JP5252876B2 - Photocatalytic hydrosol and aqueous photocatalytic coating agent - Google Patents
Photocatalytic hydrosol and aqueous photocatalytic coating agent Download PDFInfo
- Publication number
- JP5252876B2 JP5252876B2 JP2007274905A JP2007274905A JP5252876B2 JP 5252876 B2 JP5252876 B2 JP 5252876B2 JP 2007274905 A JP2007274905 A JP 2007274905A JP 2007274905 A JP2007274905 A JP 2007274905A JP 5252876 B2 JP5252876 B2 JP 5252876B2
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- JP
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- Prior art keywords
- photocatalyst
- hydrosol
- titanium oxide
- mass
- particles
- Prior art date
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- 239000011248 coating agent Substances 0.000 title claims description 37
- 230000001699 photocatalysis Effects 0.000 title description 23
- 239000011941 photocatalyst Substances 0.000 claims description 131
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 81
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 77
- 239000002245 particle Substances 0.000 claims description 56
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 45
- -1 aluminum compound Chemical class 0.000 claims description 43
- 229910052782 aluminium Inorganic materials 0.000 claims description 26
- 238000004519 manufacturing process Methods 0.000 claims description 24
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- 239000000377 silicon dioxide Substances 0.000 claims description 20
- 230000007935 neutral effect Effects 0.000 claims description 19
- 239000003995 emulsifying agent Substances 0.000 claims description 12
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- 239000011230 binding agent Substances 0.000 claims description 10
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- 239000007864 aqueous solution Substances 0.000 description 9
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- 239000002253 acid Substances 0.000 description 7
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Description
本発明は、中性の光触媒ヒドロゾル及びそれを用いた水系光触媒コーティング剤に関するものである。
具体的には、中性のｐＨ域で凝集や沈降が抑制されて安定に存在することのできる光触媒ヒドロゾルに関するものである。さらには環境負荷の小さい水系光触媒コーティング剤及び当該コーティング剤を塗布した塗装物に関する。
The present invention relates to a neutral photocatalyst hydrosol and a water-based photocatalyst coating agent using the same.
Specifically, the present invention relates to a photocatalytic hydrosol that can stably exist in a neutral pH range with aggregation and sedimentation suppressed. Furthermore, the present invention relates to a water-based photocatalyst coating agent having a small environmental load and a coated article to which the coating agent is applied.
光触媒とは、光照射によって酸化、還元反応を起こす物質のことを言う。すなわち伝導帯と価電子帯との間のエネルギーギャップよりも大きなエネルギー（すなわち短い波長）の光（励起光）を照射したときに、価電子帯中の電子の励起（光励起）が生じて、伝導電子と正孔を生成しうる物質であり、このとき、伝導帯に生成した電子の還元力および／または価電子帯に生成した正孔の酸化力を利用して、種々の化学反応を行うことができる。
また、光触媒活性とは、光照射によって酸化、還元反応を起こすことを言う。光触媒活性によって有機物質の分解作用や表面の親水化作用を示すことが知られており、光触媒は有害物の除去や防汚、防曇などに用いられる。
A photocatalyst is a substance that undergoes an oxidation or reduction reaction upon irradiation with light. That is, when light (excitation light) with an energy larger than the energy gap between the conduction band and the valence band (ie, a short wavelength) is irradiated, excitation (photoexcitation) of electrons in the valence band occurs, resulting in conduction. It is a substance that can generate electrons and holes. At this time, various chemical reactions are performed using the reducing power of electrons generated in the conduction band and / or the oxidizing power of holes generated in the valence band. Can do.
The photocatalytic activity means that an oxidation or reduction reaction is caused by light irradiation. It is known that the photocatalytic activity exhibits an organic substance decomposing action and a surface hydrophilizing action, and the photocatalyst is used for removal of harmful substances, antifouling, antifogging and the like.
このような光触媒は何らかの基体上に担持、固定して使用されることが一般的である。このとき、微粒子状の光触媒を基材に固定化すると表面を有効に使用でき、より活性が高まるために好ましい。あるいは透明性が増すことで基材の意匠性を損なわないという点でも微粒子状の光触媒が好ましい。
このような光触媒を基材に固定化するには溶媒に分散したゾル状の光触媒を塗布する方法が用いられる。光触媒のゾルとしては有機溶媒を使用したオルガノゾル、水を使用したヒドロゾルがあるが環境問題の観点からヒドロゾルを使用が望まれている。また、ヒドロゾルの中でも基材腐食防止及び作業性の観点などから中性のｐＨ域で安定な中性のゾルの要求が高まっている。
Such a photocatalyst is generally used by being supported and fixed on some substrate. At this time, it is preferable to immobilize the particulate photocatalyst on the substrate because the surface can be used effectively and the activity is further increased. Alternatively, a fine particle photocatalyst is also preferable in that it does not impair the design of the substrate by increasing the transparency.
In order to immobilize such a photocatalyst on a substrate, a method of applying a sol-like photocatalyst dispersed in a solvent is used. The photocatalyst sol includes an organosol using an organic solvent and a hydrosol using water. From the viewpoint of environmental problems, the use of a hydrosol is desired. In addition, among hydrosols, there is an increasing demand for neutral sols that are stable in a neutral pH range from the viewpoint of prevention of substrate corrosion and workability.
しかしながら、光触媒として多用されている酸化チタンは中性のｐＨでは安定性に劣るため、微粒子状の光触媒が分散した中性の光触媒ヒドロゾルを作製するのは困難であった。
この課題に対して例えば特許文献１では酸化チタンの表面に１０質量％から２５質量％の高濃度で多孔質シリカを被覆させる方法が開示されている。しかし、この方法では多量のシリカを使用しないと分散性を向上させることが困難となる。光触媒の表面に多量のシリカが被着しているとその分、光触媒の活性を犠牲にすることになるという問題点がある。
また、特許文献２では分散剤を使用して光触媒を分散させる方法が開示されている。しかし、この方法では光触媒ゾルを希釈したり濃縮したりするとそれに伴って分散剤の濃度も変わることとなり、実際にコーティング剤を調製する際には良分散性を保つのが難しいという問題点がある。
However, titanium oxide, which is frequently used as a photocatalyst, is inferior in stability at a neutral pH, and it has been difficult to produce a neutral photocatalyst hydrosol in which particulate photocatalysts are dispersed.
For example, Patent Document 1 discloses a method for coating the surface of titanium oxide with porous silica at a high concentration of 10% by mass to 25% by mass. However, in this method, it is difficult to improve dispersibility unless a large amount of silica is used. If a large amount of silica is deposited on the surface of the photocatalyst, there is a problem that the activity of the photocatalyst is sacrificed accordingly.
Patent Document 2 discloses a method of dispersing a photocatalyst using a dispersant. However, in this method, if the photocatalyst sol is diluted or concentrated, the concentration of the dispersing agent changes accordingly, and it is difficult to maintain good dispersibility when actually preparing a coating agent. .
本発明は上記の課題を解決することを目的とし、微粒子状の光触媒が良分散で安定的に存在している中性ヒドロゾルを提供することである。また、そのような光触媒を含む水系光触媒塗料、さらにはこのような光触媒塗料を塗布した光触媒塗工製品を提供することにある。 An object of the present invention is to provide a neutral hydrosol in which fine-particle photocatalysts are present in good dispersion and stably. Another object of the present invention is to provide a water-based photocatalyst paint containing such a photocatalyst, and a photocatalyst-coated product coated with such a photocatalyst paint.
本発明者らは上記課題を解決すべく鋭意検討した結果、本発明に到達した。すなわち、本発明は以下の通りである。
１）光触媒粒子の表面に光触媒粒子に対して０．５から１０質量％のアルミニウム化合物
を被着した、中性のｐＨ域で安定な光触媒ヒドロゾルであって、光触媒粒子として、粒子表面に１から１０質量％のシリカがあらかじめ被着された光触媒粒子を用いることを特徴とする光触媒ヒドロゾル、
２）光触媒が酸化チタンであることを特徴とする１）に記載の光触媒ヒドロゾル、
３）光触媒ヒドロゾルに、光触媒粒子に対して０．５から１０質量％のアルミニウム化合物を添加し、中性のｐＨ域で混合するアルミニウム化合物被着光触媒ヒドロゾルの製造方法であって、あらかじめ粒子表面に１から１０質量％のシリカが被着された光触媒粒子からなる光触媒ヒドロゾルを用いることを特徴とするアルミニウム化合物被着光触媒ヒドロゾルの製造方法、
４）１）又は２）に記載の光触媒ヒドロゾルと水系バインダーとからなる水系光触媒コーティング剤、
５）水系バインダーが、水及び乳化剤の存在下に加水分解性珪素化合物（ｂ１）及び、２級及び／又は３級アミド基を有するビニル単量体（ｂ２）を重合して得られる重合体エマルジョン粒子と無機酸化物粒子（ａ）を含むことを特徴とする４）に記載の水系光触媒コーティング剤、
６）４）または５）に記載の水系光触媒コーティング剤を塗布した光触媒塗装製品、
である。
As a result of intensive studies aimed at solving the above problems, the present inventors have reached the present invention. That is, the present invention is as follows.
1) A photocatalyst hydrosol that is stable in a neutral pH range, in which 0.5 to 10% by mass of an aluminum compound is deposited on the surface of the photocatalyst particle, and is 1 to A photocatalyst hydrosol using photocatalyst particles pre-deposited with 10% by mass of silica ,
2 ) The photocatalytic hydrosol according to 1), wherein the photocatalyst is titanium oxide,
3) the photocatalyst hydrosol, supplemented with 0.5 to 10 wt% of the aluminum compound relative to the photocatalyst particles, a luer aluminum compound deposited photocatalyst hydrosol method of manufacturing be mixed in the pH range of neutral, pre particles A method for producing an aluminum compound-adhered photocatalyst hydrosol comprising a photocatalyst hydrosol comprising photocatalyst particles having 1 to 10% by mass of silica deposited on the surface thereof ;
4 ) An aqueous photocatalyst coating agent comprising the photocatalyst hydrosol described in 1) or 2) and an aqueous binder,
5 ) Polymer emulsion obtained by polymerizing hydrolyzable silicon compound (b1) and vinyl monomer (b2) having a secondary and / or tertiary amide group in the presence of water and an emulsifier. 4) The aqueous photocatalyst coating agent according to 4) , comprising particles and inorganic oxide particles (a),
6 ) A photocatalyst-coated product to which the aqueous photocatalyst coating agent described in 4) or 5) is applied,
It is.
本発明は分散性に優れる光触媒ヒドロゾルを提供するものである。当該光触媒ヒドロゾルを使用することにより、光触媒活性及び／又は親水性を効果的に発現する光触媒コーティング剤及び光触媒塗装物を提供することができる。また、少ない環境負荷で硬化可能であって、基材及びコーティング被膜に優れた耐久性を与える光触媒組成物（光触媒ヒドロゾル又は光触媒コーティング剤）を提供することができる。さらに当該組成物は耐候性、耐水性、透明性にも優れ、長期間にわたって汚れにくい塗装物を提供できる。 The present invention provides a photocatalytic hydrosol excellent in dispersibility. By using the photocatalyst hydrosol, it is possible to provide a photocatalyst coating agent and a photocatalyst-coated product that effectively express photocatalytic activity and / or hydrophilicity. Further, it is possible to provide a photocatalyst composition (photocatalyst hydrosol or photocatalyst coating agent) that can be cured with a small environmental load and gives excellent durability to a substrate and a coating film. Furthermore, the composition is excellent in weather resistance, water resistance, and transparency, and can provide a coated product that is resistant to staining over a long period of time.
以下、本発明を詳細に説明する。
本発明において変性光触媒に使用できる光触媒とは、その結晶の伝導帯と価電子帯との間のエネルギーギャップよりも大きなエネルギー（すなわち短い波長）の光（励起光）を照射したときに、価電子帯中の電子の励起（光励起）が生じて、伝導電子と正孔を生成しうる物質をいう。中でも、光照射による酸化、還元反応を起こす能力と正孔と電子を生成させるのに必要な光のエネルギーのバランスから、バンドギャップエネルギーが１．２〜５．０ｅＶの半導体化合物が好ましく、１．５〜４．１ｅＶの半導体化合物がさらに好ましい。
Hereinafter, the present invention will be described in detail.
The photocatalyst that can be used for the modified photocatalyst in the present invention is a valence electron when irradiated with light (excitation light) having an energy (ie, short wavelength) larger than the energy gap between the conduction band and the valence band of the crystal. A substance that can generate conduction electrons and holes due to excitation (photoexcitation) of electrons in the band. Among them, a semiconductor compound having a band gap energy of 1.2 to 5.0 eV is preferable in view of the balance between the ability to cause oxidation and reduction reaction by light irradiation and the energy of light necessary for generating holes and electrons. A semiconductor compound of 5 to 4.1 eV is more preferable.
光触媒としては例えばＴｉＯ２、ＺｎＯ、ＳｒＴｉＯ３、ＣｄＳ、ＧａＰ、ＩｎＰ、ＧａＡｓ、ＢａＴｉＯ３、ＢａＴｉＯ４、ＢａＴｉ４Ｏ９、Ｋ２ＮｂＯ３、Ｎｂ２Ｏ５、Ｆｅ２Ｏ３、Ｔａ２Ｏ５、Ｋ３Ｔａ３Ｓｉ２Ｏ３、ＷＯ３、ＳｎＯ２、Ｂｉ２Ｏ３、ＢｉＶＯ４、ＮｉＯ、Ｃｕ２Ｏ、ＳｉＣ、ＭｏＳ２、ＩｎＰｂ、ＲｕＯ２、ＣｅＯ２等、さらにはＴｉ、Ｎｂ、Ｔａ、Ｖから選ばれた少なくとも１種の元素を有する層状酸化物（特開昭６２−７４４５２号公報、特開平２−１７２５３５号公報、特開平７−２４３２９号公報、特開平８−８９７９９号公報、特開平８−８９８００号公報、特開平８−８９８０４号公報、特開平８−１９８０６１号公報、特開平９−２４８４６５号公報、特開平１０−９９６９４号公報、特開平１０−２４４１６５号公報等）を挙げることができる。また、これらの光触媒にＰｔ、ＲＨ、Ｒｕ、Ｎｂ、Ｃｕ、Ｓｎ、Ｎｉ、Ｆｅなどの金属及び／又は金属の酸化物を添加あるいは固定化したものや、多孔質リン酸カルシウム等で被覆された光触媒（特開平１１−２６７５１９号公報）等も使用することもできる。 Photocatalyst The example TiO 2, ZnO, SrTiO 3, CdS, GaP, InP, GaAs, BaTiO 3, BaTiO 4, BaTi 4 O 9, K 2 NbO 3, Nb 2 O 5, Fe 2 O 3, Ta 2 O 5 , K 3 Ta 3 Si 2 O 3 , WO 3 , SnO 2 , Bi 2 O 3 , BiVO 4 , NiO, Cu 2 O, SiC, MoS 2 , InPb, RuO 2 , CeO 2 and the like, and further Ti, Nb, Layered oxides having at least one element selected from Ta and V (Japanese Patent Laid-Open Nos. 62-74452, 2-172535, 7-24329, and 8-89799) JP-A-8-89800, JP-A-8-89804, JP-A-8-198061, JP-A-9-248465, 0-99694, JP Patent Laid-Open No. 10-244165 Publication) can be exemplified. In addition, a photocatalyst coated with a metal such as Pt, RH, Ru, Nb, Cu, Sn, Ni, Fe and / or an oxide of a metal added or fixed to these photocatalysts, or a porous calcium phosphate or the like ( JP-A-11-267519) can also be used.
また、本発明の光触媒として、可視光（例えば約４００〜８００ｎｍの波長）の照射により光触媒活性及び／又は親水性を発現することが出来る可視光応答型光触媒を選択すると、本発明の光触媒組成物で処理された光触媒部材は、室内等の紫外線が十分に照射されない場所等における環境浄化効果や防汚効果が非常に大きなものとなるため好ましい。 In addition, when a visible light responsive photocatalyst capable of expressing photocatalytic activity and / or hydrophilicity by irradiation with visible light (for example, a wavelength of about 400 to 800 nm) is selected as the photocatalyst of the present invention, the photocatalyst composition of the present invention is selected. The photocatalyst member treated with is preferable because the environmental purification effect and the antifouling effect in a place where ultraviolet rays such as indoors are not sufficiently irradiated are very large.
上記可視光応答型光触媒は、可視光で光触媒活性及び／又は親水性を発現するものであれば全て使用することが出来るが、例えばＴａＯＮ、ＬａＴｉＯ２Ｎ、ＣａＮｂＯ２Ｎ、ＬａＴａＯＮ２、ＣａＴａＯ２Ｎ等のオキシナイトライド化合物（例えば特開２００２−６６３３３号公報参照）やＳｍ２Ｔｉ２Ｓ２Ｏ７等のオキシサルファイド化合物（例えば特開２００２−２３３７７０号公報参照）、ＣａＩｎ２Ｏ４、ＳｒＩｎ２Ｏ４、ＺｎＧａ２Ｏ４、Ｎａ２Ｓｂ２Ｏ６等のｄ１０電子状態の金属イオンを含む酸化物（例えば特開２００２−５９００８号公報参照）、アンモニアや尿素等の窒素含有化合物存在下でチタン酸化物前駆体（オキシ硫酸チタン、塩化チタン、アルコキシチタン等）や高表面酸化チタンを焼成して得られる窒素ドープ酸化チタン（例えば特開２００２−２９７５０号公報、特開２００２−８７８１８号公報、特開２００２−１５４８２３号公報、特開２００１−２０７０８２号公報参照）、チオ尿素等の硫黄化合物存在下にチタン酸化物前駆体（オキシ硫酸チタン、塩化チタン、アルコキシチタン等）を焼成して得られる硫黄ドープ酸化チタン、酸化チタンを水素プラズマ処理したり真空下で加熱処理したりすることによって得られる酸素欠陥型の酸化チタン（例えば特開２００１−９８２１９号公報参照）、さらには光触媒粒子をハロゲン化白金化合物で処理したり（例えば特開２００２−２３９３５３号公報参照）、タングステンアルコキシドで処理（特開２００１−２８６７５５号公報参照）することによって得られる表面処理光触媒等を好適に挙げることができる。
光触媒にはその性能向上をさせるなどのために，光触媒粒子の表面に白金、金、銀、銅、パラジウム、ロジウム、ルテニウムなどの金属や該金属の酸化物を被着しておいてもよい。
Any visible light responsive photocatalyst can be used as long as it exhibits photocatalytic activity and / or hydrophilicity with visible light. For example, TaON, LaTiO 2 N, CaNbO 2 N, LaTaON 2 , and CaTaO 2 N can be used. Such as oxysulfide compounds such as Sm 2 Ti 2 S 2 O 7 (see, for example, JP 2002-233770 A), CaIn 2 O 4 , and SrIn 2. Oxides containing metal ions in the d10 electronic state such as O 4 , ZnGa 2 O 4 , Na 2 Sb 2 O 6 (see, for example, JP-A-2002-59008), titanium in the presence of nitrogen-containing compounds such as ammonia and urea. Baked oxide precursors (titanium oxysulfate, titanium chloride, alkoxy titanium, etc.) and high surface titanium oxide Nitrogen-doped titanium oxide (see, for example, JP-A-2002-29750, JP-A-2002-87818, JP-A-2002-154823, JP-A-2001-207082), sulfur compounds such as thiourea Sulfur-doped titanium oxide obtained by firing a titanium oxide precursor (titanium oxysulfate, titanium chloride, alkoxytitanium, etc.) in the presence, obtained by hydrogen plasma treatment or heat treatment under vacuum Oxygen-deficient titanium oxide (see, for example, JP-A-2001-98219), photocatalyst particles are treated with a halogenated platinum compound (see, for example, JP-A-2002-239353), or treated with tungsten alkoxide (specialty). Surface treatment obtained by (Kaikai 2001-286755) A photocatalyst or the like can be preferably used.
In order to improve the performance of the photocatalyst, a metal such as platinum, gold, silver, copper, palladium, rhodium or ruthenium or an oxide of the metal may be deposited on the surface of the photocatalyst particles.
本発明で用いる光触媒としては光触媒のとしての性能の観点及び分散性の観点から一次粒子径が１〜４００ｎｍの範囲にあることが好ましい。１〜１００ｎｍの範囲にあることがより好ましく、５〜５０ｎｍの範囲であることがさらに好ましい。光触媒の一次粒子径は透過型電子顕微鏡にて測定することができる。
本発明に用いる光触媒はヒドロゾルの形態にある。
ここで、光触媒ヒドロゾルとは、光触媒粒子が実質的に水を分散媒とする媒体中に固形分０．０１〜７０質量％、好ましくは０．１〜５０質量％で分散されたものである。（ここで、実質的に水を分散媒とするとは、分散媒中に水が８０％程度以上含有されていることを意味する。）
また、本発明に使用される光触媒ゾルに含まれる光触媒粒子は、一次粒子と二次粒子との混合物である。
かかるゾルの調製は周知であり、容易に製造できる。例えば、粒子表面がペルオキソ基で修飾されたアナターゼ型酸化チタンゾルが特開平１０−６７５１６号公報で提案された方法によって容易に得ることができる。
The photocatalyst used in the present invention preferably has a primary particle diameter in the range of 1 to 400 nm from the viewpoint of performance as a photocatalyst and from the viewpoint of dispersibility. It is more preferably in the range of 1 to 100 nm, and further preferably in the range of 5 to 50 nm. The primary particle diameter of the photocatalyst can be measured with a transmission electron microscope.
The photocatalyst used in the present invention is in the form of a hydrosol.
Here, the photocatalyst hydrosol is one in which photocatalyst particles are dispersed at a solid content of 0.01 to 70% by mass, preferably 0.1 to 50% by mass, in a medium substantially containing water as a dispersion medium. (Here, substantially using water as a dispersion medium means that about 80% or more of water is contained in the dispersion medium.)
The photocatalyst particles contained in the photocatalyst sol used in the present invention are a mixture of primary particles and secondary particles.
The preparation of such sols is well known and can be easily manufactured. For example, an anatase-type titanium oxide sol having a particle surface modified with a peroxo group can be easily obtained by the method proposed in Japanese Patent Laid-Open No. 10-67516.
上記光触媒ヒドロゾルが酸化チタンヒドロゾルである場合は、酸化チタンヒドロゾル中の固形分は５０質量％以下、好ましくは３５質量％以下である。さらに好ましくは３５質量％以下０．１質量％以上である。このようなヒドロゾルの粘度（２０℃）は比較的低く、例えば、２０００ｃｐｓ〜０．５ｃｐｓ程度の範囲にあればよい。好ましくは１０００ｃｐｓ〜１ｃｐｓ、さらに好ましくは５００ｃｐｓ〜１ｃｐｓである。
また、例えば酸化セリウムゾル（特開平８−５９２３５号公報）やＴｉ、Ｎｂ、Ｔａ、Ｖから選ばれた少なくとも１種の元素を有する層状酸化物のゾル（特開平９−２５１２３号公報、特開平９−６７１２４号公報、特開平９−２２７１２２号公報、特開平９−２２７１２３号公報、特開平１０−２５９０２３号公報等）等、様々な光触媒ゾルの製造方法についても周知であり、酸化チタンゾルと同様に開示され
ている。
When the photocatalyst hydrosol is a titanium oxide hydrosol, the solid content in the titanium oxide hydrosol is 50% by mass or less, preferably 35% by mass or less. More preferably, it is 35 mass% or less and 0.1 mass% or more. Such a hydrosol has a relatively low viscosity (20 ° C.) and may be, for example, in the range of about 2000 cps to 0.5 cps. Preferably it is 1000 cps-1 cps, More preferably, it is 500 cps-1 cps.
Further, for example, a cerium oxide sol (JP-A-8-59235) or a layered oxide sol having at least one element selected from Ti, Nb, Ta, and V (JP-A-9-25123, JP-A-9-9). -67124, JP-A-9-227122, JP-A-9-227123, JP-A-10-259023, etc.) are also well-known, and the production method of various photocatalyst sols is well known. It is disclosed.
本発明の光触媒ヒドロゾルは光触媒粒子の表面にアルミニウム化合物を被着したものである。アルミニウム化合物を被着するためには、例えば光触媒とアルミニウム化合物を水中で混合し、必要に応じて中和する方法が用いられる。アルミニウム化合物としてはアルコキシアルミニウム化合物，アルカリ金属アルミン酸塩などを使用することができる。取り扱い及び反応性の観点からアルカリ金属アルミン酸塩を使用することが好ましく、さらにはアルミン酸ナトリウムを使用することがより好ましい。アルミン酸ナトリウムにはアルミニウムとナトリウムの比が異なる様々な化合物があるが、いずれのアルミン酸ナトリウムも使用することができる。 The photocatalytic hydrosol of the present invention is obtained by depositing an aluminum compound on the surface of photocatalyst particles. In order to deposit the aluminum compound, for example, a method in which a photocatalyst and an aluminum compound are mixed in water and neutralized as necessary is used. As the aluminum compound, an alkoxyaluminum compound, an alkali metal aluminate or the like can be used. From the viewpoint of handling and reactivity, it is preferable to use an alkali metal aluminate, and it is more preferable to use sodium aluminate. There are various compounds in sodium aluminate having different ratios of aluminum and sodium, and any sodium aluminate can be used.
光触媒粒子表面に被着するアルミニウム化合物の量は光触媒に対して０．５から１０質量％であり、好ましくは１から７質量％、さらに好ましくは２から７質量％である。当該範囲で被着することで光触媒粒子の良好な分散性と高い光触媒活性を両立することが可能となる。
これらの本発明で用いる光触媒としてはあらかじめ光触媒表面に１から１５質量％のシリカが被着されているものが好ましい。より好ましくはシリカが２から１０質量％の被着量の光触媒である。このような光触媒粒子を用いると、光触媒粒子とアルミニウム化合物との反応性が増すため、光触媒粒子表面に効率的にアルミニウム化合物を被着することができる。当該範囲のシリカ被着量であればアルミニウム化合物との良好な反応性と高い光触媒活性を両立することが可能となる。
本発明の光触媒ヒドロゾルは、該ヒドロゾル中には光触媒は一次粒子と二次粒子との混合物の状態で存在し、その混合物の数平均粒子径（［実施例］にて定義）は、好ましくは１〜８００ｎｍであり、より好ましくは１〜２００ｎｍであり、特に好ましくは５〜１００ｎｍである。この数平均粒子径が８００ｎｍ以下であると表面積が大きくなり、アルミニウム化合物との反応性及び光触媒活性の観点から好ましい。
The amount of the aluminum compound deposited on the surface of the photocatalyst particles is 0.5 to 10% by mass with respect to the photocatalyst, preferably 1 to 7% by mass, and more preferably 2 to 7% by mass. By depositing in this range, it is possible to achieve both good dispersibility of the photocatalyst particles and high photocatalytic activity.
As these photocatalysts used in the present invention, those in which 1 to 15% by mass of silica is previously deposited on the surface of the photocatalyst are preferable. More preferably, silica is a photocatalyst having a deposition amount of 2 to 10% by mass. When such photocatalyst particles are used, the reactivity between the photocatalyst particles and the aluminum compound is increased, so that the aluminum compound can be efficiently deposited on the surface of the photocatalyst particles. When the silica deposition amount is in this range, it is possible to achieve both good reactivity with the aluminum compound and high photocatalytic activity.
In the photocatalyst hydrosol of the present invention, the photocatalyst is present in a mixture of primary particles and secondary particles in the hydrosol, and the number average particle diameter of the mixture (defined in [Example]) is preferably 1. It is -800 nm, More preferably, it is 1-200 nm, Most preferably, it is 5-100 nm. When the number average particle diameter is 800 nm or less, the surface area increases, which is preferable from the viewpoints of reactivity with the aluminum compound and photocatalytic activity.
本発明で用いる光触媒粒子としてはＴｉＯ２（酸化チタン）が好ましい。酸化チタンは無害であり、化学的安定性にも優れる。また、アナターゼ、ルチル、ブルッカイトのいずれの結晶構造の酸化チタンも使用でき、複数の結晶構造の酸化チタンの混合物であってもよい。
酸化チタンとしてアナターゼ型酸化チタンを用いると光触媒活性及び／又は親水性がより強く発現する点で好ましい。また、酸化チタンとしてルチル型酸化チタンを用いると光触媒活性及び／又は親水性を発現しつつ耐候性に優れる点で好ましい。
酸化チタンの結晶構造はＸ線回折によって同定することができる。酸化チタンには、通常の酸化チタンのほかに含水酸化チタン、水和酸化チタン、オルトチタン酸、メタチタン酸、水酸化チタンと称されるものも含まれる。
As the photocatalyst particles used in the present invention, TiO 2 (titanium oxide) is preferable. Titanium oxide is harmless and has excellent chemical stability. In addition, titanium oxide having any crystal structure of anatase, rutile, or brookite can be used, and a mixture of titanium oxides having a plurality of crystal structures may be used.
Use of anatase-type titanium oxide as the titanium oxide is preferable in that the photocatalytic activity and / or hydrophilicity is more strongly expressed. In addition, it is preferable to use rutile type titanium oxide as the titanium oxide in terms of excellent weather resistance while exhibiting photocatalytic activity and / or hydrophilicity.
The crystal structure of titanium oxide can be identified by X-ray diffraction. In addition to normal titanium oxide, titanium oxide includes those called hydrous titanium oxide, hydrated titanium oxide, orthotitanic acid, metatitanic acid, and titanium hydroxide.
本発明の光触媒ヒドロゾルは水系バインダーと混合して光触媒塗料（コーティング剤）として使用することができる。本発明の光触媒ヒドロゾルはどのようなバインダーと混合してもすぐれた分散性を保持できる点で有効である。水系バインダーとは、実質的に水を分散媒とするバインダー樹脂溶液あるいはバインダー樹脂の分散体のことを言う。例えば、ポリビニルアルコール、カチオン変成ポリビニルアルコール、シラノール変性ポリビニルアルコールなどのポリビニルアルコール誘導体、ポリビニルピロリドン、ポリアクリルアミド類、デンプン及びデンプン誘導体、カルボキシメチルセルロース、ヒドロキシエチルセルロース等のセルロース誘導体、カゼイン、ゼラチン、水性媒体中でのラジカル重合、アニオン重合、カチオン重合などによって得られる従来公知のポリ（メタ）アクリレート系、ポリビニルアセテート系、酢酸ビニル−アクリル系、エチレン酢酸ビニル系、シリコーン系、ポリブタジエン系、スチレンブタジエン系、ＮＢＲ系、ポリ塩化ビニル系、塩素化ポリプロピレン系、ポリエチレン系、ポリスチレン系、塩化ビニリデン系、ポリスチレン−（メタ）アクリレート系、スチレン−無水マレイン酸系等の共重合体、シリコーン変性アクリル系、フッソ−アクリル系、アクリルシリコン、エポキシ−アクリル系等の変性共重合体の水分散体などを挙げることができる。 The photocatalyst hydrosol of the present invention can be mixed with an aqueous binder and used as a photocatalyst paint (coating agent). The photocatalyst hydrosol of the present invention is effective in that excellent dispersibility can be maintained even when mixed with any binder. The aqueous binder means a binder resin solution or binder resin dispersion substantially using water as a dispersion medium. For example, polyvinyl alcohol, cation-modified polyvinyl alcohol, polyvinyl alcohol derivatives such as silanol-modified polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamides, starch and starch derivatives, cellulose derivatives such as carboxymethyl cellulose, hydroxyethyl cellulose, casein, gelatin, in an aqueous medium Conventionally known poly (meth) acrylate type, polyvinyl acetate type, vinyl acetate-acrylic type, ethylene vinyl acetate type, silicone type, polybutadiene type, styrene butadiene type, NBR type obtained by radical polymerization, anionic polymerization, cationic polymerization, etc. , Polyvinyl chloride, chlorinated polypropylene, polyethylene, polystyrene, vinylidene chloride, polystyrene- (meth) acryl Over preparative system, a styrene - maleic anhydride copolymer-based or the like, silicone-modified acrylic-based, fluorine - acrylic, acrylic silicone, epoxy - and the like aqueous dispersion of the modified copolymer such as an acrylic.
さらに、水系バインダーにはバインダー樹脂に含まれる官能基と反応する官能基を有する化合物を含むことができる。例えば、（ポリ）イソシアネート化合物、（ポリ）エポキシ化合物、アミノ化合物、（ポリ）カルボキシ化合物、（ポリ）ヒドロキシ化合物、グリコール化合物、シラノール化合物、シリル化合物、アルコキシ化合物、（メタ）アクリレート類などを挙げることができる。
本発明では水系バインダーとして、水及び乳化剤の存在下に加水分解性珪素化合物（ｂ１）及び、２級及び／又は３級アミド基を有するビニル単量体（ｂ２）を重合して得られることを特徴とする重合体エマルジョン粒子と無機酸化物粒子を含むものであることが好ましい。
Further, the aqueous binder can contain a compound having a functional group that reacts with a functional group contained in the binder resin. Examples include (poly) isocyanate compounds, (poly) epoxy compounds, amino compounds, (poly) carboxy compounds, (poly) hydroxy compounds, glycol compounds, silanol compounds, silyl compounds, alkoxy compounds, (meth) acrylates, and the like. Can do.
In the present invention, it is obtained by polymerizing a hydrolyzable silicon compound (b1) and a vinyl monomer (b2) having a secondary and / or tertiary amide group in the presence of water and an emulsifier as an aqueous binder. It is preferable that the polymer emulsion particle | grains and inorganic oxide particle which are characterized are included.
加水分解性珪素化合物（ｂ１）としては、下記式（１）で表される化合物やその縮合生成物、シランカップリング剤を例示することができる。
ＳｉＷｘＲｙ （１）
（式中、Ｗは炭素数１〜２０のアルコキシ基、水酸基、炭素数１〜２０のアセトキシ基、ハロゲン原子、水素原子、炭素数１〜２０のオキシム基、エノキシ基、アミノキシ基、アミド基から選ばれた少なくとも１種の基を表す。Ｒは、直鎖状又は分岐状の炭素数が１〜３０個のアルキル基、炭素数５〜２０のシクロアルキル基、及び置換されていないか又は炭素数１〜２０のアルキル基若しくは炭素数１〜２０のアルコキシ基若しくはハロゲン原子で置換されている炭素数６〜２０のアリール基から選ばれる少なくとも１種の炭化水素基を表す。ｘは１以上４以下の整数であり、ｙは０以上３以下の整数である。また、ｘ＋ｙ＝４である。）
ここでシランカップリング剤とは、ビニル重合性基、エポキシ基、アミノ基、メタクリル基、メルカプト基、イソシアネート基等の有機物と反応性を有する官能基が分子内に存在する、加水分解性珪素化合物（ｂ１）を表す。
Examples of the hydrolyzable silicon compound (b1) include compounds represented by the following formula (1), condensation products thereof, and silane coupling agents.
SiW x R y (1)
(In the formula, W represents an alkoxy group having 1 to 20 carbon atoms, a hydroxyl group, an acetoxy group having 1 to 20 carbon atoms, a halogen atom, a hydrogen atom, an oxime group having 1 to 20 carbon atoms, an enoxy group, an aminoxy group, and an amide group. Represents at least one selected group, wherein R represents a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, and an unsubstituted or carbon atom. It represents at least one hydrocarbon group selected from an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms substituted with a halogen atom, where x is 1 or more and 4; And y is an integer of 0 or more and 3 or less, and x + y = 4.)
Here, the silane coupling agent is a hydrolyzable silicon compound in which a functional group having reactivity with an organic substance such as a vinyl polymerizable group, an epoxy group, an amino group, a methacryl group, a mercapto group, or an isocyanate group exists in the molecule. Represents (b1).
２級及び／又は３級アミド基を有するビニル単量体（ｂ２）としては、Ｎ−アルキル又はＮ−アルキレン置換（メタ）アクリルアミドを例示することができ、具体的には、例えばＮ−メチルアクリルアミド、Ｎ−メチルメタアクリルアミド、Ｎ−エチルアクリルアミド、Ｎ，Ｎ−ジメチルアクリルアミド、Ｎ，Ｎ−ジメチルメタアクリルアミド、Ｎ，Ｎ−ジエチルアクリルアミド、Ｎ−エチルメタアクリルアミド、Ｎ−メチル−Ｎ−エチルアクリルアミド、Ｎ−メチル−Ｎ−エチルメタアクリルアミド、Ｎ−イソプロピルアクリルアミド、Ｎ−ｎ−プロピルアクリルアミド、Ｎ−イソプロピルメタアクリルアミド、Ｎ−ｎ−プロピルメタアクリルアミド、Ｎ−メチル−Ｎ−ｎ−プロピルアクリルアミド、Ｎ−メチル−Ｎ−イソプロピルアクリルアミド、Ｎ−アクリロイルピロリジン、Ｎ−メタクリロイルピロリジン、Ｎ−アクリロイルピペリジン、Ｎ−メタクリロイルピペリジン、Ｎ−アクリロイルヘキサヒドロアゼピン、Ｎ−アクリロイルモルホリン、Ｎ−メタクリロイルモルホリン、Ｎ−ビニルピロリドン、Ｎ−ビニルカプロラクタム、Ｎ，Ｎ’−メチレンビスアクリルアミド、Ｎ，Ｎ’−メチレンビスメタクリルアミド、Ｎ−ビニルアセトアミド、ダイアセトンアクリルアミド、ダイアセトンメタアクリルアミド、Ｎ−メチロールアクリルアミド、Ｎ−メチロールメタアクリルアミド等を挙げることができる。
中でも３級アミド基を有するビニル単量体を用いると水素結合性が強まり好ましい。
Examples of the vinyl monomer (b2) having a secondary and / or tertiary amide group include N-alkyl or N-alkylene-substituted (meth) acrylamide, and specifically, for example, N-methylacrylamide. N-methylmethacrylamide, N-ethylacrylamide, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, N, N-diethylacrylamide, N-ethylmethacrylamide, N-methyl-N-ethylacrylamide, N -Methyl-N-ethylmethacrylamide, N-isopropylacrylamide, Nn-propylacrylamide, N-isopropylmethacrylamide, Nn-propylmethacrylamide, N-methyl-Nn-propylacrylamide, N-methyl- N-isopropylacryl Amide, N-acryloylpyrrolidine, N-methacryloylpyrrolidine, N-acryloylpiperidine, N-methacryloylpiperidine, N-acryloylhexahydroazepine, N-acryloylmorpholine, N-methacryloylmorpholine, N-vinylpyrrolidone, N-vinylcaprolactam, N , N′-methylenebisacrylamide, N, N′-methylenebismethacrylamide, N-vinylacetamide, diacetone acrylamide, diacetone methacrylamide, N-methylol acrylamide, N-methylol methacrylamide and the like.
Among them, it is preferable to use a vinyl monomer having a tertiary amide group because hydrogen bondability is increased.
無機酸化物粒子（ａ）としては例えば、酸化ケイ素(シリカ)、酸化アルミニウム（アルミナ）、珪酸カルシウム、酸化マグネシウム、酸化アンチモン、酸化ジルコニウム及びそれらの複合酸化物等を用いることができる。それらの中でも、表面水酸基の多い酸化ケイ素、酸化アルミニウム、酸化アンチモン、及びそれらの複合酸化物等が好ましく、二酸化ケイ素を基本単位とするシリカの水または水溶性溶媒の分散体であるコロイダルシリカがより好ましい。 As the inorganic oxide particles (a), for example, silicon oxide (silica), aluminum oxide (alumina), calcium silicate, magnesium oxide, antimony oxide, zirconium oxide, and composite oxides thereof can be used. Among them, silicon oxide, aluminum oxide, antimony oxide, and composite oxides thereof having a large number of surface hydroxyl groups are preferable, and colloidal silica that is a dispersion of water or water-soluble solvent of silica based on silicon dioxide is more preferable. preferable.
また、本発明における光触媒ヒドロゾルには乳化剤や分散安定剤を併用することもできる。当該乳化剤としては例えば、アルキルベンゼンスルホン酸、アルキルスルホン酸、アルキルスルホコハク酸、ポリオキシエチレンアルキル硫酸、ポリオキシエチレンアルキルアリール硫酸、ポリオキシエチレンジスチリルフェニルエーテルスルホン酸等の酸性乳化剤、酸性乳化剤のアルカリ金属（Ｌｉ、Ｎａ、Ｋ等）塩、酸性乳化剤のアンモニウム塩、脂肪酸石鹸等のアニオン性界面活性剤や、例えばアルキルトリメチルアンモニウムブロマイド、アルキルピリジニウムブロマイド、イミダゾリニウムラウレート等の四級アンモニウム塩、ピリジニウム塩、イミダゾリニウム塩型のカチオン性界面活性剤、ポリオキシエチレンアルキルアリールエーテル、ポリオキシエチレンソルビタン脂肪酸エステル、ポリオキシエチレンオキシプロピレンブロックコポリマー、ポリオキシエチレンジスチリルフェニルエーテル等のノニオン型界面活性剤やラジカル重合性の二重結合を有する反応性乳化剤等を例示することができる。 In addition, an emulsifier and a dispersion stabilizer can be used in combination with the photocatalytic hydrosol in the present invention. Examples of the emulsifier include acidic emulsifiers such as alkylbenzenesulfonic acid, alkylsulfonic acid, alkylsulfosuccinic acid, polyoxyethylene alkylsulfuric acid, polyoxyethylene alkylarylsulfuric acid, polyoxyethylene distyrylphenyl ether sulfonic acid, and alkali metal of acidic emulsifier. (Li, Na, K, etc.) salts, ammonium salts of acidic emulsifiers, anionic surfactants such as fatty acid soaps, quaternary ammonium salts such as alkyltrimethylammonium bromide, alkylpyridinium bromide, imidazolinium laurate, pyridinium Salt, imidazolinium salt type cationic surfactant, polyoxyethylene alkyl aryl ether, polyoxyethylene sorbitan fatty acid ester, polyoxyethyleneoxypropylene Lock copolymers may be exemplified a reactive emulsifier or the like having a nonionic surface active agent and a radical polymerizable double bond, such as polyoxyethylene distyryl phenyl ether.
上記ラジカル重合性の二重結合を有する反応性乳化剤としては、例えばスルホン酸基又はスルホネート基を有するビニル単量体、硫酸エステル基を有するビニル単量体やそれらのアルカリ金属塩、アンモニウム塩、ポリオキシエチレン等のノニオン基を有するビニル単量体、４級アンモニウム塩を有するビニル単量体等を挙げることができる。
該分散安定剤としては例えば、ポリカルボン酸およびスルホン酸塩よりなる群から選ばれる各種の水溶性オリゴマー類や、ポリビニルアルコール、ヒドロキシエチルセルロース、澱粉、マレイン化ポリブタジエン、マレイン化アルキッド樹脂、ポリアクリル酸（塩）、ポリアクリルアミド、水溶性あるいは水分散性アクリル樹脂などの合成あるいは天然の水溶性あるいは水分散性の各種の水溶性高分子物質が挙げることができる。これらの乳化剤や分散安定剤は１種または２種以上の混合物を使用することができる。
また、本発明の光触媒ヒドロゾルには基材との相互作用を制御する目的で、アルコール類などの有機溶剤を少量添加することもできる。
Examples of the reactive emulsifier having a radical polymerizable double bond include a vinyl monomer having a sulfonic acid group or a sulfonate group, a vinyl monomer having a sulfate ester group, an alkali metal salt thereof, an ammonium salt, Examples include vinyl monomers having a nonionic group such as oxyethylene, and vinyl monomers having a quaternary ammonium salt.
Examples of the dispersion stabilizer include various water-soluble oligomers selected from the group consisting of polycarboxylic acids and sulfonates, polyvinyl alcohol, hydroxyethyl cellulose, starch, maleated polybutadiene, maleated alkyd resin, polyacrylic acid ( Salt), polyacrylamide, synthetic or natural water-soluble or water-dispersible acrylic resins, and various water-soluble polymer substances that are water-soluble or water-dispersible. These emulsifiers and dispersion stabilizers can be used singly or as a mixture of two or more.
In addition, a small amount of an organic solvent such as alcohols can be added to the photocatalyst hydrosol of the present invention for the purpose of controlling the interaction with the substrate.
本発明の光触媒塗料（コーティング剤）は各種基材に塗装することができる。
本発明の光触媒組成物（光触媒ヒドロゾル或いは水系光触媒コーティング剤、以下同じ。）を塗装する基材としては、例えば合成樹脂、天然樹脂、繊維等の有機基材や、金属、セラミックス、ガラス、石、セメント、コンクリート等の無機基材や、それらの組み合わせ等を挙げることができる。
上記合成樹脂としては、熱可塑性樹脂と硬化性樹脂（熱硬化性樹脂、光硬化性樹脂、湿気硬化性樹脂等）の使用が可能であり、例えばシリコーン樹脂、アクリル樹脂、メタクリル樹脂、フッ素樹脂、アルキド樹脂、アミノアルキド樹脂、ビニル樹脂、ポリエステル樹脂、スチレン−ブタジエン樹脂、ポリオレフィン樹脂、ポリスチレン樹脂、ポリケトン樹脂、ポリアミド樹脂、ポリカーボネート樹脂、ポリアセタール樹脂、ポリエーテルエーテルケトン樹脂、ポリフェニレンオキシド樹脂、ポリスルフォン樹脂、ポリフェニレンスルホン樹脂ポリエーテル樹脂、ポリ塩化ビニル樹脂、ポリ塩化ビニリデン樹脂、尿素樹脂、フェノール樹脂、メラミン樹脂、エポキシ樹脂、ウレタン樹脂、シリコーン−アクリル樹脂等を挙げることができる。
また、上記天然樹脂としては、セルロース系樹脂、天然ゴム等のイソプレン系樹脂、カゼイン等のタンパク質系樹脂等を挙げることができる。
The photocatalyst paint (coating agent) of the present invention can be applied to various substrates.
Examples of the substrate on which the photocatalyst composition of the present invention (photocatalyst hydrosol or water-based photocatalyst coating agent, the same shall apply hereinafter) are applied include organic substrates such as synthetic resins, natural resins, and fibers, metals, ceramics, glass, stones, Examples thereof include inorganic base materials such as cement and concrete, and combinations thereof.
As the synthetic resin, a thermoplastic resin and a curable resin (thermosetting resin, photocurable resin, moisture curable resin, etc.) can be used. For example, silicone resin, acrylic resin, methacrylic resin, fluororesin, Alkyd resin, amino alkyd resin, vinyl resin, polyester resin, styrene-butadiene resin, polyolefin resin, polystyrene resin, polyketone resin, polyamide resin, polycarbonate resin, polyacetal resin, polyether ether ketone resin, polyphenylene oxide resin, polysulfone resin, Examples thereof include polyphenylene sulfone resin, polyether resin, polyvinyl chloride resin, polyvinylidene chloride resin, urea resin, phenol resin, melamine resin, epoxy resin, urethane resin, and silicone-acrylic resin.
Examples of the natural resin include cellulose resins, isoprene resins such as natural rubber, and protein resins such as casein.
本発明において、樹脂板や繊維の表面は、コロナ放電処理やフレーム処理、プラズマ処理等の表面処理がされてあっても構わないが、これらの表面処理は必須ではない。
本発明に使用する基材の種類や膜厚は用途に応じて使い分けることができる。
また、本発明の光触媒ヒドロゾルあるいは水系光触媒コーティング剤には、その用途ならびに使用方法などに応じて、通常、塗料や成型用樹脂に添加配合される成分、例えば、増粘剤、レベリング剤、チクソ化剤、消泡剤、凍結安定剤、艶消し剤、架橋反応触媒、顔料、硬化触媒、架橋剤、充填剤、皮張り防止剤、分散剤、湿潤剤、光安定剤、酸化防止剤、紫外線吸収剤、レオロジーコントロール剤、消泡剤、成膜助剤、防錆剤、染料、可塑剤、潤滑剤、還元剤、防腐剤、防黴剤、消臭剤、黄変防止剤、静電防止剤あるいは帯電調製剤等をそれぞれの目的に応じて選択、組み合わせて配合することができる。
本発明の水系光触媒コーティング剤（塗料）には、上記（ｂ１）／（ｂ２）を重合して得られる重合体エマルジョン粒子１００質量部に対し、上記無機酸化物粒子粒子１００質量武に対し、上記無機酸化物粒子（ａ）とアルミニウム化合物が被着された（又は場合により予めシリカが被着された）光触媒粒子とが、各々５〜９００質量部、０．１〜５０質量部が好ましく、更に１０〜８００質量部、０．５〜３０質量部がより好ましい。
In the present invention, the surface of the resin plate or fiber may be subjected to surface treatment such as corona discharge treatment, flame treatment, or plasma treatment, but these surface treatments are not essential.
The type and film thickness of the substrate used in the present invention can be properly used depending on the application.
In addition, the photocatalyst hydrosol or water-based photocatalyst coating agent of the present invention is usually added to and blended with paints and molding resins depending on the use and method of use, for example, thickeners, leveling agents, thixotropic agents. Agent, antifoaming agent, freezing stabilizer, matting agent, cross-linking reaction catalyst, pigment, curing catalyst, cross-linking agent, filler, anti-skinning agent, dispersant, wetting agent, light stabilizer, antioxidant, UV absorption Agent, rheology control agent, antifoaming agent, film forming aid, rust preventive agent, dye, plasticizer, lubricant, reducing agent, antiseptic, antifungal agent, deodorant, anti-yellowing agent, antistatic agent Alternatively, a charge preparation agent or the like can be selected and combined according to each purpose.
In the aqueous photocatalyst coating agent (paint) of the present invention, 100 parts by mass of the polymer emulsion particles obtained by polymerizing the above (b1) / (b2), 100 mass parts of the inorganic oxide particle particles, The inorganic oxide particles (a) and the photocatalyst particles to which the aluminum compound is deposited (or silica is optionally deposited in advance) are preferably 5 to 900 parts by weight and 0.1 to 50 parts by weight, respectively. 10-800 mass parts and 0.5-30 mass parts are more preferable.
本発明の光触媒組成物を含む塗装製品は光触媒活性及び／又は親水性に優れるとともに耐候性、耐水性、光学特性に優れる。
光触媒活性は、例えば材料表面の光照射時における色素等の有機物の分解性を測定することにより判定することができる。光触媒活性を有する表面は、優れた汚染有機物質の分解活性や耐汚染性を発現する。
ここで、光照射は光触媒のバンドギャップエネルギーよりも高いエネルギーの光の光源を用いて行う。光源としては、太陽光や室内照明灯等の一般住宅環境下で得られる光の他、ブラックライト、キセノンランプ、水銀灯、ＬＥＤ等の光が利用できる。光の照度は、０．００１ｍＷ／ｃｍ２以上あることが好ましく、０．０１ｍＷ／ｃｍ２以上だとより好ましく、０．１ｍＷ／ｃｍ２以上だとさらに好ましい。
The coated product containing the photocatalyst composition of the present invention is excellent in photocatalytic activity and / or hydrophilicity and in weather resistance, water resistance and optical properties.
The photocatalytic activity can be determined, for example, by measuring the decomposability of an organic substance such as a dye during light irradiation on the material surface. A surface having photocatalytic activity exhibits excellent decomposition activity and contamination resistance of contaminating organic substances.
Here, the light irradiation is performed using a light source having a higher energy than the band gap energy of the photocatalyst. As the light source, light such as black light, xenon lamp, mercury lamp, LED, etc. can be used in addition to light obtained in a general residential environment such as sunlight and indoor lighting. Illuminance of the light is preferably in 0.001 mW / cm 2 or more, more preferably when it 0.01 mW / cm 2 or more, further preferably it 0.1 mW / cm 2 or more.
本発明の光触媒コーティング剤は、任意の方法で塗装することができる。例えばスプレー吹き付け法、フローコーティング法、ロールコート法、刷毛塗り法、ディップコーティング法、スピンコーティング法、スクリーン印刷法、キャスティング法、グラビア印刷法、フレキソ印刷法等が挙げられる。
塗装後に、４０℃〜１２０℃程度の温度での熱処理あるいは紫外線照射等を行うことも可能である。
本発明の光触媒コーティング剤を基材上に塗膜として形成させる場合、該塗膜の厚みは０．０５〜１００μｍ、好ましくは０．１〜１０μｍである事が好ましい。透明性の面から１００μｍ以下の厚みであることが好ましく、防汚性、光触媒活性等の機能を発現するためには０．０５μｍ以上の厚みであることが好ましい。
The photocatalyst coating agent of the present invention can be applied by any method. Examples thereof include a spray spraying method, a flow coating method, a roll coating method, a brush coating method, a dip coating method, a spin coating method, a screen printing method, a casting method, a gravure printing method, and a flexographic printing method.
After coating, it is possible to perform heat treatment or ultraviolet irradiation at a temperature of about 40 ° C. to 120 ° C.
When forming the photocatalyst coating agent of this invention as a coating film on a base material, it is preferable that the thickness of this coating film is 0.05-100 micrometers, Preferably it is 0.1-10 micrometers. The thickness is preferably 100 μm or less from the viewpoint of transparency, and in order to exhibit functions such as antifouling properties and photocatalytic activity, the thickness is preferably 0.05 μm or more.
なお、本明細書では、塗膜という表現を使用しているが、必ずしも連続膜である必要はなく、不連続膜、島状分散膜等の態様であっても構わない。
本発明の塗装物の製造方法は、基材上に本発明の光触媒組成物を形成する場合に限定されない。基材と本発明の水系光触媒コーティング剤を同時に成形、たとえば、一体成形してもよい。また、本発明の光触媒コーティング剤を成形後、基材の成形を行ってもよい。また、塗装物と基材を個別に成形後、接着、融着等により製造してもよい。
In this specification, the expression “coating film” is used, but it is not necessarily a continuous film, and may be a discontinuous film, an island-shaped dispersion film, or the like.
The manufacturing method of the coated material of this invention is not limited to the case where the photocatalyst composition of this invention is formed on a base material. The base material and the aqueous photocatalyst coating agent of the present invention may be simultaneously molded, for example, integrally molded. Moreover, you may shape | mold a base material after shape | molding the photocatalyst coating agent of this invention. Alternatively, the coated product and the base material may be individually molded and then manufactured by adhesion, fusion, or the like.
以下の実施例、参考例及び比較例により本発明を具体的に説明するが、これらは本発明の範囲を限定するものではない。
実施例、参考例及び比較例中において、各種の物性は下記の方法で測定した。
１．平均一次粒子径
試料を電子顕微鏡用のメッシュ上に落とし、風乾した。メッシュ上の試料を超高分解能透過型電子顕微鏡（日立製Ｈ−９０００ＵＨＲ）で、加速電圧３００ｋＶ、１００００００倍で観察した。観察像から任意の粒子を１００個抽出し、平均の一次粒子径を求めた。
The following examples, reference examples and comparative examples will specifically explain the present invention, but these do not limit the scope of the present invention.
In Examples, Reference Examples and Comparative Examples, various physical properties were measured by the following methods.
1. Average primary particle size The sample was dropped on a mesh for an electron microscope and air-dried. The sample on the mesh was observed with an ultra high resolution transmission electron microscope (H-9000UHR manufactured by Hitachi) at an acceleration voltage of 300 kV and 1,000,000 times. 100 arbitrary particles were extracted from the observed image, and the average primary particle diameter was determined.
２．数平均粒子径
試料中の固形分含有量が２０質量％となるよう適宜溶媒を加えて希釈し、湿式粒度分析計（日機装製マイクロトラックＵＰＡ−９２３０）を用いて測定した。
３．固形分濃度
光触媒ゾルまたは光触媒コーティング剤試料を約２ｇアルミ皿にとり、１５０℃で１時間加熱した。加熱前後のサンプル量の差から固形分を計算した。
2. Number average particle diameter A solvent was appropriately added and diluted so that the solid content in the sample was 20% by mass, and measurement was performed using a wet particle size analyzer (Nikkiso Microtrac UPA-9230).
3. Solid content concentration About 2 g of a photocatalyst sol or photocatalyst coating agent sample was placed in an aluminum pan and heated at 150 ° C. for 1 hour. The solid content was calculated from the difference in sample amount before and after heating.
４．塗工膜厚
ＭＯＲＩＴＥＸ製ＭＨＦ−Ｄ１００ＬＲを用いて測定した。
５．透明性（ヘイズ）
日本電色工業製濁度計ＮＤＨ２０００を用いてＪＩＳ−Ｋ７１０５に準じてヘイズ値及び全光線透過率を測定した。
4). Coating film thickness: Measured using MHF-D100LR manufactured by MORITEX.
5. Transparency (haze)
A haze value and a total light transmittance were measured according to JIS-K7105 using a Nippon Denshoku turbidimeter NDH2000.
６．光触媒活性（分解指数）
基準認証研究開発事業 光触媒試験方法の標準化（日本ファインセラミックス協会）に記載されている、日本工業規格（案）光触媒材料のセルフクリーニング性能試験方法第２部：湿式分解性能に基づき６６４ｎｍの吸光度から分解指数を求めた。
このときにメチレンブルーには和光純薬工業製メチレンブルー三水和物を使用した。吸光度測定には日本分光製紫外・可視吸収スペクトル計Ｖ−５５０を使用した。
6). Photocatalytic activity (decomposition index)
Standard certification research and development business Photocatalyst test method standardization (Japan Fine Ceramics Association), Japanese Industrial Standard (draft) Self-cleaning performance test method for photocatalyst materials Part 2: Decomposition from 664 nm absorbance based on wet decomposition performance The index was determined.
At this time, methylene blue trihydrate produced by Wako Pure Chemical Industries was used as methylene blue. For the measurement of absorbance, an ultraviolet / visible absorption spectrometer V-550 manufactured by JASCO Corporation was used.
［製造例１］
石原産業製の酸性アナターゼ型酸化チタン（ＳＴＳ−０１）を純水で希釈して、酸化チタン換算２０質量％の酸化チタンゾルを５００ｍｌ調製した。その後、７０℃に昇温し、シリカ換算で４３２質量％のケイ酸ナトリウム水溶液１４．４ｍｌを２０％硫酸と同時に添加し、その後、３０分熟成した。次いで、１０％水酸化ナトリウム水溶液でｐＨを８に調製した後、２％硫酸水溶液でｐＨ６に調製し、ろ過・洗浄を行い、湿ケーキを得た。この湿ケーキを純水中にリパルプした後、超音波分散して、中性域で安定な酸化チタンゾル（固形分２０質量％）を得た。
このときの酸化チタン粒子には酸化チタン１００質量部に対して５．０質量部のシリカが被着している。
[Production Example 1]
An acidic anatase type titanium oxide (STS-01) manufactured by Ishihara Sangyo Co., Ltd. was diluted with pure water to prepare 500 ml of a 20% by mass titanium oxide sol in terms of titanium oxide. Thereafter, the temperature was raised to 70 ° C., 14.4 ml of a 432 mass% sodium silicate aqueous solution in terms of silica was added simultaneously with 20% sulfuric acid, and then aging was performed for 30 minutes. Next, the pH was adjusted to 8 with a 10% aqueous sodium hydroxide solution, adjusted to pH 6 with a 2% aqueous sulfuric acid solution, filtered and washed to obtain a wet cake. The wet cake was repulped into pure water and then ultrasonically dispersed to obtain a titanium oxide sol (solid content 20% by mass) stable in the neutral region.
At this time, 5.0 parts by mass of silica is deposited on the titanium oxide particles with respect to 100 parts by mass of titanium oxide.
［製造例２］
製造例１で添加するケイ酸ナトリウム量を２３ｍｌにする以外は製造例１と同様に実施した。
このときの酸化チタン粒子には酸化チタン１００質量部に対して８．１質量部のシリカが被着している。
［製造例３］
製造例１で添加するケイ酸ナトリウム量を８．６ｍｌにする以外は製造例１と同様に実施した。
このときの酸化チタン粒子には酸化チタン１００質量部に対して２．９質量部のシリカが被着している。
［製造例４］
製造例１で添加するケイ酸ナトリウム量を４３．２ｍｌにする以外は製造例１と同様に実施した。
このときの酸化チタン粒子には酸化チタン１００質量部に対して１４．８質量部のシリカが被着している。
[Production Example 2]
The same operation as in Production Example 1 was carried out except that the amount of sodium silicate added in Production Example 1 was 23 ml.
The titanium oxide particles at this time are coated with 8.1 parts by mass of silica with respect to 100 parts by mass of titanium oxide.
[Production Example 3]
The same operation as in Production Example 1 was carried out except that the amount of sodium silicate added in Production Example 1 was 8.6 ml.
At this time, 2.9 parts by mass of silica is deposited on the titanium oxide particles with respect to 100 parts by mass of titanium oxide.
[Production Example 4]
The same operation as in Production Example 1 was carried out except that the amount of sodium silicate added in Production Example 1 was changed to 43.2 ml.
At this time, 14.8 parts by mass of silica is adhered to 100 parts by mass of titanium oxide particles.
［実施例１］
酸化チタンヒドロゾル（Ａ）の調製
製造例１で調製した酸化チタンゾルに対して、アルミン酸ナトリウムの１０質量％水溶液を酸化チタンに対してアルミナ換算で２．５質量％となるように添加した。その後、８０℃に昇温し、８０℃で１時間撹拌した。得られたサンプルをろ過して中性で安定な酸化チタンゾル（固形分２０質量％）を得た。
このときの酸化チタン粒子には酸化チタン１００質量部に対して、２．１質量部のアルミニウム化合物が被着している。
評価結果を表１に示す。
[Example 1]
Preparation of Titanium Oxide Hydrosol (A) To the titanium oxide sol prepared in Production Example 1, a 10% by mass aqueous solution of sodium aluminate was added to 2.5% by mass in terms of alumina with respect to titanium oxide. Then, it heated up at 80 degreeC and stirred at 80 degreeC for 1 hour. The obtained sample was filtered to obtain a neutral and stable titanium oxide sol (solid content: 20% by mass).
At this time, 2.1 parts by mass of an aluminum compound is adhered to 100 parts by mass of titanium oxide on the titanium oxide particles.
The evaluation results are shown in Table 1.
［実施例２］
酸化チタンヒドロゾル（Ｂ）の調製
製造例２で調製した酸化チタンゾルに対して、アルミン酸ナトリウムの１０質量％水溶液を酸化チタンに対してアルミナ換算で２．５％となるように添加した。その後、８０℃に昇温し、８０℃で１時間撹拌した。得られたサンプルをろ過して中性で安定な酸化チタンゾル（固形分２０質量％）を得た。
このときの酸化チタン粒子には酸化チタン１００質量部に対して、２．１質量部のアルミニウム化合物が被着している。
評価結果を表１に示す。
[Example 2]
Preparation of Titanium Oxide Hydrosol (B) To the titanium oxide sol prepared in Production Example 2, a 10% by mass aqueous solution of sodium aluminate was added to 2.5% in terms of alumina with respect to titanium oxide. Then, it heated up at 80 degreeC and stirred at 80 degreeC for 1 hour. The obtained sample was filtered to obtain a neutral and stable titanium oxide sol (solid content: 20% by mass).
At this time, 2.1 parts by mass of an aluminum compound is adhered to 100 parts by mass of titanium oxide on the titanium oxide particles.
The evaluation results are shown in Table 1.
［実施例３］
酸化チタンヒドロゾル（Ｃ）の調製
製造例３で調製した酸化チタンゾルに対して、アルミン酸ナトリウムの１０質量％水溶液を酸化チタンに対してアルミナ換算で５．５％となるように添加した。その後、８０℃に昇温し、８０℃で１時間撹拌した。得られたサンプルをろ過して中性で安定な酸化チタンゾル（固形分２０質量％）を得た。
このときの酸化チタン粒子には酸化チタン１００質量部に対して、５．２質量部のアルミニウム化合物が被着している。
評価結果を表１に示す。
[Example 3]
Preparation of Titanium Oxide Hydrosol (C) To the titanium oxide sol prepared in Production Example 3, a 10% by mass aqueous solution of sodium aluminate was added so as to be 5.5% in terms of alumina with respect to titanium oxide. Then, it heated up at 80 degreeC and stirred at 80 degreeC for 1 hour. The obtained sample was filtered to obtain a neutral and stable titanium oxide sol (solid content: 20% by mass).
At this time, 5.2 parts by mass of an aluminum compound is deposited on the titanium oxide particles with respect to 100 parts by mass of titanium oxide.
The evaluation results are shown in Table 1.
［参考実施例４］
酸化チタンヒドロゾル（Ｄ）の調製
テイカ製中性酸化チタンゾル（ＴＫＳ−２０３、シリカ被着なし）に対して、アルミン酸ナトリウムの１０質量％水溶液を酸化チタンに対してアルミナ換算で５．５％となるように添加した。その後、８０℃に昇温し、８０℃で１時間撹拌した。得られたサンプルをろ過して中性で安定な酸化チタンゾル（固形分２０質量％）を得た。
このときの酸化チタン粒子には酸化チタン１００質量部に対して、５．２質量部のアルミニウム化合物が被着している。
評価結果を表１に示す。
[ Reference Example 4]
Preparation of Titanium Oxide Hydrosol (D) A 10% by mass aqueous solution of sodium aluminate is 5.5% in terms of alumina with respect to titanium oxide, based on Teica neutral titanium oxide sol (TKS-203, without silica deposition). It added so that it might become. Then, it heated up at 80 degreeC and stirred at 80 degreeC for 1 hour. The obtained sample was filtered to obtain a neutral and stable titanium oxide sol (solid content: 20% by mass).
At this time, 5.2 parts by mass of an aluminum compound is deposited on the titanium oxide particles with respect to 100 parts by mass of titanium oxide.
The evaluation results are shown in Table 1.
［比較例１］
酸化チタンヒドロゾル（Ｅ）の調製
製造例４で調製した酸化チタンゾルに対して、アルミン酸ナトリウムの１０質量％水溶液を酸化チタンに対してアルミナ換算で２．５％となるように添加した。その後、８０℃に昇温し、８０℃で１時間撹拌した。得られたサンプルをろ過して中性で安定な酸化チタンゾル（固形分２０質量％）を得た。
このときの酸化チタン粒子には酸化チタン１００質量部に対して、２．２質量部のアルミニウム化合物が被着している。
評価結果を表１に示す。
[Comparative Example 1]
Preparation of Titanium Oxide Hydrosol (E) To the titanium oxide sol prepared in Production Example 4, a 10% by mass aqueous solution of sodium aluminate was added to 2.5% in terms of alumina with respect to titanium oxide. Then, it heated up at 80 degreeC and stirred at 80 degreeC for 1 hour. The obtained sample was filtered to obtain a neutral and stable titanium oxide sol (solid content: 20% by mass).
The titanium oxide particles at this time are coated with 2.2 parts by mass of an aluminum compound with respect to 100 parts by mass of titanium oxide.
The evaluation results are shown in Table 1.
［比較例２］
酸化チタンヒドロゾル（Ｆ）の調製
製造例１で調製した酸化チタンゾルに対して、アルミン酸ナトリウムの１０質量％水溶液を酸化チタンに対してアルミナ換算で１２．５％となるように添加した。その後、８０℃に昇温し、８０℃で１時間撹拌した。得られたサンプルをろ過して中性で安定な酸化チタンゾル（固形分２０質量％）を得た。
このときの酸化チタン粒子には酸化チタン１００質量部に対して、１２．２質量部のアルミニウム化合物が被着している。
評価結果を表１に示す。
［比較例３］
酸化チタンヒドロゾル（Ｇ）の調製
製造例２で調製した酸化チタンゾルを特に処理することなく酸化チタンヒドロゾル（Ｇ）とした。
評価結果を表１に示す。
[Comparative Example 2]
Preparation of Titanium Oxide Hydrosol (F) To the titanium oxide sol prepared in Production Example 1, a 10 mass% aqueous solution of sodium aluminate was added to 12.5% in terms of alumina with respect to titanium oxide. Then, it heated up at 80 degreeC and stirred at 80 degreeC for 1 hour. The obtained sample was filtered to obtain a neutral and stable titanium oxide sol (solid content: 20% by mass).
At this time, 12.2 parts by mass of an aluminum compound is deposited on 100 parts by mass of titanium oxide particles.
The evaluation results are shown in Table 1.
[Comparative Example 3]
Preparation of Titanium Oxide Hydrosol (G) The titanium oxide sol prepared in Production Example 2 was used as a titanium oxide hydrosol (G) without any particular treatment.
The evaluation results are shown in Table 1.
［製造例５］
重合体エマルジョン粒子水分散体の合成
還流冷却器、滴下槽、温度計および撹拌装置を有する反応器に、イオン交換水１７５０ｇ、ドデシルベンゼンスルホン酸２ｇを投入した後、撹拌下で温度を８０℃に加温した。
これに、アクリル酸ブチル８６ｇ、フェニルトリメトキシシラン１３３ｇ、３−メタクリロキシプロピルトリメトキシシラン１．３ｇの混合液とジエチルアクリルアミド１９７ｇ、アクリル酸３ｇ、反応性乳化剤（商品名「アデカリアソープＳＲ−１０２５」、旭電化（株）製、固形分２５％水溶液）１３ｇ、過硫酸アンモニウムの２質量％水溶液４０ｇ、イオン交換水１９５０ｇの混合液を、反応容器中の温度を８０℃に保った状態で約２時間かけて同時に滴下した。さらに反応容器中の温度が８０℃の状態で約２時間撹拌を続行した後、室温まで冷却し、１００メッシュの金網で濾過した後、イオン交換水で固形分を１０．０質量％に調整し、数平均粒子径１００ｎｍの重合体エマルジョン粒子水分散体（Ｈ）を得た。
[Production Example 5]
Synthesis of aqueous dispersion of polymer emulsion particles 1750 g of ion-exchanged water and 2 g of dodecylbenzenesulfonic acid were charged into a reactor having a reflux condenser, a dropping tank, a thermometer and a stirring device, and the temperature was raised to 80 ° C. with stirring. Warmed up.
To this, a mixed solution of 86 g of butyl acrylate, 133 g of phenyltrimethoxysilane, 1.3 g of 3-methacryloxypropyltrimethoxysilane, 197 g of diethyl acrylamide, 3 g of acrylic acid, a reactive emulsifier (trade name “Adekaria soap SR-1025 "Asahi Denka Co., Ltd., 25% solid content aqueous solution) 13 g, ammonium persulfate 2 mass% aqueous solution 40 g, ion-exchanged water 1950 g mixed liquid, about 2 with the temperature in the reaction vessel maintained at 80 ℃ It was dripped simultaneously over time. Further, stirring was continued for about 2 hours in a state where the temperature in the reaction vessel was 80 ° C., then cooled to room temperature, filtered through a 100-mesh wire mesh, and the solid content was adjusted to 10.0% by mass with ion-exchanged water. A polymer emulsion particle aqueous dispersion (H) having a number average particle diameter of 100 nm was obtained.
［実施例５］
製造例５で合成した重合体エマルジョン粒子（Ｈ）水分散体１００ｇに、数平均粒子径１２ｎｍの水分散コロイダルシリカ（商品名「スノーテックスＯ」、日産化学工業（株）製、固形分２０％）５０ｇと酸化チタンヒドロゾル（Ａ）２．５ｇを混合、攪拌する事により光触媒コーティング剤を得た。
１０ｃｍ×１０ｃｍのＰＥＴフィルムに上記水系光触媒コーティング剤を膜厚が２μｍとなるようにバーコートした後、７０℃で１０分間乾燥する事により、光触媒コーティング剤皮膜を有する試験板を得た。
得られた光触媒コーティング剤皮膜を有する試験板の評価結果を表２に示す。
［実施例６］から［実施例７］、［参考実施例８］、［実施例９］および［比較例４］から［比較例７］
酸化チタンとして表２に記載の種類と量の酸化チタンを用いる以外は実施例５と同様に
実施した。試験結果を表２に示す。
[Example 5]
To 100 g of the polymer emulsion particles (H) aqueous dispersion synthesized in Production Example 5, water-dispersed colloidal silica having a number average particle size of 12 nm (trade name “Snowtex O”, manufactured by Nissan Chemical Industries, Ltd., solid content 20% ) 50 g and titanium oxide hydrosol (A) 2.5 g were mixed and stirred to obtain a photocatalyst coating agent.
A test plate having a photocatalyst coating agent film was obtained by bar-coating the aqueous photocatalyst coating agent on a 10 cm × 10 cm PET film so as to have a film thickness of 2 μm and then drying at 70 ° C. for 10 minutes.
Table 2 shows the evaluation results of the test plate having the obtained photocatalyst coating agent film.
[Example 6] to [Example 7], [Reference Example 8], [Example 9] and [Comparative Example 4] to [Comparative Example 7]
It implemented like Example 5 except using the kind and quantity of titanium oxide of Table 2 as titanium oxide. The test results are shown in Table 2.
本発明によって提供される光触媒ヒドロゾルは分散安定性に優れるものであり、それを用いた光触媒コーティング剤は光触媒活性及び／又は親水性を効果的に発現するとともに外観にも優れるため、建築外装、外装表示用途、自動車、ディスプレイ、レンズ等のコーティング剤として有用である。 The photocatalyst hydrosol provided by the present invention has excellent dispersion stability, and the photocatalyst coating agent using the photocatalyst hydrosol effectively expresses photocatalytic activity and / or hydrophilicity and is excellent in appearance. It is useful as a coating agent for display applications, automobiles, displays, lenses and the like.
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