JP2015044922A - Heat ray-shielding dispersion material, coating liquid for forming heat ray-shielding dispersion material, and heat ray-shielding body - Google Patents
Heat ray-shielding dispersion material, coating liquid for forming heat ray-shielding dispersion material, and heat ray-shielding body Download PDFInfo
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- JP2015044922A JP2015044922A JP2013175983A JP2013175983A JP2015044922A JP 2015044922 A JP2015044922 A JP 2015044922A JP 2013175983 A JP2013175983 A JP 2013175983A JP 2013175983 A JP2013175983 A JP 2013175983A JP 2015044922 A JP2015044922 A JP 2015044922A
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- heat ray
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- ray shielding
- shielding dispersion
- heat
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Abstract
Description
本発明は、可視光領域の光は透過し近赤外線領域に吸収を持つ近赤外線遮蔽材料を用いた熱線遮蔽分散体、熱線遮蔽分散体形成用塗布液および熱線遮蔽体に関する。 The present invention relates to a heat ray shielding dispersion, a coating solution for forming a heat ray shielding dispersion, and a heat ray shielding body using a near infrared shielding material that transmits light in the visible light region and absorbs light in the near infrared region.
太陽光線は、熱線（近赤外光）、可視光、紫外光の３つに大きく分けられる。熱線は熱エネルギーとして人体に感じる波長領域であり、夏季の室内の温度上昇の原因となる。また、紫外光領域は日焼けや皮膚ガン等、人体へ悪影響を及ぼすことが指摘されている。
近年、透明基材へ、熱線としての近赤外線を遮蔽することで保温や断熱の性能を付与することを求められる場合がある。このため、ガラス、ポリカーボネート樹脂、アクリル樹脂等の透明基材に近赤外線吸収能を付与することが求められる場合がある。
Sun rays are broadly divided into three types: heat rays (near infrared light), visible light, and ultraviolet light. The heat ray is a wavelength region that is perceived by the human body as heat energy, and causes a rise in indoor temperature in summer. In addition, it has been pointed out that the ultraviolet light region adversely affects the human body, such as sunburn and skin cancer.
In recent years, it may be required to impart heat retention and heat insulation performance to a transparent substrate by shielding near infrared rays as heat rays. For this reason, it may be requested | required to provide near-infrared absorptivity to transparent base materials, such as glass, a polycarbonate resin, and an acrylic resin.
例えば、特許文献１では、透明なガラス基板上に、基板側より第１層として周期律表のIIIａ族、IVａ族、Vｂ族、VIｂ族およびVIIｂ族から成る群から選ばれた少なくとも１種の金属イオンを含有する複合酸化タングステン膜を設け、上記第１層上に第２層として透明誘電体膜を設け、第２層の透明誘電体膜上に第３層として周期律表のIIIａ族、IVａ族、Vｂ族、VIｂ族およびVIIｂ族から成る群から選ばれた少なくとも１種の金属イオンを含有する複合酸化タングステン膜を設け、かつ、上記第２層を構成する透明誘電体膜の屈折率を第１層および第３層の複合酸化タングステン膜の屈折率よりも低くすることにより、高い可視光透過率および良好な熱線遮蔽性能が要求される部位に好適に使用できる熱線遮断ガラスが提案されている。 For example, in Patent Document 1, on a transparent glass substrate, at least one selected from the group consisting of IIIa group, IVa group, Vb group, VIb group and VIIb group of the periodic table as the first layer from the substrate side. A composite tungsten oxide film containing metal ions is provided, a transparent dielectric film is provided as a second layer on the first layer, and a group IIIa of the periodic table is provided as a third layer on the second transparent dielectric film, A composite tungsten oxide film containing at least one metal ion selected from the group consisting of IVa group, Vb group, VIb group and VIIb group is provided, and the refractive index of the transparent dielectric film constituting the second layer Is made lower than the refractive index of the composite tungsten oxide film of the first layer and the third layer, and a heat ray-shielding glass that can be suitably used for a portion requiring high visible light transmittance and good heat ray shielding performance is proposed. ing.
また、特許文献２では、特許文献１と同様の方法で、透明なガラス基板上に、基板側より第１層として第１の誘電体膜を設け、この第１層上に第２層として酸化タングステン膜を設け、この第２層上に第３層として上記第１層と同じ誘電体膜を設けた熱線遮断ガラスが提案されている。 Further, in Patent Document 2, a first dielectric film is provided as a first layer from the substrate side on a transparent glass substrate in the same manner as Patent Document 1, and the second layer is oxidized on the first layer. There has been proposed a heat ray shielding glass in which a tungsten film is provided and the same dielectric film as the first layer is provided as a third layer on the second layer.
また、特許文献３では、特許文献１と同様な方法で、透明な基板上に、基板側より第１層として同様の金属元素を含有する複合酸化タングステン膜を設け、この第１層上に第２層として透明誘電体膜を設けた熱線遮断ガラスが提案されている。 In Patent Document 3, a composite tungsten oxide film containing the same metal element is provided as a first layer from the substrate side on the transparent substrate by the same method as Patent Document 1, and the first layer is formed on the first layer. Heat ray blocking glass having a transparent dielectric film as two layers has been proposed.
さらに、特許文献４では、水素、リチウム、ナトリウム、カリウム等の添加元素を含有する三酸化タングステン（ＷＯ３）、三酸化モリブデン（ＭｏＯ３）、五酸化ニオブ（Ｎｂ２Ｏ５）、五酸化タンタル（Ｔａ２Ｏ５）、五酸化バナジウム（Ｖ２Ｏ５）および二酸化バナジウム（ＶＯ２）の１種以上から選択された金属酸化物膜を、ＣＶＤ法あるいはスプレー法でガラスシートに被覆し、かつ２５０℃程度で熱分解して形成された太陽光遮蔽特性を有する太陽光制御ガラスシートが提案されている。 Further, in Patent Document 4, tungsten trioxide (WO 3 ), molybdenum trioxide (MoO 3 ), niobium pentoxide (Nb 2 O 5 ), and tantalum pentoxide containing additional elements such as hydrogen, lithium, sodium, and potassium. Coating a glass sheet with a metal oxide film selected from one or more of (Ta 2 O 5 ), vanadium pentoxide (V 2 O 5 ) and vanadium dioxide (VO 2 ) by CVD or spraying; and A solar control glass sheet having solar light shielding properties formed by thermal decomposition at about 250 ° C. has been proposed.
特許文献５では、タングステン酸を加水分解して得られたタングステン酸化物を用い、このタングステン酸化物にポリビニルピロリドンという特定の構造の有機ポリマーを添加した太陽光可変調光断熱材料が提案されている。 Patent Document 5 proposes a sunlight-modulable light heat insulating material using tungsten oxide obtained by hydrolyzing tungstic acid and adding an organic polymer having a specific structure called polyvinylpyrrolidone to the tungsten oxide. .
また、特許文献６では、六塩化タングステンをアルコールに溶解し、そのまま溶媒を蒸発させるか、または加熱還流した後に溶媒を蒸発させ、その後１００℃〜５００℃で加熱することにより、三酸化タングステン若しくはその水和物または両者の混合物から成る粉末が得られることが記指されている。そして当該タングステン酸化物微粒子を用いてエレクトロクロミック素子が得られること、多層の積層体を構成し膜中にプロトンを導入したときに当該膜の光学特性を変化させること、等が提案されている。 In Patent Document 6, tungsten trichloride or its solvent is obtained by dissolving tungsten hexachloride in alcohol and evaporating the solvent as it is, or evaporating the solvent after heating to reflux, and then heating at 100 ° C. to 500 ° C. It is noted that a powder consisting of a hydrate or a mixture of both is obtained. It has been proposed that an electrochromic element is obtained using the tungsten oxide fine particles, and that the optical characteristics of the film are changed when protons are introduced into the film by forming a multilayer stack.
また、特許文献７では、メタ型タングステン酸アンモニウムと水溶性の各種金属塩を原料とし、約３００〜７００℃に加熱しながらその混合水溶液の乾固物に対し、不活性ガス（添加量；約５０ｖｏ１％以上）または水蒸気（添加量；約１５ｖｏｌ％以下）が添加された水素ガスを供給することにより、ＭｘＷＯ３（Ｍ；アルカリ、Iａ族、IIａ族、希土類等の金属元素、０＜ｘ＜１）で表記される種々のタングステンブロンズを調製する方法が提案されている。 Further, in Patent Document 7, meta-type ammonium tungstate and various water-soluble metal salts are used as raw materials, and heated to about 300 to 700 ° C., the inert gas (addition amount; about By supplying hydrogen gas to which 50 vol. 1 or more) or water vapor (addition amount; about 15 vol.% Or less) is added, M x WO 3 (M: metal element such as alkali, group Ia, group IIa, rare earth, 0 < Methods for preparing various tungsten bronzes denoted by x <1) have been proposed.
さらに、特許文献８には、タングステン酸化物微粒子および／または複合タングステン酸化物微粒子から成る近赤外線遮蔽材料微粒子を、樹脂、ガラス等の媒体中に分散させて成る近赤外線遮蔽材料微粒子分散体、この分散体から製造される近赤外線遮蔽体、上記近赤外線遮蔽材料微粒子の製造方法、および、近赤外線遮蔽材料微粒子が提案されている。 Further, Patent Document 8 discloses a near-infrared shielding material fine particle dispersion in which near-infrared shielding material fine particles composed of tungsten oxide fine particles and / or composite tungsten oxide fine particles are dispersed in a medium such as a resin or glass. A near-infrared shielding body produced from a dispersion, a method for producing the above-mentioned near-infrared shielding material fine particles, and near-infrared shielding material fine particles have been proposed.
特許文献９には、複合タングステン酸化物微粒子を、紫外線硬化樹脂などの樹脂成分または金属アルコキシド等の媒体中に分散させた赤外線遮蔽材料微粒子分散剤と、それを用いた赤外線遮蔽膜、プラズマディスプレイ用赤外線吸収フィルターについて記載している。そして、当該赤外線遮蔽膜の経時的光学特性の低下防止を目的として、金属塩を添加することが提案されている。 Patent Document 9 discloses an infrared shielding material fine particle dispersant in which composite tungsten oxide fine particles are dispersed in a resin component such as an ultraviolet curable resin or a medium such as a metal alkoxide, an infrared shielding film using the same, and a plasma display. Describes infrared absorption filters. For the purpose of preventing deterioration of optical characteristics of the infrared shielding film over time, it has been proposed to add a metal salt.
ところが本発明者らの検討によると、特許文献１〜３に記載の近赤外線遮蔽体（熱線遮断ガラス）は、主にスパッタリング法、蒸着法、イオンプレーティング法および化学気相成長法（ＣＶＤ法）等の真空成膜方式による乾式法を用いた方法で製造される。この為、成膜には、大型の製造装置を必要とし、製造コストが高くなるという問題がある。また、真空成膜方法で製造されることから、近赤外線遮蔽体の基材が高温のプラズマに曝されたり、成膜後に加熱を必要としたりすることになる。この為、ガラスに替えてフィルム等の樹脂を基材とする場合には、別途、設備上、成膜条件の検討を行う必要があった。 However, according to the study by the present inventors, the near-infrared shielding bodies (heat ray shielding glass) described in Patent Documents 1 to 3 are mainly sputtering, vapor deposition, ion plating, and chemical vapor deposition (CVD). ) And the like using a dry method by a vacuum film formation method. For this reason, there is a problem that a large manufacturing apparatus is required for film formation, and the manufacturing cost increases. Moreover, since it is manufactured by a vacuum film forming method, the base material of the near-infrared shield is exposed to high-temperature plasma, or heating is required after film formation. For this reason, in the case of using a resin such as a film as a base material instead of glass, it is necessary to separately examine the film forming conditions on equipment.
特許文献４に記載の近赤外線遮蔽体（太陽光制御ガラスシート）は、原料である金属酸化物をＣＶＤ法またはスプレー法と熱分解法との併用によりガラス上に被膜形成する。しかし、金属酸化物の前駆体となる原料が高価であること、当該金属酸化物を高温で分解すること等から、ガラスシートに代えてフィルム等の樹脂を基材とする場合には、別途、成膜条件の検討を行う必要があった。 The near-infrared shielding body (solar control glass sheet) described in Patent Document 4 forms a metal oxide film as a raw material on glass by a CVD method or a combination of a spray method and a thermal decomposition method. However, since the raw material to be a precursor of the metal oxide is expensive, the metal oxide is decomposed at a high temperature, etc., when using a resin such as a film instead of a glass sheet, separately, It was necessary to examine the film formation conditions.
また、特許文献５に記載の太陽光可変調光断熱材料や、特許文献６に記載のエレクトロクロミック素子は、紫外線や電位差によりその色調を変化させる材料であり膜の構造が複雑である。この為、色調変化が望まれない用途分野には適用が困難という問題があった。 Further, the sunlight-modulable light insulating material described in Patent Document 5 and the electrochromic element described in Patent Document 6 are materials that change their color tone by ultraviolet rays or a potential difference, and have a complicated film structure. For this reason, there is a problem that it is difficult to apply to application fields where a change in color tone is not desired.
特許文献７にはタングステンブロンズの調製方法が記載されている。しかし、得られた粉体の粒子直径や光学特性の記載は皆無である。これは、特許文献７において、調製されたタングステンブロンズの用途として電解装置や燃料電池の電極材料および有機合成の触媒材料が考えられている為である。即ち、タングステンブロンズを、上述の近赤外線遮蔽体へ適用することを考えていないものである。 Patent Document 7 describes a method for preparing tungsten bronze. However, there is no description of the particle diameter and optical characteristics of the obtained powder. This is because in Patent Document 7, an electrode material for an electrolysis apparatus or a fuel cell and a catalyst material for organic synthesis are considered as applications of the prepared tungsten bronze. That is, it is not considered to apply tungsten bronze to the above-mentioned near-infrared shield.
他方、特許文献８に記載のタングステン酸化物微粒子および／または複合タングステン酸化物微粒子は優れた可視光透過性と良好な近赤外線遮蔽効果とを有しているため、これらを樹脂、ガラス等の媒体中に分散させて成る近赤外線遮蔽材料微粒子分散体、この分散体から製造される近赤外線遮蔽体は、各種建築物や車両の窓材等の分野において好適に利用される近赤外線遮蔽体として有望である。
しかし、本発明者らの検討によると、これら近赤外線遮蔽材料微粒子分散体、この分散体から製造される近赤外線遮蔽体の膜強度、耐湿熱性については改善すべき余地がある。
On the other hand, since the tungsten oxide fine particles and / or the composite tungsten oxide fine particles described in Patent Document 8 have excellent visible light transmittance and a good near-infrared shielding effect, they are used as a medium such as a resin or glass. A near-infrared shielding material fine particle dispersion dispersed in a near-infrared shielding body produced from this dispersion is promising as a near-infrared shielding body suitably used in the fields of various buildings and vehicle window materials. It is.
However, according to the study by the present inventors, there is room for improvement in the near-infrared shielding material fine particle dispersion, the film strength and the wet heat resistance of the near-infrared shielding body produced from this dispersion.
特許文献９には、赤外線遮蔽材料微粒子分散剤へ金属塩を添加することで、赤外線遮蔽膜の経時的光学特性の低下防止が図れたことが記載されている。
しかしながら、特許文献９においては媒体として紫外線硬化樹脂などの樹脂成分または金属アルコキシド等を用いている為、赤外線遮蔽膜の膜強度が低く、プラズマディスプレイ用赤外線吸収フィルター等の用途以外への適用が困難であった。
Patent Document 9 describes that by adding a metal salt to an infrared shielding material fine particle dispersant, it is possible to prevent deterioration of optical characteristics of the infrared shielding film over time.
However, in Patent Document 9, since a resin component such as an ultraviolet curable resin or a metal alkoxide is used as a medium, the film strength of the infrared shielding film is low, and it is difficult to apply to applications other than applications such as an infrared absorption filter for plasma displays. Met.
本発明はこのような問題点に着目してなされたもので、その課題とするところは、太陽光からの近赤外線の吸収能力を有し、膜強度が高く、耐湿熱性が高いという特徴を有する熱線遮蔽分散体と当該熱線遮蔽分散体の形成用塗布液、および当該熱線遮蔽分散体を用いた熱線遮蔽体を提供することにある。 The present invention has been made paying attention to such problems, and the problem is that it has the ability to absorb near infrared rays from sunlight, has high film strength, and high heat and humidity resistance. The object of the present invention is to provide a heat ray shielding dispersion, a coating liquid for forming the heat ray shielding dispersion, and a heat ray shielding body using the heat ray shielding dispersion.
上記目的を達成するために、本発明者らが研究を行なった結果、近赤外線吸収材料である複合タングステン酸化物微粒子と、シラン化合物、ケイ酸塩、ポリリン酸塩、シリカアルミナ、チタニア、酸化セリウム、ジルコニア、等のいずれか１種類以上を含むバインダーとを、含む熱線遮蔽分散体へ、さらに、Ｂａ化合物とＰ化合物とＺｎ化合物との混合物を添加することで、可視光領域に透過率の極大を持つとともに近赤外領域に強い吸収を持ち、優れた膜強度と耐湿熱性とを有する熱線遮蔽分散体となる、との知見を得た。本発明は、当該技術的知見に基づき完成されたものである。 As a result of studies conducted by the present inventors in order to achieve the above object, composite tungsten oxide fine particles as a near infrared absorbing material, silane compound, silicate, polyphosphate, silica alumina, titania, cerium oxide , Zirconia, and the like containing a binder containing at least one binder, and adding a mixture of a Ba compound, a P compound, and a Zn compound to the heat ray shielding dispersion, the maximum transmittance in the visible light region As well as having a strong absorption in the near-infrared region, it has become a heat ray shielding dispersion having excellent film strength and heat and moisture resistance. The present invention has been completed based on the technical knowledge.
即ち、本発明に係る第１の発明は、
一般式ＭＹＷＯＺ（０．００１≦Ｙ≦１．０、２．２≦Ｚ≦３．０）で示され、Ｍ元素がＣｓ、Ｒｂ、Ｋ、Ｔｌのうちから選択される１種類以上であり、且つ、六方晶の結晶構造を持つ複合タングステン酸化物微粒子と、
Ｂａ化合物とＰ化合物とＺｎ化合物との混合物と、
シラン化合物、ケイ酸塩、ポリリン酸塩、シリカアルミナ、チタニア、酸化セリウム、ジルコニアのいずれか１種類以上を含むバインダーとを、含み、
前記Ｂａ化合物とＰ化合物とＺｎ化合物との混合物が、前記複合タングステン酸化物微粒子１００重量部に対し０．５重量部以上、５０重量部以下含有されていることを特徴とする熱線遮蔽分散体である。
第２の発明は、
前記複合タングステン酸化物微粒子が、平均粒径４０ｎｍ以下の微粒子であることを特徴とする第１の発明に記載の熱線遮蔽分散体である。
第３の発明は、
前記シラン化合物が、オルガノシラン、アルコキシシラン、オルガノアルコキシシラン、テトラアルコキシシランのいずれか１種類以上を含むシリカバインダーであることを特徴とする第１または第２の発明に記載の熱線遮蔽分散体である。
第４の発明は、
８５℃、９０％ＲＨの環境下に７日間暴露したときの可視光透過率の変化が、３．５％以下であることを特徴とする第１から第３の発明のいずれかに記載の熱線遮蔽分散体である。
第５の発明は、
一般式ＭＹＷＯＺ（０．００１≦Ｙ≦１．０、２．２≦Ｚ≦３．０）で示され、Ｍ元素がＣｓ、Ｒｂ、Ｋ、Ｔｌのうちから選択される１種類以上であり、且つ、六方晶の結晶構造を持つ複合タングステン酸化物微粒子と、
Ｂａ化合物とＰ化合物とＺｎ化合物との混合物とを、含むことを特徴とする熱線遮蔽分散体形成用塗布液である。
第６の発明は、
第５の発明に記載の熱線遮蔽分散体形成用塗布液であって、さらに、シラン化合物、ケイ酸塩、ポリリン酸塩、シリカアルミナ、チタニア、酸化セリウム、ジルコニアのいずれか１種類以上を含むバインダーとを、含む、ことを特徴とする熱線遮蔽分散体形成用塗布液である。
第７の発明は、
前記シラン化合物が、オルガノシラン、アルコキシシラン、オルガノアルコキシシラン、テトラアルコキシシランのいずれか１種類以上を含むシリカバインダーであることを特徴とする第６の発明に記載の熱線遮蔽分散体形成用塗布液である。
第８の発明は、
第１の発明に記載の熱線遮蔽分散体が、透明基材の片面または両面に塗布されていることを特徴とする熱線遮蔽体である。
第９の発明は、
第５の発明に記載の熱線遮蔽分散体形成用塗布液が、透明基材の片面または両面に塗布され、さらに、シラン化合物、ケイ酸塩、ポリリン酸塩、シリカアルミナ、チタニア、酸化セリウム、ジルコニアのいずれか１種類以上を含むバインダーが塗布されて、熱線遮蔽分散体が形成されたことを特徴とする熱線遮蔽体である。
第１０の発明は、
第６の発明に記載の熱線遮蔽分散体形成用塗布液が、透明基材の片面または両面に塗布され、熱線遮蔽分散体が形成されたことを特徴とする熱線遮蔽体である。
第１１の発明は、
前記シラン化合物が、オルガノシラン、アルコキシシラン、オルガノアルコキシシラン、テトラアルコキシシランのいずれか１種類以上を含むシリカバインダーであることを特徴とする第９または第１０の発明に記載の熱線遮蔽体である。
That is, the first invention according to the present invention is:
One or more types represented by the general formula M Y WO Z (0.001 ≦ Y ≦ 1.0, 2.2 ≦ Z ≦ 3.0), wherein the M element is selected from Cs, Rb, K, and Tl And a composite tungsten oxide fine particle having a hexagonal crystal structure,
A mixture of a Ba compound, a P compound and a Zn compound;
A binder containing any one or more of silane compounds, silicates, polyphosphates, silica alumina, titania, cerium oxide, and zirconia,
A heat ray shielding dispersion, wherein the mixture of the Ba compound, the P compound, and the Zn compound is contained in an amount of 0.5 to 50 parts by weight with respect to 100 parts by weight of the composite tungsten oxide fine particles. is there.
The second invention is
The composite tungsten oxide fine particles are fine particles having an average particle size of 40 nm or less, in the heat ray shielding dispersion according to the first invention.
The third invention is
In the heat ray shielding dispersion according to the first or second invention, the silane compound is a silica binder containing any one or more of organosilane, alkoxysilane, organoalkoxysilane, and tetraalkoxysilane. is there.
The fourth invention is:
The change in visible light transmittance when exposed to an environment of 85 ° C. and 90% RH for 7 days is 3.5% or less, and the heat ray according to any one of the first to third inventions It is a shielding dispersion.
The fifth invention is:
One or more types represented by the general formula M Y WO Z (0.001 ≦ Y ≦ 1.0, 2.2 ≦ Z ≦ 3.0), wherein the M element is selected from Cs, Rb, K, and Tl And a composite tungsten oxide fine particle having a hexagonal crystal structure,
A coating solution for forming a heat ray shielding dispersion, comprising a mixture of a Ba compound, a P compound, and a Zn compound.
The sixth invention is:
A coating solution for forming a heat ray shielding dispersion according to the fifth invention, further comprising a binder containing any one or more of a silane compound, a silicate, a polyphosphate, silica alumina, titania, cerium oxide, and zirconia Is a coating solution for forming a heat ray shielding dispersion.
The seventh invention
The coating solution for forming a heat ray shielding dispersion according to the sixth invention, wherein the silane compound is a silica binder containing at least one of organosilane, alkoxysilane, organoalkoxysilane, and tetraalkoxysilane. It is.
The eighth invention
A heat ray shielding body, wherein the heat ray shielding dispersion described in the first invention is applied to one side or both sides of a transparent substrate.
The ninth invention
The coating solution for forming a heat ray shielding dispersion described in the fifth invention is applied to one or both sides of a transparent substrate, and further, a silane compound, a silicate, a polyphosphate, silica alumina, titania, cerium oxide, zirconia A heat ray shielding body characterized in that a heat ray shielding dispersion is formed by applying a binder containing any one or more of the above.
The tenth invention is
A heat ray shielding body, wherein the heat ray shielding dispersion forming coating liquid described in the sixth invention is applied to one or both sides of a transparent substrate to form a heat ray shielding dispersion.
The eleventh invention is
The heat ray shielding body according to the ninth or tenth invention, wherein the silane compound is a silica binder containing one or more of organosilane, alkoxysilane, organoalkoxysilane, and tetraalkoxysilane. .
本発明に係る熱線遮蔽分散体および熱線遮蔽体は、膜強度と耐湿熱性とが高く、高温高湿環境に暴露された後であっても、近赤外線吸収機能の低下が抑制されていた。 The heat-ray shielding dispersion and heat-ray shielding body according to the present invention have high film strength and heat-and-moisture resistance, and even after being exposed to a high-temperature and high-humidity environment, a decrease in near-infrared absorption function was suppressed.
本発明は、一般式ＭＹＷＯＺ（０．００１≦Ｙ≦１．０、２．２≦Ｚ≦３．０）で示され、Ｍ元素がＣｓ、Ｒｂ、Ｋ、Ｔｌのうちから選択される１種類以上であり、且つ、六方晶の結晶構造を持つ複合タングステン酸化物微粒子である熱線遮蔽材料微粒子が、シラン化合物、ケイ酸塩、ポリリン酸塩、シリカアルミナ、チタニア、酸化セリウム、ジルコニア、等のいずれか１種類以上を含むバインダー中に分散してなる熱線遮蔽分散体を、所定の基材の片面または両面に設けた熱線遮蔽体である。
当該本発明に係る熱線遮蔽分散体、および当該熱線遮蔽分散体を所定の基材の片面または両面に設けた熱線遮蔽体は、膜強度と耐湿熱性とが高く、高温高湿環境下に暴露された後であっても、近赤外線吸収機能の低下が抑制されている。
The present invention is represented by the general formula M Y WO Z (0.001 ≦ Y ≦ 1.0, 2.2 ≦ Z ≦ 3.0), and the M element is selected from Cs, Rb, K, and Tl. The heat ray shielding material fine particles, which are one or more kinds of composite tungsten oxide fine particles having a hexagonal crystal structure, are silane compound, silicate, polyphosphate, silica alumina, titania, cerium oxide, zirconia, A heat ray shielding body in which a heat ray shielding dispersion formed by dispersing in a binder containing any one or more of the above is provided on one side or both sides of a predetermined substrate.
The heat ray shielding dispersion according to the present invention, and the heat ray shield provided with the heat ray shielding dispersion on one or both sides of a predetermined substrate, have high film strength and moisture and heat resistance, and are exposed to a high temperature and high humidity environment. Even after this, a decrease in the near-infrared absorption function is suppressed.
本発明において耐湿熱性とは、熱線遮蔽分散体または熱線遮蔽体を、例えば８５℃、９０％ＲＨという高温高湿環境下に暴露した場合において、暴露前と比較して、可視光透過率が低下する、日射透過率が上昇するといった光学的特性の劣化が抑制されていることを言う。つまり、本発明に係る熱線遮蔽分散体や熱線遮蔽体が、高温高湿環境下において耐久性を有することを言う。 In the present invention, the heat and moisture resistance means that when the heat ray shielding dispersion or heat ray shield is exposed to a high temperature and high humidity environment of, for example, 85 ° C. and 90% RH, the visible light transmittance is lower than before the exposure. In other words, the deterioration of optical properties such as an increase in solar transmittance is suppressed. That is, it means that the heat ray shielding dispersion and heat ray shield according to the present invention have durability in a high temperature and high humidity environment.
以下、本発明について、（１）複合タングステン酸化物微粒子、（２）バインダー、（３）Ｂａ化合物とＰ化合物とＺｎ化合物との混合物、（４）複合タングステン酸化物微粒子分散液の製造方法、（５）熱線遮蔽分散体形成用塗布液とその製造方法、（６）熱線遮蔽分散体とその形成、（７）熱線遮蔽体とその形成、（８）まとめ、の順で詳細に説明する。 Hereinafter, (1) a composite tungsten oxide fine particle, (2) a binder, (3) a mixture of a Ba compound, a P compound, and a Zn compound, (4) a method for producing a composite tungsten oxide fine particle dispersion, 5) Heat ray shielding dispersion forming coating solution and production method thereof, (6) Heat ray shielding dispersion and formation thereof, (7) Heat ray shielding body and formation thereof, and (8) Summary will be described in detail.
（１）複合タングステン酸化物微粒子
一般に、自由電子を含む物質は、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にある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とすると、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。
(1) Composite tungsten oxide fine particles In general, it is known that a substance containing free electrons exhibits a reflection / absorption response to electromagnetic waves in the vicinity of a solar ray region having a wavelength of 200 nm to 2600 nm by plasma oscillation. When the powder of such a substance is a fine particle 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 is obtained.
ここで、一般にはＷＯ３中に有効な自由電子が存在しないため、ＷＯ３は近赤外線領域の吸収反射特性が少なく、近赤外線吸収材料としては有効ではない。一方、酸素欠損を持つ３酸化タングステンや、３酸化タングステンにＮａ等の陽性元素を添加したいわゆるタングステンブロンズは、導電性材料であり、自由電子を持つ材料である。そして、これらの物質の単結晶等を分析した結果から、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。
本発明者等は、当該酸素欠損を持つ３酸化タングステンやタングステンブロンズにおいて、タングステンと酸素との組成範囲が特定範囲にあるとき、近赤外線吸収材料として特に有効なものとなることを見出した。
Here, generally because there is no effective free electrons in WO 3, WO 3 is less absorption reflection characteristics in the near infrared region, is not effective as a near-infrared-absorbing material. On the other hand, tungsten trioxide having oxygen vacancies or so-called tungsten bronze obtained by adding a positive element such as Na to tungsten trioxide is a conductive material and a material having free electrons. The results of analyzing single crystals of these substances suggest the response of free electrons to light in the infrared region.
The present inventors have found that the tungsten trioxide or tungsten bronze having oxygen deficiency is particularly effective as a near-infrared absorbing material when the composition range of tungsten and oxygen is in a specific range.
本発明に適用される近赤外線吸収機能を有する微粒子は、一般式ＭＹＷＯＺ（０．００１≦Ｙ≦１．０、２．２≦Ｚ≦３．０）で示され、且つ六方晶の結晶構造を持つ複合タングステン酸化物微粒子である。当該複合タングステン酸化物微粒子は、熱線遮蔽分散体や熱線遮蔽体に適用された場合、熱線吸収成分として有効に機能する。
当該一般式ＭＹＷＯＺ（０．００１≦Ｙ≦１．０、２．２≦Ｚ≦３．０）で示され、且つ六方晶の結晶構造を持つ複合タングステン酸化物微粒子としては、例えばＭ元素が、Ｃｓ、Ｒｂ、Ｋ、Ｔｌのうちの１種類以上を含むような複合タングステン酸化物微粒子が挙げられる。添加元素Ｍの添加量は、０．１以上０．５以下が好ましく、更に好ましくは０．３３付近が好ましい。これは六方晶の結晶構造から理論的に算出される値が０．３３であり、この前後の添加量で好ましい光学特性が得られるからである。典型的な例としてはＣｓ０．３３ＷＯ３、Ｒｂ０．３３ＷＯ３、Ｋ０．３３ＷＯ３、Ｔｌ０．３３ＷＯ３などを挙げることができるが、Ｙ，Ｚの値が上述の範囲に収まるものであれば、有用な熱線吸収特性を得ることができる。
The fine particles having a near-infrared absorbing function applied to the present invention are represented by a general formula M Y WO Z (0.001 ≦ Y ≦ 1.0, 2.2 ≦ Z ≦ 3.0), and are hexagonal crystals. It is a composite tungsten oxide fine particle having a crystal structure. The composite tungsten oxide fine particles function effectively as a heat ray absorbing component when applied to a heat ray shielding dispersion or a heat ray shielding body.
As the composite tungsten oxide fine particles represented by the general formula M Y WO Z (0.001 ≦ Y ≦ 1.0, 2.2 ≦ Z ≦ 3.0) and having a hexagonal crystal structure, for example, M Examples thereof include composite tungsten oxide fine particles in which the element contains one or more of Cs, Rb, K, and Tl. The amount of additive element M added is preferably 0.1 or more and 0.5 or less, and more preferably around 0.33. This is because the value theoretically calculated from the hexagonal crystal structure is 0.33, and preferable optical characteristics can be obtained with the addition amount before and after this. Typical examples include Cs 0.33 WO 3 , Rb 0.33 WO 3 , K 0.33 WO 3 , Tl 0.33 WO 3 and the like. If it falls within the range, useful heat ray absorption characteristics can be obtained.
さらに、熱線遮蔽分散体や熱線遮蔽体の意匠性を考慮すると、可視光領域の透明性を保持したまま近赤外線領域の効率良い遮蔽を行なうことが求められる。一方、本発明に係る複合タングステン酸化物微粒子を含有する近赤外線吸収材料は、近赤外線領域、特に波長９００ｎｍから２２００ｎｍ付近の光を大きく吸収するため、その透過色調は青色系から緑色系となる物が多い。 Furthermore, considering the design properties of the heat ray shielding dispersion and heat ray shield, it is required to efficiently shield the near infrared region while maintaining the transparency of the visible light region. On the other hand, the near-infrared absorbing material containing the composite tungsten oxide fine particles according to the present invention greatly absorbs light in the near-infrared region, particularly in the wavelength range from 900 nm to 2200 nm, so that the transmitted color tone is from blue to green. There are many.
また、当該複合タングステン酸化物微粒子の分散粒子径が８００ｎｍよりも小さい場合、可視光を遮蔽ないため、可視光領域の透明性を保持したまま効率良く近赤外線を遮蔽することが可能となる。尤も、特に可視光領域の透明性を重視する場合には、分散粒子径は２００ｎｍ以下がよく、さらに好ましくは１００ｎｍ以下がよい。
これは、微粒子の分散粒子径が小さいと、幾何学散乱もしくは回折散乱によって波長４００ｎｍから７８０ｎｍの可視光領域の光を散乱して曇りガラスのようになり、十分な透明性が得られなくなる現象を回避出来るからである。さらに、分散粒子径が２００ｎｍ以下になると、上述の散乱が低減してミー散乱もしくはレイリー散乱領域になる。特に、レイリー散乱領域まで分散粒子径が減少すると、散乱光は分散粒子径の６乗に反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。さらに、分散粒子径が１００ｎｍ以下になると散乱光は非常に少なくなり好ましい。当該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い。一方、分散粒子径が１ｎｍ以上であれば工業的な製造は容易である。
In addition, when the dispersed particle diameter of the composite tungsten oxide fine particles is smaller than 800 nm, visible light is not blocked, so that it is possible to efficiently shield near infrared rays while maintaining transparency in the visible light region. However, when emphasizing transparency in the visible light region, the dispersed particle size is preferably 200 nm or less, and more preferably 100 nm or less.
This is because when the dispersed particle size of the fine particles is small, light in the visible light region having a wavelength of 400 nm to 780 nm is scattered by geometric scattering or diffraction scattering to become like frosted glass, and sufficient transparency cannot be obtained. This is because it can be avoided. Furthermore, when the dispersed particle diameter is 200 nm or less, the above-mentioned scattering is reduced and a Mie scattering or Rayleigh scattering region is obtained. In particular, when the dispersed particle diameter decreases to the Rayleigh scattering region, the scattered light decreases in inverse proportion to the sixth power of the dispersed particle diameter, so that the scattering is reduced and the transparency is improved as the dispersed particle diameter decreases. Furthermore, when the dispersed particle diameter is 100 nm or less, the scattered light is preferably extremely small. From the viewpoint of avoiding the light scattering, it is preferable that the dispersed particle diameter is small. On the other hand, if the dispersed particle diameter is 1 nm or more, industrial production is easy.
また、複合タングステン酸化物微粒子の単位重量あたりの熱線吸収能力は非常に高く、ＩＴＯ（インジウム錫酸化物）やＡＴＯ（アンチモン錫酸化物）と比較して、４〜１０分の１程度の使用量でその効果を発揮する。 In addition, the composite tungsten oxide fine particles have a very high heat-absorbing ability per unit weight, which is about 4 to 10 times less than ITO (indium tin oxide) or ATO (antimony tin oxide). To demonstrate its effect.
（２）バインダー
本発明に係るバインダーとしては、シラン化合物、ケイ酸塩、ポリリン酸塩、シリカアルミナ、チタニア、酸化セリウム、ジルコニア、等のいずれか１種類以上を含むバインダーを用いることが出来る。
なかでも、シラン化合物は、金属元素または珪素が、酸素を介して互いに結合した構造を有する化合物を含むものである。金属元素または珪素が、酸素を介して互いに結合した構造をとることで、高い膜強度を有する熱線遮蔽分散体および熱線遮蔽体が得られるので好ましい。
さらに、当該シラン化合物は、オルガノシラン、アルコキシシラン、オルガノアルコキシシラン、テトラアルコキシシラン、等から選択される１種類以上を含むシリカバインダーである。好ましいシリカバインダーとして、オルガノシランを含むシリカバインダーが挙げられる。オルガノシランはシロキサン結合を持ち強度に優れる上、末端基にメチル基等の有機基を持つため、耐水性にも優れるからである。
(2) Binder As the binder according to the present invention, a binder containing any one or more of silane compounds, silicates, polyphosphates, silica alumina, titania, cerium oxide, zirconia, and the like can be used.
Among them, the silane compound includes a compound having a structure in which metal elements or silicon are bonded to each other through oxygen. A structure in which metal elements or silicon are bonded to each other via oxygen is preferable because a heat ray shielding dispersion and a heat ray shielding member having high film strength can be obtained.
Further, the silane compound is a silica binder containing one or more selected from organosilane, alkoxysilane, organoalkoxysilane, tetraalkoxysilane, and the like. As a preferred silica binder, a silica binder containing an organosilane can be mentioned. This is because organosilane has a siloxane bond and excellent strength, and also has an organic group such as a methyl group at the terminal group, and therefore has excellent water resistance.
（３）Ｂａ化合物とＰ化合物とＺｎ化合物との混合物
本発明に係るＢａ化合物とＰ化合物とＺｎ化合物との混合物は、熱線遮蔽分散体および熱線遮蔽体の耐湿熱性を向上させ、長期間使用された際の光学特性の変化を抑制する目的で添加するものである。当該熱線遮蔽分散体や熱線遮蔽体の耐湿熱性が向上することで、長期間使用された際の光学特性の変化を抑制することが出来るからである。
(3) Mixture of Ba compound, P compound, and Zn compound The mixture of Ba compound, P compound, and Zn compound according to the present invention improves the heat and heat resistance of the heat ray shielding dispersion and heat ray shield, and is used for a long time. It is added for the purpose of suppressing the change in optical characteristics during the process. It is because the change in optical characteristics when used for a long period of time can be suppressed by improving the heat and heat resistance of the heat ray shielding dispersion and the heat ray shielding body.
本発明に係るＢａ化合物とＰ化合物とＺｎ化合物との混合物について説明する。
Ｂａ化合物としては、ステアリン酸Ｂａ、ラウリン酸Ｂａ、リシノ−ル酸Ｂａ、オレイン酸Ｂａ、オクタン酸Ｂａ等のＢａの脂肪族カルボン酸塩や、安息香酸Ｂａ、ｐ−第三ブチル安息香酸Ｂａ等の芳香族カルボン酸Ｂａ、アミノ酸Ｂａ塩、リン酸エステルＢａ塩のような有機酸のＢａ塩、酸化Ｂａ、炭酸Ｂａ等の無機Ｂａ塩、等を挙げることが出来る。
The mixture of the Ba compound, the P compound and the Zn compound according to the present invention will be described.
Examples of Ba compounds include Ba fatty carboxylates such as stearic acid Ba, lauric acid Ba, ricinoleic acid Ba, oleic acid Ba, and octanoic acid Ba, benzoic acid Ba, and p-tert-butylbenzoic acid Ba. An organic acid Ba salt such as an aromatic carboxylic acid Ba, an amino acid Ba salt, and a phosphoric acid ester Ba salt, an inorganic Ba salt such as Ba oxide and Ba carbonate, and the like.
Ｐ化合物としては、トリアルキルホスファイト、アルキルアリルフォスファイト、トリアリルフォスファイト、ジフェニルデシルホスファイト、トリフェニルホスファイト、トリス（ノニルフェニル）ホスファイト、トリデシルホスファイト、トリス（２−エチルヘキシル）ホスファイト、トリステアリルホスファイト、オクチルジフェニルホスファイト、ジフェニルアシッドホスファイト、ジオクチルアシッドホスファイト、トリスノニルフェニルホスファイト、トリス（２，４−ジ第三ブチルフェニル）ホスファイト、トリス〔２−第三ブチル−４−（３−第三ブチル−４−ヒドロキシ−５−メチルフェニルチオ）−５−メチルフェニル〕ホスファイト、ジ（デシル）モノフェニルホスファイト、ジ（トリデシル）ペンタエリスリトールジホスファイト、ジステアリルペンタエリスリトールジホスファイト、ジ（ノニルフェニル）ペンタエリスリトールジホスファイト、ビス（２，４−ジ第三ブチルフェニル）ペンタエリスリトールジホスファイト、ビス（２，６−ジ第三ブチル−４−メチルフェニル）ペンタエリスリトールジホスファイト、ビス（２，４，６−トリ第三ブチルフェニル）ペンタエリスリトールジホスファイト、テトラ（トリデシル）イソプロピリデンジフェノールジホスファイト、テトラ（トリデシル）−４，４’−ｎ−ブチリデンビス（２−第三ブチル−５−メチルフェノール）ジホスファイト、ヘキサ（トリデシル）−１，１，３−トリス（２−メチル−４−ヒドロキシ−５−第三ブチルフェニル）ブタントリホスファイト、テトラキス（２，４−ジ第三ブチルフェニル）ビフェニレンジホスホナイト、９，１０−ジハイドロ−９−オキサ−１０−ホスファフェナンスレン−１０−オキサイド、２，２’−メチレンビス（４−メチル−６−第三ブチルフェニル）−２−エチルヘキシルホスファイト等の有機ホスファイトを挙げることが出来る。 P compounds include trialkyl phosphite, alkyl allyl phosphite, triallyl phosphite, diphenyl decyl phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, tridecyl phosphite, tris (2-ethylhexyl) phos Phyto, tristearyl phosphite, octyl diphenyl phosphite, diphenyl acid phosphite, dioctyl acid phosphite, trisnonyl phenyl phosphite, tris (2,4-ditertiary butylphenyl) phosphite, tris [2-tertiary butyl -4- (3-tert-butyl-4-hydroxy-5-methylphenylthio) -5-methylphenyl] phosphite, di (decyl) monophenyl phosphite, di (tridecyl) pentaerythritol Phosphite, distearyl pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4-ditert-butylphenyl) pentaerythritol diphosphite, bis (2,6-ditert-butyl) -4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tritert-butylphenyl) pentaerythritol diphosphite, tetra (tridecyl) isopropylidenediphenol diphosphite, tetra (tridecyl) -4 , 4'-n-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl) -1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane Triphosphite, tetrakis (2,4-di- Butylphenyl) biphenylenediphosphonite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2,2'-methylenebis (4-methyl-6-tert-butylphenyl) -2 -Organic phosphites such as ethylhexyl phosphite can be mentioned.
Ｚｎ化合物としては、ステアリン酸Ｚｎ、ラウリン酸Ｚｎ、リシノール酸Ｚｎ、オレイン酸Ｚｎ、オクタン酸Ｚｎ等のＺｎの脂肪族カルボン酸塩や、安息香酸Ｚｎ、ｐ−第三ブチル安息香酸Ｚｎ等の芳香族カルボン酸Ｚｎ、アミノ酸Ｚｎ塩、リン酸エステルＺｎ塩のような有機酸のＺｎ塩、酸化Ｚｎ、炭酸Ｚｎ等の無機Ｚｎ塩、等とそれらの混合物を挙げることが出来る。
本発明に係るＢａ化合物とＰ化合物とＺｎ化合物との混合物中における、Ｂａ化合物、Ｐ化合物、Ｚｎ化合物の混合比率は、特に限定されない。
そしてこれらのＢａ化合物とＰ化合物とＺｎ化合物との混合物は、ポリ塩化ビニルの安定剤として多用されているものなので、例えば、株式会社ＡＤＥＫＡ製のアデカスタブＡＣ−２５５、アデカスタブＡＣ−２８５、アデカスタブＡＣ−２９３、アデカスタブＡＣ−７５５などを、好適に用いることができる。
Examples of the Zn compound include Zn aliphatic carboxylates such as Zn stearate, Zn laurate, Zn ricinoleate, Zn oleate and Zn octoate, and fragrances such as Zn benzoate and Zn p-tert-butylbenzoate. Examples thereof include Zn salts of organic acids such as zinc group carboxylates, amino acid Zn salts, and phosphate ester Zn salts, inorganic Zn salts such as Zn oxide and Zn carbonate, and the like, and mixtures thereof.
The mixing ratio of the Ba compound, the P compound, and the Zn compound in the mixture of the Ba compound, the P compound, and the Zn compound according to the present invention is not particularly limited.
The mixture of these Ba compound, P compound and Zn compound is often used as a stabilizer for polyvinyl chloride. For example, ADEKA STAB AC-255, ADEKA STAB AC-285, ADEKA STAB AC- manufactured by ADEKA CORPORATION 293, Adekastab AC-755, etc. can be used suitably.
本発明に係るＢａ化合物とＰ化合物とＺｎ化合物との混合物が熱線遮蔽体の耐湿熱性を向上させる詳細理由については明らかではない。しかし、上述したシラン化合物、ケイ酸塩、ポリリン酸塩、シリカアルミナ、チタニア、酸化セリウム、ジルコニア、等のいずれか１種類以上を含むバインダーが、Ｂａ化合物とＰ化合物とＺｎ化合物との混合物と反応し、当該バインダー膜が緻密になることで、熱線遮蔽体への湿熱の影響が低減することが原因だと推察される。 It is not clear about the detailed reason why the mixture of the Ba compound, the P compound and the Zn compound according to the present invention improves the heat and heat resistance of the heat shield. However, the binder containing any one or more of the above-mentioned silane compounds, silicates, polyphosphates, silica aluminas, titanias, cerium oxides, zirconias, etc. reacts with a mixture of Ba compounds, P compounds and Zn compounds. And it is guessed that the influence of the wet heat to a heat ray shield reduces because the said binder film | membrane becomes dense.
（４）複合タングステン酸化物微粒子分散液の製造方法
（i）複合タングステン酸化物微粒子の分散液
本発明に係る複合タングステン酸化物微粒子分散液は、以下の方法により得られる。
最初に、複合タングステン酸化物微粒子と溶媒と分散剤とを混合し、分散処理を行う。分散処理の方法については、複合タングステン酸化物微粒子が所望の分散粒子径となるものであれば、特に制限はない。当該分散処理は、複合タングステン酸化物微粒子の分散粒子径が２００ｎｍ以下となるまで行う。複合タングステン酸化物微粒子の分散粒子径が１００ｎｍ以下となればさらに好ましい。
これは複合タングステン酸化物微粒子の分散粒子径が小さいほど、最終的に得られる熱線遮蔽分散体や熱線遮蔽体の透明性が向上するためである。
(4) Manufacturing method of composite tungsten oxide fine particle dispersion (i) Dispersion of composite tungsten oxide fine particles The composite tungsten oxide fine particle dispersion according to the present invention is obtained by the following method.
First, composite tungsten oxide fine particles, a solvent, and a dispersing agent are mixed and a dispersion treatment is performed. The dispersion treatment method is not particularly limited as long as the composite tungsten oxide fine particles have a desired dispersed particle size. The dispersion treatment is performed until the dispersed particle diameter of the composite tungsten oxide fine particles becomes 200 nm or less. More preferably, the dispersed particle diameter of the composite tungsten oxide fine particles is 100 nm or less.
This is because the transparency of the finally obtained heat ray shielding dispersion or heat ray shielding body is improved as the dispersed particle size of the composite tungsten oxide fine particles is smaller.
複合タングステン酸化物微粒子分散液の製造に用いる分散剤としては、複合タングステン酸化物微粒子の分散性を向上させる効果が得られればよく、分散剤の種類に、特に制限はない。 The dispersant used for the production of the composite tungsten oxide fine particle dispersion is not particularly limited as long as the effect of improving the dispersibility of the composite tungsten oxide fine particles can be obtained.
複合タングステン酸化物微粒子分散液の製造に用いる溶媒としては、複合タングステン酸化物微粒子の分散が出来るものであれば、特に制限はない。例えば、水、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、メチルイソブチルケトンなどのケトン類といった各種の有機溶媒も使用可能である。 The solvent used in the production of the composite tungsten oxide fine particle dispersion is not particularly limited as long as the composite tungsten oxide fine particles can be dispersed. For example, water, ethanol, propanol, butanol, isopropyl alcohol, isobutyl alcohol, diacetone alcohol and other alcohols, ethers such as methyl ether, ethyl ether, propyl ether, esters, acetone, methyl ethyl ketone, diethyl ketone, cyclohexanone, methyl Various organic solvents such as ketones such as isobutyl ketone can also be used.
（ii）複合タングステン酸化物微粒子への、Ｂａ化合物とＰ化合物とＺｎ化合物との混合物の混合
複合タングステン酸化物微粒子と、Ｂａ化合物とＰ化合物とＺｎ化合物との混合物との混合は、まず複合タングステン酸化物微粒子を上述したように分散処理し分散液とした後に、当該複合タングステン酸化物微粒子分散液へ、Ｂａ化合物とＰ化合物とＺｎ化合物との混合物を添加すれば良い。
また、予め、複合タングステン酸化物微粒子と、Ｂａ化合物とＰ化合物とＺｎ化合物との混合物とを混合した後、当該混合物に対して分散処理を行って分散液としてもよい。
(Ii) Mixing of the mixture of Ba compound, P compound and Zn compound into the composite tungsten oxide fine particles The mixing of the composite tungsten oxide fine particles with the mixture of Ba compound, P compound and Zn compound is performed first by combining composite tungsten. After the oxide fine particles are dispersed as described above to obtain a dispersion, a mixture of a Ba compound, a P compound, and a Zn compound may be added to the composite tungsten oxide fine particle dispersion.
Alternatively, the composite tungsten oxide fine particles and a mixture of a Ba compound, a P compound, and a Zn compound may be mixed in advance, and the mixture may be subjected to a dispersion treatment to obtain a dispersion.
（iii）複合タングステン酸化物微粒子と、Ｂａ化合物とＰ化合物とＺｎ化合物との混合物との混合比率
複合タングステン酸化物微粒子と、Ｂａ化合物とＰ化合物とＺｎ化合物との混合物との混合比率は、複合タングステン酸化物微粒子１００重量部に対しＢａ化合物とＰ化合物とＺｎ化合物との混合物が０．１重量部以上、５０重量部以下の範囲であることが好ましく、１０重量部以上、３０重量部以下の範囲であることがより好ましい。
Ｂａ化合物とＰ化合物とＺｎ化合物との混合物の添加量が上述の範囲にあれば、シラン化合物、ケイ酸塩、ポリリン酸塩、シリカアルミナ、チタニア、酸化セリウム、ジルコニア、等のいずれか１種類以上を含むバインダーと組み合わせたときの複合タングステン酸化物微粒子の耐湿熱性向上の効果があり、且つ、製造される熱線遮蔽分散体や熱線遮蔽体における、膜強度（機械的特性）や光学的特性に悪影響を及ぼすことがないからである。
(Iii) Mixing ratio of composite tungsten oxide fine particles and a mixture of Ba compound, P compound and Zn compound The mixing ratio of composite tungsten oxide fine particles and a mixture of Ba compound, P compound and Zn compound is a composite ratio. The mixture of the Ba compound, P compound and Zn compound is preferably in the range of 0.1 to 50 parts by weight with respect to 100 parts by weight of the tungsten oxide fine particles, preferably 10 to 30 parts by weight. A range is more preferable.
If the addition amount of the mixture of Ba compound, P compound and Zn compound is in the above range, any one or more of silane compound, silicate, polyphosphate, silica alumina, titania, cerium oxide, zirconia, etc. It has the effect of improving the heat and moisture resistance of the composite tungsten oxide fine particles when combined with a binder containing, and adversely affects the film strength (mechanical properties) and optical properties of the heat ray shielding dispersion and heat ray shielding produced. It is because it does not exert.
また、必要に応じて、複合タングステン酸化物微粒子と、Ｂａ化合物とＰ化合物とＺｎ化合物との混合物との、混合物へ、酸やアルカリを添加してｐＨ値を調整してもよい。さらに、複合タングステン酸化物微粒子分散液中における、複合タングステン酸化物微粒子の分散安定性を一層向上させるために、各種の界面活性剤、カップリング剤などを添加することも可能である。 If necessary, the pH value may be adjusted by adding acid or alkali to the mixture of the composite tungsten oxide fine particles and the mixture of Ba compound, P compound and Zn compound. Furthermore, in order to further improve the dispersion stability of the composite tungsten oxide fine particles in the composite tungsten oxide fine particle dispersion, various surfactants, coupling agents and the like can be added.
（５）熱線遮蔽分散体形成用塗布液とその製造方法
上述の方法により製造された複合タングステン酸化物微粒子分散液を、上述したバインダーと混合し、必要に応じて溶媒で希釈することにより塗布液が得られる。
ここで、当該熱線遮蔽分散体形成用塗布液における上述したバインダーの混合量は、５質量％以上であることが好ましい。バインダーの量が５質量％以上あれば、熱線遮蔽効果の高い熱線遮蔽分散体の形成が容易である。
(5) Coating solution for forming a heat ray shielding dispersion and its production method The composite tungsten oxide fine particle dispersion produced by the above-mentioned method is mixed with the above-mentioned binder, and diluted with a solvent as necessary. Is obtained.
Here, the mixing amount of the binder described above in the coating solution for forming a heat ray shielding dispersion is preferably 5% by mass or more. If the amount of the binder is 5% by mass or more, it is easy to form a heat ray shielding dispersion having a high heat ray shielding effect.
また、複合タングステン酸化物微粒子分散液に前記バインダーを添加せず、適宜、溶媒で希釈することで熱線遮蔽分散体形成用塗布液としても良い。この場合は、当該熱線遮蔽分散体形成用塗布液を用いて熱線遮蔽分散体を形成後に、前記バインダーを含む塗布液を塗布して、当該熱線遮蔽分散体に前記バインダーを含浸させれば良い。 Moreover, it is good also as a coating liquid for heat ray shielding dispersion formation by not adding the said binder to composite tungsten oxide fine particle dispersion, but diluting with a solvent suitably. In this case, after forming the heat ray shielding dispersion using the heat ray shielding dispersion forming coating solution, a coating solution containing the binder may be applied, and the heat ray shielding dispersion may be impregnated with the binder.
熱線遮蔽分散体形成用塗布液の濃度については、塗布方法に合わせて、適宜、最適な濃度を選択することができる。
熱線遮蔽分散体形成用塗布液を、適宜、希釈するのに用いる溶媒としては、例えば、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、メチルイソブチルケトンなどのケトン類といった各種の有機溶媒や、水が使用可能である。
About the density | concentration of the coating liquid for heat ray shielding dispersion formation, an optimal density | concentration can be suitably selected according to the coating method.
Solvents used for appropriately diluting the coating solution for forming a heat ray shielding dispersion include, for example, alcohols such as ethanol, propanol, butanol, isopropyl alcohol, isobutyl alcohol, diacetone alcohol, methyl ether, ethyl ether, propyl Various organic solvents such as ethers such as ether, esters, acetone, methyl ethyl ketone, diethyl ketone, cyclohexanone, and methyl isobutyl ketone, and water can be used.
また、必要に応じて、当該溶媒へ、酸やアルカリを添加してｐＨ値を調整してもよい。
さらに、複合タングステン酸化物微粒子の分散安定性を一層向上させるために、各種の界面活性剤、カップリング剤などを添加することも可能である。
さらに、複合タングステン酸化物微粒子分散液の色調などの調整のため、各種顔料、染料を加えても良い。
If necessary, the pH value may be adjusted by adding an acid or alkali to the solvent.
Furthermore, in order to further improve the dispersion stability of the composite tungsten oxide fine particles, various surfactants, coupling agents and the like can be added.
Furthermore, various pigments and dyes may be added to adjust the color tone of the composite tungsten oxide fine particle dispersion.
（６）熱線遮蔽分散体の形成方法
熱線遮蔽分散体形成用塗布液を用いた、熱線遮蔽分散体の形成方法について説明する。
上述の方法により製造された熱線遮蔽分散体形成用塗布液を、適宜な透明基材上に塗布し、分散媒を蒸発させ、加熱硬化させる。これにより、複合タングステン酸化物微粒子と、バインダーと、Ｂａ化合物とＰ化合物とＺｎ化合物との混合物とを、含む熱線遮蔽分散体が得られる。
(6) Method for forming heat ray shielding dispersion A method for forming a heat ray shielding dispersion using a coating solution for forming a heat ray shielding dispersion will be described.
The coating solution for forming a heat ray shielding dispersion produced by the above-described method is applied on an appropriate transparent substrate, the dispersion medium is evaporated, and heat-cured. Thereby, the heat ray shielding dispersion containing the composite tungsten oxide fine particles, the binder, and the mixture of the Ba compound, the P compound, and the Zn compound is obtained.
（７）熱線遮蔽体とその形成
適宜な透明基材表面へ熱線遮蔽分散体を形成することで、熱線遮蔽体を製造することが出来る。
適宜な透明基材表面への熱線遮蔽分散体形成用塗布液の塗布方法としては、均一に塗布できれば特に制限はなく、例えば、バーコート法、グラビヤコート法、スプレーコート法、ディップコート法、フローコート法、スピンコート法、ロールコート法、スクリーン印刷法、ブレードコート法などを用いることができる。
これらの塗布方法により形成された複合タングステン酸化物微粒子を含有する熱線遮蔽分散体の層は、スパッタリング法、蒸着法、イオンプレーティング法および化学気相成長法（ＣＶＤ法）などの乾式法や、スプレー法で製造した層（膜）に比べて、光の干渉効果を用いなくても、特に近赤外線領域の光を効率よく吸収する。同時に当該層は、可視光領域の光を透過させることができる。
(7) Heat ray shielding body and formation thereof A heat ray shielding body can be produced by forming a heat ray shielding dispersion on an appropriate transparent substrate surface.
There is no particular limitation on the method for applying the coating solution for forming the heat ray shielding dispersion on the surface of the appropriate transparent substrate as long as it can be uniformly applied. For example, the bar coating method, gravure coating method, spray coating method, dip coating method, flow A coating method, a spin coating method, a roll coating method, a screen printing method, a blade coating method, or the like can be used.
The layer of the heat ray shielding dispersion containing the composite tungsten oxide fine particles formed by these coating methods is a dry method such as sputtering method, vapor deposition method, ion plating method and chemical vapor deposition method (CVD method), Compared with a layer (film) manufactured by the spray method, light in the near-infrared region is efficiently absorbed particularly without using the light interference effect. At the same time, the layer can transmit light in the visible light region.
適宜な透明基材表面への熱線遮蔽分散体形成用塗布液の塗布後、１００℃以上、２００℃未満の加熱をすることが好ましい。透明基材加熱温度を１００℃以上とすることで、熱線遮蔽分散体中に含まれる本発明に係るバインダーの重合反応を殆ど完結させることが出来る。当該重合反応を殆ど完結させることで、熱線遮蔽分散体中に水や有機溶媒が残留することによる、可視光透過率の低減の原因を回避できる。当該観点からは、さらに好ましい加熱温度は１２０℃以上である。
また、基材加熱温度を２００℃未満とすることで、複合タングステン酸化物微粒子の酸化を回避し、熱線遮蔽能の損失を回避することが出来る。
It is preferable to heat at 100 ° C. or more and less than 200 ° C. after applying the heat ray shielding dispersion-forming coating solution onto an appropriate transparent substrate surface. By setting the transparent substrate heating temperature to 100 ° C. or higher, the polymerization reaction of the binder according to the present invention contained in the heat ray shielding dispersion can be almost completed. By almost completing the polymerization reaction, it is possible to avoid the cause of reduction in visible light transmittance due to the remaining water or organic solvent in the heat ray shielding dispersion. From this viewpoint, a more preferable heating temperature is 120 ° C. or higher.
Moreover, the base-material heating temperature shall be less than 200 degreeC, and the oxidation of composite tungsten oxide microparticles | fine-particles can be avoided and the loss of heat ray shielding ability can be avoided.
上述の方法により製造された熱線遮蔽体や熱線遮蔽分散体は、膜強度が高く、耐湿熱性に優れている。
具体的には、本発明に係る熱線遮蔽分散体の表面硬度は、ＪＩＳ Ｋ ５６００塗料一般試験方法の４．４引っかき強度（鉛筆法）で評価した。熱線遮蔽体の表面硬度は２Ｈ以上となり、さらには４Ｈ以上であった。
そして、上述の方法により製造された熱線遮蔽体や熱線遮蔽分散体は、高温高湿環境下（例えば８５℃、９０％ＲＨ）に暴露された後であっても、近赤外線吸収機能の低下が抑制されていた。
具体的には、８５℃、９０％ＲＨ環境下に７日間暴露した際に、可視光透過率の変化が３．５％以下、さらには２．５％以下。また、日射透過率の変化は３．５％以下、さらには３．０％以下であった。
The heat ray shielding body and heat ray shielding dispersion produced by the above-described method have high film strength and excellent moisture and heat resistance.
Specifically, the surface hardness of the heat ray shielding dispersion according to the present invention was evaluated by 4.4 scratch strength (pencil method) of the JIS K 5600 paint general test method. The surface hardness of the heat ray shield was 2H or higher, and further 4H or higher.
And even if the heat ray shielding body and heat ray shielding dispersion manufactured by the above-mentioned method are exposed to a high-temperature and high-humidity environment (for example, 85 ° C., 90% RH), the near-infrared absorption function is reduced. It was suppressed.
Specifically, when exposed to an environment of 85 ° C. and 90% RH for 7 days, the change in visible light transmittance is 3.5% or less, and further 2.5% or less. Further, the change in solar radiation transmittance was 3.5% or less, and further 3.0% or less.
さらに、上記方法で得られた本発明に係る熱線遮蔽分散体膜において、複合タングステン酸化物微粒子は導電性材料であるため、当該微粒子が連接して連続的な膜となっている場合には、携帯電話等の電波を吸収反射して妨害する恐れがある。しかし、複合タングステン酸化物微粒子を、例えばビーズミルを用いて分散することで、微粒子としてマトリックス中に分散した場合には、粒子一つ一つが孤立した状態で分散しているため、電波透過性を発揮することができ、汎用性を有している。 Furthermore, in the heat ray shielding dispersion film according to the present invention obtained by the above method, since the composite tungsten oxide fine particles are conductive materials, when the fine particles are connected to form a continuous film, There is a risk of interference by absorbing and reflecting radio waves from mobile phones. However, when the composite tungsten oxide fine particles are dispersed using, for example, a bead mill and dispersed in the matrix as fine particles, each particle is dispersed in an isolated state, so that radio wave transmission is exhibited. And can be versatile.
熱線遮蔽体に用いる透明基材としては、例えば、フィルム、樹脂基板もしくはガラス基板等が挙げられる。但し、これらの材料を基材として用いる場合は、それぞれの使用状況に応じた機械的強度を有することが求められる。
樹脂基板もしくはフィルムであれば、一般的に、透過性があり散乱の少ない、無色透明の樹脂が適しており、用途に適した樹脂を選択すればよい。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（ＰＥＴ）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などが挙げられるが、中でもポリエチレンテレフタレート樹脂が好適である。
As a transparent base material used for a heat ray shield, a film, a resin substrate, a glass substrate, etc. are mentioned, for example. However, when using these materials as a base material, it is calculated | required to have mechanical strength according to each use condition.
In the case of a resin substrate or film, generally, a colorless and transparent resin having transparency and low scattering is suitable, and a resin suitable for the application may be selected. Specifically, polyethylene resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl alcohol resin, polystyrene resin, polypropylene resin, ethylene vinyl acetate copolymer, polyester resin, polyethylene terephthalate (PET) resin, fluorine resin, polycarbonate resin , Acrylic resin, polyvinyl butyral resin, etc., among which polyethylene terephthalate resin is preferred.
また、これら樹脂基板もしくはフィルムを用いる場合、その表面は、無機バインダーとの結着性向上を目的とした表面処理が施されていてもよく、その代表的な処理方法としては、コロナ表面処理、プラズマ処理、スパッタリング処理等の放電処理、火炎処理、金属ナトリウム処理、プライマー層コート処理等が挙げられる。 Moreover, when using these resin substrates or films, the surface thereof may be subjected to a surface treatment for the purpose of improving the binding property with an inorganic binder, and a typical treatment method thereof is corona surface treatment, Examples thereof include discharge treatment such as plasma treatment and sputtering treatment, flame treatment, metal sodium treatment, primer layer coating treatment and the like.
樹脂基板もしくはフィルムの意匠性を重視する場合には、あらかじめ着色された基材や、型どりされた基材を使用することもできる。
樹脂基板上、または、フィルム上等に形成された分散体を、ガラス等の基材に貼り付けるため、接着面に接着層と離型フィルム層とを積層してもよい。自動車のバックウィンドウのように曲面に貼り付け易いように、ドライヤーなどの熱で簡単に軟化するフィルムを使用してもよい。
接着剤中に紫外線遮蔽剤を添加すれば、フィルムや樹脂の紫外線劣化を防止できる。紫外線吸収剤には、ベンゾフェノン系紫外線吸収剤、ベンゾトリアゾール系紫外線吸収剤や、ＣｅＯ２、ＴｉＯ２、ＺｎＯ等が挙げられる。
When emphasizing the design properties of the resin substrate or film, a pre-colored base material or a shaped base material can be used.
In order to attach the dispersion formed on the resin substrate or the film to a base material such as glass, an adhesive layer and a release film layer may be laminated on the adhesive surface. A film that is easily softened by heat, such as a dryer, may be used so that it can be easily attached to a curved surface like a back window of an automobile.
If an ultraviolet shielding agent is added to the adhesive, it is possible to prevent ultraviolet degradation of the film or resin. Examples of the ultraviolet absorber include benzophenone ultraviolet absorbers, benzotriazole ultraviolet absorbers, CeO 2 , TiO 2 , and ZnO.
また、熱線遮蔽分散体形成用塗布液が、本発明に係るバインダーを含まない場合、透明基材上に得られる熱線遮蔽分散体の膜は、前記複合タングステン酸化物微粒子と、Ｂａ化合物とＰ化合物とＺｎ化合物との混合物のみが堆積した膜構造になる。この場合、当該膜上へ、さらに本発明に係るバインダーを含む塗布液を塗布して多層膜とする。当該構成を採ることにより、本発明に係るバインダー成分が、第１層のタングステン酸化物の微粒子の堆積した間隙を埋めて成膜されるため、膜のヘイズが低減して可視光透過率が向上し、また微粒子の基材への結着性が向上する。 When the coating solution for forming the heat ray shielding dispersion does not contain the binder according to the present invention, the film of the heat ray shielding dispersion obtained on the transparent substrate is composed of the composite tungsten oxide fine particles, the Ba compound, and the P compound. Only the mixture of Zn and Zn compound is deposited. In this case, a coating liquid containing the binder according to the present invention is further applied onto the film to form a multilayer film. By adopting this configuration, the binder component according to the present invention is formed by filling the gap in which the fine particles of tungsten oxide in the first layer are deposited, so that the haze of the film is reduced and the visible light transmittance is improved. In addition, the binding property of the fine particles to the base material is improved.
（８）まとめ
上述したように本発明によれば、複合タングステン酸化物微粒子と本発明に係るバインダーとの中に、Ｂａ化合物とＰ化合物とＺｎ化合物との混合物を含有させることで、太陽光からの近赤外線の吸収能力を有し、膜強度が高く、耐湿熱性が高い上、簡便な方法で製造でき、低コストである熱線遮蔽分散体および熱線遮蔽体を提供することを可能とした。
本発明の熱線遮蔽分散体および熱線遮蔽体は、自動車のはめ込みガラス、サイドガラスおよびリヤガラス、鉄道車両の扉ガラスや窓ガラスおよび室内ドアガラス、ビル等の建物における窓ガラスおよび室内ドアガラス等、室内展示用ショーケースおよびショーウィンドー等、種々の用途に使用することができる。
(8) Summary As described above, according to the present invention, the composite tungsten oxide fine particles and the binder according to the present invention contain a mixture of a Ba compound, a P compound, and a Zn compound from sunlight. It is possible to provide a heat ray shielding dispersion and a heat ray shield that have a near infrared absorption capability, high film strength, high moisture and heat resistance, and can be manufactured by a simple method, and are low in cost.
The heat ray shielding dispersion and heat ray shield of the present invention are used for indoor display such as automotive glass, side glass and rear glass, railcar door glass and window glass, indoor door glass, window glass and indoor door glass in buildings, etc. It can be used for various applications such as a showcase and a show window.
以下、実施例を用いて本発明をより詳細に説明する。ただし、本発明は下記実施例に限定されるものではない。
本実施例において、可視光透過率、日射透過率は、日立製作所製の分光光度計を用いて波長２００〜２５００ｎｍの光の透過率により測定し、ＪＩＳ Ｒ ３１０６に従って算出した。なお、当該日射透過率は、熱線遮蔽分散体および熱線遮蔽体の熱線遮蔽性能を示す指標である。
微粒子の分散粒子径は、日機装製のマイクロトラック粒度分布計を用いて測定を行った。微粒子の平均粒径はＤ５０とした。
熱線遮蔽体における光学特性変化の耐湿熱性の評価は、試験サンプル（熱線遮蔽体）を８５℃、９０％ＲＨ環境に設定した恒温恒湿槽に７日間暴露し、当該耐湿熱性の加速試験前後における可視光透過率、日射透過率の変化を測定することにより行なった。
熱線遮蔽体における表面硬度の評価は、試験サンプル（熱線遮蔽体）をＪＩＳ Ｋ ５６００塗料一般試験方法の４．４引っかき強度（鉛筆法）に従って評価した。
Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.
In this example, the visible light transmittance and the solar radiation transmittance were measured according to the transmittance of light having a wavelength of 200 to 2500 nm using a spectrophotometer manufactured by Hitachi, Ltd., and calculated according to JIS R 3106. The solar radiation transmittance is an index indicating the heat ray shielding performance of the heat ray shielding dispersion and the heat ray shielding member.
The dispersed particle size of the fine particles was measured using a Nikkiso Microtrac particle size distribution meter. The average particle size of the fine particles was D50.
Evaluation of the heat and heat resistance of the change in optical properties of the heat ray shield is performed by exposing the test sample (heat ray shield) to a constant temperature and humidity chamber set at 85 ° C. and 90% RH for 7 days, before and after the accelerated heat and heat resistance test. This was done by measuring changes in visible light transmittance and solar transmittance.
Evaluation of the surface hardness in a heat ray shield evaluated the test sample (heat ray shield) according to 4.4 scratch strength (pencil method) of a JIS K5600 paint general test method.
（実施例１）
Ｃｓ０．３３ＷＯ３微粒子２０質量％、分散媒として４−メチル−２−ペンタノン７０質量％、微粒子分散用分散剤１０質量％を混合し、媒体攪拌ミルで分散処理を行ない、平均分散粒子径８０ｎｍのＣｓ０．３３ＷＯ３微粒子の分散液を製造した（以下、「Ａ液」と記載する場合がある）。
同様に、市販のＢａ化合物とＰ化合物とＺｎ化合物との混合物である株式会社ＡＤＥＫＡ製アデカスタブＡＣ−２８５（液体）を用意した（以下、「Ｂ液」と記載する場合がある）。
このＡ液を５ｇ、Ｂ液を０．１ｇ秤量して混合後、当該混合液とシリカバインダー（固形分２５％）１１．７ｇを混合し、塗布液とした。
即ち、Ａ液中の酸化タングステン微粒子重量：５ｇ×２０質量％＝１ｇ、シリカバインダー重量：１１．７ｇ×２５％＝２．９２５ｇより、酸化タングステン微粒子重量部：Ｂ液重量部：シリカバインダー重量部＝１ｇ：０．１ｇ：２．９２５ｇ＝１００：１０：２９２．５である。以下、実施例２〜４、比較例２、３でも同様の方法により算出する。
(Example 1)
Cs 0.33 WO 3 20% by mass of fine particles, 70% by mass of 4-methyl-2-pentanone as a dispersion medium, and 10% by mass of a dispersing agent for fine particle dispersion are mixed and dispersed with a medium stirring mill, and the average dispersed particle size A dispersion of 80 nm Cs 0.33 WO 3 fine particles was produced (hereinafter sometimes referred to as “liquid A”).
Similarly, Adeka Stab AC-285 (liquid) manufactured by ADEKA Co., Ltd., which is a mixture of a commercially available Ba compound, P compound, and Zn compound, was prepared (hereinafter sometimes referred to as “liquid B”).
5 g of this A liquid and 0.1 g of B liquid were weighed and mixed, and then the mixed liquid and 11.7 g of a silica binder (solid content 25%) were mixed to obtain a coating liquid.
That is, tungsten oxide fine particle weight in liquid A: 5 g × 20 mass% = 1 g, silica binder weight: 11.7 g × 25% = 2.925 g, tungsten oxide fine particle weight part: B liquid weight part: silica binder weight part = 1 g: 0.1 g: 2.925 g = 100: 10: 292.5. Hereinafter, the same method is used for Examples 2 to 4 and Comparative Examples 2 and 3.
この塗布液を、バーコーター（Ｎｏ.２０）を用いて基材（無機ガラス）上に塗布、成膜した。この膜を１８０℃で３０分間乾燥し、分散媒を蒸発させて硬化させ、熱線遮蔽体を製造した。製造された熱線遮蔽体の光学特性、引っかき強度（鉛筆法）を表１に示す。
製造された熱線遮蔽体を試験サンプルとし、８５℃、９０％ＲＨ環境下に７日間暴露し、耐湿熱性の加速試験後の可視光透過率、日射透過率を測定した。そして、当該耐湿熱性の加速試験前後における可視光透過率の変化を算出した。この結果を表１に示す。
This coating solution was applied and formed on a substrate (inorganic glass) using a bar coater (No. 20). This film was dried at 180 ° C. for 30 minutes, and the dispersion medium was evaporated and cured to produce a heat ray shield. Table 1 shows the optical characteristics and scratch strength (pencil method) of the manufactured heat ray shield.
The manufactured heat ray shield was used as a test sample, exposed to an environment of 85 ° C. and 90% RH for 7 days, and the visible light transmittance and solar transmittance after the accelerated heat and heat resistance test were measured. And the change of the visible light transmittance before and behind the said accelerated test of the heat-and-moisture resistance was computed. The results are shown in Table 1.
（実施例２）
Ａ液を５ｇ、Ｂ液を０．３ｇ秤量して混合した以外は、実施例１と同様にして熱線遮蔽体を製造した。製造された熱線遮蔽体の光学特性を表１に示す。
製造された熱線遮蔽体を試験サンプルとし、８５℃、９０％ＲＨ環境下に７日間暴露し、耐湿熱性の加速試験後の可視光透過率、日射透過率を測定した。耐湿熱性の加速試験前後のこの結果を表１に示す。
(Example 2)
A heat ray shield was produced in the same manner as in Example 1 except that 5 g of liquid A and 0.3 g of liquid B were weighed and mixed. Table 1 shows optical characteristics of the manufactured heat ray shield.
The manufactured heat ray shield was used as a test sample, exposed to an environment of 85 ° C. and 90% RH for 7 days, and the visible light transmittance and solar transmittance after the accelerated heat and heat resistance test were measured. Table 1 shows the results before and after the accelerated heat and heat resistance test.
（実施例３）
Ａ液を５ｇ、Ｂ液を０．５ｇ秤量して混合した以外は、実施例１と同様にして熱線遮蔽体を製造した。製造された熱線遮蔽体の光学特性を表１に示す。
製造された熱線遮蔽体を試験サンプルとし、８５℃、９０％ＲＨ環境下に７日間暴露し、耐湿熱性の加速試験後の可視光透過率、日射透過率を測定した。耐湿熱性の加速試験前後のこの結果を表１に示す。
Example 3
A heat ray shield was produced in the same manner as in Example 1 except that 5 g of liquid A and 0.5 g of liquid B were weighed and mixed. Table 1 shows optical characteristics of the manufactured heat ray shield.
The manufactured heat ray shield was used as a test sample, exposed to an environment of 85 ° C. and 90% RH for 7 days, and the visible light transmittance and solar transmittance after the accelerated heat and heat resistance test were measured. Table 1 shows the results before and after the accelerated heat and heat resistance test.
（実施例４）
Ａ液を５ｇ、Ｂ液を０．０５ｇ秤量して混合した以外は、実施例１と同様にして熱線遮蔽体を製造した。製造された熱線遮蔽体の光学特性を表１に示す。
製造された熱線遮蔽体を試験サンプルとし、８５℃、９０％ＲＨ環境下に７日間暴露し、耐湿熱性の加速試験後の可視光透過率、日射透過率を測定した。耐湿熱性の加速試験前後のこの結果を表１に示す。
Example 4
A heat ray shielding body was produced in the same manner as in Example 1 except that 5 g of liquid A and 0.05 g of liquid B were weighed and mixed. Table 1 shows optical characteristics of the manufactured heat ray shield.
The manufactured heat ray shield was used as a test sample, exposed to an environment of 85 ° C. and 90% RH for 7 days, and the visible light transmittance and solar transmittance after the accelerated heat and heat resistance test were measured. Table 1 shows the results before and after the accelerated heat and heat resistance test.
（実施例５）
市販のＢａ化合物とＰ化合物とＺｎ化合物との混合物である株式会社ＡＤＥＫＡ製アデカスタブＡＣ−２５５（液体）（以下、「Ｃ液」と記載する場合がある）を用意し、Ａ液を５ｇ、Ｃ液を０．１ｇ秤量して混合した以外は、実施例１と同様にして熱線遮蔽体を製造した。製造された熱線遮蔽体の光学特性を表１に示す。
製造された熱線遮蔽体を試験サンプルとし、８５℃、９０％ＲＨ環境下に７日間暴露し、耐湿熱性の加速試験後の可視光透過率、日射透過率を測定した。耐湿熱性の加速試験前後のこの結果を表１に示す。
即ち、Ａ液中の酸化タングステン微粒子重量：５ｇ×２０質量％＝１ｇ、シリカバインダー重量：１１．７ｇ×２５％＝２．９２５ｇより、酸化タングステン微粒子重量部：Ｃ液重量部：シリカバインダー重量部＝１ｇ：０．１ｇ：２．９２５ｇ＝１００：１０：２９２．５である。以下、実施例６でも同様の方法により算出する。
(Example 5)
Adeka Stab AC-255 (liquid) (hereinafter sometimes referred to as “C liquid”) manufactured by ADEKA Co., Ltd., which is a mixture of a commercially available Ba compound, P compound, and Zn compound, is prepared. A heat shield was produced in the same manner as in Example 1 except that 0.1 g of the liquid was weighed and mixed. Table 1 shows optical characteristics of the manufactured heat ray shield.
The manufactured heat ray shield was used as a test sample, exposed to an environment of 85 ° C. and 90% RH for 7 days, and the visible light transmittance and solar transmittance after the accelerated heat and heat resistance test were measured. Table 1 shows the results before and after the accelerated heat and heat resistance test.
That is, tungsten oxide fine particle weight in liquid A: 5 g × 20 mass% = 1 g, silica binder weight: 11.7 g × 25% = 2.925 g, tungsten oxide fine particle weight part: C liquid weight part: silica binder weight part = 1 g: 0.1 g: 2.925 g = 100: 10: 292.5. Hereinafter, the same method is used in Example 6.
（実施例６）
Ａ液を５ｇ、Ｃ液を０．３ｇ秤量して混合した以外は、実施例１と同様にして熱線遮蔽体を製造した。製造された熱線遮蔽体の光学特性を表１に示す。
(Example 6)
A heat ray shielding body was produced in the same manner as in Example 1 except that 5 g of liquid A and 0.3 g of liquid C were weighed and mixed. Table 1 shows optical characteristics of the manufactured heat ray shield.
（実施例７）
市販のＢａ化合物とＰ化合物とＺｎ化合物との混合物である株式会社ＡＤＥＫＡ製アデカスタブＡＣ−７５５（液体）（以下、「Ｄ液」と記載する場合がある）を用意し、Ａ液を５ｇ、Ｄ液を０．１ｇ秤量して混合した以外は、実施例１と同様にして熱線遮蔽体を製造した。製造された熱線遮蔽体の光学特性を表１に示す。
即ち、Ａ液中の酸化タングステン微粒子重量：５ｇ×２０質量％＝１ｇ、シリカバインダー重量：１１．７ｇ×２５％＝２．９２５ｇより、酸化タングステン微粒子重量部：Ｄ液重量部：シリカバインダー重量部＝１ｇ：０．１ｇ：２．９２５ｇ＝１００：１０：２９２．５である。以下、実施例８でも同様の方法により算出する。
(Example 7)
Adeka Stab AC-755 (liquid) (hereinafter sometimes referred to as “Liquid D”) manufactured by ADEKA Corporation, which is a mixture of a commercially available Ba compound, P compound, and Zn compound, is prepared. A heat shield was produced in the same manner as in Example 1 except that 0.1 g of the liquid was weighed and mixed. Table 1 shows optical characteristics of the manufactured heat ray shield.
That is, tungsten oxide fine particle weight in liquid A: 5 g × 20 mass% = 1 g, silica binder weight: 11.7 g × 25% = 2.925 g, tungsten oxide fine particle weight part: D liquid weight part: silica binder weight part = 1 g: 0.1 g: 2.925 g = 100: 10: 292.5. Hereinafter, the same method is used in Example 8.
（実施例８）
Ａ液を５ｇ、Ｄ液を０．３ｇ秤量して混合した以外は、実施例１と同様にして熱線遮蔽体を製造した。製造された熱線遮蔽体の光学特性を表１に示す。
(Example 8)
A heat ray shielding body was produced in the same manner as in Example 1 except that 5 g of liquid A and 0.3 g of liquid D were weighed and mixed. Table 1 shows optical characteristics of the manufactured heat ray shield.
（比較例１）
Ｂ液を混合しなかった以外は、実施例１と同様にして熱線遮蔽体を製造した。製造された熱線遮蔽体の光学特性を表１に示す。
製造された熱線遮蔽体を試験サンプルとし、８５℃、９０％ＲＨ環境下に７日間暴露し、耐湿熱性の加速試験後の可視光透過率、日射透過率を測定した。耐湿熱性の加速試験前後のこの結果を表１に示す。
(Comparative Example 1)
A heat shield was produced in the same manner as in Example 1 except that the liquid B was not mixed. Table 1 shows optical characteristics of the manufactured heat ray shield.
The manufactured heat ray shield was used as a test sample, exposed to an environment of 85 ° C. and 90% RH for 7 days, and the visible light transmittance and solar transmittance after the accelerated heat and heat resistance test were measured. Table 1 shows the results before and after the accelerated heat and heat resistance test.
（比較例２）
Ａ液を５ｇ、Ｂ液を０．０３ｇ秤量して混合した以外は、実施例１と同様にして熱線遮蔽体を製造した。製造された熱線遮蔽体の光学特性を表１に示す。
製造された熱線遮蔽体を試験サンプルとし、８５℃、９０％ＲＨ環境下に７日間暴露し、耐湿熱性の加速試験後の可視光透過率、日射透過率を測定した。耐湿熱性の加速試験前後のこの結果を表１に示す。
(Comparative Example 2)
A heat ray shield was produced in the same manner as in Example 1 except that 5 g of liquid A and 0.03 g of liquid B were weighed and mixed. Table 1 shows optical characteristics of the manufactured heat ray shield.
The manufactured heat ray shield was used as a test sample, exposed to an environment of 85 ° C. and 90% RH for 7 days, and the visible light transmittance and solar transmittance after the accelerated heat and heat resistance test were measured. Table 1 shows the results before and after the accelerated heat and heat resistance test.
（比較例３）
Ａ液を５ｇ、Ｂ液を０．５５ｇ秤量して混合した以外は、実施例１と同様にして熱線遮蔽体を製造した。製造された熱線遮蔽体の光学特性を表１に示す。
製造された熱線遮蔽体を試験サンプルとし、８５℃、９０％ＲＨ環境下に７日間暴露し、耐湿熱性の加速試験後の可視光透過率、日射透過率を測定した。耐湿熱性の加速試験前後のこの結果を表１に示す。
(Comparative Example 3)
A heat ray shielding body was produced in the same manner as in Example 1 except that 5 g of liquid A and 0.55 g of liquid B were weighed and mixed. Table 1 shows optical characteristics of the manufactured heat ray shield.
The manufactured heat ray shield was used as a test sample, exposed to an environment of 85 ° C. and 90% RH for 7 days, and the visible light transmittance and solar transmittance after the accelerated heat and heat resistance test were measured. Table 1 shows the results before and after the accelerated heat and heat resistance test.
（比較例４）
Ｂ液を混合せず、シリカバインダーの代わりにアクリル樹脂を固形分として１００％含む有機樹脂バインダー２．５gを混合した以外は、実施例１と同様にして熱線遮蔽体を製造した。製造された熱線遮蔽体の光学特性を表１に示す。
製造された熱線遮蔽体を試験サンプルとし、８５℃、９０％ＲＨ環境下に７日間暴露し、耐湿熱性の加速試験後の可視光透過率、日射透過率を測定した。耐湿熱性の加速試験前後のこの結果を表１に示す。
(Comparative Example 4)
A heat ray shielding body was produced in the same manner as in Example 1 except that 2.5 g of an organic resin binder containing 100% of acrylic resin as a solid content was mixed instead of the silica binder without mixing the B liquid. Table 1 shows optical characteristics of the manufactured heat ray shield.
The manufactured heat ray shield was used as a test sample, exposed to an environment of 85 ° C. and 90% RH for 7 days, and the visible light transmittance and solar transmittance after the accelerated heat and heat resistance test were measured. Table 1 shows the results before and after the accelerated heat and heat resistance test.
[評価]
実施例１〜８においては、高い可視光透過性と、優れた熱線遮蔽特性とを有する熱線遮蔽体が得られた。また、Ｂａ化合物とＰ化合物とＺｎ化合物との混合物が添加されたことで、高温高湿条件下に曝された複合タングステン酸化物微粒子の経時劣化が抑制され、光学特性変化が少ないという高い耐湿熱性を発揮した。この結果、例えば屋外のような過酷な使用条件においても熱線遮蔽特性の変化の少ない熱線遮蔽体が得られた。また、無機バインダーを用いることで、表面硬度が６Ｈの熱線遮蔽体が得られた。
[Evaluation]
In Examples 1-8, the heat ray shielding body which has high visible light transmittance | permeability and the outstanding heat ray shielding characteristic was obtained. In addition, the addition of a mixture of a Ba compound, a P compound, and a Zn compound suppresses deterioration with time of the composite tungsten oxide fine particles exposed to high temperature and high humidity conditions, and has high moisture and heat resistance with little change in optical properties. Demonstrated. As a result, a heat ray shield with little change in heat ray shielding characteristics was obtained even under severe use conditions such as outdoors. Moreover, the heat ray shielding body whose surface hardness is 6H was obtained by using an inorganic binder.
比較例１は、Ｂａ化合物とＰ化合物とＺｎ化合物との混合物を添加しなかったため、耐湿熱性試験において可視光透過率や日射透過率の変化が大であった。また比較例２ではＢａ化合物とＰ化合物とＺｎ化合物との混合物の添加量が少なく、可視光透過率や日射透過率の変化が十分に抑制できなかった。比較例３ではＢａ化合物とＰ化合物とＺｎ化合物との混合物の添加量が多すぎたため、可視光透過率や日射透過率の変化が十分に抑制できなかった。比較例４では樹脂バインダーを用いたため、可視光透過率や日射透過率の変化が大きく、且つ、表面硬度もＨと低かった。 In Comparative Example 1, since a mixture of a Ba compound, a P compound, and a Zn compound was not added, changes in visible light transmittance and solar radiation transmittance were large in a moist heat resistance test. In Comparative Example 2, the addition amount of the mixture of the Ba compound, the P compound, and the Zn compound was small, and changes in visible light transmittance and solar light transmittance could not be sufficiently suppressed. In Comparative Example 3, since the addition amount of the mixture of the Ba compound, the P compound, and the Zn compound was too large, changes in visible light transmittance and solar light transmittance could not be sufficiently suppressed. In Comparative Example 4, since a resin binder was used, the change in visible light transmittance and solar transmittance was large, and the surface hardness was as low as H.
Claims (11)
Ｂａ化合物とＰ化合物とＺｎ化合物との混合物と、
シラン化合物、ケイ酸塩、ポリリン酸塩、シリカアルミナ、チタニア、酸化セリウム、ジルコニアのいずれか１種類以上を含むバインダーとを、含み、
前記Ｂａ化合物とＰ化合物とＺｎ化合物との混合物が、前記複合タングステン酸化物微粒子１００重量部に対し０．５重量部以上、５０重量部以下含有されていることを特徴とする熱線遮蔽分散体。 One or more types represented by the general formula M Y WO Z (0.001 ≦ Y ≦ 1.0, 2.2 ≦ Z ≦ 3.0), wherein the M element is selected from Cs, Rb, K, and Tl And a composite tungsten oxide fine particle having a hexagonal crystal structure,
A mixture of a Ba compound, a P compound and a Zn compound;
A binder containing any one or more of silane compounds, silicates, polyphosphates, silica alumina, titania, cerium oxide, and zirconia,
The heat ray shielding dispersion, wherein the mixture of the Ba compound, the P compound and the Zn compound is contained in an amount of 0.5 to 50 parts by weight with respect to 100 parts by weight of the composite tungsten oxide fine particles.
Ｂａ化合物とＰ化合物とＺｎ化合物との混合物とを、含むことを特徴とする熱線遮蔽分散体形成用塗布液。 One or more types represented by the general formula M Y WO Z (0.001 ≦ Y ≦ 1.0, 2.2 ≦ Z ≦ 3.0), wherein the M element is selected from Cs, Rb, K, and Tl And a composite tungsten oxide fine particle having a hexagonal crystal structure,
A coating solution for forming a heat ray shielding dispersion, comprising a mixture of a Ba compound, a P compound, and a Zn compound.
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| US20170367450A1 (en) * | 2016-06-27 | 2017-12-28 | Samsonite Ip Holdings S.A R.L. | Spinner wheel assembly for a luggage case |
| JP2019500208A (en) * | 2015-12-11 | 2019-01-10 | ミシェルズ グループ | Method for producing a coated polymer substrate having low emissivity |
| JP2020050867A (en) * | 2018-09-21 | 2020-04-02 | キーリング アンド ウォーカー リミテッド | Compositions, and methods and uses relating thereto |
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