JP2003176132A - Antimony-tin oxide particle for shielding insolation, coating solution for forming insolation shielding film and insolation shielding film - Google Patents
Antimony-tin oxide particle for shielding insolation, coating solution for forming insolation shielding film and insolation shielding filmInfo
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- JP2003176132A JP2003176132A JP2002281196A JP2002281196A JP2003176132A JP 2003176132 A JP2003176132 A JP 2003176132A JP 2002281196 A JP2002281196 A JP 2002281196A JP 2002281196 A JP2002281196 A JP 2002281196A JP 2003176132 A JP2003176132 A JP 2003176132A
- Authority
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- Prior art keywords
- solar radiation
- shielding film
- radiation shielding
- tin oxide
- film
- Prior art date
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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、電話ボックス等の窓、ショーウィンド
ー、照明用ランプ、透明ケース等に使用される日射遮蔽
機能を有するガラス、プラスチックス等の透明基材上に
形成される日射遮蔽膜、これら日射遮蔽膜へ用いるアン
チモン錫酸化物粒子、およびこれを用いた日射遮蔽膜形
成用塗布液に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a glass or plastic having a solar radiation shielding function used for windows of vehicles, buildings, offices, general houses, telephone boxes, etc., show windows, lighting lamps, transparent cases and the like. The present invention relates to a solar radiation shielding film formed on a transparent substrate such as a glass, antimony tin oxide particles used for the solar radiation shielding film, and a coating liquid for forming a solar radiation shielding film using the same.
【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、ガラス等の透明基
材の表面へ、熱効果に大きく寄与する赤外線を反射する
材料を含有する膜を形成し、熱線反射透明基材とするこ
とが行われていた。そして、その赤外線を反射する材料
にはＦｅＯｘ、ＣｏＯｘ、ＣｒＯｘ、ＴｉＯｘなどの金
属酸化物やＡｇ、Ａｕ、Ｃｕ、Ｎｉ、Ａｌなどの自由電
子を多量にもつ金属が用いられてきた。しかし、これら
の金属酸化物や金属は、赤外線だけでなく、可視光をも
反射もしくは吸収する性質があるため、熱線反射透明基
材の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 for removing / reducing heat components from an external light source such as sunlight or a light bulb, the surface of a transparent substrate such as glass contains a material that reflects infrared rays, which greatly contributes to the heat effect. It has been carried out to form a film and use it as a heat ray reflective transparent substrate. As a material that reflects the infrared rays, metal oxides such as FeOx, CoOx, CrOx, and TiOx, and metals having a large amount of free electrons such as Ag, Au, Cu, Ni, and Al have been used. However, since these metal oxides and metals have a property of reflecting or absorbing not only infrared rays but also visible light, there is a problem that the visible light transmittance of the heat ray reflective transparent base material is lowered.
【０００３】さらに、建物、車両、電話ボックス等の窓
材に用いられるガラス等の透明基材は、可視光領域にお
ける高い透過率が必要とされることから、前記金属酸化
物や金属を含有する膜を形成する場合は、その膜厚を非
常に薄くしなければならない。そこで前記金属酸化物や
金属を透明基材上に形成するときは、スプレー焼付けや
ＣＶＤ法などの化学成膜法、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、いずれも大がかりな装置や真
空設備を必要とし、生産性の向上や大面積化には多額の
投資が必要であるため膜の製造コストが高いといった問
題点がある。Further, a transparent base material such as glass used for a window material of a building, a vehicle, a telephone box, etc., needs to have a high transmittance in the visible light region, and therefore contains the metal oxide or the metal. When forming a film, the film thickness must be very thin. Therefore, when the metal oxide or metal is formed on the transparent substrate, a thin film of 10 nm level is formed by using a chemical film forming method such as spray baking or a CVD method, or a physical film forming method such as a sputtering method or a vacuum evaporation method. It has been commonly practiced to form a film on a substrate and use it. However, all of these film forming methods require large-scale equipment and vacuum equipment, and a large amount of investment is required to improve productivity and increase the area. .
【０００４】また、前記金属酸化物や金属による膜で日
射遮蔽特性（波長域３００〜２１００ｎｍの光を遮蔽す
る特性）を高くしようとすると、同時に可視光領域の反
射率も高くなってしまう傾向があるため、透明基材に鏡
のようなギラギラした外観を与えて、美観を損ねてしま
うという問題点もある。さらに、前記金属酸化物や金属
により成膜された膜は、電気抵抗が比較的低くなって電
波に対する反射が高くなり、例えば携帯電話やＴＶ、ラ
ジオなどの電波を反射して受信不能にさせたり、周辺地
域に電波障害を引き起こすなどの問題点もある。Further, if an attempt is made to enhance the solar radiation shielding property (the property of shielding light in the wavelength range of 300 to 2100 nm) with the metal oxide or metal film, the reflectance in the visible light region tends to increase at the same time. Therefore, there is also a problem that the transparent base material has a mirror-like glaring appearance, which impairs aesthetics. Further, the film formed of the metal oxide or the metal has a relatively low electric resistance and a high reflection to a radio wave, for example, a radio wave of a mobile phone, a TV, a radio, etc. is reflected to make it unreceivable. There are also problems such as causing radio interference in the surrounding area.
【０００５】このような問題点を改善するためには、可
視光領域の反射率が低いすなわち可視光領域の透過率が
高くて、赤外線領域の反射率が高いすなわち日射透過率
が低く、かつ表面抵抗値が、概ね１０6Ω／□以上の物
理的特性を有する膜を透明基材上に形成する必要があ
る。ここで、可視光透過率が高く、しかも日射遮蔽機能
を持つ安価な材料の一つとしてアンチモン錫酸化物が知
られている。In order to solve such problems, the reflectance in the visible light region is low, that is, the transmittance in the visible light region is high, and the reflectance in the infrared region is high, that is, the solar radiation transmittance is low, and the surface is It is necessary to form a film having a physical property with a resistance value of approximately 10 6 Ω / □ or more on a transparent substrate. Here, antimony tin oxide is known as one of inexpensive materials having a high visible light transmittance and a solar radiation shielding function.
【０００６】例えば、特許文献１には、酸化錫を主成分
として酸化アンチモンおよび酸化ケイ素を含有する比表
面積４０ｍ2／ｇ以上の導電性微粉末に関して提案され
ている。この公報の記載によれば、粉末の比表面積を、
４０ｍ2／ｇ以上に維持させるため焼結防止剤として酸
化ケイ素を添加しているが、酸化ケイ素の添加によって
日射遮蔽機能が阻害されるといった問題がある。また、
アンチモン錫酸化物の物理特性と日射遮蔽機能に関した
発明はこれまで開示されていなかった。For example, Patent Document 1 proposes a conductive fine powder containing tin oxide as a main component and containing antimony oxide and silicon oxide and having a specific surface area of 40 m 2 / g or more. According to the description of this publication, the specific surface area of the powder is
Although silicon oxide is added as a sintering inhibitor in order to maintain 40 m 2 / g or more, there is a problem that the addition of silicon oxide hinders the solar radiation shielding function. Also,
An invention relating to the physical properties of antimony tin oxide and the solar radiation shielding function has not been disclosed so far.
【０００７】さらに、従来のアンチモン錫酸化物粉体を
用いて日射遮蔽膜を形成した場合、膜に、所謂ヘイズが
発生し満足な透明性を得ることができない。ヘイズとは
透明な基材の曇りとして観察される現象で、全透過率に
対する拡散透過光の割合をヘイズ値として数値化したも
のである。そしてヘイズ値が高いと、人間の目には透明
基材の曇りとして認識されるものである。具体的には、
日射遮蔽膜の可視光透過率が８０％のとき、ヘイズ値は
１％以下が望まれている。さらに、可視光透過率および
日射遮蔽の観点からも、従来のアンチモン錫酸化物の高
い可視光透過率を維持しつつ、より高い日射遮蔽効果が
求められており、具体的には、日射遮蔽膜の可視光透過
率が８０％のとき、日射透過率は６５％以下が望まれて
いる。このため、可視光透過率、日射遮蔽および透明性
を要求される窓材等へは、従来のアンチモン錫酸化物を
用いることは問題が多かった。Further, when the solar radiation shielding film is formed by using the conventional antimony tin oxide powder, so-called haze is generated in the film, and satisfactory transparency cannot be obtained. Haze is a phenomenon observed as cloudiness of a transparent substrate, and is a numerical value of the ratio of diffuse transmitted light to the total transmittance as a haze value. When the haze value is high, it is perceived by human eyes as cloudiness of the transparent substrate. In particular,
When the visible light transmittance of the solar radiation shielding film is 80%, the haze value is desired to be 1% or less. Further, from the viewpoint of visible light transmittance and solar radiation shielding, a higher solar radiation shielding effect is required while maintaining the high visible light transmittance of the conventional antimony tin oxide. When the visible light transmittance is 80%, the solar radiation transmittance is desired to be 65% or less. For this reason, there are many problems in using conventional antimony tin oxide for window materials and the like which are required to have visible light transmittance, solar radiation shielding and transparency.
【０００８】[0008]
【特許文献１】特許第２８４４０１１号公報[Patent Document 1] Japanese Patent No. 2844011
【０００９】[0009]
【本発明が解決しようとする課題】そこで本発明は、ガ
ラス等の透明基材上に成膜された際、高い可視光透過率
と低い日射透過率とを有しながら、ヘイズ値が低いとい
う光学特性を有する膜を形成できるアンチモン錫酸化物
と、このアンチモン錫酸化物を含有し簡便な塗布法で日
射遮蔽膜を成膜できる日射遮蔽膜形成用塗布液と、この
アンチモン錫酸化物を含有する日射遮蔽膜とを提供する
ことを目的とする。Therefore, according to the present invention, when it is formed on a transparent substrate such as glass, it has a high haze value while having a high visible light transmittance and a low solar radiation transmittance. Antimony tin oxide capable of forming a film having optical properties, a coating solution for forming a solar radiation shielding film containing the antimony tin oxide and capable of forming a solar radiation shielding film by a simple coating method, and containing the antimony tin oxide It aims at providing the solar radiation shielding film which performs.
【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、ガラス等の透明基材上に成膜された
際、高い可視光透過率と低い日射透過率とを有しなが
ら、ヘイズ値が低いという光学特性を有する膜を形成で
きるアンチモン錫酸化物が満たすべき要件を検討した。In order to achieve the above object, the inventors of the present invention have a high visible light transmittance and a low solar radiation transmittance when formed on a transparent substrate such as glass. However, the requirements to be satisfied by antimony tin oxide capable of forming a film having an optical property of low haze value were examined.
【００１１】日射遮蔽膜に含まれているアンチモン錫酸
化物粒子は、入射光との干渉効果、粉体粒子の電子状態
に起因する光の吸収・放出効果、等を介して、入射して
くる可視光や赤外光と相互作用をおこない、透過、吸
収、反射等の光学現象を起こす。一方、一般にアンチモ
ン錫酸化物のような複合酸化物は、その製造の際の条件
により、粒子の表面状態や電子状態において様々な諸性
状を有するアンチモン錫酸化物が調製され得る。The antimony tin oxide particles contained in the solar radiation shielding film enter through the interference effect with incident light, the light absorption / emission effect due to the electronic state of the powder particles, and the like. It interacts with visible light and infrared light and causes optical phenomena such as transmission, absorption, and reflection. On the other hand, in general, a composite oxide such as antimony tin oxide can be prepared as an antimony tin oxide having various properties in the surface state and electronic state of particles, depending on the conditions during the production.
【００１２】そこで、本発明者らは、様々な物理特性を
有するアンチモン錫酸化物粒子と、日射遮蔽機能との関
係を調べ、高日射遮蔽を達成する条件を求めた。その結
果、特定の範囲の粉体色を有し、かつ特定の範囲の比表
面積を有し、さらに残留不純物量がある値以下であると
いう条件を満たすとき、このアンチモン錫酸化物粒子を
含有する日射遮蔽膜は、可視光領域においては高い透過
率を持つとともに、可視光領域に近い近赤外域において
は強いプラズマ吸収を発現して低い日射透過率を持ち、
かつヘイズ値が極めて低くなるという現象を見出し、本
発明を完成したものである。Therefore, the present inventors investigated the relationship between antimony tin oxide particles having various physical properties and the solar radiation shielding function, and sought the conditions for achieving high solar radiation shielding. As a result, when the powder has a specific color range, has a specific surface area within a specific range, and further the amount of residual impurities is less than a certain value, the antimony tin oxide particles are contained. The solar radiation shielding film has a high transmittance in the visible light region and a strong solar absorption in the near infrared region close to the visible light region to have a low solar radiation transmittance,
The present invention has been completed by finding a phenomenon that the haze value becomes extremely low.
【００１３】すなわち、第１の発明は、Ｌ*ａ*ｂ*表色
系による粉体色のＬ*が４５〜５５、ａ*が−３．５〜−
２、ｂ*が−８〜−４であり、かつ比表面積が５〜５５
ｍ2／ｇであり、かつ残留不純物量が１．５重量％以下
であることを特徴とする日射遮蔽用アンチモン錫酸化物
粒子である。[0013] That is, the first invention, L * a * b * color system of the powder color by L * is 45 to 55, a * is -3.5～-
2, b * is -8 to -4, and the specific surface area is 5 to 55
m 2 / g, and the amount of residual impurities is 1.5% by weight or less, the antimony tin oxide particles for solar radiation shielding.
【００１４】アンチモン錫酸化物粒子の粉体色、比表面
積、残留不純物量が前記範囲内であるとき、このアンチ
モン錫酸化物粒子の表面付近における電子の状態、粒子
表面の状態、粒子の粒径等も所定の範囲内にあるものと
考えられる。本発明に係るアンチモン錫酸化物粒子の粒
径は数ｎｍから１００ｎｍ程度の単分散の粒子であり、
その比表面積が５〜５５ｍ2／ｇの範囲にあると、粒子
の平均粒径は好ましい範囲となる。この結果、良好な日
射遮蔽機能を持つアンチモン錫酸化物量の割合が多くな
るため、その粒子を用いて形成された日射遮蔽膜では、
高い可視光透過率と、低い日射透過率とを得ることがで
きる。When the powder color, the specific surface area and the amount of residual impurities of the antimony tin oxide particles are within the above ranges, the state of electrons near the surface of the antimony tin oxide particles, the state of the particle surface, the particle size of the particles Etc. are considered to be within a predetermined range. The antimony tin oxide particles according to the present invention are monodisperse particles having a particle size of several nm to 100 nm,
When the specific surface area is in the range of 5 to 55 m 2 / g, the average particle diameter of the particles is in the preferable range. As a result, since the ratio of the amount of antimony tin oxide having a good solar radiation shielding function is large, the solar radiation shielding film formed by using the particles,
High visible light transmittance and low solar radiation transmittance can be obtained.
【００１５】さらに、残留不純物が１．５重量％以下で
あれば、日射遮蔽膜における日射遮蔽膜機能の低下およ
びヘイズ値の上昇を回避することができ好ましい。Further, if the residual impurities are 1.5% by weight or less, it is possible to avoid a decrease in the function of the solar radiation shielding film and an increase in the haze value in the solar radiation shielding film, which is preferable.
【００１６】第２の発明は、第１の発明に記載の日射遮
蔽用アンチモン錫酸化物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である。A second invention is a coating solution for forming a solar radiation shielding film, which comprises the antimony tin oxide particles for solar radiation shielding described in the first invention dispersed in a solvent.
【００１７】第３の発明は、バインダーとして、無機バ
インダーおよび／または樹脂バインダーを含有すること
を特徴とする第２の発明に記載の日射遮蔽膜形成用塗布
液である。A third invention is the coating solution for forming a solar radiation shielding film according to the second invention, which contains an inorganic binder and / or a resin binder as a binder.
【００１８】第４の発明は、第２または第３の発明に記
載の日射遮蔽膜形成用塗布液から形成されたことを特徴
とする日射遮蔽膜である。A fourth invention is a solar radiation shielding film formed from the coating liquid for forming a solar radiation shielding film according to the second or third invention.
【００１９】第５の発明は、第４の発明に記載の日射遮
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日
射遮蔽膜である。A fifth invention is a solar radiation shielding film characterized in that an oxide film of silicon, zirconium, titanium or aluminum is formed on the solar radiation shielding film described in the fourth invention.
【００２０】第６の発明は、可視光透過率８０％以上で
あって、波長域３００〜２１００ｎｍにおける日射透過
率が６５％未満で、かつヘイズ値が１％未満であること
を特徴とする第４または第５の発明に記載の日射遮蔽膜
である。A sixth invention is characterized in that the visible light transmittance is 80% or more, the solar radiation transmittance in the wavelength region of 300 to 2100 nm is less than 65%, and the haze value is less than 1%. The solar radiation shielding film according to the fourth or fifth invention.
【００２１】第７の発明は、第４から第６の発明のいず
れかに記載の日射遮蔽膜が形成されていることを特徴と
する日射遮蔽用透明基材である。A seventh aspect of the present invention is a transparent solar radiation-shielding base material on which the solar radiation shielding film according to any one of the fourth to sixth aspects is formed.
【００２２】[0022]
【発明の実施の形態】以下、本発明の実施の形態につい
て、詳細に説明する。日射遮蔽膜に適用可能なアンチモ
ン錫酸化物を検討するため、まず各種のアンチモン錫酸
化物についてその粉体色、比表面積、残留不純物量を測
定した。その結果を図１に示す。図１は、準備したアン
チモン錫酸化物より代表的な１０種類のアンチモン錫酸
化物（ａ〜ｊ）を選択し、それらのアンチモン錫酸化物
の有する粉体色、比表面積、不純物量を測定した結果
と、この１０種類のアンチモン錫酸化物（ａ〜ｊ）の各
々を、後述する方法により日射遮蔽膜形成用塗布液と
し、この塗布液を透明基材上へ塗布して膜Ａ〜Ｊとした
後、膜Ａ〜Ｊの光学特性を測定した結果を記載した表で
ある。BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described in detail below. In order to study antimony tin oxide applicable to the solar radiation shielding film, first, the powder color, specific surface area, and amount of residual impurities of various antimony tin oxides were measured. The result is shown in FIG. In FIG. 1, ten typical antimony tin oxides (a to j) were selected from the prepared antimony tin oxides, and the powder color, specific surface area, and amount of impurities of these antimony tin oxides were measured. Each of the results and each of the 10 kinds of antimony tin oxides (a to j) was used as a coating solution for forming a solar radiation shielding film by the method described below, and the coating solution was applied onto a transparent substrate to form films A to J. 3 is a table in which the results of measuring the optical properties of the films A to J after measurement are shown.
【００２３】尚、粉体色は、国際照明委員会（ＣＩＥ）
で規格化されＪＩＳＺ８７２９に採用されたＬ*ａ*ｂ*
表色系を用いて評価した。比表面積は、窒素吸着法より
評価した。残留不純物の塩素量は、イオンクロマト法に
より測定した。日射遮蔽膜の光学特性の測定において
は、日射遮蔽膜の可視光透過率を８０％に規格化し、こ
のときの日射透過率とヘイズ値とを測定した。The powder color is represented by the International Commission on Illumination (CIE).
L * a * b * standardized by JIS and adopted in JISZ8729
It evaluated using the color system. The specific surface area was evaluated by the nitrogen adsorption method. The chlorine content of residual impurities was measured by an ion chromatography method. In measuring the optical characteristics of the solar radiation shielding film, the visible light transmittance of the solar radiation shielding film was standardized to 80%, and the solar radiation transmittance and the haze value at this time were measured.
【００２４】図１の結果より明らかなように、粉体色が
Ｌ*４５〜５５、ａ*が−３．５〜−２、ｂ*が−８〜−
４であり、かつ比表面積が５〜５５ｍ2／ｇで、残留不
純物量が１．５重量％以下であるという特徴を有してい
るアンチモン錫酸化物を用いて成膜した日射遮蔽膜は、
望ましい光学的特性を有していることが判明した。As is clear from the results of FIG. 1, the powder color is L * 45 to 55, a * is -3.5 to -2, and b * is -8 to-.
4, the specific surface area is 5 to 55 m 2 / g, and the amount of residual impurities is 1.5 wt% or less, the solar radiation shielding film formed using antimony tin oxide,
It has been found to have desirable optical properties.
【００２５】この理由は、以下のように考えられる。一
般的な光と物質内の電子との相互作用において、ある物
質には固有のプラズマ周波数があり、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ωpは式（１）で表され
る。
ωp 2＝ｎｑ2／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。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／ｃｍ3台、アンチモン錫酸化物で１０20／ｃ
ｍ3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、アンチモン錫酸化物では、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。The reason for this is considered as follows. It is known that in a general interaction between light and electrons in a substance, a substance has an inherent plasma frequency, light having a wavelength longer than this frequency is reflected, and light having a shorter wavelength is transmitted. There is. The plasma frequency ω p is expressed by equation (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. Generally, as the conduction electron density increases, the plasma frequency also increases, so that light on the short wavelength side is also reflected. The conduction electron density is 10 22 / cm 3 for metal and 10 20 / c for antimony tin oxide.
Since the metal has a m 3 level, the reflectance is already high in the visible light region, but in antimony tin oxide, visible light is transmitted and the reflectance is high in the near infrared region, so it can be used as a solar radiation shielding film. .
【００２６】アンチモン錫酸化物はアンチモンのドープ
量、焼成温度等によってその粉体色が微妙に変化する。
例えば、焼成温度が４００℃以下または１０００℃以
上、またはアンチモン添加量が１重量％未満の場合には
Ｌ*がより高い方へ変化し、形成される日射遮蔽膜の日
射遮蔽機能が低下する。これは、アンチモンのドープ
量、焼成温度等が、アンチモン錫酸化物粒子の表面付近
における電子の状態、粒子表面の状態を規定し、さらに
この電子の状態、粒子表面の状態が粉体色に反映してい
るためであると考えられる。さらに残留不純物に関して
残留量が１．５重量％を超えなければ、形成された日射
遮蔽膜の日射遮蔽膜機能が低下したり、ヘイズ値が上昇
することがないので、１．５重量％以下であることが好
ましい。加えて、残留不純物として例えば塩素イオンが
１．５重量％以上残留していると、アンチモン錫酸化物
の調製工程中の焼成工程において、アンチモンの固溶が
阻害されると考えられる。そして、焼成工程においてア
ンチモンの固溶が阻害された場合、得られたアンチモン
錫酸化物粒子は、所望の光学的特性を示さない。この結
果、アンチモン錫酸化物が、特定の範囲の粉体色を有
し、特定の範囲の比表面積を有し、残留不純物量が所定
値以下であるとき、このアンチモン錫酸化物を含有する
日射遮蔽膜は、可視光領域に高い透過率を持つととも
に、可視光領域に近い近赤外域においては強いプラズマ
吸収を発現して低い日射透過率を持ち、かつヘイズ値が
極めて低くなるという優れた効果を発揮しているものと
考えられる。The powder color of antimony tin oxide slightly changes depending on the doping amount of antimony, the firing temperature, and the like.
For example, when the firing temperature is 400 ° C. or lower, or 1000 ° C. or higher, or when the amount of antimony added is less than 1% by weight, L * changes to a higher side, and the solar radiation shielding function of the formed solar radiation shielding film deteriorates. This is because the doping amount of antimony, the firing temperature, etc. determine the electron state and the particle surface state in the vicinity of the surface of the antimony tin oxide particles, and the electron state and the particle surface state are reflected in the powder color. It is thought to be because it is doing. Furthermore, if the residual amount of residual impurities does not exceed 1.5% by weight, the solar radiation shielding film function of the formed solar radiation shielding film does not deteriorate and the haze value does not increase. Preferably there is. In addition, if chlorine ions, for example, remain at 1.5 wt% or more as residual impurities, it is considered that solid solution of antimony is hindered in the firing step during the preparation step of antimony tin oxide. When the solid solution of antimony is hindered in the firing step, the obtained antimony tin oxide particles do not show desired optical characteristics. As a result, when the antimony tin oxide has a powder color within a specific range, a specific surface area within a specific range, and the amount of residual impurities is not more than a predetermined value, the solar radiation containing this antimony tin oxide. The shielding film has a high transmittance in the visible light region, exhibits a strong plasma absorption in the near infrared region close to the visible light region, has a low solar radiation transmittance, and has an excellent effect that the haze value becomes extremely low. Is considered to be exerting.
【００２７】本発明に係る日射遮蔽膜形成用塗布液は、
上記の粉体色、比表面積、残留不純物量を有するアンチ
モン錫酸化物粒子を溶媒中に分散したものである。溶媒
は特に限定されるものではなく、塗布条件、塗布環境、
さらに無機バインダーおよび／または樹脂バインダーを
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
の添加も好ましい構成である。The coating solution for forming a solar radiation shielding film according to the present invention is
The antimony tin oxide particles having the above powder color, specific surface area and amount of residual impurities are dispersed in a solvent. The solvent is not particularly limited, coating conditions, coating environment,
When an inorganic binder and / or a resin binder is further contained, it is appropriately selected according to the binder. For example, water, ethanol, propanol, butanol, isopropyl alcohol, isobutyl alcohol,
Various 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. If necessary, acid or alkali may be added to adjust the pH. Further, in order to further improve the dispersion stability of the particles in the coating liquid, addition of various surfactants, coupling agents and the like is also a preferable constitution.
【００２８】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ない。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の装置を使った方法が好ましく
適用できる。調製された塗布液を用いて日射遮蔽膜を形
成したとき、膜の導電性は、アンチモン錫酸化物粒子の
接触個所を経由した導電パスの数による。そこで、例え
ば塗布液に添加する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れば膜の導
電性を低下させ、１０6Ω／□以上の表面抵抗値とする
ことは容易である。The method of dispersing the particles is not particularly limited as long as it is a method of uniformly dispersing the particles in the coating liquid. For example, a method using a device such as a bead mill, a ball mill, a sand mill, a paint shaker or an ultrasonic homogenizer can be preferably applied. When a solar radiation shielding film is formed using the prepared coating liquid, the conductivity of the film depends on the number of conductive paths passing through the contact points of the antimony tin oxide particles. Therefore, for example, if the amount of surfactant or coupling agent added to the coating solution is adjusted, the conductivity of the film will be reduced if the conductive path is partially cut, and the surface resistance value of 10 6 Ω / □ or more will be reduced. Is easy to do.
【００２９】上述した日射遮蔽膜形成用塗布液を、透明
基材上に形成した日射遮蔽膜は、基材上にアンチモン錫
酸化物粒子のみが堆積した膜の構造になる。この膜はこ
のままでも日射遮蔽効果を示すが、上述した粒子の分散
時に無機バインダーおよび／または樹脂バインダーを添
加するのも好ましい構成である。日射遮蔽膜形成用塗布
液へバインダーを添加することで、形成される日射遮蔽
膜において、バインダーの添加量の加減による導電性の
制御、基材上へ塗布された膜の硬化後にアンチモン錫酸
化物粒子の基材への密着性を向上させさらに膜の硬度の
向上を図る等、の効果を与えることができるからであ
る。The solar radiation shielding film obtained by forming the above-mentioned coating liquid for forming a solar radiation shielding film on a transparent substrate has a film structure in which only antimony tin oxide particles are deposited on the substrate. Although this film exhibits the solar radiation shielding effect as it is, it is also a preferable constitution to add an inorganic binder and / or a resin binder at the time of dispersing the above-mentioned particles. By adding a binder to the coating solution for forming the solar radiation shielding film, in the solar radiation shielding film to be formed, the conductivity is controlled by adjusting the addition amount of the binder, and the antimony tin oxide is cured after the film coated on the substrate is cured. This is because such effects as improving the adhesion of the particles to the base material and further improving the hardness of the film can be provided.
【００３０】上記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 above-mentioned inorganic binder or resin binder is not particularly limited, but as the inorganic binder, a metal alkoxide of silicon, zirconium, titanium, or aluminum, or a partially hydrolyzed polycondensation product or organosilazane thereof is used. As the resin binder, a thermoplastic resin such as an acrylic resin or a thermosetting resin such as an epoxy resin can be used.
【００３１】さらに、このようにして得られた膜上に、
珪素、ジルコニウム、チタン、またはアルミニウムの金
属アルコキシド、またはこれらの部分加水分解縮重合物
を有する塗布液を塗布した後、加熱して、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を有す
るコーティング膜を形成し多層膜とするのも好ましい構
成である。この構成を採ることにより、コーティング成
分が第１層のアンチモン錫酸化物粒子の堆積した間隙を
埋めて成膜され、可視光の屈折を抑制するため、膜のヘ
イズがより低減して可視光透過率が向上し、また粒子の
基材への密着性が向上するからである。Further, on the film thus obtained,
A coating film containing a metal alkoxide of silicon, zirconium, titanium, or aluminum, or a partially hydrolyzed polycondensate thereof is applied and then heated to form a coating film containing an oxide of silicon, zirconium, titanium, or aluminum. It is also a preferable structure to form a multilayer film. By adopting this configuration, the coating component is formed by filling the gaps in which the antimony tin oxide particles of the first layer are deposited, and suppressing the refraction of visible light, so that the haze of the film is further reduced and the visible light is transmitted. This is because the rate is improved and the adhesion of the particles to the base material is improved.
【００３２】ここで、アンチモン錫酸化物粒子単体ある
いはアンチモン錫酸化物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
るコーティング膜を形成する方法としては、成膜操作の
容易さやコストの観点から塗布法が有効である。コーテ
ィング液は、水やアルコール等の溶媒中に、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
換算で全コーティング液中の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
整することも好ましい。このようなコーティング液を、
アンチモン錫酸化物粒子を主成分とする膜上へ、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形成する
ことが可能である。さらに加えて、本発明に係る塗布液
に使用するバインダー成分またはコーティング液の成分
として、オルガノシラザン溶液を用いるのも好ましい。Here, a coating composed of a metal alkoxide of silicon, zirconium, titanium, or aluminum or a partially hydrolyzed polycondensate thereof is formed on a film containing antimony tin oxide particles alone or an antimony tin oxide particle as a main component. As a method of forming a film, a coating method is effective from the viewpoint of easiness of film forming operation and cost. The coating liquid contains, in a solvent such as water or alcohol, one or more kinds of metal alkoxides of silicon, zirconium, titanium, and aluminum, and partially hydrolyzed polycondensates thereof, the content of which is after heating. It is preferably 40% by weight or less of the total coating liquid in terms of the obtained oxide. It is also preferable to add acid or alkali to adjust the pH, if necessary. Such a coating liquid,
It is possible to easily form an oxide coating film of silicon, zirconium, titanium, aluminum or the like by applying the second layer on a film containing antimony tin oxide particles as a main component and heating. In addition, it is also preferable to use an organosilazane solution as a binder component or a coating liquid component used in the coating liquid according to the present invention.
【００３３】本発明に係る日射遮蔽膜成膜用塗布液、お
よび前記コーティング液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
に塗布する方法が好ましく適用できる。The coating solution for forming the solar radiation shielding film according to the present invention and the method for applying the coating solution are not particularly limited. For example, spin coating method, bar coating method, spray coating method, dip coating method, screen printing method, roll coating method, flow coating method, and the like can be preferably applied to apply the treatment liquid evenly and thinly.
【００３４】無機バインダーやコーティング膜として、
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日射
遮蔽膜成膜用塗布液の塗布後の基材加熱温度は、１００
℃未満であると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、１００℃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。As an inorganic binder or coating film,
The substrate heating temperature after application of the coating solution for forming a solar radiation shielding film containing a metal alkoxide of silicon, zirconium, titanium, or aluminum and a hydrolysis polymer thereof is 100.
If the temperature is lower than ℃, the polymerization reaction of alkoxide or its hydrolyzed polymer contained in the coating film often remains uncompleted, and water or organic solvent remains in the film and the visible light transmission of the film after heating. The temperature is preferably 100 ° C. or higher, and more preferably, the heating is performed at the boiling point or higher of the solvent in the coating liquid, as it causes a decrease in the rate.
【００３５】日射遮蔽膜成膜用塗布液へ樹脂バインダー
を添加した場合は、それぞれの樹脂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。この構成を採る
と、既存の窓ガラス等への現場での塗布が可能である。When a resin binder is added to the coating solution for forming the solar radiation shielding film, it may be cured according to the curing method of each resin. For example, an ultraviolet curable resin may be appropriately irradiated with ultraviolet rays, and a room temperature curable resin may be left as it is after being applied. By adopting this configuration, it is possible to apply to existing window glass etc. on site.
【００３６】本発明に係る日射遮蔽膜では、膜中にアン
チモン錫酸化物粒子が分散している、このため物理的成
膜法により成膜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。ここで可視光領域の反射をさらに抑制した
い場合には、本発明の日射遮蔽膜の上に、ＳｉＯ2やＭ
ｇＦ2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 solar radiation shielding film according to the present invention, the antimony tin oxide particles are dispersed in the film. Therefore, crystals are densely formed in the film like an oxide thin film formed by a physical film forming method. Compared with a film having a mirror-like surface filled with, there is less reflection in the visible light region, and it is possible to avoid exhibiting a glaring appearance. Here, if it is desired to further suppress the reflection in the visible light region, SiO 2 or M is formed on the solar radiation shielding film of the present invention.
By forming a film having a low refractive index such as gF 2 , a multilayer film having a luminous reflectance of 1% or less can be easily obtained.
【００３７】本発明に係るアンチモン錫酸化物粒子、日
射遮蔽膜形成用塗布液、日射遮蔽膜へ、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粒子、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
添加するのも好ましい構成である。In order to impart a further ultraviolet ray shielding function to the antimony tin oxide particles, the coating solution for forming a solar radiation shielding film, and the solar radiation shielding film according to the present invention, particles of inorganic titanium oxide, zinc oxide, cerium oxide, etc., It is also a preferable configuration to add one kind or two or more kinds of organic benzophenone, benzotriazole and the like.
【００３８】本発明に係る日射遮蔽膜は、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成膜さ
れ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。さらに、アンチモン錫酸
化物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ず好ま
しい。上記のようにして形成した本発明に係る日射遮蔽
膜は、可視光透過率８０％以上としたとき、波長３００
〜２１００ｎｍの赤外光に対する日射透過率が６５％未
満で、ヘイズ値も１％未満である日射遮蔽膜を実現し
た。Since the solar radiation shielding film according to the present invention is not formed by utilizing decomposition of the coating components or chemical reaction due to heat during baking, it forms a transparent film having stable characteristics and a uniform film thickness. can do. Furthermore, since antimony tin oxide particles are an inorganic material, they have much higher weather resistance than organic materials. For example, even when used in areas exposed to sunlight (ultraviolet rays), there is almost no deterioration in color or various functions. preferable. The solar radiation shielding film according to the present invention formed as described above has a wavelength of 300 when the visible light transmittance is 80% or more.
A solar radiation shielding film having a solar radiation transmittance of less than 65% for infrared light of ˜2100 nm and a haze value of less than 1% was realized.
【００３９】（実施例）
（アンチモン錫酸化物の調製）本発明に係るアンチモン
錫酸化物ａ〜ｊの調製方法には各種の方法があるが、こ
こではその一例について説明する。尚、本発明の日射遮
蔽材料において、酸化錫に対する元素換算でのアンチモ
ン含有量は１〜１５重量％が好ましい。(Example) (Preparation of antimony tin oxide) There are various methods for preparing the antimony tin oxides a to j according to the present invention, and one example thereof will be described here. In the solar radiation shielding material of the present invention, the content of antimony in terms of element with respect to tin oxide is preferably 1 to 15% by weight.
【００４０】本発明で沈殿剤として用いるアルカリ溶液
として、炭酸水素アンモニウム、アンモニア水、水酸化
ナトリウム、水酸化カリウム、等の各水溶液が挙げられ
るが、特に、炭酸水素アンモニウムやアンモニア水が好
ましい。そしてこのアルカリ溶液のアルカリ濃度は、塩
化錫と塩化アンチモンが水酸化物となるのに必要な化学
当量以上あればよいが、より好ましくは当量〜当量×
１．５倍の範囲である。Examples of the alkaline solution used as the precipitant in the present invention include aqueous solutions of ammonium hydrogen carbonate, aqueous ammonia, sodium hydroxide, potassium hydroxide, and the like, with ammonium hydrogen carbonate and aqueous ammonia being particularly preferred. The alkali concentration of this alkaline solution may be at least the chemical equivalent required for tin chloride and antimony chloride to become hydroxides, but more preferably equivalent to equivalent x
The range is 1.5 times.
【００４１】本発明では、塩化錫を溶解した水溶液の温
度を５０℃以下とし、この水溶液中へ、塩化アンチモン
を溶解したアルコール溶液とアルカリ溶液とを並行滴下
する。In the present invention, the temperature of the aqueous solution in which tin chloride is dissolved is set to 50 ° C. or lower, and the alcohol solution in which antimony chloride is dissolved and the alkaline solution are dropped in parallel into this aqueous solution.
【００４２】前記アルコール溶液とアルカリ溶液との滴
下時間は、３０分間未満で終了してよい。滴下終了後も
系内の均一化を図るために、水溶液の攪拌を継続して行
うが、そのときの水溶液の温度は、共沈の際の温度と同
温とし５０℃以下とすることが好ましい。攪拌の継続時
間は特に限定されないが、生産性の観点から、好ましく
は３０分間以下、あるいは１５分間以下でもよい。The dropping time of the alcohol solution and the alkaline solution may be less than 30 minutes. After the dropping, the aqueous solution is continuously stirred in order to homogenize the inside of the system, and the temperature of the aqueous solution at that time is preferably the same as the temperature at the time of coprecipitation and 50 ° C. or less. . The duration of stirring is not particularly limited, but from the viewpoint of productivity, it may be 30 minutes or less, or 15 minutes or less.
【００４３】得られたアンチモン錫酸化物共沈物はデカ
ンテーションを繰り返し行うことによって、塩素イオン
が０．２重量％以下になるまで十分洗浄した後、乾燥す
る。ここで不純物としての塩素イオンが１．５重量％以
上残留すると、次工程の焼成工程において、アンチモン
の固溶が阻害され、調製されたアンチモン錫酸化物が所
望の光学的特性を示さなくなるからである。The antimony tin oxide coprecipitate thus obtained is repeatedly washed by decantation until the chlorine ion content is 0.2% by weight or less, and then dried. If 1.5% by weight or more of chlorine ions as impurities remain here, the solid solution of antimony is hindered in the subsequent firing step, and the prepared antimony tin oxide does not exhibit desired optical characteristics. is there.
【００４４】乾燥後のアンチモン錫酸化物共沈物を大気
雰囲気下にて６００〜１０００℃で、３０分〜５時間焼
成しアンチモン錫酸化物を得た。図１に記載したアンチ
モン錫酸化物の焼成条件は、ａが７００℃で１時間、ｂ
が８００℃で１時間、ｃが６００℃で１時間、ｄが５０
０℃で１時間、ｅが５００℃で２時間、ｆが４００℃で
１時間、ｇが７００℃で１時間、ｈが９００℃で１時
間、ｉが７００℃で１時間、ｊが７００℃で１時間であ
る。尚、試料ｉのみ、焼成前の乾燥をスプレー乾燥で行
った。また、アンチモンの含有量はｅが８重量％、ｊが
６重量％、その他は１０重量％である。得られたアンチ
モン錫酸化物の粉体色は、光源として、標準光源Ｃ，１
０・視野を用い、日立製作所（株）製の分光光度系Ｕ−
４０００を用いて測定した。得られたアンチモン錫酸化
物は、暗青色を呈していた。The dried antimony tin oxide coprecipitate was calcined in the atmosphere at 600 to 1000 ° C. for 30 minutes to 5 hours to obtain antimony tin oxide. The firing conditions for the antimony tin oxide shown in FIG. 1 are that a is 700 ° C. for 1 hour, and b is
Is 800 ° C for 1 hour, c is 600 ° C for 1 hour, d is 50
0 ° C. for 1 hour, e is 500 ° C. for 2 hours, f is 400 ° C. for 1 hour, g is 700 ° C. for 1 hour, h is 900 ° C. for 1 hour, i is 700 ° C. for 1 hour, j is 700 ° C. It is one hour. Only sample i was dried by spray drying before firing. The content of antimony is 8% by weight for e, 6% by weight for j, and 10% by weight for others. The powder color of the obtained antimony tin oxide is the standard light source C, 1 as the light source.
0-field of view, Hitachi Ltd. spectrophotometric system U-
It measured using 4000. The obtained antimony tin oxide had a dark blue color.
【００４５】尚、アンチモン錫酸化物の調製法方法とし
ては、この例以外にも、Ｓｎ（ＯＣ 4Ｈ9）4とＳｂ（Ｏ
Ｃ4Ｈ9）3とを含むｎ−ブタノール溶液へ加水分解に必
要な理論水量の１．１倍の水を添加して加水分解させた
後、乾燥・焼成するアルコキシド加水分解法等、種々の
方法を用いることができる。As a method for preparing antimony tin oxide,
In addition to this example, Sn (OC FourH9)FourAnd Sb (O
CFourH9)3Necessary for hydrolysis into an n-butanol solution containing and
Hydrolysis was performed by adding 1.1 times the required theoretical amount of water.
Various methods such as alkoxide hydrolysis method of drying and baking afterwards
Any method can be used.
【００４６】（日射遮蔽膜形成用塗布液の調製）前記得
られたアンチモン錫酸化物ａ〜ｊ：２０重量％、トルエ
ン：７０重量％、分散剤：１０重量％を秤量した。一
方、ペイントシェーカーに充填率６３％相当の０．３ｍ
ｍφのジルコニアビーズを装填し、そこへ前記秤量物を
投入し、１２時間分散させた。次に、この分散物７７．
７重量％へ、バインダーとしてアクリル系ＵＶ硬化樹脂
（固形分７０％）を２２．３重量％を添加して日射遮蔽
膜形成用塗布液を得た。(Preparation of coating solution for forming solar radiation shielding film) The obtained antimony tin oxides a to j: 20% by weight, toluene: 70% by weight, and dispersant: 10% by weight were weighed. On the other hand, a paint shaker with a filling rate of 63% is equivalent to 0.3 m.
Mφ zirconia beads were loaded, and the weighed material was put therein and dispersed for 12 hours. This dispersion 77.
22.3% by weight of an acrylic UV curable resin (solid content 70%) was added as a binder to 7% by weight to obtain a coating solution for forming a solar radiation shielding film.
【００４７】（日射遮蔽膜の調製）前記日射遮蔽膜形成
用塗布液を、バーコーター法により５０μｍ厚のＰＥＴ
フィルム上へ塗布した。塗布の際には、番手６０、２
４、６の３種のバーを使用し３種類の膜厚で塗布した。
塗布した膜を８０℃で３０秒間乾燥した後、紫外光を照
射して、図１に示すように、アンチモン錫酸化物の試料
ａ〜ｊより日射遮蔽膜の試料Ａ〜Ｊを得た。(Preparation of solar radiation shielding film) The coating liquid for forming the solar radiation shielding film was applied to a PET film having a thickness of 50 μm by a bar coater method.
It was applied onto a film. When applying, count 60, 2
Coating was performed with three kinds of film thickness using three kinds of bars of Nos. 4 and 6.
The coated film was dried at 80 ° C. for 30 seconds and then irradiated with ultraviolet light to obtain, as shown in FIG. 1, samples A to J of the solar radiation shielding film from samples a to j of antimony tin oxide.
【００４８】（光学特性の測定）得られた日射遮蔽膜Ａ
〜Ｊの、可視光透過率および波長３００〜２１００ｎｍ
の赤外光に対する日射透過率は、日立製作所（株）製の
分光光度系Ｕ−４０００を用いて測定し、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。日射透過率およびヘイズ値の評価においては、前
記３種の膜厚を有する日射遮蔽膜が可視光透過率８０％
を示すときの膜厚を算定して規格化し、その規格化した
膜厚における日射透過率およびヘイズ値を、前記膜厚の
３点プロットから算出して求めた。(Measurement of Optical Properties) Obtained Solar Shielding Film A
To J, visible light transmittance and wavelength 300 to 2100 nm
The solar radiation transmittance to infrared light of is measured using a spectrophotometric system U-4000 manufactured by Hitachi, Ltd., and the haze value is
It was measured using HR-200 manufactured by Murakami Color Research Laboratory. In the evaluation of the solar radiation transmittance and haze value, the solar radiation shielding film having the above-mentioned three types of film thickness has a visible light transmittance of 80%.
Was calculated and standardized, and the solar radiation transmittance and the haze value in the standardized film thickness were calculated and calculated from a three-point plot of the film thickness.
【００４９】得られた日射遮蔽膜Ａ〜Ｊの、光学的特性
の結果を図１に示す。図１は、上述したアンチモン錫酸
化物の試料ａ〜ｊの粉体色、比表面積、残留不純物の測
定結果と、試料ａ〜ｊを用いて成膜した日射遮蔽膜試料
である膜Ａ〜Ｊの光学特性を測定した結果とを並記した
一覧表である。図１に示すように、膜Ａ、膜Ｂ、膜Ｈ、
膜I、膜Ｊはいずれも日射透過率が６５％未満で、かつ
ヘイズ値が１％未満であった。一方、比較例の膜Ｃ〜Ｆ
は、いずれもヘイズ値は１％未満であるが、日射透過率
は６５％を超えるものであった。また膜Ｇは、日射透過
率は６５％未満であるがヘイズ値が１％を超えるもので
あった。以上のことより、Ｌ*ａ*ｂ*表色系による粉体
色のＬ*が４５〜５５、ａ*が−３．５〜−２、ｂ*が−
８〜−４であり、かつ比表面積が５〜５５ｍ2／ｇで、
かつ残留不純物量が１．５重量％以下であるアンチモン
錫酸化物粒子より調製した日射遮蔽膜は、可視光透過率
を８０％に規格化したとき、波長３００〜２１００ｎｍ
の赤外光に対する日射透過率が６５％未満で、ヘイズ値
も１％未満であるという、優れた光学特性を有している
ことが判明した。The results of the optical characteristics of the obtained solar radiation shielding films A to J are shown in FIG. FIG. 1 shows the measurement results of the powder color, the specific surface area, and the residual impurities of the above-mentioned antimony tin oxide samples a to j, and the films A to J which are the solar radiation shielding film samples formed by using the samples a to j. 3 is a list in which the results of measuring the optical characteristics of (1) and (2) are listed together. As shown in FIG. 1, the film A, the film B, the film H,
Both the film I and the film J had a solar radiation transmittance of less than 65% and a haze value of less than 1%. On the other hand, the films C to F of the comparative example
In all cases, the haze value was less than 1%, but the solar radiation transmittance was more than 65%. Further, the film G had a solar radiation transmittance of less than 65% but a haze value of more than 1%. From the above, L * a * b * of the powder color by colorimetric system L * is 45 to 55, a * is -3.5~-2, b * is -
8 to -4 and a specific surface area of 5 to 55 m 2 / g,
The solar radiation shielding film prepared from antimony tin oxide particles having a residual impurity amount of 1.5% by weight or less has a wavelength of 300 to 2100 nm when the visible light transmittance is normalized to 80%.
It was found that the solar cell had excellent optical characteristics that the solar radiation transmittance for infrared light was less than 65% and the haze value was less than 1%.
【００５０】[0050]
【発明の効果】以上、詳述したように本発明は、高い可
視光透過率と低い日射透過率とを有しながら、ヘイズ値
が低いという光学特性を有する膜を形成できるアンチモ
ン錫酸化物として、粉体色がＬ*４５〜５５、ａ*が−
３．５〜−２、ｂ*が−８〜−４．１であり、かつ比表
面積が５〜５５ｍ2／ｇで、残留不純物量が１．５重量
％以下であるという特徴を有しているものを調製した。
このアンチモン錫酸化物を用いて日射遮蔽膜形成用塗布
液を調製し日射遮蔽膜を形成したところ、高い可視光透
過率と低い日射透過率とを有しながら、ヘイズ値が低い
日射遮蔽膜を形成することができた。INDUSTRIAL APPLICABILITY As described above in detail, the present invention provides an antimony tin oxide capable of forming a film having a high visible light transmittance and a low solar radiation transmittance while having a low haze optical property. , Powder color is L * 45-55, a * is −
3.5 to -2, b * is -8 to -4.1, the specific surface area is 5 to 55 m 2 / g, and the amount of residual impurities is 1.5% by weight or less. Was prepared.
When a solar radiation shielding film was formed by preparing a coating liquid for forming a solar radiation shielding film using this antimony tin oxide, a solar radiation shielding film having a low haze value while having a high visible light transmittance and a low solar radiation transmittance. Could be formed.
【図１】調製したアンチモン錫酸化物の粉体色、比表面
積、不純物量と、成膜後の光学特性測定結果とを記載し
た表である。FIG. 1 is a table showing the powder color, the specific surface area, the amount of impurities of the prepared antimony tin oxide, and the optical property measurement results after film formation.
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4G048 AA03 AB02 AB05 AC08 AD02 AD06 AE05 4J038 AA011 CG001 DB001 HA146 HA216 MA10 NA19 PB05 ─────────────────────────────────────────────────── ─── Continued front page F-term (reference) 4G048 AA03 AB02 AB05 AC08 AD02 AD06 AE05 4J038 AA011 CG001 DB001 HA146 HA216 MA10 NA19 PB05
Claims (7)
５〜５５、ａ*が−３．５〜−２、ｂ*が−８〜−４であ
り、かつ比表面積が５〜５５ｍ2／ｇで、かつ残留不純
物量が１．５重量％以下であることを特徴とする日射遮
蔽用アンチモン錫酸化物粒子。1. A L * a * b * of the powder color by colorimetric system L * 4
5 to 55, a * is -3.5~-2, b * is -8-4, and a specific surface area of 5~55m 2 / g, and in the amount of residual impurities 1.5 wt% or less Antimony tin oxide particles for solar radiation shielding, characterized by being present.
錫酸化物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。2. A coating solution for forming a solar radiation shielding film, comprising the antimony tin oxide particles for solar radiation shielding according to claim 1 dispersed in a solvent.
び／または樹脂バインダーを含有することを特徴とする
請求項２に記載の日射遮蔽膜形成用塗布液。3. The coating liquid for forming a solar radiation shielding film according to claim 2, which contains an inorganic binder and / or a resin binder as the binder.
成用塗布液から形成されたことを特徴とする日射遮蔽
膜。4. A solar radiation shielding film formed from the coating liquid for forming a solar radiation shielding film according to claim 2 or 3.
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日射遮蔽膜。5. A solar shading film, characterized in that an oxide film of silicon, zirconium, titanium, or aluminum is formed on the solar shading film according to claim 4.
域３００〜２１００ｎｍにおける日射透過率が６５％未
満で、かつヘイズ値が１％未満であることを特徴とする
請求項４または５記載の日射遮蔽膜。6. A visible light transmittance of 80% or more, a solar radiation transmittance of less than 65% in a wavelength range of 300 to 2100 nm, and a haze value of less than 1%. The solar radiation shielding film described.
遮蔽膜が形成されていることを特徴とする日射遮蔽用透
明基材。7. A transparent substrate for solar radiation shielding, comprising the solar radiation shielding film according to any one of claims 4 to 6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002281196A JP2003176132A (en) | 2001-09-28 | 2002-09-26 | Antimony-tin oxide particle for shielding insolation, coating solution for forming insolation shielding film and insolation shielding film |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001302067 | 2001-09-28 | ||
| JP2001-302067 | 2001-09-28 | ||
| JP2002281196A JP2003176132A (en) | 2001-09-28 | 2002-09-26 | Antimony-tin oxide particle for shielding insolation, coating solution for forming insolation shielding film and insolation shielding film |
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| Publication Number | Publication Date |
|---|---|
| JP2003176132A true JP2003176132A (en) | 2003-06-24 |
Family
ID=26623343
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002281196A Pending JP2003176132A (en) | 2001-09-28 | 2002-09-26 | Antimony-tin oxide particle for shielding insolation, coating solution for forming insolation shielding film and insolation shielding film |
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