JP2021075676A - Composite tungsten oxide fine particle dispersion and composite tungsten oxide fine particle dispersion liquid - Google Patents
Composite tungsten oxide fine particle dispersion and composite tungsten oxide fine particle dispersion liquid Download PDFInfo
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- JP2021075676A JP2021075676A JP2020052583A JP2020052583A JP2021075676A JP 2021075676 A JP2021075676 A JP 2021075676A JP 2020052583 A JP2020052583 A JP 2020052583A JP 2020052583 A JP2020052583 A JP 2020052583A JP 2021075676 A JP2021075676 A JP 2021075676A
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- Prior art keywords
- tungsten oxide
- oxide fine
- composite tungsten
- fine particle
- particle dispersion
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- 239000010419 fine particle Substances 0.000 title claims abstract description 187
- 239000002131 composite material Substances 0.000 title claims abstract description 175
- 229910001930 tungsten oxide Inorganic materials 0.000 title claims abstract description 175
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- 239000006185 dispersion Substances 0.000 title claims abstract description 113
- 239000007788 liquid Substances 0.000 title claims abstract description 55
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical group [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 17
- 229910052721 tungsten Inorganic materials 0.000 claims description 16
- 239000010937 tungsten Substances 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
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Images
Abstract
Description
本発明は、可視光透過率が良好で、且つ優れた赤外線吸収特性を有しながら、所定の色味を有する複合タングステン酸化物微粒子分散体および複合タングステン酸化物微粒子分散液に関する。 The present invention relates to a composite tungsten oxide fine particle dispersion and a composite tungsten oxide fine particle dispersion having a predetermined color while having good visible light transmittance and excellent infrared absorption characteristics.
近年、赤外線吸収体の需要が急増しており、赤外線吸収体に関する多数の特許出願が為されている。これらの出願を機能的観点から俯瞰すると、例えば、各種建築物や車両の窓材等の分野において、可視光線を十分に取り入れながら赤外領域の光を遮蔽することにより、明るさを維持しつつ室内の温度上昇を抑制することを目的としたものがある。 In recent years, the demand for infrared absorbers has increased rapidly, and many patent applications have been filed for infrared absorbers. Looking at these applications from a functional point of view, for example, in the fields of window materials for various buildings and vehicles, while maintaining brightness by blocking light in the infrared region while sufficiently taking in visible light. Some are aimed at suppressing the temperature rise in the room.
本発明者等は特許文献１において、赤外線遮蔽材料微粒子が媒体中に分散してなる赤外線遮蔽材料微粒子分散体、および当該赤外線遮蔽材料微粒子分散体の優れた光学特性、導電性、製造方法について開示した。中でも、当該赤外線遮蔽材料微粒子分散体の赤外線遮蔽特性は、従来の遮蔽材料よりも卓越したものであった。 The present inventors disclose in Patent Document 1 an infrared shielding material fine particle dispersion in which infrared shielding material fine particles are dispersed in a medium, and excellent optical properties, conductivity, and a manufacturing method of the infrared shielding material fine particle dispersion. did. Above all, the infrared shielding property of the infrared shielding material fine particle dispersion was superior to that of the conventional shielding material.
上述した赤外線遮蔽材料微粒子は、一般式ＷｙＯｚ（但し、Ｗはタングステン、Ｏは酸素、２．２≦ｚ／ｙ≦２．９９９）で表記されるタングステン酸化物の微粒子、または／および、一般式ＭｘＷｙＯｚ（但し、Ｍは、Ｈ、Ｈｅ、アルカリ金属、アルカリ土類金属、希土類元素、Ｍｇ、Ｚｒ、Ｃｒ、Ｍｎ、Ｆｅ、Ｒｕ、Ｃｏ、Ｒｈ、Ｉｒ、Ｎｉ、Ｐｄ、Ｐｔ、Ｃｕ、Ａｇ、Ａｕ、Ｚｎ、Ｃｄ、Ａｌ、Ｇａ、Ｉｎ、Ｔｌ、Ｓｉ、Ｇｅ、Ｓｎ、Ｐｂ、Ｓｂ、Ｂ、Ｆ、Ｐ、Ｓ、Ｓｅ、Ｂｒ、Ｔｅ、Ｔｉ、Ｎｂ、Ｖ、Ｍｏ、Ｔａ、Ｒｅ、Ｂｅ、Ｈｆ、Ｏｓ、Ｂｉ、Ｉのうちから選択される１種類以上の元素、Ｗはタングステン、Ｏは酸素、０．００１≦ｘ／ｙ≦１、２．２≦ｚ／ｙ≦３．０）で表記される複合タングステン酸化物の微粒子であって、当該赤外線遮蔽材料微粒子の粒子直径が１ｎｍ以上８００ｎｍ以下である。 The above-mentioned infrared shielding material fine particles are the fine particles of tungsten oxide represented by the general formula WyOz (where W is tungsten and O is oxygen, 2.2 ≦ z / y ≦ 2.999), and / and the general formula. MxWyOz (However, M is H, He, alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, One or more elements selected from Be, Hf, Os, Bi, and I, W is tungsten, O is oxygen, 0.001 ≦ x / y ≦ 1, 2.2 ≦ z / y ≦ 3.0 ), The particle diameter of the infrared shielding material fine particles is 1 nm or more and 800 nm or less.
特許文献２には、複合タングステン酸化物の微粒子または／および６ホウ化物の微粒子が分散された紫外線硬化樹脂が、ガラス板間に充填された合わせガラスであって、優れた赤外線吸収機能を有しながらヘイズ値が低く、可視光透明性に優れたものが提案されている。
In
しかし、特許文献１、２に開示されている赤外線遮蔽材料微粒子分散体や合わせガラスは、いずれも複合タングステン酸化物を含有している影響で青味を有することから、意匠性の観点から改良が必要とされていた。
However, since the infrared shielding material fine particle dispersion and the laminated glass disclosed in
そこで、例えば特許文献３のように、上述の複合タングステン酸化物と、波長３００〜５００ｎｍの領域に極大吸収を有する化合物とを含有させることで、複合タングステン酸化物特有の青味を抑制または除去した近赤外線遮蔽フィルタが提案されていた。 Therefore, for example, as in Patent Document 3, by incorporating the above-mentioned composite tungsten oxide and a compound having maximum absorption in the wavelength region of 300 to 500 nm, the bluish tint peculiar to the composite tungsten oxide is suppressed or removed. A near-infrared shielding filter has been proposed.
しかしながら、本発明者らの検討によると、例えば特許文献３で開示されている青味を抑制または除去したとされる近赤外線遮蔽フィルタは、青味の抑制が不十分なものであった。
一方、例えば、特許文献４に開示されている赤外線吸収特性を持つ各種のフィルタにおいては、Ｌ＊ａ＊ｂ＊表色系のうちｂ＊が負の値を示していた。ところが、当該フィルタにおいて複合タングステン酸化物と共に用いられている波長３００〜５００ｎｍの領域に極大吸収を有する化合物が有機系材料であるため耐候性が低く、各種建築物や車両の窓材等の分野における使用環境に耐えられるものではなかった。
However, according to the study by the present inventors, for example, the near-infrared ray shielding filter disclosed in Patent Document 3 which suppresses or removes the bluish tint is insufficiently suppressed in the bluish tint.
On the other hand, for example, in various filters having infrared absorption characteristics disclosed in Patent Document 4, b * in the L * a * b * color system showed a negative value. However, since the compound used together with the composite tungsten oxide in the filter and having maximum absorption in the wavelength region of 300 to 500 nm is an organic material, it has low weather resistance, and is used in fields such as window materials for various buildings and vehicles. It could not withstand the usage environment.
ここで本発明者らは、複合タングステン酸化物微粒子において、当該微粒子の粒径が増大する程、ｂ＊の値は負から正へ変化することを知見した。そして本発明等らは、複合タングステン酸化物微粒子の粒径を増大させることで上述の問題解決を図った。ところが、当該微粒子の粒径が増大する程、短波長領域の光散乱が増大し、複合タングステン酸化物微粒子の可視光透過性が低下して、優れた赤外線吸収特性を担保することが出来なくなることを知見した。 Here, the present inventors have found that in the composite tungsten oxide fine particles, the value of b * changes from negative to positive as the particle size of the fine particles increases. Then, the present inventions and others have tried to solve the above-mentioned problems by increasing the particle size of the composite tungsten oxide fine particles. However, as the particle size of the fine particles increases, light scattering in the short wavelength region increases, and the visible light transmittance of the composite tungsten oxide fine particles decreases, making it impossible to ensure excellent infrared absorption characteristics. Was found.
本発明は、上述の状況の下で為されたものであり、その解決しようとする課題は、優れた赤外線吸収特性および耐候性を担保しながら、ｂ＊の値が正の値となる程度に青味が抑制された複合タングステン酸化物微粒子分散体および複合タングステン酸化物微粒子分散液を提供することである。 The present invention has been made under the above-mentioned circumstances, and the problem to be solved is to the extent that the value of b * becomes a positive value while ensuring excellent infrared absorption characteristics and weather resistance. It is an object of the present invention to provide the composite tungsten oxide fine particle dispersion and the composite tungsten oxide fine particle dispersion liquid in which the bluish tint is suppressed.
上述の課題を解決する為、本発明者らは優れた赤外線吸収特性および耐候性を担保しつつ、複合タングステン酸化物微粒子が有する青味を除去する構成について研究を行った。その結果、複合タングステン酸化物微粒子分散体および複合タングステン微粒子分散液に、結晶子径が２５ｎｍ以上８５ｎｍ以下である複合タングステン酸化物微粒子を含有させことによって上述の課題を解決することが出来ることに想到し、本発明を完成した。 In order to solve the above-mentioned problems, the present inventors have studied a configuration for removing the bluish tint of the composite tungsten oxide fine particles while ensuring excellent infrared absorption characteristics and weather resistance. As a result, it was conceived that the above-mentioned problems can be solved by containing the composite tungsten oxide fine particles having a crystallite diameter of 25 nm or more and 85 nm or less in the composite tungsten oxide fine particle dispersion and the composite tungsten fine particle dispersion liquid. Then, the present invention was completed.
即ち、上述の課題を解決するための第１の発明は、
結晶子径が２５ｎｍ以上８５ｎｍ以下である複合タングステン酸化物微粒子と、固体媒体とを含む複合タングステン酸化物微粒子分散体である。
That is, the first invention for solving the above-mentioned problems is
It is a composite tungsten oxide fine particle dispersion containing a composite tungsten oxide fine particle having a crystallite diameter of 25 nm or more and 85 nm or less and a solid medium.
本発明に係る複合タングステン酸化物微粒子分散体および複合タングステン酸化物微粒子分散液は、優れた赤外線吸収特性および耐候性を有しながら青味が除去されており、意匠性に優れている。 The composite tungsten oxide fine particle dispersion and the composite tungsten oxide fine particle dispersion according to the present invention have excellent infrared absorption characteristics and weather resistance, but have a bluish tint removed, and are excellent in design.
本発明を実施するための形態について、［１］複合タングステン酸化物微粒子とその製造方法、［２］所定の結晶子径を有する複合タングステン酸化物微粒子分散液とその製造方法、［３］複合タングステン酸化物微粒子分散粉末とその製造方法、［４］複合タングステン酸化物微粒子分散体とその製造方法、の順に説明する。 Regarding the embodiment for carrying out the present invention, [1] composite tungsten oxide fine particles and a method for producing the same, [2] a composite tungsten oxide fine particle dispersion having a predetermined crystallite diameter and a method for producing the same, and [3] composite tungsten. The oxide fine particle dispersion powder and its production method, and [4] the composite tungsten oxide fine particle dispersion and its production method will be described in this order.
［１］複合タングステン酸化物微粒子とその製造方法
一般に、自由電子を含む材料は、プラズマ振動によって波長２００ｎｍから２６００ｎｍの太陽光線の領域周辺の電磁波に反射吸収応答を示すことが知られている。このような物質の粉末を、光の波長より小さい微粒子にすると、可視光領域（波長３８０ｎｍから７８０ｎｍ）の幾何学散乱が低減されて可視光領域の透明性が得られることが知られている。尚、本発明において「透明性」とは、「可視光領域の光に対して散乱が少なく透過性が高い。」という意味で用いている。
[1] Composite tungsten oxide fine particles and a method for producing the same It is generally known that a material containing free electrons exhibits a reflection absorption response to electromagnetic waves around a region of sunlight having a wavelength of 200 nm to 2600 nm due to plasma oscillation. It is known that when the powder of such a substance is made into fine particles smaller than the wavelength of light, geometric scattering in the visible light region (wavelength 380 nm to 780 nm) is reduced and transparency in the visible light region can be obtained. In the present invention, "transparency" is used to mean "less scattering and high transparency with respect to light in the visible light region."
一般に、タングステン酸化物（ＷＯ３）中には有効な自由電子が存在しない為、赤外線領域の吸収反射特性が少なく、赤外線吸収微粒子としては有効ではない。
一方、酸素欠損を持つＷＯ３や、ＷＯ３にＮａ等の陽性元素を添加した複合タングステン酸化物は、導電性材料であり、自由電子を持つ材料であることが知られている。そして、これらの自由電子を持つ材料の単結晶等の分析により、赤外線領域の光に対する自由電子の応答が示唆されている。
In general, since there are no effective free electrons in tungsten oxide (WO 3 ), the absorption and reflection characteristics in the infrared region are small, and it is not effective as infrared absorption fine particles.
On the other hand, WO 3 having an oxygen deficiency and composite tungsten oxide obtained by adding a positive element such as Na to WO 3 are known to be conductive materials and materials having free electrons. Analysis of single crystals and the like of materials having these free electrons suggests the response of free electrons to light in the infrared region.
以下、本発明に係る所定の組成を有する複合タングステン酸化物微粒子（Ａ）と、その製造方法について、（１）複合タングステン酸化物微粒子（Ａ）の組成、（２）複合タングステン酸化物微粒子（Ａ）の結晶構造、（３）複合タングステン酸化物微粒子（Ａ）の光学特性、（４）複合タングステン酸化物微粒子（Ａ）の製造方法、の順に説明する。 Hereinafter, the composite tungsten oxide fine particles (A) having a predetermined composition according to the present invention and the method for producing the same are described in (1) the composition of the composite tungsten oxide fine particles (A) and (2) the composite tungsten oxide fine particles (A). ), (3) Optical characteristics of the composite tungsten oxide fine particles (A), and (4) A method for producing the composite tungsten oxide fine particles (A) will be described in this order.
（１）複合タングステン酸化物微粒子（Ａ）の組成
本発明者等は、当該タングステンと酸素との組成範囲の特定部分において、赤外線吸収微粒子として特に有効な範囲があることを見出し、可視光領域においては透明で、赤外線領域においては吸収を持つ複合タングステン酸化物微粒子に想到した。
(1) Composition of Composite Tungsten Oxide Fine Particles (A) The present inventors have found that there is a particularly effective range as infrared absorbing fine particles in a specific portion of the composition range of the tungsten and oxygen, and in the visible light region. Came up with composite tungsten oxide fine particles that are transparent and have absorption in the infrared region.
また、上述したＷＯ３へ、後述する元素Ｍを添加し複合タングステン酸化物とすることで、当該ＷＯ３中に自由電子が生成され、特に近赤外線領域に自由電子由来の強い吸収特性が発現し、波長１０００ｎｍ付近の赤外線吸収微粒子として有効となる。 Further, by adding the element M described later to the above-mentioned WO 3 to form a composite tungsten oxide, free electrons are generated in the WO 3 , and a strong absorption property derived from the free electrons is exhibited especially in the near infrared region. , Effective as infrared absorbing fine particles having a wavelength of around 1000 nm.
即ち、当該ＷＯ３に対し、酸素量の制御と、自由電子を生成する元素Ｍの添加とを併用することで、より効率の良い複合タングステン酸化物微粒子を得ることが出来る。この酸素量の制御と、自由電子を生成する元素Ｍの添加とを併用した複合タングステン酸化物微粒子の一般式をＭｘＷｙＯｚ（但し、Ｍは、前記Ｍ元素、Ｗはタングステン、Ｏは酸素）と記載したとき、０．００１≦ｘ／ｙ≦１、２．０≦ｚ／ｙ≦３の関係を満たす複合タングステン酸化物微粒子が望ましい。 That is, by using the control of the amount of oxygen and the addition of the element M that generates free electrons in combination with respect to the WO 3, more efficient composite tungsten oxide fine particles can be obtained. The general formula of the composite tungsten oxide fine particles in which the control of the amount of oxygen and the addition of the element M that generates free electrons are used in combination is described as MxWyOz (where M is the M element, W is tungsten, and O is oxygen). When this is done, composite tungsten oxide fine particles satisfying the relationships of 0.001 ≦ x / y ≦ 1 and 2.0 ≦ z / y ≦ 3 are desirable.
まず、元素Ｍの添加量を示すｘ／ｙの値について説明する。
ｘ／ｙの値が０．００１より大きければ、複合タングステン酸化物において十分な量の自由電子が生成され目的とする赤外線吸収効果を得ることが出来る。そして、元素Ｍの添加量が多いほど、自由電子の供給量が増加し、赤外線吸収効率も上昇するが、ｘ／ｙの値が１程度で当該効果も飽和する。また、ｘ／ｙの値が１より小さければ、当該複合タングステン酸化物微粒子中に不純物相が生成されるのを回避できるので好ましい。
First, the value of x / y indicating the amount of the element M added will be described.
If the value of x / y is larger than 0.001, a sufficient amount of free electrons are generated in the composite tungsten oxide, and the desired infrared absorption effect can be obtained. Then, as the amount of the element M added increases, the amount of free electrons supplied increases and the infrared absorption efficiency also increases, but the effect is saturated when the value of x / y is about 1. Further, when the value of x / y is smaller than 1, it is preferable because it is possible to avoid the formation of an impurity phase in the composite tungsten oxide fine particles.
また、元素Ｍは、Ｈ、Ｈｅ、アルカリ金属、アルカリ土類金属、希土類元素、Ｍｇ、Ｚｒ、Ｃｒ、Ｍｎ、Ｆｅ、Ｒｕ、Ｃｏ、Ｒｈ、Ｉｒ、Ｎｉ、Ｐｄ、Ｐｔ、Ｃｕ、Ａｇ、Ａｕ、Ｚｎ、Ｃｄ、Ａｌ、Ｇａ、Ｉｎ、Ｔｌ、Ｓｉ、Ｇｅ、Ｓｎ、Ｐｂ、Ｓｂ、Ｂ、Ｆ、Ｐ、Ｓ、Ｓｅ、Ｂｒ、Ｔｅ、Ｔｉ、Ｎｂ、Ｖ、Ｍｏ、Ｔａ、Ｒｅ、Ｂｅ、Ｈｆ、Ｏｓ、Ｂｉ、Ｉ、Ｙｂのうちから選択される１種類以上であることが好ましい。 The element M is H, He, alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au. , Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be , Hf, Os, Bi, I, Yb, preferably one or more.
ここで、元素Ｍを添加された当該ＭｘＷｙＯｚにおける安定性の観点から、元素Ｍは、アルカリ金属、アルカリ土類金属、希土類元素、Ｍｇ、Ｚｒ、Ｃｒ、Ｍｎ、Ｆｅ、Ｒｕ、Ｃｏ、Ｒｈ、Ｉｒ、Ｎｉ、Ｐｄ、Ｐｔ、Ｃｕ、Ａｇ、Ａｕ、Ｚｎ、Ｃｄ、Ａｌ、Ｇａ、Ｉｎ、Ｔｌ、Ｓｉ、Ｇｅ、Ｓｎ、Ｐｂ、Ｓｂ、Ｂ、Ｆ、Ｐ、Ｓ、Ｓｅ、Ｂｒ、Ｔｅ、Ｔｉ、Ｎｂ、Ｖ、Ｍｏ、Ｔａ、Ｒｅのうちのうちから選択される１種類以上の元素であることがより好ましい。そして、赤外線吸収微粒子としての光学特性、耐候性を向上させる観点から、元素Ｍは、アルカリ土類金属元素、遷移金属元素、４Ｂ族元素、５Ｂ族元素に属するものであることがさらに好ましい。 Here, from the viewpoint of stability in the MxWyOz to which the element M is added, the element M is an alkali metal, an alkaline earth metal, a rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir. , Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti , Nb, V, Mo, Ta, Re, more preferably one or more elements selected from. From the viewpoint of improving the optical properties and weather resistance of the infrared absorbing fine particles, the element M is more preferably one belonging to an alkaline earth metal element, a transition metal element, a group 4B element, or a group 5B element.
酸素量の制御を示すｚ／ｙの値については、２．０≦ｚ／ｙ≦３．０において、上述した元素Ｍの添加量による自由電子の供給がある。この為、２．０≦ｚ／ｙ≦３．０が好ましく、より好ましくは２．２≦ｚ／ｙ≦３．０、さらに好ましくは２．４５≦ｚ／ｙ≦３．０である。 Regarding the value of z / y indicating the control of the amount of oxygen, in 2.0 ≦ z / y ≦ 3.0, there is a supply of free electrons depending on the amount of the element M added as described above. Therefore, 2.0 ≦ z / y ≦ 3.0 is preferable, 2.2 ≦ z / y ≦ 3.0 is more preferable, and 2.45 ≦ z / y ≦ 3.0 is more preferable.
（２）複合タングステン酸化物微粒子（Ａ）の結晶構造
本発明に係る複合タングステン酸化物微粒子（Ａ）が、六方晶の結晶構造を有する場合、当該微粒子の可視光領域の透過が向上し赤外領域の吸収が向上する。この六方晶の結晶構造について、模式的な平面図である図１を参照しながら説明する。
(2) Crystal Structure of Composite Tungsten Oxide Fine Particles (A) When the composite tungsten oxide fine particles (A) according to the present invention have a hexagonal crystal structure, the transmission of the fine particles in the visible light region is improved and infrared rays are present. Area absorption is improved. The crystal structure of this hexagonal crystal will be described with reference to FIG. 1, which is a schematic plan view.
図１において、符号１１で示すＷＯ６単位にて形成される８面体が６個集合して六角形の空隙が構成され、当該空隙中に、符号１２で示す元素Ｍが配置して１箇の単位を構成し、この１箇の単位が多数集合して六方晶の結晶構造を構成する。
そして、可視光領域における光の透過を向上させ、赤外領域における光の吸収を向上させる効果を得る為には、複合タングステン酸化物微粒子中に、図１を用いて説明した単位構造が含まれていれば良く、当該複合タングステン酸化物微粒子（Ａ）が結晶質であっても非晶質であっても構わない。
In FIG. 1, six octahedrons formed by WO 6 units indicated by reference numeral 11 are assembled to form a hexagonal void, and an element M indicated by reference numeral 12 is arranged in the void to form one. Units are formed, and a large number of these one unit are assembled to form a hexagonal crystal structure.
Then, in order to obtain the effect of improving the light transmission in the visible light region and improving the light absorption in the infrared region, the composite tungsten oxide fine particles include the unit structure described with reference to FIG. The composite tungsten oxide fine particles (A) may be crystalline or amorphous.
この六角形の空隙に元素Ｍの陽イオンが添加されて存在するとき、可視光領域における光の透過が向上し、赤外領域における光の吸収が向上する。ここで一般的には、イオン半径の大きな元素Ｍを添加したとき当該六方晶が形成され易い。具体的には、Ｃｓ、Ｋ、Ｒｂ、Ｔｌ、Ｉｎ、Ｂａ、Ｌｉ、Ｃａ、Ｓｒ、Ｆｅ、Ｓｎを添加したとき六方晶が形成され易い。勿論これら以外の元素でも、ＷＯ６単位で形成される六角形の空隙に上述した元素Ｍが存在すれば良く、上述の元素に限定される訳ではない。 When the cation of the element M is added to the hexagonal voids and exists, the transmission of light in the visible light region is improved and the absorption of light in the infrared region is improved. Here, in general, the hexagonal crystal is likely to be formed when the element M having a large ionic radius is added. Specifically, hexagonal crystals are likely to be formed when Cs, K, Rb, Tl, In, Ba, Li, Ca, Sr, Fe, and Sn are added. Of course, elements other than these are not limited to the above-mentioned elements as long as the above-mentioned element M exists in the hexagonal voids formed in WO 6 units.
六方晶の結晶構造を有する複合タングステン酸化物微粒子（Ａ）が均一な結晶構造を有するとき、添加元素Ｍの添加量は、ｘ／ｙの値で０．２以上０．５以下が好ましく、更に好ましくは０．３３である。ｘ／ｙの値が０．３３となることで、上述した元素Ｍが六角形の空隙の全てに配置されると考えられる。 When the composite tungsten oxide fine particles (A) having a hexagonal crystal structure have a uniform crystal structure, the amount of the additive element M added is preferably 0.2 or more and 0.5 or less in terms of x / y, and further. It is preferably 0.33. When the value of x / y is 0.33, it is considered that the above-mentioned element M is arranged in all the hexagonal voids.
また、六方晶以外であって、正方晶、立方晶の複合タングステン酸化物も赤外線吸収微粒子として有効である。結晶構造によって、赤外線領域の吸収位置が変化する傾向があり、立方晶＜正方晶＜六方晶の順に、吸収位置が長波長側に移動する傾向がある。また、それに付随して可視光線領域の吸収が少ないのは、六方晶、正方晶、立方晶の順である。従って、より可視光領域の光を透過し、より赤外線領域の光を吸収する用途には、六方晶の複合タングステン酸化物を用いることが好ましい。ただし、ここで述べた光学特性の傾向は、あくまで大まかな傾向であり、添加元素の種類や、添加量、酸素量によって変化するものであり、本発明がこれに限定されるわけではない。 In addition to hexagonal crystals, tetragonal and cubic composite tungsten oxides are also effective as infrared absorbing fine particles. The absorption position in the infrared region tends to change depending on the crystal structure, and the absorption position tends to move to the longer wavelength side in the order of cubic <tetragonal <hexagonal. Hexagonal, tetragonal, and cubic crystals absorb less in the visible light region. Therefore, it is preferable to use a hexagonal composite tungsten oxide for applications in which light in a more visible light region is transmitted and light in a more infrared region is absorbed. However, the tendency of the optical characteristics described here is only a rough tendency and changes depending on the type of added element, the amount of added element, and the amount of oxygen, and the present invention is not limited to this.
（３）複合タングステン酸化物微粒子（Ａ）の光学特性
本発明に係る複合タングステン酸化物微粒子（Ａ）は、近赤外線領域、特に波長１０００ｎｍ付近の光を大きく吸収するため、その透過色調は青色系となる物が多い。
(3) Optical Characteristics of Composite Tungsten Oxide Fine Particles (A) Since the composite tungsten oxide fine particles (A) according to the present invention largely absorb light in the near infrared region, particularly in the vicinity of a wavelength of 1000 nm, the transmitted color tone is bluish. There are many things that become.
（４）複合タングステン酸化物微粒子（Ａ）の製造方法
本発明に係る複合タングステン酸化物微粒子（Ａ）は、タングステン化合物である出発原料を還元性ガス雰囲気中で熱処理して複合タングステン酸化物微粒子を得、当該微粒子の結晶子径を、上述した所定の値とすることで得ることができる。
以下、本発明に係る複合タングステン酸化物（Ａ）について、（ｉ）出発原料、（ｉｉ）熱処理、の順に説明する。
(4) Method for Producing Composite Tungsten Oxide Fine Particles (A) In the composite tungsten oxide fine particles (A) according to the present invention, a starting material which is a tungsten compound is heat-treated in a reducing gas atmosphere to obtain composite tungsten oxide fine particles. It can be obtained by setting the crystallite diameter of the fine particles to the above-mentioned predetermined value.
Hereinafter, the composite tungsten oxide (A) according to the present invention will be described in the order of (i) starting material and (ii) heat treatment.
（ｉ）出発原料
本発明に係る複合タングステン酸化物の出発原料は、タングステン、元素Ｍそれぞれの単体もしくは化合物を含有する混合物である。タングステン原料としてはタングステン酸粉末、三酸化タングステン粉末、二酸化タングステン粉末、酸化タングステンの水和物粉末、六塩化タングステン粉末、タングステン酸アンモニウム粉末、または、六塩化タングステン粉末をアルコール中に溶解させた後乾燥して得られるタングステン酸化物の水和物粉末、または、六塩化タングステンをアルコール中に溶解させたのち水を添加して沈殿させこれを乾燥して得られるタングステン酸化物の水和物粉末、または、タングステン酸アンモニウム水溶液を乾燥して得られるタングステン化合物粉末、金属タングステン粉末、から選ばれたいずれか１種類以上であることが好ましい。元素Ｍの原料としては、元素Ｍ単体、元素Ｍの塩化物塩、硝酸塩、硫酸塩、シュウ酸塩、酸化物、炭酸塩、タングステン酸塩、水酸化物等が挙げられるが、これらには限定されない。
(I) Starting Material The starting material for the composite tungsten oxide according to the present invention is a simple substance or a mixture containing a compound of tungsten and element M, respectively. As the raw material for tungsten, tungstic acid powder, tungsten trioxide powder, tungsten dioxide powder, tungsten oxide hydrate powder, tungsten hexachloride powder, ammonium tungstate powder, or tungsten hexachloride powder is dissolved in alcohol and then dried. Tungsten oxide hydrate powder obtained in the above, or tungsten oxide hydrate powder obtained by dissolving tungsten hexachloride in alcohol, adding water to precipitate, and drying this. , Any one or more selected from tungsten compound powder and metallic tungsten powder obtained by drying an aqueous solution of ammonium tungstate is preferable. Examples of the raw material of the element M include element M alone, element M chloride salt, nitrate, sulfate, oxalate, oxide, carbonate, tungstate, hydroxide and the like, but are limited thereto. Not done.
上述した出発原料を秤量し、本発明に係る複合タングステン酸化物を、一般式を用いてＭｘＷｙＯｚ（但し、Ｍは、前記Ｍ元素、Ｗはタングステン、Ｏは酸素）と標記したとき、０．００１＜ｘ／ｙ≦１を満たす所定量をもって配合し混合する。このとき、タングステン、元素Ｍに係るそれぞれの原料が出来るだけ均一に、可能ならば分子レベルで均一に混合していることが好ましい。従って、前述の各出発原料は、それぞれ原料溶液の形で混合することがもっとも好ましい。この為、各出発原料は、水や有機溶剤等の溶媒に溶解可能なものであることが好ましい。 When the above-mentioned starting material is weighed and the composite tungsten oxide according to the present invention is labeled as MxWyOz (where M is the M element, W is tungsten, and O is oxygen) using a general formula, 0.001 Mix and mix in a predetermined amount that satisfies <x / y ≦ 1. At this time, it is preferable that the raw materials for tungsten and the element M are mixed as uniformly as possible, preferably at the molecular level. Therefore, it is most preferable that each of the above-mentioned starting materials is mixed in the form of a raw material solution. Therefore, it is preferable that each starting material is soluble in a solvent such as water or an organic solvent.
各出発原料が水や有機溶剤等の溶媒に可溶であれば、各出発原料と溶媒とを十分に混合した後、これらを混合し、さらに当該溶媒を揮発させることで、本発明に係るタングステン化合物の出発原料の混合物を製造することができる。
尤も、各出発原料を可溶な溶媒が準備出来ない場合、各出発原料をボールミル等の公知の手段で十分に均一に混合することによっても、タングステン化合物の出発原料の混合物を製造することが出来る。
If each starting material is soluble in a solvent such as water or an organic solvent, the tungsten according to the present invention is obtained by sufficiently mixing each starting material and the solvent, mixing them, and further volatilizing the solvent. A mixture of starting materials for the compounds can be produced.
However, when a soluble solvent cannot be prepared for each starting material, a mixture of starting materials of the tungsten compound can also be produced by sufficiently and uniformly mixing each starting material by a known means such as a ball mill. ..
（ｉｉ）熱処理
次に、還元性ガス雰囲気中における熱処理について説明する。熱処理温度は、同処理に供する出発原料の量によって適宜選択すればよいが、例えば、３００℃以上９００℃以下で熱処理することが好ましく、５００℃以上８５０℃以下がより好ましい。３００℃以上であれば本発明にかかる六方晶構造を持つ複合タングステン酸化物の生成反応が進行し、９００℃以下であれば六方晶以外の構造を持つ複合タングステン酸化物微粒子や金属タングステンといった意図しない副反応物が生成し難く好ましい。
(Ii) Heat treatment Next, heat treatment in a reducing gas atmosphere will be described. The heat treatment temperature may be appropriately selected depending on the amount of the starting raw material to be subjected to the treatment. For example, the heat treatment is preferably performed at 300 ° C. or higher and 900 ° C. or lower, and more preferably 500 ° C. or higher and 850 ° C. or lower. If the temperature is 300 ° C. or higher, the reaction for producing a composite tungsten oxide having a hexagonal structure according to the present invention proceeds, and if the temperature is 900 ° C. or lower, the composite tungsten oxide fine particles having a structure other than hexagonal or metallic tungsten is not intended. It is preferable that a side reaction product is hard to be formed.
この時の還元性ガスは、特に限定されないが、Ｈ２が好ましい。そして、還元性ガスとしてＨ２を用いる場合は、還元性雰囲気の組成として、熱処理に供する出発原料の量によって適宜選択すればよいが、例えば、Ａｒ、Ｎ２等の不活性ガスにＨ２を体積％で０．１％以上５．０％以下混合したものが好ましい。
必要に応じて、還元性ガス雰囲気中にて還元処理を行った後、不活性ガス雰囲気中にて熱処理を行ってもよい。この場合の不活性ガス雰囲気中での熱処理は４００℃以上１２００℃以下の温度で行うことが好ましい。
The reducing gas at this time is not particularly limited, but H 2 is preferable. When H 2 is used as the reducing gas, the composition of the reducing atmosphere may be appropriately selected depending on the amount of the starting material to be subjected to the heat treatment. For example, H 2 is used for the inert gas such as Ar and N 2. A mixture of 0.1% or more and 5.0% or less in volume% is preferable.
If necessary, the reduction treatment may be carried out in a reducing gas atmosphere, and then the heat treatment may be carried out in an inert gas atmosphere. In this case, the heat treatment in the atmosphere of the inert gas is preferably performed at a temperature of 400 ° C. or higher and 1200 ° C. or lower.
［２］所定の結晶子径を有する複合タングステン酸化物微粒子分散液とその製造方法
複合タングステン酸化物微粒子（Ａ）、即ち赤外線吸収微粒子を液状の溶媒中に分散させることで、複合タングステン酸化物微粒子分散液を製造することが出来る。本発明においては、結晶子径が２５ｎｍ以上８５ｎｍ以下である複合タングステン酸化物微粒子（Ａ）が、所定の溶媒中に分散した複合タングステン酸化物微粒子分散液（Ｂ）を製造する。
[2] Composite tungsten oxide fine particle dispersion having a predetermined crystallite diameter and its manufacturing method By dispersing the composite tungsten oxide fine particles (A), that is, the infrared absorbing fine particles in a liquid solvent, the composite tungsten oxide fine particles A dispersion can be produced. In the present invention, the composite tungsten oxide fine particle dispersion (B) in which the composite tungsten oxide fine particles (A) having a crystallite diameter of 25 nm or more and 85 nm or less are dispersed in a predetermined solvent is produced.
当該所定の結晶子径を有する複合タングステン酸化物微粒子分散液（Ｂ）は、複合タングステン酸化物微粒子（Ａ）および所望により適量の分散剤、カップリング剤、界面活性剤等を、液状の溶媒へ添加し、異なる条件下において湿式の粉砕・分散処理を行うことで得ることが出来る。 The composite tungsten oxide fine particle dispersion liquid (B) having the predetermined crystallite diameter is prepared by adding the composite tungsten oxide fine particle (A) and, if desired, an appropriate amount of a dispersant, a coupling agent, a surfactant, or the like to a liquid solvent. It can be obtained by adding and performing wet pulverization / dispersion treatment under different conditions.
以下、所定の結晶子径を有する複合タングステン酸化物微粒子分散液（Ｂ）について、（１）溶媒、（２）分散剤、（３）複合タングステン酸化物微粒子（Ａ）の結晶子径、（４）複合タングステン酸化物微粒子（Ａ）の分散粒子径、（５）所定の結晶子径を有する複合タングステン酸化物微粒子（Ａ）の製造方法、の順に説明する。 Hereinafter, regarding the composite tungsten oxide fine particle dispersion liquid (B) having a predetermined crystallite diameter, (1) solvent, (2) dispersant, (3) crystallite diameter of the composite tungsten oxide fine particle (A), (4). ) The dispersed particle size of the composite tungsten oxide fine particles (A) and (5) the method for producing the composite tungsten oxide fine particles (A) having a predetermined crystallite diameter will be described in this order.
（１）溶媒
当該複合タングステン酸化物微粒子分散液の溶媒には、複合タングステン酸化物微粒子の分散性を保つための機能と、複合タングステン酸化物微粒子分散液を塗布する際に塗布欠陥を生じさせないための機能が要求される。
(1) Solvent The solvent of the composite tungsten oxide fine particle dispersion liquid has a function of maintaining the dispersibility of the composite tungsten oxide fine particle dispersion liquid and does not cause coating defects when the composite tungsten oxide fine particle dispersion liquid is applied. Function is required.
溶媒としては水、有機溶媒、植物油、植物油由来の化合物、石油系溶媒、油脂、液状樹脂、液状のプラスチック用可塑剤あるいはこれらの混合物を選択し複合タングステン酸化物微粒子分散液を製造することができる。上記の要求を満たす有機溶媒としては、アルコール系、ケトン系、炭化水素系、グリコール系、水系など、種々のものを選択することが可能である。 As the solvent, water, an organic solvent, a vegetable oil, a compound derived from a vegetable oil, a petroleum solvent, an oil or fat, a liquid resin, a liquid plastic for plastics, or a mixture thereof can be selected to produce a composite tungsten oxide fine particle dispersion. .. As the organic solvent satisfying the above requirements, various solvents such as alcohol-based, ketone-based, hydrocarbon-based, glycol-based, and aqueous-based solvents can be selected.
具体的には、メタノール、エタノール、１−プロパノール、イソプロパノール、ブタノール、ペンタノール、ベンジルアルコール、ジアセトンアルコールなどのアルコール系溶剤；アセトン、メチルエチルケトン、メチルプロピルケトン、メチルイソブチルケトン、シクロヘキサノン、イソホロンなどのケトン系溶剤；３−メチル−メトキシ−プロピオネートなどのエステル系溶剤；エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールイソプロピルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールメチルエーテルアセテート、プロピレングリコールエチルエーテルアセテートなどのグリコール誘導体；フォルムアミド、Ｎ−メチルフォルムアミド、ジメチルホルムアミド、ジメチルアセトアミド、Ｎ−メチル−２−ピロリドンなどのアミド類；トルエン、キシレンなどの芳香族炭化水素類；エチレンクロライド、クロルベンゼンなどのハロゲン化炭化水素類などを挙げることができる。これらの中でも極性の低い有機溶剤が好ましく、特に、イソプロピルアルコール、エタノール、１−メトキシ−２−プロパノール、ジメチルケトン、メチルエチルケトン、メチルイソブチルケトン、トルエン、プロピレングリコールモノメチルエーテルアセテート、酢酸ｎ−ブチルなどがより好ましい。これらの溶媒は１種または２種以上を組み合わせて用いることができる。 Specifically, alcohol solvents such as methanol, ethanol, 1-propanol, isopropanol, butanol, pentanol, benzyl alcohol and diacetone alcohol; ketones such as acetone, methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone, cyclohexanone and isophorone. Solvents: Ester solvents such as 3-methyl-methoxy-propionate; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol isopropyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol methyl ether acetate, propylene Glycol derivatives such as glycol ethyl ether acetate; amides such as formamide, N-methylformamide, dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone; aromatic hydrocarbons such as toluene and xylene; ethylene chloride, Examples thereof include halogenated hydrocarbons such as chlorbenzene. Among these, organic solvents having low polarity are preferable, and isopropyl alcohol, ethanol, 1-methoxy-2-propanol, dimethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, toluene, propylene glycol monomethyl ether acetate, n-butyl acetate and the like are more preferable. preferable. These solvents can be used alone or in combination of two or more.
植物油としては、アマニ油、ヒマワリ油、桐油、ゴマ油、綿実油、菜種油、大豆油、米糠油、オリーブ油、ヤシ油、パーム油、脱水ヒマシ油などが好ましい。 As the vegetable oil, linseed oil, sunflower oil, tung oil, sesame oil, cottonseed oil, rapeseed oil, soybean oil, rice bran oil, olive oil, palm oil, palm oil, dehydrated sunflower oil and the like are preferable.
植物油由来の化合物としては、植物油の脂肪酸とモノアルコールを直接エステル反応させた脂肪酸モノエステル、エーテル類などの植物油などが好ましい。 As the compound derived from vegetable oil, fatty acid monoester obtained by directly transesterifying a fatty acid of vegetable oil with monoalcohol, vegetable oil such as ethers, and the like are preferable.
石油系溶剤としては、アイソパーＥ、エクソールＨｅｘａｎｅ、エクソールＨｅｐｔａｎｅ、エクソールＥ、エクソールＤ３０、エクソールＤ４０、エクソールＤ６０、エクソールＤ８０、エクソールＤ９５、エクソールＤ１１０、エクソールＤ１３０（以上、エクソンモービル社製）などが好ましい。 As the petroleum-based solvent, Isopar E, Exor Hexane, Exor Heptane, Exor E, Exor D30, Exor D40, Exor D60, Exor D80, Exor D95, Exor D110, Exor D130 (all manufactured by Exor Mobile Co., Ltd.) and the like are preferable.
液状の樹脂としては、メタクリル酸メチル等が好ましい。液状のプラスチック用可塑剤としては、一価アルコールと有機酸エステルとの化合物である可塑剤や、多価アルコール有機酸エステル化合物等のエステル系である可塑剤、有機リン酸系可塑剤等のリン酸系である可塑剤などが好ましい例として挙げられる。なかでもトリエチレングリコールジ−２−エチルヘキサオネート、トリエチレングリコールジ−２−エチルブチレート、テトラエチレングリコールジ−２−エチルヘキサオネートは、加水分解性が低い為、さらに好ましい。 As the liquid resin, methyl methacrylate and the like are preferable. Examples of the liquid plasticizer for plastics include a plasticizer which is a compound of a monohydric alcohol and an organic acid ester, an ester-based plasticizer such as a polyhydric alcohol organic acid ester compound, and phosphorus such as an organic phosphoric acid-based plasticizer. A preferable example is an acid-based plasticizer. Of these, triethylene glycol di-2-ethylhexaonete, triethylene glycol di-2-ethylbutyrate, and tetraethylene glycol di-2-ethylhexaonate are more preferable because they have low hydrolyzability.
（２）分散剤
分散剤、カップリング剤、界面活性剤は用途に合わせて選定可能であるが、アミンを含有する基、水酸基、カルボキシル基、または、エポキシ基を官能基として有することが好ましい。これらの官能基は、複合タングステン酸化物微粒子の表面に吸着し、複合タングステン酸化物微粒子の凝集を防ぎ、赤外線吸収膜中でも本発明に係る複合タングステン酸化物微粒子を均一に分散させる効果を持つ。
(2) Dispersant The dispersant, coupling agent, and surfactant can be selected according to the intended use, but it is preferable to have an amine-containing group, a hydroxyl group, a carboxyl group, or an epoxy group as a functional group. These functional groups have the effect of adsorbing on the surface of the composite tungsten oxide fine particles, preventing the composite tungsten oxide fine particles from aggregating, and uniformly dispersing the composite tungsten oxide fine particles according to the present invention even in the infrared absorbing film.
好適に用いることのできる分散剤としては、リン酸エステル化合物、高分子系分散剤、シラン系カップリング剤、チタネート系カップリング剤、アルミニウム系カップリング剤、等があるが、これらに限定されるものではない。高分子系分散剤としては、アクリル系高分子分散剤、ウレタン系高分子分散剤、アクリル・ブロックコポリマー系高分子分散剤、ポリエーテル類分散剤、ポリエステル系高分子分散剤などが挙げられる。 Dispersants that can be preferably used include, but are limited to, phosphoric acid ester compounds, polymer-based dispersants, silane-based coupling agents, titanate-based coupling agents, aluminum-based coupling agents, and the like. It's not a thing. Examples of the polymer-based dispersant include acrylic-based polymer dispersants, urethane-based polymer dispersants, acrylic block copolymer-based polymer dispersants, polyether dispersants, polyester-based polymer dispersants, and the like.
当該分散剤の添加量は、複合タングステン酸化物微粒子１００質量部に対し１０質量部以上１０００質量部以下の範囲であることが望ましく、より好ましくは２０質量部以上２００質量部以下の範囲である。分散剤添加量が上記範囲にあれば、複合タングステン酸化物微粒子が分散液中で凝集を起こすことがなく、分散安定性が保たれる。 The amount of the dispersant added is preferably in the range of 10 parts by mass or more and 1000 parts by mass or less, and more preferably in the range of 20 parts by mass or more and 200 parts by mass or less with respect to 100 parts by mass of the composite tungsten oxide fine particles. When the amount of the dispersant added is within the above range, the composite tungsten oxide fine particles do not aggregate in the dispersion liquid, and the dispersion stability is maintained.
（３）複合タングステン酸化物微粒子（Ａ）の結晶子径
本発明に係る複合タングステン酸化物微粒子（Ａ）は、優れた赤外線吸収特性を担保しながら、ｂ＊の値が正の値となる程度に青味が抑制された微粒子とする観点から、結晶子径が２５ｎｍ以上８５ｎｍ以下、好ましくは３０ｎｍ以上５０ｎｍ以下であることが肝要である。
(3) Crystalline Diameter of Composite Tungsten Oxide Fine Particles (A) In the composite tungsten oxide fine particles (A) according to the present invention, the value of b * becomes a positive value while ensuring excellent infrared absorption characteristics. From the viewpoint of producing fine particles with suppressed bluish tint, it is important that the crystallite diameter is 25 nm or more and 85 nm or less, preferably 30 nm or more and 50 nm or less.
本発明に係る複合タングステン酸化物微粒子（Ａ）の結晶子径の測定には、粉末Ｘ線回折法（θ―２θ法）によるＸ線回折パターンの測定と、リートベルト法による解析を用いる。
結晶子径は、ＸＲＤ（Ｘ線回折法）の分析結果に基づくリートベルト解析によって求めることができる。具体的には、スペクトリス株式会社ＰＡＮａｌｙｔｉｃａｌ社製の粉末Ｘ線回折装置「Ｘ’Ｐｅｒｔ−ＰＲＯ／ＭＰＤ」装置を用い、Ｃｕ線源で回折角２θ＝１０°〜１２０°に出現する複合タングステン酸化物微粒子の回折ピーク位置に基づいて、リートベルト解析を行うことによって結晶子径を求めることができる。
For the measurement of the crystallite diameter of the composite tungsten oxide fine particles (A) according to the present invention, the measurement of the X-ray diffraction pattern by the powder X-ray diffraction method (θ-2θ method) and the analysis by the Rietveld method are used.
The crystallite diameter can be determined by Rietveld analysis based on the analysis result of XRD (X-ray diffraction method). Specifically, a composite tungsten oxide appearing at a diffraction angle of 2θ = 10 ° to 120 ° at a Cu radiation source using a powder X-ray diffractometer "X'Pert-PRO / MPD" manufactured by Spectris Co., Ltd. PANalytical Co., Ltd. The crystallite diameter can be obtained by performing Rietveld analysis based on the diffraction peak position of the fine particles.
（４）複合タングステン酸化物微粒子（Ａ）の分散粒子径
後述する、本発明に係る複合タングステン酸化物微粒子の分散粒子径をその使用目的によって各々選定する為、分散液（Ｂ）中に分散している複合タングステン酸化物微粒子（Ａ）の分散粒子径を各々選定することができる。
(4) Dispersed Particle Size of Composite Tungsten Oxide Fine Particles (A) Dispersed in the dispersion liquid (B) in order to select the dispersed particle size of the composite tungsten oxide fine particles according to the present invention, which will be described later, according to the purpose of use. The dispersed particle size of the composite tungsten oxide fine particles (A) can be selected.
まず、透明性を保持したい応用に使用する場合、分散粒子は８００ｎｍ以下の粒子径を有していることが好ましい。これは、８００ｎｍよりも小さい粒子は、散乱により光を完全に遮蔽することが無く、可視光線領域の視認性を保持し、同時に効率良く透明性を保持することができるからである。特に可視光領域の透明性を重視する場合は、さらに粒子による散乱を考慮することが好ましい。 First, when used in an application in which transparency is desired to be maintained, the dispersed particles preferably have a particle size of 800 nm or less. This is because particles smaller than 800 nm do not completely block light due to scattering, and can maintain visibility in the visible light region and at the same time efficiently maintain transparency. In particular, when the transparency in the visible light region is emphasized, it is preferable to further consider scattering by particles.
この粒子による散乱の低減を重視するとき、分散粒子径は２００ｎｍ以下、好ましくは１５０ｎｍ以下が良い。この理由は、粒子の分散粒子径が小さければ、幾何学散乱もしくはミー散乱による、波長４００〜７８０ｎｍの可視光線領域の光の散乱が低減される結果、赤外線吸収膜が曇りガラスのようになり、鮮明な透明性が得られなくなるのを回避できる。即ち、分散粒子径が２００ｎｍ以下になると、上記幾何学散乱もしくはミー散乱が低減し、レイリー散乱領域になる。レイリー散乱領域では、散乱光は粒子径の６乗に比例して低減するため、分散粒子径の減少に伴い散乱が低減し透明性が向上するからである。
さらに分散粒子径が１５０ｎｍ以下になると、散乱光は非常に少なくなり好ましい。光の散乱を回避する観点からは、分散粒子径が小さい方が好ましく、分散粒子径が１ｎｍ以上あれば工業的な製造は容易である。
When the reduction of scattering by the particles is emphasized, the dispersed particle size is preferably 200 nm or less, preferably 150 nm or less. The reason for this is that if the dispersed particle size of the particles is small, the scattering of light in the visible light region having a wavelength of 400 to 780 nm due to geometric scattering or Mie scattering is reduced, and as a result, the infrared absorbing film becomes like frosted glass. It is possible to avoid the loss of clear transparency. That is, when the dispersed particle size is 200 nm or less, the geometrical scattering or Mie scattering is reduced, and a Rayleigh scattering region is formed. This is because in the Rayleigh scattering region, the scattered light is reduced in proportion to the sixth power of the particle size, so that the scattering is reduced and the transparency is improved as the dispersed particle size is reduced.
Further, when the dispersed particle size is 150 nm or less, the scattered light becomes very small, which is preferable. From the viewpoint of avoiding light scattering, it is preferable that the dispersed particle size is small, and if the dispersed particle size is 1 nm or more, industrial production is easy.
上記分散粒子径を８００ｎｍ以下とすることにより、本発明に係る複合タングステン酸化物微粒子分散液（Ｂ）や複合タングステン酸化物微粒子分散体（Ｂ）のヘイズ値は、可視光透過率８５％以下でヘイズ３０％以下とすることができる。ヘイズが３０％よりも大きい値であると、曇りガラスのようになり、鮮明な透明性が得られない。
尚、複合タングステン酸化物微粒子（Ａ）の分散粒子径は、動的光散乱法を原理とした大塚電子株式会社製ＥＬＳ−８０００等を用いて測定することができる。
By setting the dispersed particle size to 800 nm or less, the haze value of the composite tungsten oxide fine particle dispersion liquid (B) and the composite tungsten oxide fine particle dispersion (B) according to the present invention has a visible light transmittance of 85% or less. The haze can be 30% or less. If the haze is a value larger than 30%, it becomes like frosted glass and clear transparency cannot be obtained.
The dispersed particle size of the composite tungsten oxide fine particles (A) can be measured by using ELS-8000 or the like manufactured by Otsuka Electronics Co., Ltd. based on the dynamic light scattering method.
（５）所定の結晶子径を有する複合タングステン酸化物微粒子（Ａ）の製造方法
複合タングステン酸化物微粒子（Ａ）、分散剤、および所望によりカップリング剤、界面活性剤等を、液状の溶媒へ添加し、湿式の粉砕・分散処理を行うことで、本発明に係る複合タングステン酸化物微粒子分散液を得ることができる。
このとき、当該湿式の粉砕・分散処理の条件を制御することにより、所定の結晶子径を有する複合タングステン酸化物微粒子（Ａ）が液状の溶媒中に分散している、本発明に係る複合タングステン酸化物微粒子分散液（Ｂ）を製造することが出来る。
(5) Method for producing composite tungsten oxide fine particles (A) having a predetermined crystallite diameter The composite tungsten oxide fine particles (A), a dispersant, and if desired, a coupling agent, a surfactant, or the like are added to a liquid solvent. The composite tungsten oxide fine particle dispersion liquid according to the present invention can be obtained by adding and performing a wet pulverization / dispersion treatment.
At this time, by controlling the conditions of the wet pulverization / dispersion treatment, the composite tungsten oxide fine particles (A) having a predetermined crystallite diameter are dispersed in a liquid solvent. The oxide fine particle dispersion liquid (B) can be produced.
湿式粉砕・分散処理の方法は、当該複合タングステン酸化物微粒子が均一に溶媒中へ分散する方法であれば公知の方法から任意に選択でき、たとえばビーズミル、ボールミル、サンドミル、超音波分散などの方法を用いることができる。
均一な複合タングステン酸化物微粒子分散液（Ｂ）を得るために、各種添加剤や分散剤を添加したり、ｐＨ調整したりしても良い。
The wet pulverization / dispersion treatment method can be arbitrarily selected from known methods as long as the composite tungsten oxide fine particles are uniformly dispersed in the solvent. For example, a bead mill, a ball mill, a sand mill, an ultrasonic dispersion, or the like can be used. Can be used.
In order to obtain a uniform composite tungsten oxide fine particle dispersion liquid (B), various additives and dispersants may be added or the pH may be adjusted.
湿式粉砕・分散処理の具体的条件は、湿式粉砕装置の仕様、分散剤や溶媒の種類に拠る。そこで、所定の湿式粉砕装置、分散剤や溶媒を決め、複合タングステン酸化物微粒子分散液を試作して、結晶子径が２５ｎｍ以上８５ｎｍ以下である複合タングステン酸化物微粒子（Ａ）が得られる湿式粉砕・分散処理条件を見出し、これを設定する。 The specific conditions of the wet pulverization / dispersion treatment depend on the specifications of the wet pulverizer and the types of dispersants and solvents. Therefore, a predetermined wet pulverizer, a dispersant and a solvent are determined, and a composite tungsten oxide fine particle dispersion liquid is prototyped to obtain a composite tungsten oxide fine particle (A) having a crystallite diameter of 25 nm or more and 85 nm or less. -Discover the distributed processing conditions and set them.
［３］複合タングステン酸化物微粒子分散粉末とその製造方法
上述した本発明に係る複合タングステン酸化物微粒子分散液（Ｂ）から、溶媒の除去を行うことにより、複合タングステン酸化物微粒子分散粉末（Ｃ）を得ることが出来る。
複合タングステン酸化物微粒子分散液（Ｂ）から、溶媒の除去を行うには、複合タングステン酸化物微粒子分散液（Ｂ）を減圧乾燥することが好ましい。具体的には、複合タングステン酸化物微粒子分散液（Ｂ）を攪拌しながら減圧乾燥し、複合タングステン酸化物微粒子含有組成物と溶媒成分とを分離すればよい。乾燥工程の減圧の際の圧力は適宜選択される。
当該減圧乾燥法を用いることで、複合タングステン酸化物微粒子分散液（Ｂ）からの溶媒の除去効率が向上するとともに、本発明にかかる混合複合タングステン酸化物微粒子粉末が長時間高温に曝されることがないので、該微粒子中に分散している混合複合タングステン酸化物微粒子の凝集が起こらず好ましい、さらに混合複合タングステン酸化物微粒子の生産性も上がり、蒸発した溶媒を回収することも容易で、環境的配慮からも好ましい。
[3] Composite tungsten oxide fine particle dispersion powder and its production method The composite tungsten oxide fine particle dispersion powder (C) is obtained by removing the solvent from the composite tungsten oxide fine particle dispersion liquid (B) according to the present invention described above. Can be obtained.
In order to remove the solvent from the composite tungsten oxide fine particle dispersion liquid (B), it is preferable to dry the composite tungsten oxide fine particle dispersion liquid (B) under reduced pressure. Specifically, the composite tungsten oxide fine particle dispersion liquid (B) may be dried under reduced pressure while stirring to separate the composite tungsten oxide fine particle-containing composition and the solvent component. The pressure at the time of depressurization in the drying step is appropriately selected.
By using the vacuum drying method, the efficiency of removing the solvent from the composite tungsten oxide fine particle dispersion (B) is improved, and the mixed composite tungsten oxide fine particle powder according to the present invention is exposed to a high temperature for a long time. Therefore, it is preferable that the mixed composite tungsten oxide fine particles dispersed in the fine particles do not agglomerate. Further, the productivity of the mixed composite tungsten oxide fine particles is increased, and it is easy to recover the evaporated solvent. It is also preferable from the viewpoint of consideration.
［４］複合タングステン酸化物微粒子分散体とその製造方法
本発明に係る複合タングステン酸化物微粒子分散液（Ｂ）、または、複合タングステン酸化物微粒子分散粉末（Ｃ）を、固体状の媒体中へ分散することで、分散粉やマスターバッチ、赤外線吸収フィルム、赤外線吸収プラスチック成形体などの複合タングステン酸化物微粒子分散体（Ｄ）を製造することができる。
[4] Composite tungsten oxide fine particle dispersion and its production method The composite tungsten oxide fine particle dispersion liquid (B) or the composite tungsten oxide fine particle dispersion powder (C) according to the present invention is dispersed in a solid medium. By doing so, it is possible to produce a composite tungsten oxide fine particle dispersion (D) such as a dispersion powder, a master batch, an infrared absorbing film, and an infrared absorbing plastic molded product.
一般的な使用方法の例として、本発明に係る複合タングステン酸化物微粒子分散液（Ｂ）を用いた赤外線吸収フィルムの製造方法について述べる。前述した複合タングステン酸化物微粒子分散液（Ｂ）をプラスチックあるいはモノマーと混合して塗布液を作製し、公知の方法で基材上にコーティング膜を形成することで、赤外線吸収フィルムを作製することができる。尚、赤外線吸収フィルムは本発明に係る複合タングステン酸化物微粒子分散体（Ｄ）の一例である。 As an example of a general usage method, a method for producing an infrared absorbing film using the composite tungsten oxide fine particle dispersion liquid (B) according to the present invention will be described. An infrared absorbing film can be produced by mixing the above-mentioned composite tungsten oxide fine particle dispersion (B) with a plastic or a monomer to prepare a coating liquid and forming a coating film on a substrate by a known method. it can. The infrared absorbing film is an example of the composite tungsten oxide fine particle dispersion (D) according to the present invention.
上記コーティング膜の媒体は、例えば、ＵＶ硬化樹脂、熱硬化樹脂、電子線硬化樹脂、常温硬化樹脂、熱可塑樹脂等が目的に応じて選定可能である。具体的には、ポリエチレン樹脂、ポリ塩化ビニル樹脂、ポリ塩化ビニリデン樹脂、ポリビニルアルコール樹脂、ポリスチレン樹脂、ポリプロピレン樹脂、エチレン酢酸ビニル共重合体、ポリエステル樹脂、ポリエチレンテレフタレート樹脂、ふっ素樹脂、ポリカーボネート樹脂、アクリル樹脂、ポリビニルブチラール樹脂が挙げられる。これらの樹脂は、単独使用であっても混合使用であっても良い。また、金属アルコキシドを用いたバインダーの利用も可能である。上記金属アルコキシドとしては、Ｓｉ、Ｔｉ、Ａｌ、Ｚｒ等のアルコキシドが代表的である。これら金属アルコキシドを用いたバインダーは、加熱等により加水分解・縮重合させることで、酸化物膜を形成することが可能である。 As the medium of the coating film, for example, UV curable resin, thermosetting resin, electron beam curable resin, room temperature curable resin, thermoplastic resin and the like can be selected according to the purpose. Specifically, polyethylene resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl alcohol resin, polystyrene resin, polypropylene resin, ethylene vinyl acetate copolymer, polyester resin, polyethylene terephthalate resin, fluorine resin, polycarbonate resin, acrylic resin. , Polyvinyl butyral resin can be mentioned. These resins may be used alone or in combination. It is also possible to use a binder using a metal alkoxide. Typical examples of the metal alkoxide are alkoxides such as Si, Ti, Al, and Zr. Binders using these metal alkoxides can form an oxide film by hydrolyzing and polycondensing by heating or the like.
上記基材としては上述したようにフィルムでも良いが、所望によってはボードでも良く、形状は限定されない。透明基材材料としては、ＰＥＴ、アクリル、ウレタン、ポリカーボネート、ポリエチレン、エチレン酢酸ビニル共重合体、塩化ビニル、ふっ素樹脂等が、各種目的に応じて使用可能である。また、樹脂以外ではガラスを用いることができる。 The base material may be a film as described above, but may be a board if desired, and the shape is not limited. As the transparent base material, PET, acrylic, urethane, polycarbonate, polyethylene, ethylene-vinyl acetate copolymer, vinyl chloride, fluororesin and the like can be used according to various purposes. In addition to resin, glass can be used.
そして、本発明に係る複合タングステン酸化物微粒子分散体（Ｄ）は、耐候性が低い有機系材料を含有していない為、耐候性が高く、各種建築物や車両の窓材等の分野における使用環境に耐えることが出来るものである。 Since the composite tungsten oxide fine particle dispersion (D) according to the present invention does not contain an organic material having low weather resistance, it has high weather resistance and is used in fields such as window materials for various buildings and vehicles. It can withstand the environment.
以下、実施例を参照しながら本発明を具体的に説明する。
但し、本発明は以下の実施例に限定されるものではない。
Hereinafter, the present invention will be specifically described with reference to Examples.
However, the present invention is not limited to the following examples.
複合タングステン酸化物微粒子の結晶子径は、Ｘ線回折パターンをリートベルト法により解析することで算出した。Ｘ線回折パターンは、粉末Ｘ線回折装置（スペクトリス株式会社ＰＡＮａｌｙｔｉｃａｌ製Ｘ’Ｐｅｒｔ−ＰＲＯ／ＭＰＤ）を用いて粉末Ｘ線回折法（θ―２θ法）により測定した。
少なくとも１種類以上の複合タングステン酸化物微粒子から成る分散液および少なくとも１種類以上の複合タングステン酸化物微粒子から成る分散体の光学特性は、分光光度計（日立製作所株式会社製 Ｕ−４１００）を用いて、波長２００〜２６００ｎｍの範囲において５ｎｍの間隔で透過光プロファイルとして測定し、可視光透過率と日射透過率をＪＩＳＲ３１０６に従って算出した。表色系はＪＩＳ Ｚ ８７０１に基づくＬ＊ａ＊ｂ＊表色系（Ｄ６５光源／１０度視野）を用い、ｂ＊の値を測定した。
The crystallite diameter of the composite tungsten oxide fine particles was calculated by analyzing the X-ray diffraction pattern by the Rietveld method. The X-ray diffraction pattern was measured by a powder X-ray diffraction method (θ-2θ method) using a powder X-ray diffractometer (X'Pert-PRO / MPD manufactured by PANalytical Co., Ltd.).
The optical characteristics of the dispersion composed of at least one type of composite tungsten oxide fine particles and the dispersion composed of at least one type of composite tungsten oxide fine particles were determined by using a spectrophotometer (U-4100 manufactured by Hitachi, Ltd.). , Measured as a transmitted light profile at intervals of 5 nm in the wavelength range of 200 to 2600 nm, and the visible light transmittance and the solar radiation transmittance were calculated according to JIS R3106. As the color system, the L * a * b * color system (D65 light source / 10-degree field of view) based on JIS Z 8701 was used, and the value of b * was measured.
［実施例１］
Ｃｓ／Ｗ（モル比）＝０．３３の六方晶セシウムタングステンブロンズ（Ｃｓ０．３３ＷＯｚ、２．０≦ｚ≦３．０）粉末（（登録商標）住友金属鉱山株式会社製ＹＭ−０１）８質量％と、ポリアクリレート系分散剤２４質量％と、溶媒としてトルエン６８質量％とを混合して混合液を得た。得られた混合液２００ｇを０．３ｍｍφＺｒＯ２ビーズ７５０ｇと共に、ペイントシェイカー（淺田鉄工株式会社製）に装填し、７時間の粉砕・分散処理を行い、実施例１に係る複合タングステン酸化物微粒子分散液を得た。
[Example 1]
Hexagonal cesium tungsten bronze (Cs 0.33 WOz, 2.0 ≤ z ≤ 3.0) powder with Cs / W (molar ratio) = 0.33 (YM-01 manufactured by Sumitomo Metal Mining Co., Ltd.) A mixed solution was obtained by mixing 8% by mass, 24% by mass of the polyacrylate-based dispersant, and 68% by mass of toluene as a solvent. 200 g of the obtained mixed solution was loaded into a paint shaker (manufactured by Asada Iron Works Co., Ltd.) together with 750 g of 0.3 mmφZrO 2 beads, and pulverized and dispersed for 7 hours. Got
実施例１に係る複合タングステン酸化物微粒子分散液を、溶媒であるトルエンを使って可視光透過率が８０％となるように希釈した。そして、分光光度計の測定用ガラスセル（ジーエルサイエンス株式会社製、型番：Ｓ−１０−ＳＱ−１、材質：合成石英、光路長：１ｍｍ）にて透過光プロファイルを測定した。尚、当該測定前に、分散液の溶媒であるトルエンを当該ガラスセルに満たした状態で透過光プロファイルのベースラインを測定した。
当該ベースラインの測定により、分光光度計用ガラスセル表面の光反射や、溶媒の光吸収による寄与をキャンセルすることが出来、複合タングステン酸化物微粒子による光吸収のみが透過光プロファイルに反映されることとなる。
得られた透過光プロファイルから、実施例１に係る複合タングステン酸化物微粒子分散液の可視光透過率、日射透過率、ｂ＊を算出した。当該評価結果を表１に示す。
The composite tungsten oxide fine particle dispersion according to Example 1 was diluted with toluene as a solvent so that the visible light transmittance was 80%. Then, the transmitted light profile was measured with a glass cell for measurement of a spectrophotometer (manufactured by GL Sciences Co., Ltd., model number: S-10-SQ-1, material: synthetic quartz, optical path length: 1 mm). Prior to the measurement, the baseline of the transmitted light profile was measured with the glass cell filled with toluene, which is the solvent of the dispersion liquid.
By measuring the baseline, the light reflection on the surface of the glass cell for the spectrophotometer and the contribution of the light absorption of the solvent can be canceled, and only the light absorption by the composite tungsten oxide fine particles is reflected in the transmitted light profile. It becomes.
From the obtained transmitted light profile, the visible light transmittance, the solar radiation transmittance, and b * of the composite tungsten oxide fine particle dispersion liquid according to Example 1 were calculated. The evaluation results are shown in Table 1.
次いで、実施例１に係る複合タングステン酸化物微粒子分散液から真空流動乾燥により溶媒を蒸発させ、実施例１に係る複合タングステン酸化物微粒子分散粉末を得た。真空流動乾燥は、真空擂潰機（株式会社石川工場製２４Ｐ）を用いて行った。回転数は４５ｒｐｍ／ｍｉｎ、ヒーター温度設定は７０℃とした。
得られた実施例１に係る複合タングステン酸化物微粒子分散粉末に含まれる、実施例１に係る複合タングステン酸化物微粒子の結晶子径を測定したところ、４８ｎｍであった。
Next, the solvent was evaporated from the composite tungsten oxide fine particle dispersion liquid according to Example 1 by vacuum flow drying to obtain a composite tungsten oxide fine particle dispersion powder according to Example 1. Vacuum flow drying was performed using a vacuum crusher (24P manufactured by Ishikawa Factory Co., Ltd.). The rotation speed was 45 rpm / min, and the heater temperature was set to 70 ° C.
The crystallite diameter of the composite tungsten oxide fine particles according to Example 1 contained in the obtained composite tungsten oxide fine particle dispersion powder according to Example 1 was measured and found to be 48 nm.
実施例１に係る複合タングステン酸化物微粒子分散粉末とポリカーボネート樹脂とを、後に得られる実施例１に係る合タングステン酸化物微粒子分散体である赤外線吸収シートの可視光透過率が８０％前後になるようにドライブレンドした（この例では、複合タングステン酸化物微粒子の濃度が０．０４５質量％となるようにブレンドした。）。得られたブレンド物を、二軸押出機を用いて２９０℃で混練し、Ｔダイより押出して、カレンダーロール法により０．７５ｍｍ厚のシート材とし、実施例１に係る合タングステン酸化物微粒子分散体である赤外線吸収シートを得た。 The composite tungsten oxide fine particle dispersion powder according to Example 1 and the polycarbonate resin are used so that the visible light transmittance of the infrared absorbing sheet which is the combined tungsten oxide fine particle dispersion according to Example 1 obtained later is about 80%. (In this example, the composite tungsten oxide fine particles were blended so as to have a concentration of 0.045% by mass). The obtained blend was kneaded at 290 ° C. using a twin-screw extruder and extruded from a T-die to obtain a sheet material having a thickness of 0.75 mm by a calendar roll method. I got an infrared absorbing sheet which is a body.
得られた赤外線吸収シートの透過光プロファイルを測定した。得られた透過光プロファイルから、実施例１に係る合タングステン酸化物微粒子分散体の可視光透過率、日射透過率、ｂ＊を算出した。評価結果を表１に示す。また、実施例１に係る複合タングステン酸化物微粒子分散液の透過光プロファイルを図２に実線で示す。 The transmitted light profile of the obtained infrared absorbing sheet was measured. From the obtained transmitted light profile, the visible light transmittance, the solar radiation transmittance, and b * of the combined tungsten oxide fine particle dispersion according to Example 1 were calculated. The evaluation results are shown in Table 1. Further, the transmitted light profile of the composite tungsten oxide fine particle dispersion liquid according to Example 1 is shown by a solid line in FIG.
［実施例２］
実施例１にて説明した、湿式粉砕・分散処理の処理時間を１３時間に変更したこと以外は、実施例１と同様の操作をすることで、実施例２に係る複合タングステン酸化物微粒子分散液を得た。得られた分散液の溶媒除去を行い、得られた実施例２に係る複合タングステン酸化物微粒子分散粉末に含まれる、実施例２に係る複合タングステン酸化物微粒子の結晶子径を測定したところ、３２ｎｍであった。
[Example 2]
By performing the same operation as in Example 1 except that the treatment time for the wet pulverization / dispersion treatment described in Example 1 was changed to 13 hours, the composite tungsten oxide fine particle dispersion liquid according to Example 2 was performed. Got The solvent of the obtained dispersion was removed, and the crystallite diameter of the composite tungsten oxide fine particles according to Example 2 contained in the obtained composite tungsten oxide fine particle dispersion powder according to Example 2 was measured and found to be 32 nm. Met.
実施例１に係る複合タングステン酸化物微粒子分散液の代わりに、実施例２に係る複合タングステン酸化物微粒子分散液を用いたこと以外は、実施例１と同様の操作をすることで、実施例２に係る複合タングステン酸化物微粒子分散液、実施例２に係る複合タングステン酸化物微粒子分散粉末を得て、実施例１と同様の評価を実施した。評価結果を表１に示す。また、実施例２に係る複合タングステン酸化物微粒子分散液の透過光プロファイルを図２に長破線で示す。 Example 2 is performed in the same manner as in Example 1 except that the composite tungsten oxide fine particle dispersion according to Example 2 is used instead of the composite tungsten oxide fine particle dispersion according to Example 1. The composite tungsten oxide fine particle dispersion liquid according to Example 2 and the composite tungsten oxide fine particle dispersion powder according to Example 2 were obtained, and the same evaluation as in Example 1 was carried out. The evaluation results are shown in Table 1. Further, the transmitted light profile of the composite tungsten oxide fine particle dispersion liquid according to Example 2 is shown by a long broken line in FIG.
［比較例１］
実施例１にて説明した、湿式粉砕・分散処理の処理時間を２時間に変更したこと以外は、実施例１と同様の操作をすることで、比較例１に係る複合タングステン酸化物微粒子分散液を得た。得られた分散液の溶媒除去を行い、得られた比較例１に係る複合タングステン酸化物微粒子分散粉末に含まれる、比較例１に係る複合タングステン酸化物微粒子の結晶子径を測定したところ、８８ｎｍであった。
[Comparative Example 1]
By performing the same operation as in Example 1 except that the treatment time for the wet pulverization / dispersion treatment described in Example 1 was changed to 2 hours, the composite tungsten oxide fine particle dispersion liquid according to Comparative Example 1 was performed. Got The solvent of the obtained dispersion was removed, and the crystallite diameter of the composite tungsten oxide fine particles according to Comparative Example 1 contained in the obtained composite tungsten oxide fine particle dispersion powder according to Comparative Example 1 was measured and found to be 88 nm. Met.
実施例１に係る複合タングステン酸化物微粒子分散液の代わりに、比較例１に係る複合タングステン酸化物微粒子分散液を用いたこと以外は、実施例１と同様の操作をすることで、比較例１に係る複合タングステン酸化物微粒子分散液、および、比較例１に係る複合タングステン酸化物微粒子分散粉末を得て、実施例１と同様の評価を実施した。評価結果を表１に示す。 Comparative Example 1 was performed in the same manner as in Example 1 except that the composite tungsten oxide fine particle dispersion according to Comparative Example 1 was used instead of the composite tungsten oxide fine particle dispersion according to Example 1. The composite tungsten oxide fine particle dispersion liquid according to Comparative Example 1 and the composite tungsten oxide fine particle dispersion powder according to Comparative Example 1 were obtained, and the same evaluation as in Example 1 was carried out. The evaluation results are shown in Table 1.
［比較例２］
実施例１にて説明した、湿式粉砕・分散処理の処理時間を３０時間に変更したこと以外は、実施例１と同様の操作をすることで、比較例２に係る複合タングステン酸化物微粒子分散液を得た。得られた分散液の溶媒除去を行い、得られた比較例２に係る複合タングステン酸化物微粒子分散粉末に含まれる、比較例２に係る複合タングステン酸化物微粒子の結晶子径を測定したところ、２２ｎｍであった。
[Comparative Example 2]
By performing the same operation as in Example 1 except that the treatment time for the wet pulverization / dispersion treatment described in Example 1 was changed to 30 hours, the composite tungsten oxide fine particle dispersion liquid according to Comparative Example 2 was performed. Got The solvent of the obtained dispersion was removed, and the crystallite diameter of the composite tungsten oxide fine particles according to Comparative Example 2 contained in the obtained composite tungsten oxide fine particle dispersion powder according to Comparative Example 2 was measured and found to be 22 nm. Met.
実施例１に係る複合タングステン酸化物微粒子分散液の代わりに、比較例２に係る複合タングステン酸化物微粒子分散液を用いたこと以外は、実施例１と同様の操作をすることで、比較例２に係る複合タングステン酸化物微粒子分散液、および、比較例２に係る複合タングステン酸化物微粒子分散粉末を得て、実施例１と同様の評価を実施した。評価結果を表１に示す。また、比較例２に係る複合タングステン酸化物微粒子分散液の透過光プロファイルを図２に短破線で示す。 Comparative Example 2 was performed in the same manner as in Example 1 except that the composite tungsten oxide fine particle dispersion according to Comparative Example 2 was used instead of the composite tungsten oxide fine particle dispersion according to Example 1. The composite tungsten oxide fine particle dispersion liquid according to Comparative Example 2 and the composite tungsten oxide fine particle dispersion powder according to Comparative Example 2 were obtained, and the same evaluation as in Example 1 was carried out. The evaluation results are shown in Table 1. Further, the transmitted light profile of the composite tungsten oxide fine particle dispersion liquid according to Comparative Example 2 is shown by a short broken line in FIG.
［まとめ］
表１から明らかなように、実施例１または２に係る複合タングステン酸化物微粒子分散液（複合タングステン微粒子成分のみで測定）と、実施例１に係る複合タングステン酸化物微粒子分散体とは、いずれも可視光透過率が８０％の時の日射透過率が４５％以下で、かつｂ＊が０以上であった。この結果より、光学的特性に優れ、且つ、青味の抑制されたものとなっていることが判明した。
さらに、実施例１または２に係る複合タングステン酸化物微粒子分散液は、比較例１に係る複合タングステン酸化物微粒子分散液と比較して、いずれも可視光透過率が８０％の時の日射透過率が明らかに低く、優れた赤外線吸収特性を有していることが確認された。一方、比較例２に係る複合タングステン酸化物微粒子分散液は、ｂ＊値が０未満である。
また、図２のグラフより、実施例１または２に係る複合タングステン酸化物微粒子分散液は、比較例２に係る複合タングステン酸化物微粒子分散液と比較して、プロファイルが長波長側へピークシフトしていることが判明した。
[Summary]
As is clear from Table 1, the composite tungsten oxide fine particle dispersion liquid according to Example 1 or 2 (measured only with the composite tungsten fine particle component) and the composite tungsten oxide fine particle dispersion according to Example 1 are both. When the visible light transmittance was 80%, the solar radiation transmittance was 45% or less, and b * was 0 or more. From this result, it was found that the optical characteristics were excellent and the bluish tint was suppressed.
Further, the composite tungsten oxide fine particle dispersion liquid according to Example 1 or 2 has a solar radiation transmittance when the visible light transmittance is 80% as compared with the composite tungsten oxide fine particle dispersion liquid according to Comparative Example 1. Was clearly low, and it was confirmed that it had excellent infrared absorption characteristics. On the other hand, the composite tungsten oxide fine particle dispersion liquid according to Comparative Example 2 has a b * value of less than 0.
Further, from the graph of FIG. 2, the profile of the composite tungsten oxide fine particle dispersion liquid according to Example 1 or 2 is peak-shifted to the longer wavelength side as compared with the composite tungsten oxide fine particle dispersion liquid according to Comparative Example 2. It turned out that.
Claims (7)
A claim, wherein the solvent is one or more solvents selected from organic solvents, fats and oils, liquid plasticizers for plastics, vegetable oils, compounds derived from vegetable oils, petroleum-based solvents, liquid resins, and water. Item 5. The composite tungsten oxide fine particle dispersion liquid according to Item 5 or 6.
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