JP2006299087A - Coating liquid for forming sunlight-shielding film and sunlight-shielding film and substrate having sunlight-shielding function - Google Patents
Coating liquid for forming sunlight-shielding film and sunlight-shielding film and substrate having sunlight-shielding function Download PDFInfo
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本発明は、ガラス、プラスチック、その他の日射遮蔽機能を必要とする透明基材を始めとする各種の基材に適用可能な、日射遮蔽膜形成用塗布液、および該日射遮蔽膜形成用塗布液が硬化した日射遮蔽膜、ならびに該日射遮蔽膜が少なくとも片面に形成された日射遮蔽機能を有する基材に関する。 The present invention relates to a coating solution for forming a solar shading film and a coating solution for forming the solar shading film that can be applied to various substrates including glass, plastic, and other transparent base materials that require a solar shading function. The present invention relates to a solar radiation shielding film in which is cured, and a substrate having a solar radiation shielding function in which the solar radiation shielding film is formed on at least one surface.
太陽光線は、近赤外線、可視光線、紫外線の３つに大きく分けることができる。このうち、長波長領域の近赤外線（熱線）は、熱エネルギーとして人体に感じる波長領域の光であり、室内、車内の温度上昇の原因ともなるものである。一方、短波長領域の紫外線は、日焼け、しみ、そばかす、発癌、視力障害など人体への悪影響があり、物品の機械的強度の低下、色褪せなどの外観の劣化、食品の劣化、印刷物の色調の低下なども引き起こすものである。 Sun rays can be broadly divided into three types: near infrared rays, visible rays, and ultraviolet rays. Of these, near infrared rays (heat rays) in the long wavelength region are light in a wavelength region that is perceived by the human body as thermal energy, and cause a rise in temperature in the room and in the vehicle. On the other hand, ultraviolet rays in the short wavelength region have adverse effects on the human body such as sunburn, blotches, freckles, carcinogenesis, and visual impairment, resulting in decreased mechanical strength of products, deterioration of appearance such as fading, deterioration of food, deterioration of print color It also causes a decline.
これらの不要な、近赤外線（熱線）や有害な紫外線のうち、近赤外線（熱線）を遮蔽するために、該近赤外線（熱線）を遮蔽する日射遮蔽膜を基材上に形成して、日射遮蔽機能を持たせたガラス基板、プラスチック板、フィルムなどの透明基材が使用されている。そして、従来から、前記日射遮蔽膜として、金、銀、銅、アルミニウムなどのような伝導電子を多量に持つ金属材料の薄膜を日射遮蔽材料とした日射遮蔽膜が用いられている。 Of these unnecessary near infrared rays (heat rays) and harmful ultraviolet rays, in order to shield the near infrared rays (heat rays), a solar radiation shielding film for shielding the near infrared rays (heat rays) is formed on the base material, A transparent substrate such as a glass substrate, a plastic plate, or a film having a shielding function is used. Conventionally, as the solar shading film, a solar shading film using a thin film of a metal material having a large amount of conduction electrons such as gold, silver, copper, and aluminum has been used.
一方、日射遮蔽材料を含有する塗布液を適宜な基材上に塗布し、日射遮蔽膜を当該基材上に形成することによって簡単、かつ低コストで日射遮蔽機能を持たせた透明基材を製造することも提案されている。 On the other hand, by applying a coating solution containing a solar shading material on an appropriate base material, and forming a solar shading film on the base material, a transparent base material having a solar shading function at a low cost is obtained. Producing is also proposed.
例えば、特開平１１−６９３９８４号公報には、六ホウ化物が、自由電子を多量に保有しており、これらを微粒子化し高度に分散させることによって可視光領域に透過率の極大を持つとともに、可視光領域に近い近赤外領域に強いプラズマ反射を発現して透過率の極小を持つようになることが開示されている。そして、特開２００１−２６２０６１号公法には、バインダー中に日射遮蔽材料として六ホウ化物を含有した日射遮蔽膜形成用塗布液について記載されている。 For example, in JP-A-11-69984, hexaboride possesses a large amount of free electrons, and has a maximum transmittance in the visible light region by making these fine particles finely dispersed and visible. It is disclosed that a strong plasma reflection occurs in the near-infrared region close to the light region and the transmittance becomes minimum. Japanese Patent Application Laid-Open No. 2001-262061 describes a coating solution for forming a sunscreen film containing hexaboride as a sunscreen material in a binder.
基材上に日射遮蔽膜として金属の薄膜を形成しようとした場合、スパッタリング法や蒸着法が用られている。しかし、これらの方法は、大がかりな真空装置を必要とするため生産性が劣り、日射遮蔽膜の製造コストが高くなり、また大面積の成膜が困難であった。
他方、日射遮蔽材料を含有する塗布液を適宜な基材上に塗布して、日射遮蔽膜を得ようとした場合、日射遮蔽材料として、金属材料を用いた場合は微粒子化に伴う酸化が問題となり、またＡｕを用いた場合は原料コストが高くなるという問題があった。また、六ホウ化物を用いた場合は、優れた日射遮蔽能を得ようとして六ホウ化物の添加量を増やすと、可視光透過率まで低下してしまうという問題があった。
When a metal thin film is to be formed on a substrate as a solar shading film, a sputtering method or a vapor deposition method is used. However, these methods require a large-scale vacuum apparatus, so that the productivity is inferior, the production cost of the solar radiation shielding film is high, and the film formation on a large area is difficult.
On the other hand, when applying a coating solution containing a solar shading material on an appropriate substrate to obtain a solar shading film, if a metal material is used as the solar shading material, oxidation due to micronization is a problem. In addition, when Au is used, there is a problem that the raw material cost increases. Further, when hexaboride is used, there is a problem that when the addition amount of hexaboride is increased in order to obtain an excellent solar shading ability, the visible light transmittance is lowered.
本発明は、これら従来の技術の問題点を解決し、既存の各種の基材に適応でき、２０℃から２５℃程度の常温における塗膜形成も可能で、かつ優れた膜強度を得られる日射遮蔽膜形成用塗布液、およびこれを用いて形成された日射遮蔽能が高く表面硬度の高い日射遮蔽膜、ならびに日射遮蔽機能を有する透明基材を始めとする各種の日射遮蔽機能を有する基材を、提供することを目的とする。 The present invention solves the problems of these conventional techniques, can be applied to various existing substrates, can form a coating film at a room temperature of about 20 ° C. to 25 ° C., and can obtain excellent film strength. Coating liquid for forming a shielding film, a solar radiation shielding film having a high solar radiation shielding ability and a high surface hardness, and a substrate having various solar radiation shielding functions including a transparent base material having a solar radiation shielding function Is intended to provide.
発明者らは鋭意研究を重ねた結果、グリシドキシプロピル基含有アルコキシシランとアミノプロピル基含有アルコキシシランを混合反応させてなる反応物をバインダー成分として用い、さらに近赤外光遮蔽成分として複合タングステン酸化物の微粒子を用いて日射遮蔽膜形成用塗布液を製造し、該日射遮蔽膜形成用塗布液を適宜な基材上で硬化させることで前記目的を達成できることを見出し、本発明を完成するに至った。 As a result of intensive studies, the inventors have used a reaction product obtained by mixing and reacting a glycidoxypropyl group-containing alkoxysilane and an aminopropyl group-containing alkoxysilane as a binder component, and further using composite tungsten as a near infrared light shielding component. It is found that the object can be achieved by manufacturing a coating solution for forming a solar shading film using fine particles of oxide, and curing the coating solution for forming a solar shading film on an appropriate substrate, thereby completing the present invention. It came to.
すなわち、第１の発明は、
バインダー成分と、近赤外線遮蔽成分と、希釈溶媒と、硬化触媒とを含有する日射遮蔽膜形成用塗布液であって、
前記バインダー成分の少なくとも１種が、グリシドキシプロピル基含有アルコキシシランとアミノプロピル基含有アルコキシシランとをモル比で２：１〜１：１の範囲で反応させてなる一般式（化１）で表される反応物であり、
前記近赤外線遮蔽成分が、複合タングステン酸化物から選ばれた少なくとも１種を含む平均粒径２００ｎｍ以下の微粒子であることを特徴とする日射遮蔽膜形成用塗布液を提供する。
A coating solution for forming a solar shading film containing a binder component, a near-infrared shielding component, a diluting solvent, and a curing catalyst,
At least one of the binder components is a general formula (Chemical Formula 1) obtained by reacting a glycidoxypropyl group-containing alkoxysilane and an aminopropyl group-containing alkoxysilane in a molar ratio of 2: 1 to 1: 1. The reactant represented,
There is provided a coating solution for forming a solar radiation shielding film, wherein the near-infrared shielding component is fine particles having an average particle diameter of 200 nm or less containing at least one selected from composite tungsten oxide.
第２の発明は、
前記近赤外線遮蔽成分が１〜１０重量％含まれ、且つ、前記バインダー成分が１０〜４０重量％含まれることを特徴とする第１の発明記載の日射遮蔽膜形成用塗布液を提供する。
The second invention is
The near-infrared shielding component is contained in an amount of 1 to 10% by weight, and the binder component is contained in an amount of 10 to 40% by weight.
第３の発明は、
前記複合タングステン酸化物が、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であることを特徴とする第１または第２の発明記載の日射遮蔽膜形成用塗布液を提供する。
The third invention is
The composite tungsten oxide has the general formula MxWyOz (where 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, one or more elements, W is tungsten, O is oxygen, 0.001 ≦ x / y ≦ 1, 2. A coating solution for forming a solar radiation shielding film according to the first or second invention, characterized in that the composite tungsten oxide is represented by 2 ≦ z / y ≦ 3.0).
第４の発明は、
前記複合タングステン酸化物微粒子が、六方晶、正方晶、立方晶の結晶構造のいずれか１つ以上を含むことを特徴とする第１から３の発明いずれか記載の日射遮蔽膜形成用塗布液を提供する。
The fourth invention is:
The coating solution for forming a solar radiation shielding film according to any one of the first to third inventions, wherein the composite tungsten oxide fine particles include any one or more of hexagonal, tetragonal, and cubic crystal structures. provide.
第５の発明は、
前記Ｍ元素が、Ｃｓ、Ｒｂ、Ｋ、Ｔｌ、Ｉｎ、Ｂａ、Ｌｉ、Ｃａ、Ｓｒ、Ｆｅ、Ｓｎから選択される１種類以上の元素であることを特徴とする第３または第４の発明記載の日射遮蔽膜形成用塗布液を提供する。
The fifth invention is:
The third or fourth invention, wherein the M element is one or more elements selected from Cs, Rb, K, Tl, In, Ba, Li, Ca, Sr, Fe, and Sn. A coating solution for forming a solar shading film is provided.
第６の発明は、
第１から第５の発明いずれか記載の日射遮蔽膜形成用塗布液であって、
さらに、ベンゾフェノン系および／またはベンゾトリアゾール系の有機紫外線吸収剤を含有することを特徴とする日射遮蔽膜形成用塗布液を提供する。
The sixth invention is:
A coating liquid for forming a solar radiation shielding film according to any one of the first to fifth inventions,
Furthermore, the present invention provides a coating solution for forming a solar radiation shielding film, which contains a benzophenone-based and / or benzotriazole-based organic ultraviolet absorber.
第７の発明は、
第１から第６の発明いずれか記載の日射遮蔽膜形成用塗布液であって、
さらに、紫外線吸収剤として、ＣｅＯ2、ＺｎＯ、Ｆｅ2Ｏ3、ＦｅＯＯＨから選択される少なくとも１種類以上の無機紫外線遮蔽成分であって、平均粒径が１００ｎｍ以下の微粒子を含有することを特徴とする日射遮蔽膜形成用塗布液を提供する。
The seventh invention
A coating solution for forming a solar radiation shielding film according to any one of the first to sixth inventions,
Furthermore, the composition contains at least one inorganic ultraviolet shielding component selected from CeO 2 , ZnO, Fe 2 O 3 , and FeOOH as an ultraviolet absorber, and contains fine particles having an average particle diameter of 100 nm or less. A coating solution for forming a solar shading film is provided.
第８の発明は、
第１から第７の発明いずれかに記載された日射遮蔽膜形成用塗布液が、硬化したものであることを特徴とする日射遮蔽膜を提供する。
The eighth invention
Provided is a solar shading film characterized in that the solar shading film forming coating liquid described in any of the first to seventh inventions is cured.
第９の発明は、
第８の発明記載の日射遮蔽膜が少なくとも片面に形成され、かつ透明性を有することを特徴とする日射遮蔽機能を有する基材を提供する。
The ninth invention
The solar radiation shielding film according to the eighth invention is formed on at least one surface, and has transparency, and provides a substrate having a solar radiation shielding function.
第１から第７の発明のいずれかに記載の日射遮蔽膜形成用塗布液は、常温であっても硬化し得るものであり、高い日射遮蔽能と表面強度とを有する日射遮蔽膜を形成することができる。
第８の発明に記載の日射遮蔽膜は、高い日射遮蔽能と機械的強度とを有する日射遮蔽膜である。
第９の発明に記載の日射遮蔽機能を有する基材は、高い日射遮蔽能と機械的強度と透明性とを有する日射遮蔽膜である。
The coating solution for forming a solar radiation shielding film according to any one of the first to seventh inventions can be cured even at room temperature, and forms a solar radiation shielding film having high solar radiation shielding ability and surface strength. be able to.
The solar radiation shielding film described in the eighth invention is a solar radiation shielding film having high solar radiation shielding ability and mechanical strength.
The base material having a solar radiation shielding function according to the ninth invention is a solar radiation shielding film having high solar radiation shielding ability, mechanical strength and transparency.
以下、本発明について詳細に説明する。
１．近赤外遮蔽成分
本発明において近赤外遮蔽成分として用いられる近赤外線吸収材料は、平均分散粒子径が２００ｎｍ以下である複合タングステン酸化物の微粒子を含んでいる。
当該複合タングステン酸化物は、一般式ＭｘＷｙＯｚ（但し、Ｍ元素は、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）で示される複合タングステン酸化物微粒子であり、十分な量の自由電子が生成されるため近赤外線吸収成分として有効に機能する。
Hereinafter, the present invention will be described in detail.
1. Near-infrared shielding component The near-infrared absorbing material used as the near-infrared shielding component in the present invention contains fine particles of composite tungsten oxide having an average dispersed particle size of 200 nm or less.
The composite tungsten oxide has the general formula MxWyOz (where the M element 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, One or more elements selected from Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, and I, W is tungsten, O is oxygen, 0.001 ≦ x / y ≦ 1, .2 ≦ z / y ≦ 3.0), and functions effectively as a near-infrared absorbing component because a sufficient amount of free electrons are generated.
前記一般式ＭｘＷｙＯｚで表記される複合タングステン酸化物の微粒子は、六方晶、正方晶、立方晶の結晶構造を有する場合に耐久性に優れることから、該六方晶、正方晶、立方晶から選ばれる1つ以上の結晶構造を含むことが好ましい。さらに、例えば、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の場合であれば、好ましいＭ元素として、Ｃｓ、Ｒｂ、Ｋ、Ｔｌ、Ｉｎ、Ｂａ、Ｌｉ、Ｃａ、Ｓｒ、Ｆｅ、Ｓｎの各元素から選択される１種類以上の元素を含む複合タングステン酸化物微粒子が挙げられる。 The fine particles of the composite tungsten oxide represented by the general formula MxWyOz are selected from the hexagonal, tetragonal, and cubic crystals because they have excellent durability when they have a hexagonal, tetragonal, or cubic crystal structure. Preferably it contains one or more crystal structures. Further, for example, in the case of composite tungsten oxide fine particles having a hexagonal crystal structure, preferable M elements include Cs, Rb, K, Tl, In, Ba, Li, Ca, Sr, Fe, and Sn. Examples thereof include composite tungsten oxide fine particles containing one or more elements selected from elements.
このとき、添加されるＭ元素の添加量ｘは、ｘ／ｙの値で０.００１以上、１．０以下が好ましく、更に好ましくは０.３３付近である。これは六方晶の結晶構造から理論的に算出されるｘの値が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。一方、酸素の存在量は、ｚ／ｙの値で２．２以上３．０以下が好ましい。典型的な例としてはＣｓ0.33ＷＯ3、Ｒｂ0.33ＷＯ3、Ｋ0.33ＷＯ3、Ｂａ0.33ＷＯ3などを挙げることができるが、ｙ,ｚが上記の範囲に収まるものであれば、有用な近赤外線吸収特性を得ることができる。 At this time, the addition amount x of M element to be added is preferably 0.001 or more and 1.0 or less in terms of x / y, and more preferably around 0.33. This is because the value of x calculated theoretically from the hexagonal crystal structure is 0.33, and preferable optical characteristics can be obtained with the addition amount before and after this value. On the other hand, the abundance of oxygen is preferably 2.2 or more and 3.0 or less in terms of z / y. Typical examples include Cs 0.33 WO 3 , Rb 0.33 WO 3 , K 0.33 WO 3 , Ba 0.33 WO 3, and the like, but useful as long as y and z fall within the above ranges. Infrared absorption characteristics can be obtained.
以上説明した複合タングステン酸化物微粒子は、単独で使用してもよいが、二種類以上を混合使用することも好ましい。本発明者らの実験によればこれらの微粒子を十分細かく、かつ均一に分散した膜では、透過率が波長４００〜７００ｎｍの間に極大値を持ち、かつ７００〜１８００ｎｍの間に極小値を持つことが観察された。可視光波長が３８０〜７８０ｎｍであり、視感度が５５０ｎｍ付近をピークとする釣鐘型であることを考慮すると、このような膜では可視光を有効に透過し、それ以外の波長の光を有効に吸収・反射することが理解できる。 The composite tungsten oxide fine particles described above may be used alone, but it is also preferable to use a mixture of two or more. According to the experiments of the present inventors, in a film in which these fine particles are sufficiently finely and uniformly dispersed, the transmittance has a maximum value between wavelengths of 400 to 700 nm and a minimum value between 700 and 1800 nm. It was observed. Considering that the visible light wavelength is 380 to 780 nm and the visibility is a bell-shaped peak with a peak near 550 nm, such a film effectively transmits visible light and effectively emits light of other wavelengths. It can be understood that it absorbs and reflects.
当該複合タングステン酸化物微粒子の平均粒径は、２００ｎｍ以下、好ましくは１００ｎｍ以下とすることが好ましい。その理由は、平均粒径が２００ｎｍ以下であると微粒子同士の凝集傾向が強くならず、塗布液中における微粒子の沈降が回避できるからであり、また平均粒径が２００ｎｍ以下の微粒子は、光散乱による可視光透過率の低下の原因とならないからである。 The composite tungsten oxide fine particles have an average particle size of 200 nm or less, preferably 100 nm or less. The reason is that if the average particle size is 200 nm or less, the tendency of aggregation between the fine particles is not strong, so that precipitation of the fine particles in the coating solution can be avoided, and fine particles having an average particle size of 200 nm or less are light scattering. This is because it does not cause a decrease in visible light transmittance.
なお、平均粒径は、２００ｎｍ以下、好ましくは１００ｎｍ以下であれば、小さいほど好ましい。現在の技術において、粒径２ｎｍ程度までの微粒子は容易に商業的に製造できる。 The average particle size is 200 nm or less, preferably 100 nm or less, the smaller the better. In the current technology, fine particles having a particle size of about 2 nm can be easily produced commercially.
２．近赤外遮蔽成分（複合タングステン酸化物微粒子）の製造方法
上記一般式ＭｘＷｙＯｚで表記される複合タングステン酸化物微粒子は、タングステン化合物出発原料を不活性ガス雰囲気もしくは還元性ガス雰囲気中で熱処理して得ることができる。
2. Manufacturing method of near-infrared shielding component (composite tungsten oxide fine particles) The composite tungsten oxide fine particles represented by the general formula MxWyOz are obtained by heat-treating a tungsten compound starting material in an inert gas atmosphere or a reducing gas atmosphere. be able to.
複合タングステン化合物出発原料には、３酸化タングステン粉末、もしくは酸化タングステンの水和物、もしくは、６塩化タングステン粉末、もしくはタングステン酸アンモニウム粉末、もしくは、６塩化タングステン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、もしくは、６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、もしく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一種類以上であることが好ましい。 The composite tungsten compound starting material is tungsten trioxide powder, tungsten oxide hydrate, tungsten hexachloride powder, ammonium tungstate powder, or tungsten hexachloride dissolved in alcohol and dried. Tungsten oxide hydrate powder obtained, or tungsten oxide hydrate powder obtained by dissolving tungsten hexachloride in alcohol and then adding water to precipitate it and drying it It is preferable that it is at least one selected from a tungsten compound powder obtained by drying an aqueous ammonium solution and a metal tungsten powder.
ここで、複合タングステン酸化物微粒子を製造する場合には製造工程の容易さの観点より、タングステン酸化物の水和物粉末、もしく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、を用いることがさらに好ましい。さらに、出発原料が溶液であると各元素を容易に均一混合可能となる観点より、タングステン酸アンモニウム水溶液や、６塩化タングステン溶液を用いることが好ましい。これら原料を用い、これを不活性ガス雰囲気もしくは還元性ガス雰囲気中で熱処理して、上述した粒径の複合タングステン酸化物微粒子を得ることができる。 Here, when producing composite tungsten oxide fine particles, tungsten oxide hydrate powder or tungsten compound powder obtained by drying ammonium tungstate aqueous solution is used from the viewpoint of ease of production process. Is more preferable. Furthermore, it is preferable to use an ammonium tungstate aqueous solution or a tungsten hexachloride solution from the viewpoint that each element can be easily and uniformly mixed when the starting material is a solution. By using these raw materials and heat-treating them in an inert gas atmosphere or a reducing gas atmosphere, composite tungsten oxide fine particles having the above-mentioned particle diameter can be obtained.
さらに元素Ｍも、水や有機溶媒等の溶媒に溶解可能なものであることが好ましい。例えば、元素Ｍを含有するタングステン酸塩、塩化物塩、硝酸塩、硫酸塩、シュウ酸塩、酸化物、等が挙げられるが、これらに限定されず、溶液状になるものであれば好ましい。 Furthermore, the element M is also preferably soluble in a solvent such as water or an organic solvent. Examples thereof include tungstate, chloride, nitrate, sulfate, oxalate, oxide, and the like containing element M, but are not limited to these and are preferably in the form of a solution.
ここで、不活性雰囲気中における熱処理条件としては、６５０℃以上が好ましい。６５０℃以上で熱処理された出発原料は、十分な着色力を有し複合タングステン酸化物微粒子として効率が良い。不活性ガスとしてはＡｒ、Ｎ2等の不活性ガスを用いることが良い。また、還元性雰囲気中の熱処理条件としては、まず出発原料を還元性ガス雰囲気中にて１００℃以上、６５０℃以下で熱処理し、次いで不活性ガス雰囲気中で６５０℃以上、１２００℃以下の温度で熱処理することが良い。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。また還元性ガスとしてＨ2を用いる場合は、還元雰囲気の組成として、Ｈ2が体積比で０．１％以上が好ましく、さらに好ましくは２％以上が良い。０．１％以上であれば効率よく還元を進めることができる。 Here, the heat treatment condition in the inert atmosphere is preferably 650 ° C. or higher. The starting material heat-treated at 650 ° C. or higher has sufficient coloring power and is efficient as composite tungsten oxide fine particles. As the inert gas, an inert gas such as Ar or N 2 is preferably used. As the heat treatment conditions in the reducing atmosphere, the starting material is first heat-treated at 100 ° C. or more and 650 ° C. or less in the reducing gas atmosphere, and then at a temperature of 650 ° C. or more and 1200 ° C. or less in the inert gas atmosphere. It is better to heat-treat with. 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 volume ratio of H 2 is preferably 0.1% or more, more preferably 2% or more, as the composition of the reducing atmosphere. If it is 0.1% or more, the reduction can proceed efficiently.
水素で還元された原料粉末はマグネリ相を含み、良好な近赤外遮蔽特性を示し、この状態で近赤外遮蔽微粒子として使用可能である。しかし、複合タングステン酸化物微粒子中に含まれる水素が不安定であるため、耐候性の面で応用が限定される可能性がある。そこで、この水素を含む複合タングステン酸化物微粒子を、不活性雰囲気中、６５０℃以上で熱処理することで、さらに安定なものとすることができる。この６５０℃以上の熱処理時の雰囲気は特に限定されないが、工業的観点から、Ｎ2、Ａｒが好ましい。当該６５０℃以上の熱処理により、複合タングステン酸化物微粒子中にマグネリ相が得られ耐候性が向上する。 The raw material powder reduced with hydrogen contains a magnetic phase and exhibits good near-infrared shielding characteristics, and can be used as near-infrared shielding particles in this state. However, since hydrogen contained in the composite tungsten oxide fine particles is unstable, the application may be limited in terms of weather resistance. Therefore, the composite tungsten oxide fine particles containing hydrogen can be further stabilized by heat treatment at 650 ° C. or higher in an inert atmosphere. The atmosphere during the heat treatment at 650 ° C. or higher is not particularly limited, but N 2 and Ar are preferable from an industrial viewpoint. By the heat treatment at 650 ° C. or higher, a magnetic phase is obtained in the composite tungsten oxide fine particles, and the weather resistance is improved.
上述したように、得られた複合タングステン酸化物微粒子の表面が、Ｓｉ、Ｔｉ、Ｚｒ、Ａｌの一種類以上の金属を含有する酸化物で被覆されていることは、耐候性の向上の観点から好ましい。被覆方法は特に限定されないが、当該複合タングステン酸化物微粒子を分散した溶液中へ、上記金属のアルコキシドを添加することで、複合タングステン酸化物微粒子の表面を被覆することが可能である。 As described above, the surface of the obtained composite tungsten oxide fine particles is covered with an oxide containing one or more kinds of metals of Si, Ti, Zr, and Al from the viewpoint of improving weather resistance. preferable. Although the coating method is not particularly limited, it is possible to coat the surface of the composite tungsten oxide fine particles by adding the metal alkoxide to the solution in which the composite tungsten oxide fine particles are dispersed.
３．バインダー成分
本発明において用いられるバインダー成分の少なくとも１種は、グリシドキシプロピル基を含有するアルコキシシランとアミノプロピル基を含有するアルコキシシランをと混合反応させて得られた反応物である。グリシドキシプロピル基を含有するアルコキシシランとしては、グリシドキシプロピルトリメトキシシラン、グリシドキシプロピルメチルジメトキシシラン、グリシドキシプロピルトリエトキシシラン、グリシドキシプロピルメチルジエトキシシランなどを挙げることができ、またアミノプロピル基を含有するアルコキシシランとしては、アミノプロピルトリエトキシシラン、アミノプロピルトリメトキシシランなどが挙げられる。
3. Binder Component At least one binder component used in the present invention is a reaction product obtained by mixing and reacting an alkoxysilane containing a glycidoxypropyl group and an alkoxysilane containing an aminopropyl group. Examples of the alkoxysilane containing a glycidoxypropyl group include glycidoxypropyltrimethoxysilane, glycidoxypropylmethyldimethoxysilane, glycidoxypropyltriethoxysilane, and glycidoxypropylmethyldiethoxysilane. Examples of the alkoxysilane containing an aminopropyl group include aminopropyltriethoxysilane and aminopropyltrimethoxysilane.
４．バインダー成分の製造方法
上記反応においては、グリシドキシプロピル基を含有するアルコキシシランとアミノプロピル基を含有するアルコキシシランとの配合比は、モル比で２：１〜１：１とするのが好ましい。グリシドキシプロピル基を含有するアルコキシシランとアミノプロピル基を含有するアルコキシシランとの配合比が、モル比で２：１以下であれば膜の硬化が速く、強度も強くなり、１：１以上であれば膜が白化することがないからである。
4). Production method of binder component In the above reaction, the compounding ratio of alkoxysilane containing glycidoxypropyl group and alkoxysilane containing aminopropyl group is preferably 2: 1 to 1: 1 by molar ratio. . If the compounding ratio of alkoxysilane containing glycidoxypropyl group and alkoxysilane containing aminopropyl group is 2: 1 or less in terms of molar ratio, the film will cure quickly and the strength will be strong, and 1: 1 or more. This is because the film does not whiten.
得られる反応物の基本構造は下記の一般式（化１）で示される。
上記反応物を得るためには、常温で２週間程度の熟成が必要である。ここで、混合後に加熱することによって、熟成時間を短縮することも可能である。その際の加熱温度は４０〜８０℃が好ましい。加熱温度が４０℃以上あれば、熟成時間短縮の効果があり、８０℃以下であれば反応物が着色することがないからである。 In order to obtain the reaction product, aging is required at room temperature for about 2 weeks. Here, the aging time can be shortened by heating after mixing. The heating temperature at that time is preferably 40 to 80 ° C. This is because if the heating temperature is 40 ° C. or higher, the aging time is shortened, and if it is 80 ° C. or lower, the reaction product is not colored.
本発明に係るバインダー成分は、前記一般式（化１）の基本構造に示すように、分子両端にアルコキシル基を持ち、分子内にフレキシブルなメチレン鎖を持つ。このアルコキシル基は室温で加水分解して反応性の高いシラノールを生じ、これが縮合重合することによって自身で高分子化、あるいは他の成分と結合することができる。また分子中のメチレン鎖は、前記縮合重合時の歪みを吸収し塗膜のクラック発生を抑制する。 As shown in the basic structure of the general formula (Formula 1), the binder component according to the present invention has an alkoxyl group at both ends of the molecule and a flexible methylene chain in the molecule. This alkoxyl group is hydrolyzed at room temperature to produce highly reactive silanol, which can be polymerized by itself or combined with other components by condensation polymerization. In addition, the methylene chain in the molecule absorbs strain during the condensation polymerization and suppresses the generation of cracks in the coating film.
さらに、本発明に係る日射遮蔽膜形成用塗布液の硬化は、バインダー成分中のアルコキシル基の加水分解と、それに続くシラノールの縮合重合による高分子化とによって起こる。このとき形成されたシロキサン結合は強固であり、堅牢な塗膜を形成することができる。 Furthermore, the curing of the coating solution for forming a solar shading film according to the present invention occurs by hydrolysis of the alkoxyl group in the binder component and subsequent polymerization by silanol condensation polymerization. The siloxane bond formed at this time is strong, and a firm coating film can be formed.
５．希釈溶媒
日射遮蔽膜形成用塗布液中の希釈溶媒は、特に限定されるものではなく塗布条件や、塗布環境、塗布液中の固形分の種類に合わせて選択可能であり、例えばメタノール、エタノール、イソブチルアルコールなどのアルコール類、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などのエーテルアルコール類、酢酸メチルや酢酸エチルなどのエステル類、メチルエチルケトンやシクロヘキサノンなどのケトン類など各種溶媒が使用可能である。また用途によって、前記１種または２種以上の溶媒を組み合わせて使用することもできる。
5. Diluting solvent The diluting solvent in the coating solution for forming the solar shading film is not particularly limited and can be selected according to the coating conditions, coating environment, type of solid content in the coating solution, for example, methanol, ethanol, Various solvents such as alcohols such as isobutyl alcohol, ether alcohols such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether, esters such as methyl acetate and ethyl acetate, and ketones such as methyl ethyl ketone and cyclohexanone can be used. Moreover, the said 1 type, or 2 or more types of solvent can also be used in combination according to a use.
６．硬化触媒
上述のバインダー成分には湿気硬化性があるが、常温での硬化速度を実用的なものとするために、日射遮蔽膜形成用塗布液に硬化触媒の添加を行うことが好ましい。そして、この硬化触媒としては、三弗化ホウ素などが好適に用いられる。さらに、当該硬化触媒の添加量を調整することによって、硬化時間を制御することが可能となる。この結果、当該日射遮蔽膜形成用塗布液の応用範囲が広がることとなる。ここで、硬化触媒の含有量は０．０１〜３重量％が好ましい。
6). Curing Catalyst Although the binder component described above has moisture curing properties, it is preferable to add a curing catalyst to the coating solution for forming a solar shading film in order to make the curing rate at room temperature practical. As the curing catalyst, boron trifluoride or the like is preferably used. Furthermore, the curing time can be controlled by adjusting the addition amount of the curing catalyst. As a result, the application range of the solar shading film forming coating solution is expanded. Here, the content of the curing catalyst is preferably 0.01 to 3% by weight.
７．紫外線吸収剤
形成される日射遮蔽膜の紫外線遮蔽能を強化するために、日射遮蔽膜形成用塗布液へ、紫外線吸収剤として有機紫外線吸収剤および／または無機紫外線遮蔽成分を含有させることもできる。
この際、有機紫外線吸収剤としては、ベンゾフェノン系（例えば、ベンゾフェノン）とべンゾトリアゾール系（例えば、ベンゾトリアゾール）の有機紫外線吸収剤のいずれか一方、または両方を含有させることができ、その含有量は０．５〜７重量％が好ましい。紫外線吸収剤の含有量が０．５重量％以上あれば、形成される日射遮蔽膜の紫外線遮蔽能が十分であり、一方、７重量％以下であれば紫外線吸収剤が日射遮蔽膜の表面に滲み出したり、日射遮蔽膜に曇りが生じたりするのを回避できるからである。
7). Ultraviolet Absorber In order to enhance the ultraviolet shielding ability of the solar radiation shielding film to be formed, an organic ultraviolet radiation absorber and / or an inorganic ultraviolet radiation shielding component can also be contained in the solar radiation shielding film forming coating solution as the ultraviolet radiation absorber.
At this time, as the organic ultraviolet absorber, either or both of a benzophenone-based (for example, benzophenone) and benzotriazole-based (for example, benzotriazole) organic ultraviolet absorber can be contained, and the content thereof Is preferably 0.5 to 7% by weight. If the content of the ultraviolet absorber is 0.5% by weight or more, the ultraviolet shielding ability of the formed solar shielding film is sufficient. On the other hand, if the content is 7% by weight or less, the ultraviolet absorbent is on the surface of the solar shielding film. This is because it is possible to avoid bleeding and clouding of the solar shading film.
また用途によっては、紫外線吸収剤として無機紫外線遮蔽成分を含有させてもよい。この場合の無機紫外線遮蔽成分として、平均粒径が１００ｎｍ以下のＣｅＯ2、ＺｎＯ、Ｆｅ2Ｏ3、ＦｅＯＯＨ微粒子の中から選ばれた１種もしくは２種以上を選択することができる。平均粒径を１００ｎｍ以下とした理由は、粒径が１００ｎｍ以下であれば微粒子同士の凝集傾向が強くならず、塗布液中における微粒子の沈降の原因とならないこと、また粒径が１００ｎｍ以下であれば、当該微粒子に起因する光散乱による可視光透過率の低下の原因となることを回避できるからである。 Depending on the application, an inorganic ultraviolet shielding component may be included as an ultraviolet absorber. In this case, one or more selected from among CeO 2 , ZnO, Fe 2 O 3 , and FeOOH fine particles having an average particle diameter of 100 nm or less can be selected as the inorganic ultraviolet shielding component. The reason for setting the average particle size to 100 nm or less is that if the particle size is 100 nm or less, the tendency of aggregation of the fine particles does not become strong and does not cause sedimentation of the fine particles in the coating solution, and the particle size is 100 nm or less. This is because it can be avoided that the visible light transmittance is reduced due to light scattering caused by the fine particles.
また、無機紫外線遮蔽成分の含有量は０．１〜５重量％が好ましい。無機紫外線遮蔽成分の含有量が０．１％以上あれば形成される日射遮蔽膜の紫外線遮蔽能が十分に発揮され、一方、５重量％以下であれば該無機紫外線遮蔽成分に起因する可視光透過率の低下や塗膜のムラが顕著になることを回避できるからである。 Further, the content of the inorganic ultraviolet shielding component is preferably 0.1 to 5% by weight. If the content of the inorganic ultraviolet shielding component is 0.1% or more, the ultraviolet shielding ability of the formed solar radiation shielding film is sufficiently exerted. On the other hand, if it is 5% by weight or less, visible light resulting from the inorganic ultraviolet shielding component is exhibited. It is because it can avoid that the transmittance | permeability fall and the nonuniformity of a coating film become remarkable.
さらに、無機紫外線遮蔽成分としてＦｅ2Ｏ3、ＦｅＯＯＨ微粒子を選択することによって、塗布膜に赤味や黄色味を持たせることも可能である。そして、これらの無機紫外線遮蔽成分は経時変化が少ない。なお、無機紫外線遮蔽成分の平均粒径は小さいほど好ましい。そして、無機紫外線遮蔽成分においても現在の技術において、粒径２ｎｍ程度までの微粒子は容易に商業的に製造できる。 Further, by selecting Fe 2 O 3 and FeOOH fine particles as inorganic ultraviolet shielding components, it is possible to give the coating film a reddish or yellowish color. And these inorganic ultraviolet-ray shielding components have little change with time. In addition, it is so preferable that the average particle diameter of an inorganic ultraviolet-ray shielding component is small. In the inorganic ultraviolet shielding component, fine particles having a particle size of up to about 2 nm can be easily produced commercially with the current technology.
８．日射遮蔽膜形成用塗布液の調製
本発明に係る日射遮蔽膜形成用塗布液の調製において、近赤外遮蔽成分である複合タングステン酸化物微粒子を１〜１０重量％、バインダー成分を１０〜４０重量％、所望により紫外線吸収剤を添加する場合は１〜１５重量％を添加し、さらに希釈溶剤を添加することによって総計で１００重量％となるように秤量し、混合すれば良い。
ここで、近赤外遮蔽成分の配合量が１重量％以上あれば形成される日射遮蔽膜の近赤外遮蔽能が十分に確保でき、一方、１０重量％以下であれば日射遮蔽膜の透明性および良好な膜外観が確保できる。
バインダーの配合量が１０重量％以上あれば形成される日射遮蔽膜の表面硬度が十分に確保でき、一方、４０重量％以下であれば塗布液の粘度が過剰に高くなるのを回避でき、均一な塗布が容易である。
紫外線吸収剤の配合量が１重量％以上あれば形成される日射遮蔽膜の紫外線遮蔽能が十分に確保でき、一方、１５重量％以下であれば良好な膜外観が確保できる。
8). Preparation of solar shading film-forming coating solution In the preparation of the solar shading film-forming coating solution according to the present invention, 1 to 10% by weight of composite tungsten oxide fine particles as a near-infrared shielding component and 10 to 40% by weight of a binder component. When adding an ultraviolet absorber if desired, 1 to 15% by weight may be added, and further by adding a diluting solvent, the total may be weighed to 100% by weight and mixed.
Here, if the blending amount of the near-infrared shielding component is 1% by weight or more, the near-infrared shielding ability of the formed solar shielding film can be sufficiently secured, while if it is 10% by weight or less, the solar radiation shielding film is transparent. And good film appearance can be secured.
If the blending amount of the binder is 10% by weight or more, the surface hardness of the formed solar shading film can be sufficiently secured. On the other hand, if it is 40% by weight or less, the viscosity of the coating solution can be prevented from becoming excessively high and uniform Easy application.
If the blending amount of the ultraviolet absorber is 1% by weight or more, the ultraviolet shielding ability of the formed solar shading film can be sufficiently secured, while if it is 15% by weight or less, a good film appearance can be secured.
一方、硬化触媒の配合量が０．０１重量％以上あれば形成される日射遮蔽膜の硬化に対して促進効果が得られ、３重量％以下であれば塗布時の液のレベリング性が確保され、混合した塗布液が塗布前に硬化してしまうこともない。
尤も、硬化触媒が日射遮蔽膜形成用塗布液に添加されると、バインダー成分の硬化が開始するので、該日射遮蔽膜形成用塗布液の塗布の直前に添加することが好ましい。
さらに、該硬化触媒は、メタノール、エタノール、イソブチルアルコールなどのアルコール類、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などのエーテルアルコール類、酢酸メチルや酢酸エチルなどのエステル類、メチルエチルケトンやシクロヘキサノンなどのケトン類などの各種溶媒に、予め溶解させておくことが好ましい。溶液の形態であれば、添加が容易で且つ直ちに均一化できるからである。
On the other hand, if the blending amount of the curing catalyst is 0.01% by weight or more, an effect of promoting the curing of the formed solar shading film is obtained, and if it is 3% by weight or less, the leveling property of the liquid at the time of application is secured. The mixed coating solution does not harden before coating.
However, since the curing of the binder component starts when the curing catalyst is added to the solar shading film forming coating solution, it is preferably added immediately before the application of the solar shading film forming coating solution.
Further, the curing catalyst includes alcohols such as methanol, ethanol and isobutyl alcohol, ether alcohols such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether, esters such as methyl acetate and ethyl acetate, ketones such as methyl ethyl ketone and cyclohexanone. It is preferable to dissolve in advance in various solvents such as This is because, in the form of a solution, it can be easily added and can be made uniform immediately.
９．日射遮蔽膜の形成と日射遮蔽機能を有する基材
本発明に係る日射遮蔽膜形成用塗布液を、ガラス基板、プラスチック板、フィルムなどの透明基材を始めとする所定の基材の片面あるいは両面に塗布し、常温で硬化させることによって前記透明基材の表面上に表面硬度の高い日射遮蔽能を持つ日射遮蔽膜を形成することができる。日射遮蔽膜形成用塗布液の塗布方法は特に限定されるものではなく、スピンコート法、スプレーコート法、ディップコート法、スクリーン印刷法、布や刷毛による塗布方法など、処理液を平坦で、薄く、かつ均一に塗布できる方法であればいかなる方法でも用いることができる。この結果、日射遮蔽膜の形成の生産性は非常に高いものとなった。得られた日射遮蔽膜は、表面硬度が高く透明性に優れながら、高い日射遮蔽機能を有していた。さらに、当該日射遮蔽膜が片面あるいは両面に形成された透明基材は、高い機械的耐久性と透明性とを有し、高い日射遮蔽機能を有していた。そして、当該日射遮蔽膜が紫外線吸収剤を含有する場合は、紫外線遮蔽能も発揮する他、前記基材自体の紫外線による劣化をも抑制する。
9. Base material having solar shading film formation and solar shading function The coating liquid for solar shading film formation according to the present invention is applied to one or both sides of a predetermined base material including a transparent base material such as a glass substrate, a plastic plate, or a film. By applying the coating on the surface of the transparent substrate and curing it at room temperature, it is possible to form a solar shading film having high surface hardness on the surface of the transparent substrate. The coating method of the solar shading film forming coating solution is not particularly limited, and the processing solution is flat and thin, such as spin coating method, spray coating method, dip coating method, screen printing method, coating method using cloth or brush. Any method can be used as long as it can be applied uniformly. As a result, the productivity of forming the solar shading film was very high. The obtained solar shading film had a high solar shading function while having high surface hardness and excellent transparency. Furthermore, the transparent base material on which the solar radiation shielding film is formed on one side or both sides has high mechanical durability and transparency, and has a high solar radiation shielding function. And when the said solar radiation shielding film contains a ultraviolet absorber, in addition to exhibiting ultraviolet shielding ability, the deterioration by the ultraviolet-ray of the said base material itself is also suppressed.
以下、本発明を、実施例および比較例を用いてさらに詳細に説明する。
なお、当該実施例および比較例に用いた日射遮蔽膜形成用塗布液の構成成分を表１に示し、該日射遮蔽膜形成用塗布液を用いて形成した日射遮蔽膜の特性を表２に示した。
Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.
The constituent components of the solar shading film forming coating solution used in the examples and comparative examples are shown in Table 1, and the characteristics of the solar shading film formed using the solar shading film forming coating solution are shown in Table 2. It was.
［実施例１］
６塩化タングステンと２塩化銅とを、ＷとＣｕとのモル比が１対０.２となるように所定量秤量し、エタノールに少量ずつ溶解し混合溶液を得た。この混合溶液を１３０℃で乾燥し、粉末状の出発原料とした。この出発原料を、還元雰囲気（アルゴン／水素＝９５／５体積比）中において５５０℃で１時間加熱した。そして、一度室温に戻した後８００℃アルゴン雰囲気中で１時間加熱することで、Ｃｕ0.2ＷＯ2.72の粉末を製造した。このＣｕ0.2ＷＯ2.72は、Ｘ線回折による結晶相の同定の結果、Ｗ18Ｏ49の結晶相が観察され、比表面積は３０ｍ2／ｇであった。
[Example 1]
A predetermined amount of tungsten hexachloride and copper dichloride was weighed so that the molar ratio of W to Cu was 1: 0.2, and dissolved in ethanol little by little to obtain a mixed solution. This mixed solution was dried at 130 ° C. to obtain a powdery starting material. This starting material was heated at 550 ° C. for 1 hour in a reducing atmosphere (argon / hydrogen = 95/5 volume ratio). Then, once by heating 1 hour at 800 ° C. in an argon atmosphere it was returned to room temperature to produce a powder of Cu 0.2 WO 2.72. As a result of identification of the crystal phase by X-ray diffraction, the crystal phase of W 18 O 49 was observed for this Cu 0.2 WO 2.72 , and the specific surface area was 30 m 2 / g.
このＣｕ0.2ＷＯ2.72粉末を２０重量％、トルエン７５重量％、分散剤５重量％を混合して分散処理を行い、平均分散粒子径が８０ｎｍの分散液（Ａ液）とした。 20% by weight of this Cu 0.2 WO 2.72 powder, 75% by weight of toluene and 5% by weight of a dispersing agent were mixed and subjected to dispersion treatment to obtain a dispersion liquid (A liquid) having an average dispersed particle diameter of 80 nm.
グリシドキシプロピルトリメトキシシラン６０ｇとアミノプロピルトリエトキシシラン４０ｇとを混合し、マグネティックスターラーで１時間撹拌後、室温で１４日間熟成させて目的のバインダー成分１００ｇ（合成液）を得た。
２０ｇの合成液と、３０ｇのイソブチルアルコールと、２５ｇのプロピレングリコールモノエチルエーテルと、１５ｇのＡ液とを混合撹拌し、さらに触媒として三弗化ホウ素ピペリジンのイソブチルアルコール溶液（濃度：１重量％）１０ｇを加えて撹拌することによって日射遮蔽膜形成用塗布液を製造した。
60 g of glycidoxypropyltrimethoxysilane and 40 g of aminopropyltriethoxysilane were mixed, stirred for 1 hour with a magnetic stirrer, and then aged at room temperature for 14 days to obtain 100 g of the desired binder component (synthetic solution).
20 g of synthesis solution, 30 g of isobutyl alcohol, 25 g of propylene glycol monoethyl ether, and 15 g of solution A are mixed and stirred, and boron trifluoride piperidine in isobutyl alcohol as a catalyst (concentration: 1% by weight) A coating solution for forming a solar shading film was prepared by adding 10 g and stirring.
この日射遮蔽膜形成用塗布液を、厚さ３ｍｍのソーダライム系ガラス基板上にバーコーターを用いて塗布し、常温で放置して日射遮蔽膜を得た。
得られた日射遮蔽膜における光の透過率を、日立製作所（社）製の分光光度計を用いて測定し、ＪＩＳ Ｒ ３１０６にしたがって可視光透過率（τｖ）、日射透過率（τｅ）を、ＩＳＯ ９０５０にしたがって紫外線透過率（τｕｖ）を算出した。またテーバー摩耗試験機に摩耗輪ＣＳ１０ｆを用い、荷重２５０ｇ、５０回転の摩耗試験を行い、試験前後のへイズの変化量（ΔＨ）で膜の表面硬度を評価した。なおへイズは村上色彩技術研究所（社）製の反射・透過率計で測定した。
This solar shading film-forming coating solution was applied onto a 3 mm thick soda lime glass substrate using a bar coater and allowed to stand at room temperature to obtain a solar shading film.
The light transmittance in the obtained solar shading film was measured using a spectrophotometer manufactured by Hitachi, Ltd., and the visible light transmittance (τv) and solar transmittance (τe) were measured according to JIS R 3106. The ultraviolet transmittance (τuv) was calculated according to ISO 9050. Further, a wear wheel CS10f was used as a Taber abrasion tester, a wear test was performed at a load of 250 g and 50 rotations, and the surface hardness of the film was evaluated by the amount of change (ΔH) in haze before and after the test. The haze was measured with a reflection / transmittance meter manufactured by Murakami Color Research Laboratory.
実施例１で得られた日射遮蔽膜形成用塗布液は常温で硬化可能であり、容易に日射遮蔽膜を得ることができた。また膜のτｖは７８．５％、τｅは５４．８％であり、可視光透過性があり、日射遮蔽能があることが判明した。またΔＨは３．５％であり表面硬度の非常に高い膜が形成されていた。 The coating solution for forming a sunscreen film obtained in Example 1 was curable at room temperature, and a sunscreen film could be easily obtained. Further, it was found that τv of the film was 78.5% and τe was 54.8%, so that it had visible light permeability and had a sunlight shielding ability. Further, ΔH was 3.5%, and a film having a very high surface hardness was formed.
［比較例１］
比較のため、３ｍｍのソーダライム系ガラス基板のみを試料として、実施例１と同様の測定を行った。
その結果、当該ソーダライム系ガラス基板のτｖは９０．３％、τｅは８７．３％、τｕｖは７０．７％であった。
[Comparative Example 1]
For comparison, the same measurement as in Example 1 was performed using only a 3 mm soda lime glass substrate as a sample.
As a result, the soda-lime glass substrate had τv of 90.3%, τe of 87.3%, and τuv of 70.7%.
［実施例２］
メタタングステンアンモニウム水溶液（ＷＯ3換算で５０ｗｔ％）と塩化セシウムの水溶液とを、ＷとＣｓとのモル比が１対０.３３となるように所定量秤量し、両液を混合して混合溶液を得た。この混合溶液を１３０℃で乾燥し、粉末状の出発原料とした。この出発原料を、還元雰囲気（アルゴン／水素＝９５／５体積比）中において５５０℃で１時間加熱した。そして、一度室温に戻した後、８００℃アルゴン雰囲気中で１時間加熱することで、Ｃｓ0.33ＷＯ3の粉末を製造した。この粉末の比表面積は２０ｍ2／ｇであった。また、当該Ｃｓ0.33ＷＯ3粉末についてＸ線回折による結晶相の同定の結果、六方晶タングステンブロンズ（複合タングステン酸化物微粒子）の結晶相が観察された。
[Example 2]
A predetermined amount of an aqueous metatungsten ammonium solution (50 wt% in terms of WO 3 ) and an aqueous solution of cesium chloride are weighed so that the molar ratio of W and Cs is 1: 0.33, and both solutions are mixed to obtain a mixed solution. Got. This mixed solution was dried at 130 ° C. to obtain a powdery starting material. This starting material was heated at 550 ° C. for 1 hour in a reducing atmosphere (argon / hydrogen = 95/5 volume ratio). Then, once After returning to room temperature, by heating 1 hour at 800 ° C. in an argon atmosphere to prepare a powder of the Cs 0.33 WO 3. The specific surface area of this powder was 20 m 2 / g. As a result of identifying the crystal phase of the Cs 0.33 WO 3 powder by X-ray diffraction, a crystal phase of hexagonal tungsten bronze (composite tungsten oxide fine particles) was observed.
このＣｓ0.33ＷＯ3粉末２０重量％と、トルエン７５重量％と、分散剤５重量％とを混合し分散処理を行い、平均分散粒子径８０ｎｍの分散液（Ｂ液）とした。
２０ｇの実施例１に記載した合成液と、３０ｇのイソブチルアルコールと、２５ｇのプロピレングリコールモノエチルエーテルと、１５ｇのＢ液とを混合撹拌し、さらに触媒として三弗化ホウ素ピペリジンのイソブチルアルコール溶液（濃度：１重量％）１０ｇを加えて撹拌することによって日射遮蔽膜形成用塗布液を製造した。
20% by weight of this Cs 0.33 WO 3 powder, 75% by weight of toluene, and 5% by weight of a dispersant were mixed and dispersed to obtain a dispersion (liquid B) having an average dispersed particle diameter of 80 nm.
20 g of the synthesis solution described in Example 1, 30 g of isobutyl alcohol, 25 g of propylene glycol monoethyl ether, and 15 g of solution B were mixed and stirred, and further a boron trifluoride piperidine solution in isobutyl alcohol (as a catalyst) A coating solution for forming a solar shading film was prepared by adding 10 g of (concentration: 1% by weight) and stirring.
つぎに実施例１と同様な手順で日射遮蔽膜を形成し、膜の評価を行った。
実施例２により得られた日射遮蔽膜のτｖは８３．３％、τｅは５２．２％であり、可視光透過性があって日射遮蔽能があることが分った。またΔＨは３．４％であり表面硬度の非常に高い膜が形成されていた。
Next, a solar shading film was formed in the same procedure as in Example 1, and the film was evaluated.
The solar shading film obtained in Example 2 had a τv of 83.3% and τe of 52.2%, and was found to have visible light permeability and a solar shading ability. ΔH was 3.4%, and a film having a very high surface hardness was formed.
［実施例３］
ＦｅＯＯＨ微粒子１５重量％と、プロピレングリコールモノエチルエーテル８０重量％と、分散剤５重量％とを混合して分散処理を行い、平均分散粒子径８０ｎｍの分散液（Ｃ液）を製造した。
２０ｇの実施例１に記載した合成液と、３０ｇのイソブチルアルコールと、１５ｇのプロピレングリコールモノエチルエーテルと、１５ｇのＢ液と、８ｇのＣ液と、べンゾトリアゾール系有機紫外線吸収剤２ｇとを混合撹拌し、さらに触媒として三弗化ホウ素ピペリジンのイソブチルアルコール溶液（濃度：１重量％）１０ｇを加えて撹拌することによって日射遮蔽膜形成用塗布液を製造した。
[Example 3]
Dispersion treatment was performed by mixing 15% by weight of FeOOH fine particles, 80% by weight of propylene glycol monoethyl ether, and 5% by weight of a dispersant to produce a dispersion liquid (liquid C) having an average dispersed particle diameter of 80 nm.
20 g of the synthesis solution described in Example 1, 30 g of isobutyl alcohol, 15 g of propylene glycol monoethyl ether, 15 g of B solution, 8 g of C solution, and 2 g of benzotriazole organic ultraviolet absorber Were mixed and stirred, and 10 g of an isobutyl alcohol solution of boron trifluoride piperidine (concentration: 1% by weight) was added as a catalyst and stirred to prepare a coating solution for forming a solar shading film.
つぎに実施例１と同様な手順で日射遮蔽膜を形成し、膜の評価を行った。
実施例３により得られた日射遮蔽膜のτｖは７７．８％、τｅは４５．６％であり、可視光透過性があって日射遮蔽能があることが分った。τｕｖは０．５％であり紫外光の遮蔽能は優れていた。またΔＨは４．３％であり表面硬度の非常に高い膜が形成されていた。
Next, a solar shading film was formed in the same procedure as in Example 1, and the film was evaluated.
The solar radiation shielding film obtained in Example 3 had a τv of 77.8% and a τe of 45.6%, and was found to have visible light permeability and a solar radiation shielding ability. τuv was 0.5%, and the ultraviolet light shielding ability was excellent. Further, ΔH was 4.3%, and a film having a very high surface hardness was formed.
［比較例２］
２０ｇの実施例１に記載した合成液と、５ｇのイソブチルアルコールと、６５ｇのＢ液とを混合撹拌し、さらに触媒として三弗化ホウ素ピペリジンのイソブチルアルコール溶液（濃度：１重量％）１０ｇを加えて撹拌することによって日射遮蔽膜形成用塗布液を製造した。
つぎに実施例１と同様な手順で日射遮蔽膜を形成した。しかし、比較例２により得られた日射遮蔽膜は、濃淡ムラが生じ不均一なものであった。
[Comparative Example 2]
20 g of the synthesis solution described in Example 1, 5 g of isobutyl alcohol, and 65 g of solution B were mixed and stirred, and 10 g of an isobutyl alcohol solution of boron trifluoride piperidine (concentration: 1% by weight) was added as a catalyst. The coating solution for forming a solar shading film was produced by stirring the mixture.
Next, a solar radiation shielding film was formed in the same procedure as in Example 1. However, the solar radiation shielding film obtained in Comparative Example 2 was uneven due to uneven density.
［比較例３］
２０ｇの実施例１に記載した合成液と、３０ｇのイソブチルアルコールと、３７．５ｇのプロピレングリコールモノエチルエーテルと、２．５ｇのＢ液とを混合撹拌し、さらに触媒として三弗化ホウ素ピペリジンのイソブチルアルコール溶液（濃度：１重量％）１０ｇを加えて撹拌することによって日射遮蔽膜形成用塗布液を製造した。
つぎに実施例１と同様な手順で日射遮蔽膜を形成し、膜の評価を行った。
比較例３により得られた日射遮蔽膜のτｖは８６．７％、τｅは７０．１％であり、可視光透過性はあるものの日射遮蔽能は不十分であることが分った。
[Comparative Example 3]
20 g of the synthesis solution described in Example 1, 30 g of isobutyl alcohol, 37.5 g of propylene glycol monoethyl ether, and 2.5 g of B solution were mixed and stirred, and further boron trifluoride piperidine as a catalyst. The coating liquid for solar radiation shielding film formation was manufactured by adding and stirring 10 g of isobutyl alcohol solutions (concentration: 1 weight%).
Next, a solar shading film was formed in the same procedure as in Example 1, and the film was evaluated.
The solar radiation shielding film obtained in Comparative Example 3 had a τv of 86.7% and a τe of 70.1%, and it was found that the solar radiation shielding ability was insufficient although it had visible light permeability.
［比較例４］
５０ｇの実施例１に記載した合成液と、２０ｇのイソブチルアルコールと、５ｇのプロピレングリコールモノエチルエーテルと、１５ｇのＢ液とを混合撹拌し、さらに触媒として三弗化ホウ素ピペリジンのイソブチルアルコール溶液（濃度：１重量％）１０ｇを加えて撹拌することによって日射遮蔽膜形成用塗布液を製造した。
つぎに実施例１と同様な手順で日射遮蔽膜を形成し、膜の評価を行った。
比較例４により得られた日射遮蔽膜形成用塗布液は粘度が著しく高く、均一な塗布が行えなかった。
[Comparative Example 4]
50 g of the synthesis solution described in Example 1, 20 g of isobutyl alcohol, 5 g of propylene glycol monoethyl ether, and 15 g of solution B were mixed and stirred, and a boron trifluoride piperidine solution in isobutyl alcohol (as a catalyst) A coating solution for forming a solar shading film was prepared by adding 10 g of (concentration: 1% by weight) and stirring.
Next, a solar shading film was formed in the same procedure as in Example 1, and the film was evaluated.
The coating solution for forming a solar shading film obtained in Comparative Example 4 had a very high viscosity and could not be applied uniformly.
［比較例５］
５ｇの実施例１に記載した合成液と、３０ｇのイソブチルアルコールと、４０ｇのプロピレングリコールモノエチルエーテルと、１５ｇのＢ液とを混合撹拌し、さらに触媒として三弗化ホウ素ピペリジンのイソブチルアルコール溶液（濃度：１重量％）１０ｇを加えて撹拌することによって日射遮蔽膜形成用塗布液を調製した。
つぎに実施例１と同様な手順で日射遮蔽膜を形成し、膜の評価を行った。
比較例５により得られた日射遮蔽膜のτｖは７３．２％、τｅは３６．７％であり、可視光透過性があって日射遮蔽能があることが判明したが、ΔＨは２５．５％であり表面硬度が非常に低く、爪で擦ると傷がついた。
[Comparative Example 5]
5 g of the synthesis solution described in Example 1, 30 g of isobutyl alcohol, 40 g of propylene glycol monoethyl ether, and 15 g of solution B were mixed and stirred, and a boron trifluoride piperidine solution in isobutyl alcohol (as a catalyst) A coating solution for forming a solar shading film was prepared by adding 10 g of (concentration: 1% by weight) and stirring.
Next, a solar shading film was formed in the same procedure as in Example 1, and the film was evaluated.
The solar radiation shielding film obtained in Comparative Example 5 had a τv of 73.2% and a τe of 36.7%, and was found to have visible light permeability and solar radiation shielding ability, but ΔH was 25.5. %, The surface hardness is very low, and scratches were made when rubbed with a nail.
［比較例６］
Ｃｓ0.33ＷＯ3として、平均粒径２５０ｎｍの粗大粒子を用いた以外は、実施例２と同様の手順で日射遮蔽膜形成用塗布液を製造した。
つぎに実施例１と同様な手順で日射遮蔽膜を形成し、膜の評価を行った。
比較例６により得られた日射遮蔽膜のτｖは７７．８％、τｅは４８．９％であり、可視光透過性があって日射遮蔽能があることが判明した。しかし、可視光の散乱が強く、曇りがあって実用には向かなかった。
[Comparative Example 6]
A coating solution for forming a solar shading film was produced in the same procedure as in Example 2 except that coarse particles having an average particle diameter of 250 nm were used as Cs 0.33 WO 3 .
Next, a solar shading film was formed in the same procedure as in Example 1, and the film was evaluated.
The solar radiation shielding film obtained in Comparative Example 6 had a τv of 77.8% and a τe of 48.9%, and was found to have visible light permeability and a solar radiation shielding ability. However, the scattering of visible light was strong and cloudy, making it unsuitable for practical use.
［比較例７］
ＬａＢ6微粒子１０重量％と、ジアセトンアルコール８６重量％と、微粒子分散用カップリング剤４重量％とを混合し、分散処理を行い、平均分散粒子系９０ｎｍの分散液（Ｄ液）とした。
２０ｇの実施例１に記載した合成液と、３０ｇのイソブチルアルコールと、３５ｇのプロピレングリコールモノエチルエーテルと、５ｇのＤ液とを混合撹拌し、さらに触媒として三弗化ホウ素ピペリジンのイソブチルアルコール溶液（濃度：１重量％）１０ｇを加えて撹拌することによって日射遮蔽膜形成用塗布液を製造した。
つぎに実施例１と同様な手順で日射遮蔽膜を形成し、膜の評価を行った。
比較例７により得られた日射遮蔽膜のτｖは７６．８％、τｅは６０．５％であり、可視光透過性があって日射遮蔽能があることが判明した。しかし、実施例１から３に比べ、日射遮蔽能が低くなった。
[Comparative Example 7]
10% by weight of LaB 6 fine particles, 86% by weight of diacetone alcohol and 4% by weight of a coupling agent for dispersing fine particles were mixed and subjected to dispersion treatment to obtain a dispersion liquid (D liquid) having an average dispersed particle system of 90 nm.
20 g of the synthesis solution described in Example 1, 30 g of isobutyl alcohol, 35 g of propylene glycol monoethyl ether, and 5 g of D solution were mixed and stirred, and a solution of boron trifluoride piperidine in isobutyl alcohol (as a catalyst) A coating solution for forming a solar shading film was prepared by adding 10 g of (concentration: 1% by weight) and stirring.
Next, a solar shading film was formed in the same procedure as in Example 1, and the film was evaluated.
The solar radiation shielding film obtained in Comparative Example 7 had a τv of 76.8% and a τe of 60.5%, and was found to have visible light permeability and solar radiation shielding ability. However, compared with Examples 1 to 3, the solar radiation shielding ability was low.
Claims (9)
前記バインダー成分の少なくとも１種が、グリシドキシプロピル基含有アルコキシシランとアミノプロピル基含有アルコキシシランとをモルで比２：１〜１：１の範囲で反応させてなる一般式（化１）で表される反応物であり、
前記近赤外線遮蔽成分が、複合タングステン酸化物から選ばれた少なくとも１種を含む平均粒径２００ｎｍ以下の微粒子であることを特徴とする日射遮蔽膜形成用塗布液。
At least one of the binder components is a general formula (Formula 1) obtained by reacting a glycidoxypropyl group-containing alkoxysilane and an aminopropyl group-containing alkoxysilane in a molar ratio of 2: 1 to 1: 1. The reactant represented,
The near-infrared shielding component is a fine particle having an average particle size of 200 nm or less containing at least one selected from composite tungsten oxides.
さらに、ベンゾフェノン系および／またはベンゾトリアゾール系の有機紫外線吸収剤を含有することを特徴とする日射遮蔽膜形成用塗布液。 It is a coating liquid for solar radiation shielding film formation in any one of Claim 1 to 5,
Furthermore, the coating liquid for solar radiation shielding film formation characterized by containing the organic ultraviolet absorber of a benzophenone series and / or a benzotriazole type.
さらに、紫外線吸収剤として、ＣｅＯ2、ＺｎＯ、Ｆｅ2Ｏ3、ＦｅＯＯＨから選択される少なくとも１種類以上の無機紫外線遮蔽成分であって、平均粒径が１００ｎｍ以下の微粒子を含有することを特徴とする日射遮蔽膜形成用塗布液。 It is a coating liquid for solar radiation shielding film formation in any one of Claim 1 to 6,
Furthermore, the composition contains at least one inorganic ultraviolet shielding component selected from CeO 2 , ZnO, Fe 2 O 3 , and FeOOH as an ultraviolet absorber, and contains fine particles having an average particle diameter of 100 nm or less. A coating solution for forming a solar shielding film.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008101111A (en) * | 2006-10-19 | 2008-05-01 | Sumitomo Metal Mining Co Ltd | Coating liquid for forming sun radiation shielding film, sun radiation shielding film and base material having sun radiation shielding function |
| JP2009046609A (en) * | 2007-08-21 | 2009-03-05 | Sumitomo Metal Mining Co Ltd | Coating liquid for forming heat ray and uv ray shielding film, heat ray and uv ray shielding film, and heat ray and uv ray shielding substrate |
| WO2010055570A1 (en) * | 2008-11-13 | 2010-05-20 | 住友金属鉱山株式会社 | Infrared blocking particle, method for producing the same, infrared blocking particle dispersion using the same, and infrared blocking base |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001262064A (en) * | 2000-03-15 | 2001-09-26 | Sumitomo Metal Mining Co Ltd | Coating liquid for forming cold-setting solar radiation- screening film, solar radiation-screening film using the same base material having solar radiation-screening function |
| JP2001262061A (en) * | 2000-03-15 | 2001-09-26 | Sumitomo Metal Mining Co Ltd | Coating liquid for forming cold-setting solar radiation- screening film, solar radiation-screening film using the same and base material having solar radiation-screening function |
| WO2005037932A1 (en) * | 2003-10-20 | 2005-04-28 | Sumitomo Metal Mining Co., Ltd. | Infrared shielding material microparticle dispersion, infrared shield, process for producing infrared shielding material microparticle, and infrared shielding material microparticle |
-
2005
- 2005-04-20 JP JP2005122687A patent/JP4826126B2/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001262064A (en) * | 2000-03-15 | 2001-09-26 | Sumitomo Metal Mining Co Ltd | Coating liquid for forming cold-setting solar radiation- screening film, solar radiation-screening film using the same base material having solar radiation-screening function |
| JP2001262061A (en) * | 2000-03-15 | 2001-09-26 | Sumitomo Metal Mining Co Ltd | Coating liquid for forming cold-setting solar radiation- screening film, solar radiation-screening film using the same and base material having solar radiation-screening function |
| WO2005037932A1 (en) * | 2003-10-20 | 2005-04-28 | Sumitomo Metal Mining Co., Ltd. | Infrared shielding material microparticle dispersion, infrared shield, process for producing infrared shielding material microparticle, and infrared shielding material microparticle |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008101111A (en) * | 2006-10-19 | 2008-05-01 | Sumitomo Metal Mining Co Ltd | Coating liquid for forming sun radiation shielding film, sun radiation shielding film and base material having sun radiation shielding function |
| JP2009046609A (en) * | 2007-08-21 | 2009-03-05 | Sumitomo Metal Mining Co Ltd | Coating liquid for forming heat ray and uv ray shielding film, heat ray and uv ray shielding film, and heat ray and uv ray shielding substrate |
| WO2010055570A1 (en) * | 2008-11-13 | 2010-05-20 | 住友金属鉱山株式会社 | Infrared blocking particle, method for producing the same, infrared blocking particle dispersion using the same, and infrared blocking base |
| JPWO2010055570A1 (en) * | 2008-11-13 | 2012-04-05 | 住友金属鉱山株式会社 | Infrared shielding fine particles, method for producing the same, infrared shielding fine particle dispersion using the same, and infrared shielding base material |
| US8470212B2 (en) | 2008-11-13 | 2013-06-25 | Sumitomo Metal Mining Co., Ltd. | Infrared shielding nanoparticle, its manufacturing method, infrared shielding nanoparticle dispersion using the same, and infrared shielding base material |
| TWI722334B (en) * | 2017-11-13 | 2021-03-21 | 日商住友金屬礦山股份有限公司 | Surface-treated infrared absorbing fine particles, surface-treated infrared absorbing fine particle powder, infrared absorbing fine particle dispersion liquid using the surface-treated infrared absorbing fine particles, infrared absorbing fine particle dispersion body, and method for producing the same |
| CN113667375A (en) * | 2021-07-30 | 2021-11-19 | 哈尔滨工业大学 | Nano rare earth oxide composite powder for shielding neutrons and gamma rays, composite material thereof and preparation method thereof |
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