JP2002201027A - Ito microparticle for daylight screening, method for producing the same, and coating liquid and daylight screening film using the same - Google Patents

Ito microparticle for daylight screening, method for producing the same, and coating liquid and daylight screening film using the same

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Publication number
JP2002201027A
JP2002201027A JP2001082557A JP2001082557A JP2002201027A JP 2002201027 A JP2002201027 A JP 2002201027A JP 2001082557 A JP2001082557 A JP 2001082557A JP 2001082557 A JP2001082557 A JP 2001082557A JP 2002201027 A JP2002201027 A JP 2002201027A
Authority
JP
Japan
Prior art keywords
film
fine particles
solar
ito
less
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.)
Pending
Application number
JP2001082557A
Other languages
Japanese (ja)
Inventor
Takeshi Naganami
武 長南
Hiroko Kuno
裕子 久野
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sumitomo Metal Mining Co Ltd
Original Assignee
Sumitomo Metal Mining Co Ltd
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Filing date
Publication date
Application filed by Sumitomo Metal Mining Co Ltd filed Critical Sumitomo Metal Mining Co Ltd
Priority to JP2001082557A priority Critical patent/JP2002201027A/en
Publication of JP2002201027A publication Critical patent/JP2002201027A/en
Pending legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/23Oxides
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/006Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
    • C03C17/007Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character containing a dispersed phase, e.g. particles, fibres or flakes, in a continuous phase
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C2217/00Coatings on glass
    • C03C2217/20Materials for coating a single layer on glass
    • C03C2217/21Oxides
    • C03C2217/23Mixtures
    • C03C2217/231In2O3/SnO2
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C2217/00Coatings on glass
    • C03C2217/40Coatings comprising at least one inhomogeneous layer
    • C03C2217/42Coatings comprising at least one inhomogeneous layer consisting of particles only

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Composite Materials (AREA)
  • Laminated Bodies (AREA)
  • Surface Treatment Of Glass (AREA)

Abstract

PROBLEM TO BE SOLVED: To obtain indium tin oxide (ITO) microparticles for forming a daylight screening film having high transmittance of visible light, low transmittance of daylight and low haze, to obtain a coating liquid capable of forming a film by a simple coating method without using physical film forming method of high cost, and to obtain a daylight screening film using this. SOLUTION: This ITO microparticles are characterized by having <=100 nm average particle size, and a powder color according to L*a*b* colorimetric system (JIS Z8729) of 20 to 52 L*, -4.4 to -0.1 a* and -10 to -3 b*. This coating liquid for forming a daylight screening film is a dispersion of the ITO microparticles in a solvent where a resin binder or an inorganic binder is added. This method for producing ITO microparticles comprises treating ITO microparticles having <=100 nm average particle size at 200 to 300 deg.C for >=10 minutes under inert atmosphere containing an alcohol or, after reducing residual impurities comprising chloride ion, nitrate ion and sulfate ion to 0.6% or less, under inert gas or inert gas containing an alcohol.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【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、ショーウィンド
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
いる日射遮蔽用インジウム錫酸化物微粒子およびこれを
用いた塗布液、日射遮蔽膜に関する。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention requires glass, plastics, and other solar radiation shielding functions such as windows of vehicles, buildings, offices, and general houses, telephone boxes, show windows, lighting lamps, and transparent cases. The present invention relates to indium tin oxide fine particles for solar shading used for a transparent base material to be applied, a coating solution using the fine particles, 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、ガラス表面に赤外
線を反射する材料からなる膜を形成して、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, it has been practiced to form a film made of a material that reflects infrared rays on a glass surface to obtain a heat ray reflective glass. Had been 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 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CV
D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。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、生産性や大面積
化に問題があり、膜の製造コストが高いといった欠点が
ある。また、これらの材料で日射遮蔽特性(波長域30
0〜2100nmの光を遮蔽する特性)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。さらに、これらの材料では膜の導電性
が高いものが多く、膜の導電性が高いと携帯電話やT
V、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る。
[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 CV
It has been common practice to form a thin film having a thickness of 10 nm using a physical film forming method such as a method D or a sputtering method or a vacuum evaporation method. However, these film forming methods require large-scale equipment and vacuum equipment, have problems in productivity and increase in area, and have disadvantages such as high film manufacturing cost. In addition, the solar shading characteristics (wavelength range 30
Attempting to increase the characteristic of blocking light of 0 to 2100 nm) also tends to increase the reflectance in the visible light region at the same time, giving a glare-like appearance like a mirror and impairing the aesthetic appearance. In addition, many of these materials have high conductivity of the film, and if the conductivity of the film is high, a mobile phone or a T
V, radio and other radio waves are reflected and become unreceivable,
There are drawbacks such as causing radio interference in the surrounding area.

【0004】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10Ω/□以上に制御可能な膜を形成する必要があ
った。可視光透過率が高く、しかも優れた日射遮蔽機能
を持つ材料としてはアンチモン錫酸化物や、インジウム
錫酸化物(以下、ITOと略す)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、プラズマ周波数が近赤外線領域
にあるために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。
In order to remedy the above-mentioned drawbacks of the prior art, as physical properties of the film, the reflectance of light in the visible light region is low, the reflectance in the infrared region is high, and the conductivity of the film is approximately 10%. It was necessary to form a film that could be controlled to 6 Ω / □ or more. Antimony tin oxide and indium tin oxide (hereinafter abbreviated as ITO) are known as materials having a high visible light transmittance and an excellent solar shading function. Although these materials have a relatively low visible light reflectance and do not give a glare-like appearance, the reflection and absorption effects of these films in the near infrared region close to visible light are sufficient because the plasma frequency is in the near infrared region. Was not.

【0005】そこで、不活性ガスあるいは弱還元性ガス
中で熱処理した特定の色のITO粉末を用いることによ
り、可視光に近い近赤外域の光も反射・吸収できるよう
にする方法が、特開平7−69632号公報、特開平8
−41441号に提案されている。この方法によれば、
高い可視光透過率を維持しつつ、低い日射透過率が得ら
れているが、1%を下回るようなヘイズ値の膜を形成す
るような材料は実現されていなかった。ヘイズ値は、全
透過光に対する拡散透過光の割合であり、この値が高い
と人間の目には曇って見える。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。
[0005] To solve this problem, Japanese Patent Application Laid-Open Publication No. HEI 9-205, discloses a method of using a specific color of ITO powder heat-treated in an inert gas or a weak reducing gas so that light in the near infrared region close to visible light can be reflected and absorbed. JP-A-7-69632, JP-A-Hei-8
No. 41441. According to this method,
Although a low solar radiation transmittance is obtained while maintaining a high visible light transmittance, a material that forms a film having a haze value of less than 1% has not been realized. The haze value is the ratio of the diffuse transmitted light to the total transmitted light, and when this value is high, it appears cloudy to human eyes. 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.

【0006】[0006]

【発明が解決しようとする課題】そこで、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
透過率が低く、しかもヘイズ値が低い日射遮蔽膜形成用
のITO微粒子を得ることを目的とし、さらには高コス
トの物理成膜法を用いずに簡便な塗布法で成膜できる塗
布液と、これを用いた日射遮蔽膜とを提供することを目
的とする。
SUMMARY OF THE INVENTION Accordingly, the present invention has been made to solve the above-mentioned problems of the prior art, and has a high visible light transmittance, a low solar transmittance, and a low haze value. It is another object of the present invention to provide a coating liquid capable of forming a film by a simple coating method without using an expensive physical film forming method, and a solar shading film using the same.

【0007】[0007]

【課題を解決するための手段】上記目的を達成するため
に、本発明者らは特定の粉体色を有するITO微粒子を
高度に分散した膜の作製によって、可視光領域に透過率
の極大をも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
した。すなわち、本発明の日射遮蔽用ITO微粒子は、
国際照明委員会(CIE)が推奨しているL
表色系(JIS Z8729)における粉体色が、L
が20〜52、aが−4.4〜−0.1、bが−1
0〜−3、もしくはL が52〜80、aが−10〜
−0.1、bが0〜20で、かつ平均粒径が100n
m以下であることを特徴とする。また本発明の日射遮蔽
膜形成用塗布液は、前記ITO微粒子を溶媒中に分散し
たものであって、さらには樹脂バインダーまたは無機バ
インダーを分散したものである。さらに本発明の日射遮
蔽膜は、前記ITO微粒子を含有したものであり、必要
に応じてその膜上に、さらに珪素、ジルコニウム、チタ
ン、もしくはアルミニウムの酸化物膜が形成された多層
日射遮蔽膜としてもよい。上記本発明によれば、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、ヘイズ値が1.0
%未満である日射遮蔽膜を実現できる。また本発明のI
TO微粒子は、平均粒径が100nm以下のITO微粒
子を、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、あるいは塩素イ
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、不活性ガスまたはアルコールを
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、200℃〜300℃の温度で10分
以上処理することによって、L表色系におけ
る粉体色を、Lが20〜52、aが−4.4〜−
0.1、bが−10〜−3、もしくはLが52〜8
0、aが−10〜−0.1、bが0〜20としてい
る。

In addition, the present inventors have prepared ITO fine particles having a specific powder color.
Fabrication of highly dispersed membranes allows transmission in the visible light range
Strong in the near-infrared region near the visible light region
Has plasma absorption to minimize transmittance and
Completed the present invention by finding the phenomenon that
did. That is, the solar radiation shielding ITO fine particles of the present invention are:
L recommended by the International Commission on Illumination (CIE)*a*b*
The powder color in the color system (JIS Z8729) is L *
Is 20-52, a*Is -4.4 to -0.1, b*Is -1
0-3, or L *Is 52-80, a*But -10
−0.1, b*Is 0 to 20 and the average particle size is 100 n
m or less. The solar shading of the present invention
The coating liquid for film formation is obtained by dispersing the ITO fine particles in a solvent.
And a resin binder or inorganic binder.
It is a dispersion of inders. Furthermore, the solar shading of the present invention
The shielding film contains the ITO fine particles, and
Silicon, zirconium, titanium, etc.
Or multilayer with aluminum oxide film
It may be a solar shading film. According to the above invention, the visible light
Wavelength range of 300 to 2100 nm when transmittance is 80% or more
Is less than 70% and the haze value is 1.0
% Can be realized. In addition, the I of the present invention
The TO fine particles are fine ITO particles having an average particle diameter of 100 nm or less.
Of inert gas containing alcohol or reducing gas.
In a mixed gas atmosphere of
ON, nitrate ion, sulfate ion
0.6% or less, then inert gas or alcohol
Containing inert gas or reducing gas and inert gas
10 minutes at 200 ° C to 300 ° C under mixed gas atmosphere
By performing the above processing, L*a*b*In color system
Powder color*Is 20-52, a*Is -4.4 to-
0.1, b*Is -10 to -3, or L*Is 52-8
0, a*Is -10 to -0.1, b*Is 0 to 20
You.

【0008】[0008]

【発明の実施の形態】以下、本発明の実施の形態につい
て、具体的に説明する。本発明の日射遮蔽用ITO微粒
子において、元素換算での錫含有量は1〜15重量%が
好ましい。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。ま
た、平均粒径は100nm以下とする。100nmを超
えると光散乱源となって膜に曇り、つまりヘイズを生じ
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。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。
DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be specifically described below. In the ITO fine particles for solar shading of the present invention, the tin content in terms of element is preferably 1 to 15% by weight. If less than 1% by weight, the effect of adding tin is not seen,
On the other hand, if it exceeds 15% by weight, the solid solution of tin becomes insufficient. Further, the average particle size is set to 100 nm or less. If the thickness exceeds 100 nm, the film becomes a light scattering source and fogging of the film, that is, haze occurs, or visible light transmittance is decreased, which is not preferable. In addition, although the particle size is represented by the average particle size here, a fine powder having a small particle size distribution and a small ratio of coarse powder particularly exceeding 100 nm is preferable, and the economically available minimum particle size is The fine particles are about 2 nm, but the lower limit is not limited to this.

【0009】本発明のITO微粒子は、粉体色Lが2
0〜52、aが−4.4〜−0.1、bが−10〜
−3、もしくはLが52〜80、aが−10〜−
0.1、bが0〜20とするが、以下にその理由を説
明する。一般的な光と物質内の電子の相互作用について
説明すると、ある物質には固有のプラズマ周波数があっ
てこの周波数より長波長の光は反射され、短波長の光は
透過されることが知られている。プラズマ周波数ω
下記式1で表される。
The ITO fine particles of the present invention have a powder color L * of 2
0 to 52, a * is -4.4 to -0.1, b * is -10
-3, or L * is 52 to 80, a * is -10 to-
0.1 and b * are set to 0 to 20, and the reasons will be described below. To explain the general interaction between light and electrons in a substance, it is known that a substance has a unique plasma frequency, and light with a wavelength longer than this frequency is reflected and light with a shorter wavelength is transmitted. ing. The plasma frequency ω p is represented by the following equation 1.

【0010】[0010]

【式1】ω =nq/εm (1) ここで、nは伝導電子密度、qは電子の電荷、εは誘電
率、mは電子の有効質量である。
[Formula 1] ω p 2 = nq 2 / εm (1) where n is the conduction electron density, q is the charge of the electron, ε is the dielectric constant, and m is the effective mass of the electron.

【0011】一般に、伝導電子密度が増加するとプラズ
マ周波数が大きくなるため、短波長側の光まで反射され
ることになる。伝導電子密度は金属で1022/cm
台、ITOで1021/cm台であるため、金属では
可視光領域からすでに反射率が高いが、ITOでは、可
視光線は透過し近赤外線域から反射率が高くなるため、
日射遮蔽膜として用いることができる。
In general, when the density of conduction electrons increases, the plasma frequency increases, so that light at shorter wavelengths is reflected. Conduction electron density is 10 22 / cm 3 for metal
Since the base is 10 21 / cm 3 for ITO, the reflectance is already high from the visible light region for metals, but the visible light is transmitted and the reflectance is high from the near infrared region for ITO,
It can be used as a solar shading film.

【0012】特開平8−41441号にも記載されてい
るように、ITO微粒子をアルコール含有不活性ガス、
もしくは還元性ガスと不活性ガスとの混合ガスで処理す
ると、その粉体色が黄色→黄緑色→淡青色→濃青色→暗
青色→黒色と変化すると同時に、その圧粉抵抗も減少す
る。これは、ITOを前記のようなガスで処理すること
によって空孔が生じ、この空孔が錫と同様にn型半導体
である酸化インジウムに対してドナーとして働くために
空孔の増加によって自由電子が増加したと考えられ、粉
体色と伝導電子密度、つまりプラズマ周波数とは深い関
係があることが予想されている。
As described in Japanese Patent Application Laid-Open No. 8-41441, an ITO fine particle is converted into an alcohol-containing inert gas,
Alternatively, when treated with a mixed gas of a reducing gas and an inert gas, the powder color changes from yellow to yellow green to light blue to dark blue to dark blue to black, and at the same time, the powder resistance decreases. This is because, when the ITO is treated with the above-described gas, vacancies are generated, and the vacancies act as donors for indium oxide, which is an n-type semiconductor like tin, so that free electrons are generated by the increase of vacancies. Is thought to have increased, and it is expected that there is a deep relationship between the powder color and the conduction electron density, that is, the plasma frequency.

【0013】そこで、ITO微粒子の処理による粉体色
と、これらを成膜したときの日射透過率との関係を詳し
く調査して日射遮蔽に最適な条件を求めたところ、平均
粒径が100nm以下のITO微粒子のL
色系による粉体色が、Lが20〜52、aが−4.
4〜−0.1、bが−10〜−3、もしくはLが5
2〜80、aが−10〜−0.1、bが0〜20と
なると、高い可視光透過率を維持しつつ日射透過率が低
くなり、しかもヘイズ値が低下することがわかった。
[0013] Then, the relationship between the powder color by the treatment of the ITO fine particles and the solar transmittance when these were formed into a film was investigated in detail, and the optimum conditions for solar shading were determined. The average particle size was 100 nm or less. powder color by the L * a * b * color system of the ITO fine particles, L * is 20-52, a * -4.
4 to -0.1, b * is -10 to -3, or L * is 5
When 2-80, a * was -10 to -0.1, and b * was 0 to 20, it was found that the solar radiation transmittance was reduced while maintaining a high visible light transmittance, and the haze value was reduced. .

【0014】このような粉体色にするための処理法は、
窒素、アルゴン、ヘリウムなどの不活性ガス単独または
これらの混合ガスをキャリアガスとしてアルコールを供
給、もしくは還元性ガスと不活性ガスとの混合ガスを供
給するか、ITO微粒子中の塩素イオン、硝酸イオン、
硫酸イオンといった残留不純物量を洗浄によって0.6
%以下にした後、不活性ガス単独またはこれらの混合ガ
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を供給する。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
コスト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濃度や供
給量は、前記粉体色になるように適宜選択すればよい。
The processing method for obtaining such a powder color is as follows.
Alcohol is supplied using an inert gas such as nitrogen, argon, helium or the like alone or a mixed gas thereof as a carrier gas, or a mixed gas of a reducing gas and an inert gas is supplied, or chlorine ions or nitrate ions in ITO fine particles are supplied. ,
The amount of residual impurities such as sulfate ions was reduced by 0.6
% Or less, an inert gas alone or a mixed gas thereof, an inert gas containing alcohol, or a mixed gas of a reducing gas and an inert gas is supplied. The alcohol used is not particularly limited, but methanol, ethanol, propanol and the like are preferable from the viewpoint of volatility and cost. The alcohol concentration and the supply amount in the inert gas may be appropriately selected so as to obtain the powder color.

【0015】処理温度は、200〜300℃の範囲とす
る。300℃を超えるとITO微粒子の凝集・焼結が顕
著になり、他方200℃未満では還元効率が悪く所望と
する粉体色が得られ難い。また、還元時間は温度に応じ
て適宜選択すればよいが、短すぎると所望の粉体色が得
られないため10分以上とする。なお、上記還元処理前
に、必要に応じて予め大気中で焼成処理を施してもよい
が、その際の処理温度はヘイズ値の観点から800℃未
満が好ましく、時間は特に限定されるものではない。
[0015] The processing temperature is in the range of 200 to 300 ° C. When the temperature exceeds 300 ° C., the aggregation and sintering of the ITO fine particles become remarkable. The reduction time may be appropriately selected according to the temperature. However, if the reduction time is too short, a desired powder color cannot be obtained. In addition, before the reduction treatment, if necessary, a baking treatment may be performed in the air beforehand, but the treatment temperature at that time is preferably less than 800 ° C. from the viewpoint of the haze value, and the time is not particularly limited. Absent.

【0016】ITO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、特に不活性ガス単独で還元する場合にはその残
留量が多いと所望とする粉体色にするのに長時間要し、
生産性が非常に悪くなる。従って、特に不活性ガス単独
で還元する場合は残留不純物量を洗浄によって0.6%
以下、好ましくは0.3%以下とするのがよい。
Since impurities such as chloride ions, nitrate ions, and sulfate ions remaining in the ITO fine particles act as a reduction inhibitory factor, especially when reducing with an inert gas alone, it is desirable that the residual amount is large so that the desired powder can be obtained. It takes a long time to color,
Productivity becomes very poor. Therefore, particularly when reducing with an inert gas alone, the amount of residual impurities is reduced by 0.6% by washing.
Or less, preferably 0.3% or less.

【0017】本発明の塗布液はITO微粒子を溶媒中に
分散したものであるが、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ール
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。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。
The coating liquid of the present invention is obtained by dispersing ITO fine particles in a solvent, but the solvent is not particularly limited, and the coating conditions, coating environment, and when an inorganic binder or a resin binder is contained, It is appropriately selected according to the binder. For example, water, ethanol, propanol, butanol, isopropyl alcohol, isobutyl alcohol, alcohols such as diacetone alcohol, ethers such as methyl ether, ethyl ether, propyl ether, esters, acetone, methyl ethyl ketone, diethyl ketone, cyclohexanone, isobutyl Various organic solvents such as ketones such as ketones can be used, and the pH may be adjusted by adding an acid or an alkali as needed. Furthermore, 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.

【0018】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 type 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 resin binder, a thermoplastic resin such as an acrylic resin, a thermosetting resin such as an epoxy resin, or the like can be used.

【0019】ITO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。この塗布
液を用いて膜を形成したときの膜の導電性は、ITO微
粒子の接触個所を経由した導電パスに沿って行われるた
め、例えば界面活性剤やカップリング剤の量を加減する
ことで導電パスを部分的に切断することができ、膜の導
電性を10Ω/□以上の表面抵抗値へ低下させること
は容易である。また、無機バインダー、あるいは樹脂バ
インダーの含有量の加減によっても導電性を制御でき
る。
The method of dispersing the ITO fine particles is not particularly limited as long as it is a method of uniformly dispersing the particles in the coating solution, and examples thereof include a bead mill, a ball mill, a sand mill, a paint shaker, and an ultrasonic homogenizer. When the film is formed using this coating liquid, the conductivity of the film is performed along a conductive path passing through the contact portion of the ITO fine particles. Therefore, for example, by adjusting the amount of a surfactant or a coupling agent, The conductive path can be partially cut, and it is easy to lower the conductivity of the film to a surface resistance value of 10 6 Ω / □ or more. The conductivity can also be controlled by adjusting the content of the inorganic binder or the resin binder.

【0020】本発明の日射遮蔽膜は、基板上に上記IT
O微粒子が高密度に堆積して膜形成するものであり、塗
布液中に含まれる樹脂バインダーまたは無機バインダー
は、塗布、硬化後にITO微粒子の基材への密着性を向
上させ、さらに膜の硬度を向上させる効果がある。ま
た、このようにして得られた膜上に、さらに珪素、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、これらの部分加水分解縮重合物からなる被膜を
第2層として被着し、珪素、ジルコニウム、チタン、も
しくはアルミニウムの酸化物膜を形成することで、IT
O微粒子を主成分とする膜の基材へ結着力や膜の硬度、
耐候性を一層向上させることができる。
The solar shading film of the present invention comprises the above-described IT
O particles are deposited at a high density to form a film. A resin binder or an inorganic binder contained in the coating solution improves the adhesion of the ITO particles to the substrate after coating and curing, and furthermore, the hardness of the film. Has the effect of improving. Further, a film made of silicon, zirconium, titanium, or a metal alkoxide of aluminum or a partially hydrolyzed polycondensate thereof is further applied as a second layer on the thus obtained film, and silicon, zirconium, By forming an oxide film of titanium or aluminum, IT
O-particles as the main component of the film binding strength and film hardness,
The weather resistance can be further improved.

【0021】また、塗布液中に樹脂バインダーまたは無
機バインダーを含まない場合に得られる膜は、基材上に
上記ITO微粒子のみが堆積した膜構造になる。このま
までも日射遮蔽効果を示すが、この膜上にさらに珪素、
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などの無機
バインダーまたは樹脂バインダーを含む塗布液を塗布し
て被膜を形成して多層膜とするとよい。このようにする
ことにより、塗布液成分が第1層のITO微粒子の堆積
した間隙を埋めて成膜されるため、膜のヘイズが低減し
て可視光透過率が向上し、また微粒子の基材への結着性
が向上する。
Further, the film obtained when the coating solution does not contain a resin binder or an inorganic binder has a film structure in which only the above-mentioned ITO fine particles are deposited on a substrate. Although it shows a solar shading effect as it is, silicon,
It is preferable to apply a coating solution containing an inorganic binder or a resin binder such as a metal alkoxide of zirconium, titanium, or aluminum or a partially hydrolyzed polycondensate thereof to form a coating film to form a multilayer film. By doing so, the coating liquid component is formed so as to fill the gap where the ITO fine particles of the first layer are deposited, so that the haze of the film is reduced, the visible light transmittance is improved, and the fine particle base material is formed. Improves binding to

【0022】ITO微粒子単体あるいはITO微粒子を
主成分とする膜上に、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
加水分解縮重合物からなる被膜で結着する方法として
は、成膜工程の容易さやコストの観点から塗布法が有効
である。塗布液は、水やアルコール中に珪素、ジルコニ
ウム、チタン、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を1種もしくは2種以上含む
ものであり、その含有量は加熱後に得られる酸化物換算
で全溶液中の40重量%以下が好ましい。また、必要に
応じて酸やアルカリを添加してpH調整することも可能
である。このような液をITO微粒子を主成分とする膜
上にさらに第2層として塗布し加熱することで、珪素、
ジルコニウム、チタン、アルミニウムなどの酸化物被膜
を容易に作製することが可能である。さらには、本発明
の塗布液に使用するバインダー成分として、あるいはオ
ーバーコート用の塗布液として、オルガノシラザン溶液
を用いてもよい。
As a method for binding to a film of ITO fine particles alone or a film containing ITO fine particles as a main component, using a film made of a metal alkoxide of silicon, zirconium, titanium, or aluminum or a partially hydrolyzed polycondensate thereof, the following method is used. The coating method is effective from the viewpoint of the easiness of the film process and the cost. The coating liquid contains one or more of metal alkoxides of silicon, zirconium, titanium, and aluminum and partially hydrolyzed polycondensation products thereof in water or alcohol, and the content thereof is the amount of oxide obtained after heating. It is preferably 40% by weight or less in the total solution in terms of conversion. It is also possible to adjust the pH by adding an acid or an alkali as needed. Such a liquid is further applied as a second layer on a film containing ITO fine particles as a main component, and heated, so that silicon,
An oxide film of zirconium, titanium, aluminum, or the like can be easily formed. Further, an organosilazane solution may be used as a binder component used in the coating solution of the present invention or as a coating solution for overcoating.

【0023】本発明の塗布液、および本発明で用いる被
膜形成用の塗布方法は特に限定されない。例えば、スピ
ンコート法、バーコート法、スプレーコート法、ディッ
プコート法、スクリーン印刷法、ロールコート法、流し
塗りなど、処理液を平坦かつ薄く均一に塗布できる方法
であればいずれの方法でもよい。
The coating solution of the present invention and the coating method for forming a film used in the present invention are not particularly limited. For example, any method, such as a spin coating method, a bar coating method, a spray coating method, a dip coating method, a screen printing method, a roll coating method, and a flow coating method, may be used as long as the processing liquid can be applied flat and thinly and uniformly.

【0024】無機バインダーとして、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
およびその加水分解重合物を含む塗布液の塗布後の基材
加熱温度は、100℃未満では塗膜中に含まれるアルコ
キシドまたはその加水分解重合物の重合反応が未完結で
残る場合が多く、また水や有機溶媒が膜中に残留して加
熱後の膜の可視光透過率の低減の原因となるので、10
0℃以上が好ましく、さらに好ましくは塗布液中の溶媒
の沸点以上で加熱を行う。
When the coating liquid containing a metal alkoxide of silicon, zirconium, titanium, or aluminum as an inorganic binder and a hydrolyzed polymer thereof is applied at a substrate heating temperature of less than 100 ° C., the alkoxide contained in the coating film or In many cases, the polymerization reaction of the hydrolyzed polymer remains uncompleted, and water or an organic solvent remains in the film, causing a reduction in visible light transmittance of the film after heating.
The heating is preferably performed at 0 ° C. or higher, more preferably at a temperature higher than the boiling point of the solvent in the coating solution.

【0025】樹脂バインダーを使用した場合は、それぞ
れの硬化方法に従って硬化させればよい。例えば、紫外
線硬化樹脂であれば紫外線を適宜照射すればよく、また
常温硬化樹脂であれば塗布後そのまま放置しておけばよ
い。このため、既存の窓ガラスなどへの現場での塗布が
可能である。
When a resin binder is used, it may be cured according to each curing method. For example, an ultraviolet curable resin may be appropriately irradiated with ultraviolet light, and a room temperature curable resin may be left as it is after application. Therefore, it can be applied to an existing window glass or the like on site.

【0026】本発明の膜ではITO微粒子が分散してい
るため、物理成膜法により製造された酸化物薄膜のよう
に結晶が緻密に膜内を埋めた鏡面状表面をもつ膜に比べ
ると、可視光領域での反射が少なく、ギラギラした外観
を呈することが回避できる。その一方で、上記のように
可視から近赤外域にプラズマ周波数をもつため、これに
伴うプラズマ反射が近赤外域で大きくなる。可視光領域
の反射をさらに抑制したい場合には、本発明のITO微
粒子分散膜の上に、SiOやMgFのような低屈折
率の膜を成膜することにより、容易に視感反射率1%以
下の多層膜を得ることができる。
In the film of the present invention, since the ITO fine particles are dispersed, compared with a film having a mirror-like surface in which crystals are densely filled, such as an oxide thin film produced by a physical film formation method, Reflection in the visible light region is small, and it is possible to avoid giving a glare-like appearance. On the other hand, since the plasma frequency is in the visible to near-infrared region as described above, the accompanying plasma reflection increases in the near-infrared region. When it is desired to further suppress the reflection in the visible light region, a luminous reflectance can be easily formed by forming a low refractive index film such as SiO 2 or MgF 2 on the ITO fine particle dispersion film of the present invention. A multilayer film of 1% or less can be obtained.

【0027】本発明の日射遮蔽用インジウム錫酸化物微
粒子、塗布液、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 the ultraviolet ray shielding function of the indium tin oxide particles for solar radiation shielding of the present invention, the coating liquid, and the solar radiation shielding film, fine particles of inorganic titanium oxide, zinc oxide, cerium oxide, and the like; One or more of benzophenone and benzotriazole may be added.

【0028】本発明の塗布液は焼成時の熱による塗布成
分の分解あるいは化学反応を利用して目的の日射遮蔽膜
を形成するものではないため、特性の安定した均一な膜
厚の透過膜を形成することができる。
The coating liquid of the present invention does not form a target solar radiation shielding film by utilizing decomposition or chemical reaction of coating components due to heat at the time of baking, so that a transparent film having a uniform thickness and a stable characteristic can be obtained. Can be formed.

【0029】このように本発明によれば、上記性状のI
TO微粒子の還元によって日射遮蔽効果を発揮する膜製
造が可能であるが、この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。
As described above, according to the present invention, the above properties I
It is possible to produce a film exhibiting a solar shading effect by reducing the TO fine particles. However, since the indium tin oxide fine particles are inorganic materials, they have extremely high weather resistance as compared with organic materials. Even if it is used for the corresponding part, the color and various functions hardly deteriorate.

【0030】[0030]

【実施例】以下の実施例により、本発明をさらに詳細に
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
率および粉体の色彩(標準光源C,10゜視野)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H
R−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、可視光透過率86
%のときの日射透過率およびヘイズ値を前記膜の3点プ
ロットから求めた。
The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to the following examples. In addition, the visible light transmittance and the sunlight transmittance of the obtained film and the color of the powder (standard light source C, 10 ° visual field) were measured using a spectrophotometer U-4000 manufactured by Hitachi, Ltd. In addition, the haze value is H value manufactured by Murakami Color Research Laboratory Co., Ltd.
It measured using R-200. In the film evaluation, the film was formed using three types of bar coaters having different wire diameters, and the visible light transmittance was 86.
%, The solar transmittance and the haze value were determined from a three-point plot of the film.

【0031】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ITO微粒子(住友金属鉱山(株)製)
25gを500mlのセパラブルフラスコに入れ、攪拌
しながらメタノール含有窒素ガスを供給しながら加熱
し、300℃の温度で5時間還元処理することによっ
て、Lが40.16、aが−2.821、bが−
7.279の粉体色のITO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%を、充填率63%相当の
0.3mmジルコニアビーズを入れたペイントシェーカ
ーで12時間分散した。次に、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×3mm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。膜aの日射透過率およびヘイズ値はそれぞれ6
7.2%、0.5%であった。
Example 1 ITO fine particles having a tin content of 10% by weight, a residual impurity amount of 0.7%, and an average particle diameter of 0.03 μm (manufactured by Sumitomo Metal Mining Co., Ltd.)
25 g was placed in a 500 ml separable flask, heated while supplying methanol-containing nitrogen gas with stirring, and subjected to a reduction treatment at a temperature of 300 ° C. for 5 hours, so that L * was 40.16 and a * was -2. 821, b * is-
7.279 powder-colored ITO fine particles were obtained. Subsequently, 20% by weight of the fine particles, 63.3% by weight of methyl isobutyl ketone, and 16.7% by weight of a dispersant were dispersed in a paint shaker containing 0.3 mm zirconia beads equivalent to a filling rate of 63% for 12 hours. Next, a coating liquid composed 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 coated with bars of numbers 40, 24, and 6, respectively. After coating on a soda lime glass substrate of 100 mm × 100 mm × 3 mm, it is baked at 180 ° C. for 1 hour to form a film a
I got The solar transmittance and haze value of the film a were 6
7.2% and 0.5%.

【0032】実施例2〜実施例3 還元処理の際に供給するアルコールを、メタノールから
エタノールに換えた以外は実施例1と同様にして膜b
(実施例2)を、プロパノール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に示すよう
に、実施例2の粉体色Lはそれぞれ39.6
8、−2.787、−7.190であり、実施例3の粉
体色Lはそれぞれ39.01、−2.65
3、−6.951であった。また、実施例2と実施例3
の日射透過率はそれぞれ66.4%、66.5%で、ヘ
イズ値はどちらも、0.5%であった。
Examples 2 and 3 The membrane b was prepared in the same manner as in Example 1 except that the alcohol supplied during the reduction treatment was changed from methanol to ethanol.
A film c (Example 3) was obtained in the same manner as in Example 1 except that (Example 2) was changed to propanol. As shown in Table 1, the powder colors L * a * b * of Example 2 were each 39.6.
8, -2.787 and -7.190, and the powder colors L * a * b * of Example 3 were 39.01 and -2.65, respectively.
3, -6.951. Example 2 and Example 3
Had a solar transmittance of 66.4% and 66.5%, respectively, and both had a haze value of 0.5%.

【0033】実施例4 ペイントシェーカーでの分散時間を24時間とした以外
は実施例1と同様にして膜d(実施例4)を得た。表1
に示すように、実施例4のITO微粒子の粉体色L
はそれぞれ40.16、−2.821、−7.2
79であり、日射透過率およびヘイズ値はそれぞれ6
6.4%、0.4%であった。
Example 4 A film d (Example 4) was obtained in the same manner as in Example 1 except that the dispersion time in the paint shaker was changed to 24 hours. Table 1
As shown in the figure, the powder color L * a of the ITO fine particles of Example 4
* B * is 40.16, -2.821, and -7.2, respectively.
The solar transmittance and the haze value were 6 respectively.
6.4% and 0.4%.

【0034】実施例5 還元処理温度を250℃として4時間還元した以外は実
施例1と同様にして膜e(実施例5)を得た。表1に示
すように、実施例5のITO微粒子の粉体色L
はそれぞれ43.50、−3.920、−5.473
であり、日射透過率およびヘイズ値はそれぞれ69.0
%、0.9%であった。
Example 5 A film e (Example 5) was obtained in the same manner as in Example 1 except that the reduction was performed at 250 ° C. for 4 hours. As shown in Table 1, the powder color L * a * b of the ITO fine particles of Example 5
* Indicates 43.50, -3.920, -5.473, respectively.
And the solar transmittance and the haze value were respectively 69.0.
% And 0.9%.

【0035】比較例1 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f(比較例1)を得た。表1に示すように、比較例1
のITO微粒子の粉体色はLが85.14であり、日
射透過率は70%を超え、かつヘイズ値も1%を超える
ものであった。
Comparative Example 1 A film f (Comparative Example 1) was obtained in the same manner as in Example 1 except that no reduction treatment was performed. As shown in Table 1, Comparative Example 1
The powder color of the ITO fine particles was such that L * was 85.14, the solar radiation transmittance exceeded 70%, and the haze value also exceeded 1%.

【0036】比較例2 メタノール含有窒素ガス中での還元処理温度を150℃
として4時間還元した以外は実施例1と同様にして膜g
(比較例2)を得た。表1に示すように、比較例2のI
TO微粒子の粉体色はLが80であり、比較例1同
様、日射透過率が70%を超え、かつヘイズ値も1%を
超えるものであった。
Comparative Example 2 Reduction temperature in methanol-containing nitrogen gas was 150 ° C.
G in the same manner as in Example 1 except that the
(Comparative Example 2) was obtained. As shown in Table 1, I of Comparative Example 2
The powder color of the TO fine particles had an L * of 80, as in Comparative Example 1, and the solar transmittance exceeded 70% and the haze value also exceeded 1%.

【0037】実施例6 還元処理温度を300℃として3時間還元した以外は実
施例1と同様にして膜h(実施例6)を得た。表1に示
すように、実施例6のITO微粒子の粉体色L
はそれぞれ46.37、−3.753、−9.124
であり、日射透過率およびヘイズ値はそれぞれ69.0
%、0.5%であった。
Example 6 A film h (Example 6) was obtained in the same manner as in Example 1 except that the reduction was performed at 300 ° C. for 3 hours. As shown in Table 1, the powder color L * a * b of the ITO fine particles of Example 6
* Indicates 46.37, -3.753, and -9.124, respectively.
And the solar transmittance and the haze value were respectively 69.0.
% And 0.5%.

【0038】実施例7〜実施例8 2.8%NHOH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ITO
微粒子(住友金属鉱山(株)製)を、メタノール含有窒
素ガス流通下300℃で15分還元した以外は実施例1
と同様にして膜i(実施例7)を、40分還元した以外
は実施例1と同様にして膜j(実施例8)を得た。表1
に示すように、ITO微粒子の粉体色Lはそ
れぞれ、実施例7が39.42、−1.955、−5.
470で、実施例8が35.60、−0.893、−
4.586であり、日射透過率およびヘイズ値はそれぞ
れ、実施例7が66.9%、0.5%で、実施例8が6
8.5%、0.3%であった。
Example 7 to Example 8 After washing with 2.8% NH 4 OH, water was washed six times with 600 ml of ion-exchanged water. The tin content was 10% by weight.
ITO with a residual impurity amount of 0.1% and an average particle size of 0.03 μm
Example 1 Example 1 was conducted except that fine particles (manufactured by Sumitomo Metal Mining Co., Ltd.) were reduced at 300 ° C. for 15 minutes under a flow of nitrogen gas containing methanol.
In the same manner as in Example 1, except that the film i (Example 7) was reduced for 40 minutes, a film j (Example 8) was obtained. Table 1
As shown in Table 7, the powder colors L * a * b * of the ITO fine particles were 39.42, -1.955, and -5.
470, Example 8 was 35.60, -0.893,-
4.586, the solar radiation transmittance and the haze value were 66.9% and 0.5% in Example 7, and 6 in Example 8 respectively.
8.5% and 0.3%.

【0039】比較例3 窒素ガス単独で5時間還元処理を施した以外は実施例1
と同様にして膜k(比較例3)を得た。表1に示すよう
に、比較例3のITO微粒子の粉体色Lはそ
れぞれ76.30、−3.636、21.680であ
り、日射透過率およびヘイズ値はそれぞれ71.0%、
1.0%であった。
Comparative Example 3 Example 1 except that a reduction treatment was performed for 5 hours with nitrogen gas alone.
A film k (Comparative Example 3) was obtained in the same manner as described above. As shown in Table 1, the powder colors L * a * b * of the ITO fine particles of Comparative Example 3 were 76.30, -3.636, and 21.680, respectively, and the solar transmittance and haze value were 71.30, respectively. 0%,
1.0%.

【0040】実施例9 2.8%NHOH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ITO
微粒子(住友金属鉱山(株)製)を、窒素ガス単独で3
時間還元処理を施した以外は実施例1と同様にして膜l
(実施例9)を得た。表1に示すように、実施例9のI
TO微粒子の粉体色Lはそれぞれ47.3
2、−2.297、−6.391であり、日射透過率お
よびヘイズ値はそれぞれ69.1%、0.5%であっ
た。
Example 9 After washing with 2.8% NH 4 OH, and washing with water six times with 600 ml of ion-exchanged water, the tin content was 10% by weight.
ITO with a residual impurity amount of 0.1% and an average particle size of 0.03 μm
Fine particles (Sumitomo Metal Mining Co., Ltd.)
A membrane 1 was prepared in the same manner as in Example 1 except that a time reduction treatment was performed.
(Example 9) was obtained. As shown in Table 1, I of Example 9
The powder colors L * a * b * of the TO fine particles are 47.3, respectively.
2, -2.297 and -6.391, and the solar radiation transmittance and haze value were 69.1% and 0.5%, respectively.

【0041】実施例10 実施例1と同様にして得た膜aに、テトラエチルシリケ
ートを少量の塩酸存在下で加水分解して得られたシリカ
ゾル溶液を、スピンコーター(180rpm)で塗布
し、常温で5分間乾燥した後、150℃で20分間硬化
して膜m(実施例10)を得た。表1に示すように、日
射透過率およびヘイズ値はそれぞれ68.0%、0.4
%であった。
Example 10 A silica sol solution obtained by hydrolyzing tetraethyl silicate in the presence of a small amount of hydrochloric acid was applied to a film a obtained in the same manner as in Example 1 with a spin coater (180 rpm), and the solution was heated at room temperature. After drying for 5 minutes, the film was cured at 150 ° C. for 20 minutes to obtain a film m (Example 10). As shown in Table 1, the solar transmittance and the haze value were 68.0% and 0.4, respectively.
%Met.

【0042】比較例4 錫含有量5.5重量%、残留不純物量0.15%、0.
2μmの粗大粒子が混在する平均粒径0.013μmの
インジウム錫酸化物微粒子を用いた以外は、実施例1と
同様にして膜n(比較例4)を得た。表1に示すよう
に、比較例4のITO微粒子の粉体色Lはそ
れぞれ57.22、−4.691、−9.959であ
り、日射透過率が70%を超え、かつヘイズ値も1%を
超えるものであった。
Comparative Example 4 Tin content: 5.5% by weight, residual impurity content: 0.15%, 0.1%
A film n (Comparative Example 4) was obtained in the same manner as in Example 1 except that indium tin oxide fine particles having an average particle diameter of 0.013 μm in which coarse particles of 2 μm were mixed were used. As shown in Table 1, the powder colors L * a * b * of the ITO fine particles of Comparative Example 4 were 57.22, -4.691, and -9.959, respectively, and the solar radiation transmittance exceeded 70%. And the haze value also exceeded 1%.

【0043】実施例11 錫含有量10重量%、残留不純物量0.3%、平均粒径
0.01μmのITO微粒子25gを500mlのセパ
ラブルフラスコに入れ、攪拌しながら窒素をキャリアと
した9%H2ガスを供給しながら加熱し、300℃の温
度で4.5時間還元処理することによって、Lが6
6.18、aが−6.352、bが3.960の粉
体色のITO微粒子を得た。該微粒子を用いた以外は、
実施例4と同様にして膜oを得た。表1に示すように、
膜oの日射透過率およびヘイズ値はそれぞれ64.5
%、0.3%であった。
Example 11 25 g of ITO fine particles having a tin content of 10% by weight, a residual impurity amount of 0.3% and an average particle size of 0.01 μm were put into a 500 ml separable flask, and 9% of which was stirred with nitrogen as a carrier. By heating while supplying H2 gas and performing a reduction treatment at a temperature of 300 ° C. for 4.5 hours, L * becomes 6
6.18, a * was -6.352, b * was 3.960, and powdery ITO fine particles were obtained. Except for using the fine particles,
A film o was obtained in the same manner as in Example 4. As shown in Table 1,
The solar transmittance and haze value of the film o were 64.5, respectively.
% And 0.3%.

【0044】実施例12 実施例11において、240℃の温度で6時間還元処理
した以外は実施例11と同様にして膜pを得た。表1に
示すように、膜pの日射透過率およびヘイズ値はそれぞ
れ67.5%、0.4%であった。
Example 12 A film p was obtained in the same manner as in Example 11, except that the reduction treatment was performed at a temperature of 240 ° C. for 6 hours. As shown in Table 1, the solar radiation transmittance and the haze value of the film p were 67.5% and 0.4%, respectively.

【0045】[0045]

【表1】 [Table 1]

【0046】[0046]

【発明の効果】以上述べた通り、本発明は特定のITO
微粒子を用いることにより、高コストの物理成膜法を用
いずに簡便な塗布法で成膜でき、かつ膜の可視光透過率
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 relates to a specific ITO.
By using fine particles, a film can be formed by a simple coating method without using an expensive physical film forming method, and a film having a high visible light transmittance and a low solar transmittance and a haze value can be provided. Is extremely useful.

───────────────────────────────────────────────────── フロントページの続き Fターム(参考) 4F100 AA00A AA17A AA19B AA20B AA21B AA27B AA33A AK01A AK25A BA02 CA02A CC00A DE01A GB90 JL10A JN01 4G059 AA01 AC04 AC06 AC30 FA15 FA28 FB05  ──────────────────────────────────────────────────の Continued on the front page F term (reference) 4F100 AA00A AA17A AA19B AA20B AA21B AA27B AA33A AK01A AK25A BA02 CA02A CC00A DE01A GB90 JL10A JN01 4G059 AA01 AC04 AC06 AC30 FA15 FA28 FB05

Claims (9)

【特許請求の範囲】[Claims] 【請求項1】 L表色系における粉体色が、
が20〜52、aが−4.4〜−0.1、b
−10〜−3であり、かつ平均粒径が100nm以下で
あることを特徴とする日射遮蔽用インジウム錫酸化物微
粒子。
1. The powder color in the L * a * b * color system is
Indium tin for solar shading, wherein L * is 20 to 52, a * is -4.4 to -0.1, b * is -10 to -3, and the average particle size is 100 nm or less. Oxide fine particles.
【請求項2】 L表色系における粉体色が、
が52〜80、aが−10〜−0.1、bが0
〜20であり、かつ平均粒径が100nm以下であるこ
とを特徴とする日射遮蔽用インジウム錫酸化物微粒子。
2. The powder color in the L * a * b * color system is
L * is 52 to 80, a * is -10 to -0.1, b * is 0
To 20 and an average particle diameter of 100 nm or less.
【請求項3】 請求項1または2記載の日射遮蔽用イン
ジウム錫酸化物微粒子を溶媒中に分散したことを特徴と
する日射遮蔽膜形成用塗布液。
3. A coating liquid for forming a solar shading film, wherein the indium tin oxide fine particles for solar shading according to claim 1 or 2 are dispersed in a solvent.
【請求項4】 バインダーとして、無機バインダーまた
は樹脂バインダーがさらに含有されることを特徴とする
請求項3記載の日射遮蔽膜形成用塗布液。
4. The coating solution for forming a solar shading film according to claim 3, wherein the binder further comprises an inorganic binder or a resin binder.
【請求項5】 請求項1または2記載の日射遮蔽用イン
ジウム錫酸化物微粒子を含有することを特徴とする日射
遮蔽膜。
5. A solar shading film comprising the indium tin oxide fine particles for solar shading according to claim 1 or 2.
【請求項6】 請求項5記載の日射遮蔽膜の上に、珪
素、ジルコニウム、チタン、もしくはアルミニウムの酸
化物膜が形成されたことを特徴とする請求項5記載の日
射遮蔽膜。
6. The solar shading film according to claim 5, wherein an oxide film of silicon, zirconium, titanium, or aluminum is formed on the solar shading film according to claim 5.
【請求項7】 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、ヘイズ値が1.0%未満であることを特徴とする請
求項5または6記載の日射遮蔽膜。
7. The solar cell according to claim 5, wherein the solar radiation transmittance is less than 70% and the haze value is less than 1.0% in a wavelength range of 300 to 2100 nm when the visible light transmittance is 80% or more. The solar radiation shielding film as described.
【請求項8】 平均粒径が100nm以下のインジウム
錫酸化物微粒子を、アルコールを含有する不活性ガス、
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
で200〜300℃の温度で10分以上処理することを
特徴とする請求項1または2記載の日射遮蔽用インジウ
ム錫酸化物微粒子の製造方法。
8. An alcohol-containing inert gas containing indium tin oxide fine particles having an average particle diameter of 100 nm or less,
The method for producing indium tin oxide fine particles for solar radiation shielding according to claim 1 or 2, wherein the treatment is performed at a temperature of 200 to 300 ° C for 10 minutes or more in a mixed gas atmosphere of a reducing gas and an inert gas. .
【請求項9】 平均粒径が100nm以下のインジウム
錫酸化物微粒子中の、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、不
活性ガスまた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で200
〜300℃の温度で10分以上還元することを特徴とす
る請求項1または2記載の日射遮蔽用インジウム錫酸化
物微粒子の製造方法。
9. An indium tin oxide fine particle having an average particle diameter of 100 nm or less contains an inert gas or alcohol after the amount of residual impurities comprising chlorine ions, nitrate ions and sulfate ions is reduced to 0.6% or less. In an inert gas or mixed gas atmosphere of a reducing gas and an inert gas, 200
The method for producing indium tin oxide fine particles for solar shading according to claim 1 or 2, wherein the reduction is carried out at a temperature of 300 ° C for 10 minutes or more.
JP2001082557A 2000-11-02 2001-03-22 Ito microparticle for daylight screening, method for producing the same, and coating liquid and daylight screening film using the same Pending JP2002201027A (en)

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JP2000-336408 2000-11-02
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
US20130187104A1 (en) * 2010-10-26 2013-07-25 Mitsubishi Materials Electronic Chemicals Co., Ltd. Indium tin oxide powder, method for producing same, dispersion, paint, and functional thin film
US20160137522A1 (en) * 2012-06-12 2016-05-19 Mitsubishi Materials Corporation Ito film, ito powder used in manufacturing same ito film, manufacturing method of ito powder, and manufacturing method of ito film

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
US20130187104A1 (en) * 2010-10-26 2013-07-25 Mitsubishi Materials Electronic Chemicals Co., Ltd. Indium tin oxide powder, method for producing same, dispersion, paint, and functional thin film
KR101568561B1 (en) * 2010-10-26 2015-11-11 미쓰비시 마테리알 가부시키가이샤 Indium tin oxide powder, method for producing same, dispersion, paint, and functional thin film
US20160137522A1 (en) * 2012-06-12 2016-05-19 Mitsubishi Materials Corporation Ito film, ito powder used in manufacturing same ito film, manufacturing method of ito powder, and manufacturing method of ito film

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