樹脂が使用可能である。従って、樹脂種は製品の種類
に応じて適当に選択すればよい。例えば、サンルーフや
サンバイザーにはアクリル樹脂およびメタクリル樹脂と
いった透明性が特に高い樹脂が、光ファイバーにはメタ
クリル樹脂が、またメガネレンズとしてはメタクリル樹
脂、ポリカーボネート、ポリスチレン、ジエチレングリ
コールビスアリルカーボネート、ポリ−４−メチルペン
テン−１などが使用される。The type of plastics into which the ITO powder of the present invention can be kneaded is not particularly limited, and may be selected from general-purpose resins, high-strength resins (engineering plastics), and the like.
Various resins including functional resins such as weather-resistant resins and heat-resistant resins can be used. Therefore, the resin type may be appropriately selected according to the type of the product. For example, sunroofs and sun visors are made of highly transparent resins such as acrylic resin and methacrylic resin, optical fibers are made of methacrylic resin, and eyeglass lenses are made of methacrylic resin, polycarbonate, polystyrene, diethylene glycol bisallyl carbonate, poly-4-methyl phthalate. Methylpentene-1 and the like are used.
【００２９】上述した用途以外に、赤外線反射が求めら
れる他の用途にも本発明のＩＴＯ粉末を適用することが
できる。例えば、貯蔵庫のガラスもしくはプラスチック
製透明壁面にＩＴＯ粉末を含有する透明膜またはフィル
ムを形成するか、或いは壁面材料中にＩＴＯ粉末を練り
込んでおくと、庫外表面の結露や庫内の温度上昇を防止
できる。また、貯蔵庫の壁面が不透明であっても、ＩＴ
Ｏ粉末含有膜またはフィルムを形成しておくと、外部か
ら赤外線を遮断して庫内の温度上昇とそれによる貯蔵物
品の変質を防止できる。In addition to the above-mentioned applications, the ITO powder of the present invention can be applied to other applications where infrared reflection is required. For example, when a transparent film or film containing ITO powder is formed on a transparent glass or plastic wall surface of a storage, or an ITO powder is kneaded into a wall material, dew condensation on the outer surface of the storage or a rise in temperature in the storage may occur. Can be prevented. Also, even if the walls of the storage are opaque,
If an O powder-containing film or film is formed, infrared rays can be shielded from the outside to prevent a rise in the temperature in the refrigerator and the deterioration of the stored articles due to the temperature rise.
【００３０】ビニールハウスや温室に適用した場合に
は、ハウス内の保温効果により植物の成長が促進される
という効果が得られる。この場合には、ＩＴＯ粉末は、
塗布、練り込み、或いはガラスの場合にはＩＴＯ粉末含
有フィルムの張り付けといった手段で適用することがで
きる。When applied to a greenhouse or a greenhouse, the effect of promoting the growth of plants is obtained by the heat retaining effect in the house. In this case, the ITO powder
It can be applied by means such as coating, kneading, or in the case of glass, attaching an ITO powder-containing film.
【００３１】本発明のＩＴＯ粉末を塗料化して、衣服、
布団などの繊維製品に塗布またはスプレーにより適用し
て、繊維表面にＩＴＯ粉末を含有する膜を形成すること
もできる。合成繊維の場合には、繊維自体の中にＩＴＯ
粉末を練り込んでもよい。それにより、人体から輻射さ
れる遠赤外線が繊維から反射するようになるので、保温
性が高まる。The ITO powder of the present invention is made into a paint,
It can also be applied or sprayed on textiles such as futons to form a film containing ITO powder on the fiber surface. In the case of synthetic fibers, ITO is contained in the fibers themselves.
Powder may be kneaded. Thereby, the far infrared rays radiated from the human body are reflected from the fibers, so that the heat retention is enhanced.
【００３２】焙焼室、電子レンジ、トースター、オーブ
ンなどの覗き窓に対しても、ガラス窓と同様の手法でＩ
ＴＯ粉末を適用することができる。但し、皮膜形成また
はフィルム形成に用いる樹脂としては、耐熱性樹脂
（例、ポリイミド、ポリアミノビスマレイミド、ポリス
ルホン、ポリエーテルスルホン、ポリアミドイミド、ポ
リフェニレンスルフィド、ポリエーテルイミド、ポリエ
ーテルエーテルケトン等）を使用することが好ましい。The same procedure as for glass windows is applied to viewing windows of roasting rooms, microwave ovens, toasters, ovens and the like.
TO powder can be applied. However, a heat-resistant resin (eg, polyimide, polyaminobismaleimide, polysulfone, polyethersulfone, polyamideimide, polyphenylene sulfide, polyetherimide, polyetheretherketone, etc.) is used as the resin used for film formation or film formation. Is preferred.
【００３３】ガラスヒータを用いた電気暖房機において
は、ガラスヒータの周囲にガラス窓と同様にＩＴＯ粉末
を含有する皮膜またはフィルムを形成することにより、
電気抵抗体から放射される熱が効率よく反射して、暖房
効果が高まる。この場合も、皮膜形成成分としては耐熱
性樹脂の使用が好ましい。In an electric heater using a glass heater, a film or a film containing ITO powder is formed around the glass heater in the same manner as a glass window.
The heat radiated from the electric resistor is efficiently reflected, and the heating effect is enhanced. Also in this case, it is preferable to use a heat-resistant resin as a film-forming component.
【００３４】さらには、ファウンデーションやサンスク
リーンといった化粧品に本発明のＩＴＯ粉末を混入する
こともできる。それにより近赤外線の反射効果が高ま
る。近赤外線、特に 2.5〜3 μｍの波長域は水の吸収領
域であるため、その反射効果が高まると、水分蒸発に伴
う深いしわの発生の防止に効果がある。Further, the ITO powder of the present invention can be mixed in cosmetics such as foundations and sunscreens. This enhances the near-infrared reflection effect. The near-infrared ray, particularly the wavelength range of 2.5 to 3 μm, is a water absorption region. Therefore, if its reflection effect is enhanced, it is effective in preventing the occurrence of deep wrinkles due to moisture evaporation.
【００３５】本発明のＩＴＯ粉末は、従来品に比べて、
以上の機能をより効果的に発揮することができる。The ITO powder of the present invention is
The above functions can be exhibited more effectively.
【００３６】[0036]
【実施例】次に、本発明を実施例に基づいて説明する
が、本発明は実施例のみに限定されるものでない。な
お、実施例中、％は特に指定しない限り重量％である。EXAMPLES Next, the present invention will be described based on examples, but the present invention is not limited to only the examples. In Examples,% is% by weight unless otherwise specified.
【００３７】InC13 水溶液1.8 L(In金属600 ｇ含有) と
60％SnC14 水溶液 22.92ｇ (Sn金属6.27ｇ含有) との混
合水溶液を、NH4HCO3 3000ｇ/12 L の水溶液中に、70℃
の加温下で攪拌しながら滴下し、最終ｐＨ8.5 にしてIn
−Sn共沈水酸化物を析出させた。次に、静置して沈殿を
沈降させた後、上澄み液を除去し、イオン交換水を加え
て静置・沈降と上澄み液除去の操作を６回 (水の添加量
は１回につき10 L) 繰り返すことにより、沈殿を十分に
水洗した後、吸引濾過により沈殿を濾別して、含水水酸
化物の沈殿を得た。こうして得た、全金属中のSn含有量
が１モル％の共沈含水水酸化物を、含水原料(A) とす
る。[0037] INC1 3 aq 1.8 L and (In metal 600 g containing)
The mixed aqueous solution of 60% SnCl 4 solution 22.92g (Sn metal 6.27g containing), in an aqueous solution of NH 4 HCO 3 3000g / 12 L , 70 ℃
The mixture is added dropwise while stirring with heating to a final pH of 8.5.
-Sn coprecipitated hydroxide was precipitated. Next, after allowing the precipitate to settle by standing, the supernatant is removed, and ion-exchanged water is added, and the operation of standing, settling, and removing the supernatant is performed six times (the amount of water added is 10 L each time). ) By repeating this, the precipitate was sufficiently washed with water, and then the precipitate was separated by suction filtration to obtain a hydrated hydroxide precipitate. The thus obtained coprecipitated hydrated hydroxide having a Sn content of 1 mol% in all metals is defined as a hydrated raw material (A).
【００３８】同様の方法により、60％SnC14 水溶液の使
用量を、(B) 58.1ｇ、(C) 119.2 ｇ、(D) 183.9 ｇ、
(E) 252 ｇ、(F) 323 ｇ、および(G) 453.5 ｇに増やし
て、Sn含有量がモル％でそれぞれ2.5 ％、５％、7.5
％、10％、12.5％、および15％の含水原料(B) 〜(G) を
得た。[0038] By the same method, the amount of 60% SnCl 4 solution, (B) 58.1g, (C ) 119.2 g, (D) 183.9 g,
(E) 252 g, (F) 323 g, and (G) 453.5 g, and the Sn content was 2.5%, 5%,
%, 10%, 12.5% and 15% of water-containing raw materials (B) to (G) were obtained.
【００３９】これらの原料(A) 〜(G) を、場合により、
次の表１に示すように大気中での加熱により乾燥ないし
脱水して出発原料を調製した後、この調製原料を大気中
または窒素ガス雰囲気中において表２に示す条件で３時
間加熱処理して、ＩＴＯ粉末を得た。These raw materials (A) to (G) are optionally
As shown in the following Table 1, after drying or dehydration by heating in the air to prepare a starting material, this prepared material was subjected to a heat treatment for 3 hours under the conditions shown in Table 2 in the air or in a nitrogen gas atmosphere. And ITO powder.
【００４０】[0040]
【表１】 [Table 1]
【００４１】なお、含水原料および調製原料の大気中で
の加熱および常圧窒素ガス中での加熱は、内径85 mm 、
長さ1000 mm の透明石英管を使用した管状炉を用いて、
原料250 ｇを長さ250 mmの半割石英ボートに入れて加熱
することにより行った。The heating of the water-containing raw material and the prepared raw material in the atmosphere and the heating in the normal-pressure nitrogen gas were carried out at an inner diameter of 85 mm,
Using a tubular furnace with a 1000 mm long transparent quartz tube,
250 g of the raw material was placed in a half-quartz quartz boat having a length of 250 mm and heated.
【００４２】加圧窒素雰囲気下での加熱は、内径70 mm
、長さ700 mmのインコロイ800 製チューブを使用した
密閉加圧管状炉によって、原料150 ｇを長さ250 mmの半
割石英ボートに入れて加熱することにより行った。Heating under a pressurized nitrogen atmosphere is performed with an inner diameter of 70 mm.
In a sealed pressurized tubular furnace using a tube made of Incoloy 800 having a length of 700 mm, 150 g of the raw material was placed in a half-quartz quartz boat having a length of 250 mm and heated.
【００４３】得られたＩＴＯ粉末の平均一次粒子径を、
比表面積 (BET)の測定値から、次の粒子径式： ａ (μｍ) ＝６／ (ρ×Ｂ) [ａ：平均粒子径、ρ：真比重、Ｂ：比表面積(m2/g)]に
基づいて算出した。このようにして比表面積から求めた
粒子径は透過式電子顕微鏡から直接観察した粒子径とほ
ぼ一致することが確認されている。BET 法による比表面
積は、マイクロトラック社製のベータソーブ自動表面積
計4200型を用いて測定した。The average primary particle size of the obtained ITO powder was
From the measured value of the specific surface area (BET), the following particle diameter formula: a (μm) = 6 / (ρ × B) [a: average particle diameter, ρ: true specific gravity, B: specific surface area (m 2 / g) ]. In this way, it has been confirmed that the particle size determined from the specific surface area substantially coincides with the particle size directly observed from a transmission electron microscope. The specific surface area by the BET method was measured by using an automatic surface area meter 4200 manufactured by Microtrac Co., Ltd.
【００４４】また、ＩＴＯ粉末の光透過スペクトルおよ
びｘｙ色度は、積分球付き自記分光光度計U-4000型 (日
立製作所社製) で測定し、格子定数はモノクロメーター
付き自動Ｘ線回折装置MO3X (マックサイエンス社製) を
使用して、高純度シリコン単結晶(99.9999％) で補正
し、(k, h, l) 面指数に対するピークから面間隔を自動
検索して、最小自乗法によりコンピュータ計算で求め
た。The light transmission spectrum and xy chromaticity of the ITO powder were measured with a self-recording spectrophotometer U-4000 (manufactured by Hitachi, Ltd.) with an integrating sphere, and the lattice constant was measured using an automatic X-ray diffractometer MO3X with a monochromator. (Mac Science Co., Ltd.), corrected with high-purity silicon single crystal (99.9999%), automatically searched for plane spacing from peak for (k, h, l) plane index, and computed by least squares method I asked for it.
【００４５】これらの特性データを表２に併せて示し
た。また、代表的な実施例および比較例のＩＴＯ粉末の
光透過スペクトルを図１に示した。These characteristic data are also shown in Table 2. FIG. 1 shows the light transmission spectra of the ITO powders of the typical examples and comparative examples.
【００４６】[0046]
【表２】 [Table 2]
【００４７】表２に示す測定結果から明らかなように、
ｘｙ色度図上のｘ値 0.220〜０．２９５、ｙ値 ０．２
３５〜0.325 、格子定数10.110〜10.160の条件を満たす
実施例のＩＴＯ粉末は、いずれも900 nmでは90％以上の
赤外線カットオフ率を示す、優れた赤外カットオフ機能
を有している。また、これらの実施例のＩＴＯ粉末の最
低カットオフ波長は、実施例８を除いて 700〜900 nmの
範囲内にあり、実施例８のＩＴＯ粉末の最低カットオフ
波長は695 nmであった。As is clear from the measurement results shown in Table 2,
x value 0.220 to 0.295 on xy chromaticity diagram, y value 0.2
Each of the ITO powders satisfying the conditions of 35 to 0.325 and a lattice constant of 10.110 to 10.160 has an excellent infrared cut-off function showing an infrared cut-off rate of 90% or more at 900 nm. The minimum cutoff wavelengths of the ITO powders of these examples were in the range of 700 to 900 nm except for Example 8, and the minimum cutoff wavelength of the ITO powder of Example 8 was 695 nm.
【００４８】一方、比較例を見ると、比較例１はｘｙ値
は本発明の範囲内であるが、格子定数が小さすぎ、比較
例３および４は格子定数は本発明の範囲内であるがｘｙ
値が範囲外であり、比較例２および５は、ｘｙ値と格子
定数のいずれも本発明の範囲を外れていた。これらの比
較例ではいずれも、1000 nm においても赤外線カットオ
フ率が約50％もしくはそれ以下であり、1000 nm 以下の
領域における赤外線カットオフ効果が著しく劣ってい
た。On the other hand, looking at Comparative Examples, Comparative Example 1 has xy values within the range of the present invention, but the lattice constant is too small. Comparative Examples 3 and 4 have lattice constants within the range of the present invention. xy
The values were out of the range, and in Comparative Examples 2 and 5, both the xy value and the lattice constant were out of the range of the present invention. In all of these comparative examples, the infrared cutoff ratio was about 50% or less even at 1000 nm, and the infrared cutoff effect in the region of 1000 nm or less was significantly inferior.
【００４９】[0049]
【発明の効果】以上からわかるように、本発明によれ
ば、ＩＴＯ粉末を、ｘｙ色度図上でｘ値0.220〜0.295
、ｙ値 0.235〜0.325 、格子定数10.110〜10.160に制
御することによって、従来にはない1000 nm 以下、好ま
しくは 700〜900 nmの範囲内のある波長以上の赤外線を
全面的に90％以上カットオフする機能を有する、赤外線
カットオフ効果に優れたＩＴＯ粉末が得られる。As can be seen from the above description, according to the present invention, the ITO powder is prepared on the xy chromaticity diagram with an x value of 0.220 to 0.295.
By controlling the y value to 0.235 to 0.325 and the lattice constant to 10.110 to 10.160, the infrared rays having a wavelength of 1000 nm or less, preferably 700 to 900 nm, which is not conventionally available, are cut off by 90% or more. Thus, an ITO powder having an excellent infrared cutoff effect and having the function of performing the above can be obtained.
【００５０】この粉末を分散させた塗料をハウジングの
一般窓、サンルームの屋根材、壁材、さらには自動車の
ガラス等に塗布すると、ＩＴＯ粉末の平均一次粒子径が
0.2μｍ以下であれば、着色がほとんどない透明な膜が
形成される。この透明膜は、その赤外線カットオフ効果
により夏期の太陽光の赤外線をほぼ完全に反射させ、冷
房等の電力の大幅な節減に役立つ。また、冬期は室内の
保温効果の改善にも役立つ。また、この透明膜は赤外線
の照射により検出することができるので、カード等の偽
造防止手段としても利用することができる。When the coating material in which this powder is dispersed is applied to a general window of a housing, a roof material of a solarium, a wall material, and a glass of an automobile, the average primary particle diameter of the ITO powder is reduced.
If it is 0.2 μm or less, a transparent film with little coloring is formed. This transparent film reflects infrared rays of summer sunlight almost completely due to its infrared cutoff effect, which contributes to a great saving of electric power for cooling and the like. It also helps to improve the indoor warming effect in winter. Further, since this transparent film can be detected by irradiating infrared rays, it can be used as a means for preventing forgery of a card or the like.
【図１】実施例および比較例で得たＩＴＯ粉末の光透過
スペクトルである。FIG. 1 is a light transmission spectrum of ITO powder obtained in Examples and Comparative Examples.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平３−54114（ＪＰ，Ａ) 特開 平２−120374（ＪＰ，Ａ) 特開 平３−218924（ＪＰ，Ａ) 日経ニューマテリアル，日本，日経Ｂ Ｐ社，1988年 ２月29日，第15〜16頁 (58)調査した分野(Int.Cl.7，ＤＢ名) C01G 19/00 ＷＰＩ（ＤＩＡＬＯＧ)────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-3-54114 (JP, A) JP-A-2-120374 (JP, A) JP-A-3-218924 (JP, A) Nikkei New Materials, Japan , Nikkei BP, February 29, 1988, pp. 15-16 (58) Fields investigated (Int. Cl. 7 , DB name) C01G 19/00 WPI (DIALOG)
Claims (2)
値 0.235〜0.325 の色調を有し、格子定数が10.110〜1
0.160Åであり、赤外領域またはその近傍の最低カット
オフ波長が1000 nm 以下であることを特徴とする、赤外
線カットオフ機能を有する錫ドープ酸化インジウム粉
末。1. An x-value of 0.220 to 0.295 on an xy chromaticity diagram;
It has a color tone with a value of 0.235 to 0.325 and a lattice constant of 10.110 to 1
A tin-doped indium oxide powder having an infrared cutoff function, which has a cutoff wavelength of 0.160 ° and a minimum cutoff wavelength in or near the infrared region of 1000 nm or less.
１記載の粉末。2. The powder according to claim 1, wherein the average primary particle size is 0.2 μm or less.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26024893A JP3250125B2 (en) | 1993-06-30 | 1993-10-18 | Infrared cutoff powder |
| US08/268,912 US5518810A (en) | 1993-06-30 | 1994-06-30 | Infrared ray cutoff material and infrared cutoff powder use for same |
| KR1019940015604A KR100214428B1 (en) | 1993-06-30 | 1994-06-30 | Infrared ray cutoff material and infrared cutoff powder used for the same |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16219893 | 1993-06-30 | ||
| JP5-162198 | 1993-06-30 | ||
| JP26024893A JP3250125B2 (en) | 1993-06-30 | 1993-10-18 | Infrared cutoff powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0769632A JPH0769632A (en) | 1995-03-14 |
| JP3250125B2 true JP3250125B2 (en) | 2002-01-28 |
Family
ID=26488077
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26024893A Expired - Lifetime JP3250125B2 (en) | 1993-06-30 | 1993-10-18 | Infrared cutoff powder |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3250125B2 (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4600685B2 (en) * | 1994-05-25 | 2010-12-15 | 住友金属鉱山株式会社 | UV and near infrared shielding glass |
| JPH11320769A (en) | 1998-05-20 | 1999-11-24 | Tomoegawa Paper Co Ltd | Transparent infrared cut-off film |
| JP2000155327A (en) * | 1998-11-19 | 2000-06-06 | Matsushita Electric Ind Co Ltd | Liquidcrystal display device |
| JP4349779B2 (en) | 2002-07-31 | 2009-10-21 | 住友金属鉱山株式会社 | Heat ray shielding transparent resin molding and heat ray shielding transparent laminate |
| JP3982466B2 (en) | 2002-09-25 | 2007-09-26 | 住友金属鉱山株式会社 | Heat ray shielding component dispersion, method for producing the same, heat ray shielding film forming coating solution, heat ray shielding film and heat ray shielding resin molding obtained by using this dispersion |
| JP2006213095A (en) * | 2005-02-01 | 2006-08-17 | Nippon Paint Co Ltd | Method of imparting near infrared ray reflection performance and rapid-transit railway vehicle |
| JP4590566B2 (en) * | 2006-03-31 | 2010-12-01 | Ｄｏｗａエレクトロニクス株式会社 | ITO powder and manufacturing method thereof, ITO conductive film paint, and transparent conductive film |
| EP2650341B1 (en) | 2012-01-11 | 2015-09-23 | Mitsubishi Materials Corporation | Infrared cut material, infrared cut material dispersion liquid, composition for forming infrared cut film, and infrared cut film |
| WO2013147033A1 (en) | 2012-03-29 | 2013-10-03 | 三菱マテリアル株式会社 | Infrared cut material |
| WO2013147029A1 (en) * | 2012-03-29 | 2013-10-03 | 三菱マテリアル株式会社 | Antimony-doped tin oxide powder and process for manufacturing same |
| JP6207390B2 (en) * | 2013-12-27 | 2017-10-04 | 日本化薬株式会社 | Infrared shielding sheet and use thereof |
| JP6173768B2 (en) * | 2013-05-16 | 2017-08-02 | 日本化薬株式会社 | Infrared shielding sheet and manufacturing method thereof |
| CN105324689B (en) | 2013-05-16 | 2018-10-30 | 日本化药株式会社 | Infrared shield piece and its manufacturing method with and application thereof |
| JP6241574B2 (en) | 2015-05-15 | 2017-12-06 | 住友大阪セメント株式会社 | Transparent resin composition and heat ray shielding film |
-
1993
- 1993-10-18 JP JP26024893A patent/JP3250125B2/en not_active Expired - Lifetime
Non-Patent Citations (1)
| Title |
|---|
| 日経ニューマテリアル，日本，日経ＢＰ社，１９８８年 ２月２９日，第１５〜１６頁 |
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|---|---|
| JPH0769632A (en) | 1995-03-14 |
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