JP2007273309A - Led light source, and display body using it - Google Patents
Led light source, and display body using it Download PDFInfo
- Publication number
- JP2007273309A JP2007273309A JP2006098419A JP2006098419A JP2007273309A JP 2007273309 A JP2007273309 A JP 2007273309A JP 2006098419 A JP2006098419 A JP 2006098419A JP 2006098419 A JP2006098419 A JP 2006098419A JP 2007273309 A JP2007273309 A JP 2007273309A
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- JP
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- Prior art keywords
- light
- photocatalyst
- led
- group
- resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Images
Landscapes
- Planar Illumination Modules (AREA)
- Led Device Packages (AREA)
Abstract
Description
本発明は、長期間にわたり光触媒活性及び/または高度に親水性である光触媒表層部を有し、光源からの光により発光する発光体を備えた表示体、及び該表示体に用いられるLED光源に関する。 The present invention relates to a display body having a photocatalyst activity and / or a highly hydrophilic photocatalyst surface layer for a long period of time, and a light emitting body that emits light by light from a light source, and an LED light source used for the display body. .
光源からの光により発光する発光体においては、光源から発せられ発光体の内部に導かれた光は発光体の外部に出射するまでにその内部で何度も反射を繰り返す。そのため、発光体内部での光の行程が長くなり、光が発光体から出射するまでに減衰する。このため、発光体としては透明度の良いものが要求され、光源も指向性の高いものが要求される。 In a light emitter that emits light by light from a light source, the light emitted from the light source and guided to the inside of the light emitter is repeatedly reflected inside the light emitter before being emitted to the outside of the light emitter. For this reason, the path of light inside the light emitter is lengthened and attenuated before the light is emitted from the light emitter. For this reason, a thing with good transparency is requested | required as a light-emitting body, and a thing with a high directivity is also requested | required.
また、発光体は光を発光体表面に対して直角またはそれに近い方向に出射することが望ましい。しかし、上記したように発光体の内部に導かれた光が該発光体の外部に出射するまでにその内部で何度も反射を繰り返すため、そのような光は少なく、出射光の大部分は発光体の表面に沿った方向で出て行く。その結果、従来の発光体には、人間の目にはあまり明るく感じられないという問題がある。 The light emitter preferably emits light in a direction perpendicular to or close to the surface of the light emitter. However, as described above, since the light guided to the inside of the light emitter is repeatedly reflected inside the light emitter before being emitted to the outside of the light emitter, there is little such light, and most of the emitted light is Go out in a direction along the surface of the illuminant. As a result, the conventional illuminant has a problem that it is not felt bright by human eyes.
このような問題を解決するために、例えば、特許文献1には、透明アクリル板で形成された板状光伝達部材の表面に線状の溝を形成し、該板状光伝達部材の一側面の凹所にLEDランプを挿着して発光させることによりLEDランプからの光は板状伝達部材の側面のみならず上下の面もより均一な状態で出光させることが出来る面発光体が記載されている。
In order to solve such a problem, for example, in
また、特許文献2には、透明な導光板の後面全体に直線状の溝を何本も平行に設け、この導光板の側部に、該溝に直角の方向から導光板の内部に光を放つ点状発光体を配置した面状発光体が記載されている。 Further, in Patent Document 2, a number of linear grooves are provided in parallel on the entire rear surface of the transparent light guide plate, and light is introduced into the side of the light guide plate from the direction perpendicular to the grooves to the inside of the light guide plate. A planar light emitter is described in which a pointed light emitter is provided.
また、特許文献3には、光散乱剤を含まない透明な合成樹脂層からなる透明部材と、光散乱剤を含む半透明な合成樹脂層からなる半透明部材との接合することによって面状発光体を形成し、該面状発光体の一端面側にLEDアレイを配設した発光体が記載されている。
また、特許文献4には、透明性を有する板状のアクリル部材の一端面に設けた取り付け穴にLED(Light Emitting Diode;発光ダイオード)ランプを挿入し、該アクリル部材の発光面以外に反射テープを貼り付けたものが記載されている。 In Patent Document 4, an LED (Light Emitting Diode) lamp is inserted into a mounting hole provided on one end surface of a transparent plate-like acrylic member, and a reflective tape is provided on the surface other than the light emitting surface of the acrylic member. Attached is written.
また、特許文献5には、先端部に点光源を配備した棒状の第1の導光板の側面光出射部を、板状の第2の導光板の一側端部に結合して、該第2の導光板の主面から放射光を得る面発光装置が記載されている。
Further, in
また、特許文献6には、光散乱剤を含む皮膜層と光散乱剤を含まない基材層から構成される積層板発光体が記載されている。
しかしながら、上記特許文献1,2の技術では線状の溝形成なくして面状発光体を得ることが出来ず、特許文献3の技術では透明部材と半透明部材とを接合しないと面状発光体を形成することが出来ず、特許文献4の技術では発光面は1面だけで且つ発光面以外は反射テープの貼り付けが必要という問題があり、特許文献5の技術では点光源を線状光源に変換する第1の発光体なくして面発光体が得られず、特許文献6の技術では発光性能に劣る問題があった。
However, in the techniques of
一方、ある種の物質に、その物質の伝導帯と価電子帯との間のエネルギーギャップ(バンドギャップ)よりも大きなエネルギーを持つ光、即ちその物質のバンドギャップに対応する光よりも波長の短い光(励起光)を照射すると、光エネルギーによって価電子帯中の電子の励起(光励起)が起こり、伝導帯に電子が、価電子帯に正孔が生成する。この時、伝導帯に生成した電子の還元力及び/又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。 On the other hand, light of a certain substance has energy larger than the energy gap (band gap) between the conduction band and valence band of the substance, that is, the wavelength is shorter than light corresponding to the band gap of the substance. When light (excitation light) is irradiated, excitation of electrons in the valence band (photoexcitation) occurs due to light energy, and electrons are generated in the conduction band and holes are generated in the valence band. At this time, various chemical reactions can be performed using the reducing power of electrons generated in the conduction band and / or the oxidizing power of holes generated in the valence band.
即ち、上記のような物質は、励起光照射下において触媒のように用いることができる。そのため、上記のような物質は光触媒と呼ばれており、その最も代表的な例として酸化チタンが知られている。 That is, the above substances can be used like a catalyst under excitation light irradiation. Therefore, the above substances are called photocatalysts, and titanium oxide is known as the most typical example.
この光触媒によって促進される化学反応の例としては、種々の有機物の酸化分解反応を挙げることができる。従って、この光触媒を種々の基材の表面に固定化させれば、基材の表面に付着した種々の有機物を、光エネルギーを利用して酸化分解することができることになる。 Examples of chemical reactions promoted by this photocatalyst include oxidative decomposition reactions of various organic substances. Therefore, if this photocatalyst is immobilized on the surface of various base materials, various organic substances adhering to the surface of the base material can be oxidatively decomposed using light energy.
また、光触媒の中には、酸化チタンのように、光照射により、その光触媒の表面の親水性が非常に高まるものも多く知られている。 Many photocatalysts, such as titanium oxide, are known in which the hydrophilicity of the surface of the photocatalyst is greatly increased by light irradiation.
従って、これらの光触媒を種々の基材の表面に固定化させれば、光照射による有機物分解作用及び/又は親水化作用によりその基材の表面の親水性を高めることができるようになる。 Therefore, if these photocatalysts are immobilized on the surface of various base materials, the hydrophilicity of the surface of the base material can be enhanced by the organic substance decomposing action and / or the hydrophilizing action by light irradiation.
近年、上記のような光触媒の特性を、環境浄化、種々の基材の表面への汚れの付着防止や曇りの防止を始めとする、種々の分野に応用するための研究が盛んになってきている。即ち、前記したような面発光体の表面に係る光触媒を固定化させることにより、汚れが付着しにくく、長期に亘って美観を維持する照明、さらには、面発光表示体を構成することができる。 In recent years, research for applying the above-mentioned characteristics of photocatalysts to various fields such as environmental purification, prevention of dirt adhesion to the surface of various base materials and prevention of fogging has become active. Yes. That is, by immobilizing the photocatalyst on the surface of the surface light emitter as described above, it is possible to constitute a surface light emitting display body that is not easily attached with dirt and maintains an aesthetic appearance over a long period of time. .
しかしながら、光触媒を無機基材の上に光触媒膜や光触媒粒子を支持して用いる場合は問題ないが、一部の有機材料を除き、一般に有機基材の上に光触媒膜や光触媒粒子を支持して用いる場合は、上記光触媒作用により有機基材表面部が分解するため、様々な問題が発生する。具体的には、有機基材表面部が分解すると、その上に存在している光触媒層が足場を失うため、脱落する。またそれにより、光触媒作用を利用した目的の機能(防汚性や、抗菌性、脱臭性など)が失われるだけでなく、表面光沢が低下したり、粉吹き状態になるなど、本来の外観特性や意匠性も失われてしまう。 However, there is no problem when the photocatalyst is used with an inorganic base material supporting the photocatalyst film or photocatalyst particles. However, except for some organic materials, the photocatalyst film or photocatalyst particles are generally supported on the organic base material. When used, the organic base material surface is decomposed by the photocatalytic action, and various problems occur. Specifically, when the surface portion of the organic base material is decomposed, the photocatalyst layer present on the organic base material loses a scaffold and falls off. In addition, not only the intended function (antifouling property, antibacterial property, deodorizing property, etc.) using photocatalysis is lost, but also the original appearance characteristics such as surface gloss is lowered and powder is blown. And design will be lost.
これらの問題に対し、特許文献7や特許文献8では、有機基材と光触媒層との間に、光触媒作用によって分解されにくい難分解性の中間層を介在させる方法が提案されている。しかし、この方法では中間層と光触媒層の界面での長期接着性が不十分であると共に、塗装工程が煩雑で作業性が悪く、生産ロス増加やコスト高になってしまう上、均質な皮膜を得るのが非常に困難であり、有機基材の劣化を完全に防止するのが難しいという欠点がある。また、この方法では光触媒層と難分解物質からなる層との間に明確な膜界面が存在するため、光触媒層の剥離等の問題も発生する。
In order to solve these problems,
通常、光触媒を太陽光の当たらない場所で光励起させるには、一般的に蛍光灯、白熱電球、水銀ランプのような室内照明灯が利用されている。 In general, in order to photoexcite a photocatalyst in a place where it is not exposed to sunlight, indoor lighting such as a fluorescent lamp, an incandescent lamp, and a mercury lamp is generally used.
本発明の課題は、光触媒の光励起性に優れ、屋内使用に適した省エネ、省スペースのLED光源を提供し、さらに、該LED光源と面発光体とを組み合わせて良好な面発光表示体を提供することにあり、特に、前記光触媒を面発光体の表面に固定化してなる面発光表示体において、煩雑な工程を必要とせずに、面発光体と光触媒を含む表層部との間の界面劣化や表層部自体の光触媒による劣化を生じることが無く、光照射により長期にわたり、その表面が光触媒活性及び/または親水性を発現する耐候性に優れた光触媒層を有する発光性能に優れた面発光体表示体を提供することにある。 An object of the present invention is to provide an energy-saving and space-saving LED light source that is excellent in photoexcitation of a photocatalyst and is suitable for indoor use, and further provides a good surface-emitting display by combining the LED light source and a surface light-emitting body. In particular, in a surface-emitting display body in which the photocatalyst is immobilized on the surface of the surface-emitting body, the interface deterioration between the surface-emitting body and the surface layer portion including the photocatalyst is not required without a complicated process. In addition, the surface layer itself is not deteriorated by the photocatalyst, and has a photocatalyst layer that has a photocatalyst layer with excellent weather resistance whose surface exhibits photocatalytic activity and / or hydrophilicity for a long time by light irradiation. It is to provide a display.
即ち本発明の第1は、ピーク波長350〜390nmの波長を発するLED(1)と可視光を発するLED(2)及び/又は白色光を発するLED(3)とからなることを特徴とするLED光源である。 That is, the first of the present invention comprises an LED (1) emitting a peak wavelength of 350 to 390 nm, an LED (2) emitting visible light, and / or an LED (3) emitting white light. Light source.
前記本発明のLED光源においては、LED(1)の発光時間が、LED(2)及び/又はLED(3)の単位発光時間当たり1/100〜99/100の間発光するように制御されていることが好ましい。 In the LED light source of the present invention, the light emission time of LED (1) is controlled to emit light between 1/100 and 99/100 per unit light emission time of LED (2) and / or LED (3). Preferably it is.
本発明の第2は、光源からの光により発光する面発光体の少なくとも1つ以上の側端部に上記本発明のLED光源が配設されたことを特徴とする表示体である。 A second aspect of the present invention is a display body characterized in that the LED light source according to the present invention is disposed at at least one side end of a surface light emitter that emits light by light from a light source.
前記本発明の表示体においては、下記の構成を好ましい態様として含む。
前記面発光体が、第1の光散乱剤を含む皮膜層、及び第2の光散乱剤を含む基材層とを有し、前記基材層の厚さに対する前記皮膜層の厚さの比が1/300〜1/7であり、前記基材層の光散乱剤濃度に対する前記皮膜層の光散乱剤濃度の比が100/1〜2000/1である。
前記皮膜層が第1の光透過性樹脂を含み、前記基材層が第2の光透過性樹脂を含む。
前記第1の光透過性樹脂がメタクリル樹脂である。
前記第2の光透過性樹脂がメタクリル樹脂である。
前記面発光体の表面の少なくとも一方の主面に光触媒(A)及びバインダー成分(B)を含む光触媒組成物(C)からなる光触媒層が被覆されている。
前記面発光体表面の他の主面上或いは上記一方の主面と光触媒層との間に意匠が施されている。
The display body of the present invention includes the following configuration as a preferred embodiment.
The surface light emitter has a coating layer containing a first light scattering agent and a base material layer containing a second light scattering agent, and the ratio of the thickness of the coating layer to the thickness of the base material layer Is 1/300 to 1/7, and the ratio of the light scattering agent concentration of the coating layer to the light scattering agent concentration of the base material layer is 100/1 to 2000/1.
The coating layer includes a first light transmissive resin, and the base material layer includes a second light transmissive resin.
The first light transmitting resin is a methacrylic resin.
The second light transmitting resin is a methacrylic resin.
A photocatalyst layer made of a photocatalyst composition (C) containing a photocatalyst (A) and a binder component (B) is coated on at least one main surface of the surface light emitter.
A design is applied on the other main surface of the surface light emitter surface or between the one main surface and the photocatalyst layer.
本発明によれば、特殊なLED光源を使用することにより、面発光体自体を劣化すること無しに強い光触媒活性及び/または親水性(水の接触角が20°以下、好ましくは10°以下)を発現する光触媒層を有し、降雨や簡単な水洗浄で長期にわたり面発光体の美観を保つことや、有害物質を分解することにより環境浄化ができる面発光表示体を提供することができる。特に、表示体内部の光源により光触媒が活性化されるため、屋内使用において効果的である。 According to the present invention, by using a special LED light source, strong photocatalytic activity and / or hydrophilicity (with a water contact angle of 20 ° or less, preferably 10 ° or less) without deteriorating the surface light emitter itself. Therefore, it is possible to provide a surface light emitting display body that has a photocatalyst layer that can maintain the aesthetics of the surface light emitting body for a long period of time by rain or simple water washing, and can purify the environment by decomposing harmful substances. In particular, since the photocatalyst is activated by the light source inside the display body, it is effective for indoor use.
以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明において光触媒活性とは、光照射によって酸化、還元反応を起こすことを言う。材料の表面が光触媒活性であるか否かは、該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。 In the present invention, the photocatalytic activity means that an oxidation or reduction reaction is caused by light irradiation. Whether or not the surface of the material is photocatalytically active can be determined by measuring the decomposability of an organic substance such as a dye during light irradiation on the surface of the material. A surface having photocatalytic activity exhibits excellent decomposition activity and contamination resistance of contaminating organic substances.
また、本発明において親水性とは、好ましくは20℃での水の接触角が60°以下である場合を言うが、特に水の接触角が20°以下の親水性を有する表面は、降雨等の水による自己浄化能(セルフクリーニング)による耐汚染性を発現するので好ましい。更に優れた耐汚染性発現の点からは表面の水の接触角は10°以下であることが好ましく、更に好ましくは5°以下である。 In the present invention, the term “hydrophilic” refers to a case where the contact angle of water at 20 ° C. is preferably 60 ° or less. In particular, the hydrophilic surface having a contact angle of water of 20 ° or less is used for rain, It is preferable because it exhibits stain resistance due to its self-purifying ability (self-cleaning). Further, from the standpoint of expressing excellent stain resistance, the contact angle of water on the surface is preferably 10 ° or less, more preferably 5 ° or less.
本発明のLED光源は、ピーク波長350〜390nmの波長を発するLED(1)と、可視光を発するLED(2)及び/又は白色光を発するLED(3)とを組み合わせて用いる。 The LED light source of the present invention uses an LED (1) emitting a peak wavelength of 350 to 390 nm in combination with an LED (2) emitting visible light and / or an LED (3) emitting white light.
本発明に用いられる上記LED光源(1)としては、後述する光触媒層の構成成分である光触媒(A)のバンドギャップエネルギーより高いエネルギーの光(励起光)を発するものであれば良い。具体的には、日亜化学工業株式会社製NSHU550A、NSHU590A、NSHU550B、NSHU590B、NCCU001、NCCU033等が挙げられるが、これらに制限されるものではない。 As said LED light source (1) used for this invention, what emits the light (excitation light) of energy higher than the band gap energy of the photocatalyst (A) which is a structural component of the photocatalyst layer mentioned later should just be emitted. Specific examples include NSHU550A, NSHU590A, NSHU550B, NSHU590B, NCCU001, and NCCU033 manufactured by Nichia Corporation, but are not limited thereto.
また、LED(2)は三原色のLEDを単色又は混色し、所望の色調としたものを用いることができる。更に、LED(3)としては三原色のLEDを混色するか、青色LEDと蛍光体からなる白色光等を利用できる。これらの例としては、日亜化学工業株式会社製表面実装型発光ダイオード「Power LED Series」、「Top View Series」、「Side View Series」、「Full Color Series」、「C Series」や砲弾型発光ダイオード「Warm White Series」、「F3 Series」、「F5 Series」、「F7.5 Series」、「Ovel Series/Super Ovel Series」、「Flat Series」、「Full Colar、Series」等が挙げられるが、これらに制限されるものではない。 As the LED (2), a single color or mixed color of the three primary color LEDs and a desired color tone can be used. Further, as the LED (3), three primary color LEDs can be mixed, or white light composed of a blue LED and a phosphor can be used. Examples of these include surface-mounted light emitting diodes “Power LED Series”, “Top View Series”, “Side View Series”, “Full Color Series”, “C Series”, and bullet-type light emitting manufactured by Nichia Corporation. Diodes “Warm White Series”, “F3 Series”, “F5 Series”, “F7.5 Series”, “Over Series / Super Over Series”, “Flat Series”, “Full Color, Series”, etc. However, it is not limited to these.
本発明において望ましくは、LED(1)の発光時間が、LED(2)及び/又はLED(3)の単位発光時間当たり1/100〜99/100の間、好ましくは10/100〜90/100の間、更に好ましくは20/100〜80/100の間発光するように制御する。即ち、LED(2)及び/又はLED光源(3)を継続的に発光するのに対して、LED(1)を断続的に発光させる。上記範囲内であれば、LED(1)は光触媒を励起させることができ、光透過性材料の劣化を防ぐことができる。 Desirably in the present invention, the light emission time of the LED (1) is between 1/100 and 99/100, preferably 10/100 to 90/100, per unit light emission time of the LED (2) and / or LED (3). More preferably, the light emission is controlled between 20/100 and 80/100. That is, the LED (2) and / or the LED light source (3) emit light continuously, whereas the LED (1) emits light intermittently. If it is in the said range, LED (1) can excite a photocatalyst and can prevent deterioration of a light transmissive material.
本発明の表示体は、上記LED光源を面発光体の少なくとも1つ以上の側端部に配設してなり、好ましくは該面発光体が、少なくとも第1の光散乱剤と第1の光透過性樹脂とからなる被膜層と、少なくとも第2の光散乱剤と第2の光透過性樹脂とからなる基材層とからなる。図4に本発明の表示体の一例の概略構成を示す。図中、1は面発光体、4はランプハウス、7はLED(2)又は(3)、8はLED(1)である。 In the display body of the present invention, the LED light source is disposed on at least one side end of a surface light emitter, and preferably the surface light emitter includes at least a first light scattering agent and a first light. It consists of a coating layer made of a transmissive resin and a base material layer made of at least a second light scattering agent and a second light transmissive resin. FIG. 4 shows a schematic configuration of an example of the display body of the present invention. In the figure, 1 is a surface light emitter, 4 is a lamp house, 7 is an LED (2) or (3), and 8 is an LED (1).
本発明において好ましくは、該被膜層の上に光触媒(A)及びバインダー成分(B)を含む光触媒組成物(C)からなる光触媒層を有する。各部材について説明する。 Preferably in this invention, it has a photocatalyst layer which consists of a photocatalyst composition (C) containing a photocatalyst (A) and a binder component (B) on this film layer. Each member will be described.
本発明において用いられる第1及び第2の光透過性材料としては、種々の熱可塑性樹脂が適用可能であるが、好ましくはメタクリル樹脂、ポリカーボネート樹脂、スチレン系樹脂、環状オレフィン系樹脂、非晶性ポリエステル樹脂等の光学材料であり、更に好ましくはメタクリル樹脂である。 As the first and second light-transmitting materials used in the present invention, various thermoplastic resins can be applied, but preferably a methacrylic resin, a polycarbonate resin, a styrene resin, a cyclic olefin resin, an amorphous resin. An optical material such as a polyester resin, and more preferably a methacrylic resin.
上記光透過性樹脂に光散乱剤を分散させた熱可塑性樹脂をシート状に形成することで基材層及び皮膜層が得られる。この熱可塑性樹脂シートは押出し成形法、キャスト法により得ることができる。 A base material layer and a coating layer are obtained by forming a thermoplastic resin in which a light scattering agent is dispersed in the light transmitting resin into a sheet shape. This thermoplastic resin sheet can be obtained by extrusion molding or casting.
以下、本発明において光透過性樹脂として適用可能な樹脂について、より詳細に記す。 Hereinafter, the resin applicable as the light transmissive resin in the present invention will be described in more detail.
メタクリル樹脂とは、メタクリル酸メチル或いはメタクリル酸エチルを70重量%以上と、これ等と共重合性を有する単量体とを共重合することにより得ることができる。これ等と共重合性を有する単量体としてはメタクリル酸ブチル、メタクリル酸エチル、メタクリル酸メチル、メタクリル酸プロピル、メタクリル酸シクロヘキシル、メタクリル酸フェニル、メタクリル酸2−エチルヘキシル等のメタクリル酸エステル類、アクリル酸メチル、アクリル酸エチル、アクリル酸ブチル、アクリル酸シクロヘキシル、アクリル酸フェニル、アクリル酸2−エチルヘキシル等のアクリル酸エステル類、メタクリル酸、アクリル酸等の不飽和酸類等が適用可能である。 The methacrylic resin can be obtained by copolymerizing 70% by weight or more of methyl methacrylate or ethyl methacrylate and a monomer having copolymerizability with these. As monomers having copolymerizability with these, methacrylic acid esters such as butyl methacrylate, ethyl methacrylate, methyl methacrylate, propyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, 2-ethylhexyl methacrylate, acrylic Acrylic acid esters such as methyl acid, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, phenyl acrylate, and 2-ethylhexyl acrylate, and unsaturated acids such as methacrylic acid and acrylic acid are applicable.
また、耐熱性メタクリル樹脂、低吸湿性メタクリル樹脂、耐衝撃性メタクリル樹脂等も適用可能である。耐衝撃性メタクリル樹脂とは、例えばメタクリル樹脂にゴム弾性体をブレンドしたものである。そのゴム弾性体の一例としては、アクリル系重合体芯材料の周りに弾性層及び非弾性層を交互に生成させる多段階逐次重合法により製造される多段重合体が挙げられる。このゴム弾性体をメタクリル樹脂にブレンドすることで、上記の耐衝撃性メタクリル樹脂が得られる。 Further, heat-resistant methacrylic resin, low-hygroscopic methacrylic resin, impact-resistant methacrylic resin, and the like are also applicable. The impact resistant methacrylic resin is, for example, a blend of a rubber elastic body and a methacrylic resin. An example of the rubber elastic body is a multistage polymer produced by a multistage sequential polymerization method in which an elastic layer and an inelastic layer are alternately generated around an acrylic polymer core material. By blending this rubber elastic body with a methacrylic resin, the above impact-resistant methacrylic resin can be obtained.
また、ポリカーボネート樹脂を用いる場合には、ポリカーボネート樹脂としてビスフェノールAに代表される二価フェノール系化合物から誘導される重合体が用いられる。ポリカーボネート樹脂の製造方法は、特に限定されるものではなく、ホスゲン法、エステル交換法或いは固相重合法等の周知の慣用の方法で製造されたものを適用することができる。 When a polycarbonate resin is used, a polymer derived from a dihydric phenol-based compound typified by bisphenol A is used as the polycarbonate resin. The method for producing the polycarbonate resin is not particularly limited, and a polycarbonate resin produced by a well-known conventional method such as a phosgene method, a transesterification method or a solid phase polymerization method can be applied.
環状オレフィン系樹脂とは、ノルボルネンやシクロヘキサジエン等のポリマー鎖中に環状オレフィン骨格を含む重合体若しくはこれ等を含む共重合体であり、非晶性熱可塑性樹脂に属する。その製造方法については特に限定されるものではない。例えば、ノルボルネンを主とした環状オレフィン樹脂の一例としては、エチレン・ノルボルネン共重合体であるTicona株式会社製の「Topas」(商品名)が適用可能であり、シクロペンタジエン開環重合体の一例としては日本ゼオン株式会社製の「Zeonex」(商品名)等が適用可能である。 The cyclic olefin-based resin is a polymer containing a cyclic olefin skeleton in a polymer chain such as norbornene or cyclohexadiene or a copolymer containing these, and belongs to an amorphous thermoplastic resin. The manufacturing method is not particularly limited. For example, as an example of a cyclic olefin resin mainly composed of norbornene, “Topas” (trade name) manufactured by Ticona Co., Ltd., which is an ethylene-norbornene copolymer, can be applied. As an example of a cyclopentadiene ring-opening polymer Is applicable to “Zeonex” (trade name) manufactured by Nippon Zeon Co., Ltd.
スチレン系樹脂とは、スチレンを必須成分とするホモポリマー、コポリマー又はこれ等のポリマーと他の樹脂とから得られるポリマーブレンド等である。特にポリスチレン、アクリロニトリルとスチレンの共重合体樹脂であるAS樹脂、メタクリル酸エステルとスチレンの共重合体樹脂であるMS樹脂を用いることが好ましい。 The styrenic resin is a homopolymer, a copolymer or a polymer blend obtained from such a polymer and another resin containing styrene as an essential component. In particular, it is preferable to use AS resin which is a copolymer resin of polystyrene, acrylonitrile and styrene, or MS resin which is a copolymer resin of methacrylic acid ester and styrene.
更にスチレン系樹脂相中にゴムが分布した透明強化ポリスチレンも好ましく使用できる。スチレン系樹脂の製造方法は、特に限定されるものではなく、周知慣用の方法で製造されたものを使用することができる。 Further, transparent reinforced polystyrene in which rubber is distributed in the styrene resin phase can be preferably used. The method for producing the styrene-based resin is not particularly limited, and those produced by a well-known and commonly used method can be used.
非晶性ポリエステルとは、エチレングリコール、プロピレングリコール、1,4−ブタンジオール、ネオペンチルグリコール、ヘキサエチレングリコール等の脂肪族グリコール、シクロヘキサンジメタノール等の脂環族グリコール、ビスフェノール、1,3−ビス(2−ヒドロキシエトキシ)ベンゼン、1,4−ビス(ヒドロキシエトキシ)ベンゼン等の芳香族ジヒドロキシ化合物、或いはこれ等の2種類以上から選ばれたジヒドロキシ化合物単位と、テレフタル酸、イソフタル酸、2,6−ナフタリンジカルボン酸等の芳香族ジカルボン酸、シュウ酸、アジピン酸、セバシン酸、コハク酸、ウンデカジカルボン酸等の脂肪族ジカルボン酸、ヘキサヒドロテレフタル酸等の脂肪族ジカルボン酸、或いはこれ等の2種類以上から選ばれたジカルボン酸単位とから形成されるポリエステルの中で非晶性の樹脂が適用可能である。 Amorphous polyesters include aliphatic glycols such as ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, hexaethylene glycol, alicyclic glycols such as cyclohexanedimethanol, bisphenol, 1,3-bis. Aromatic dihydroxy compounds such as (2-hydroxyethoxy) benzene and 1,4-bis (hydroxyethoxy) benzene, or dihydroxy compound units selected from two or more of these, terephthalic acid, isophthalic acid, 2,6 -An aromatic dicarboxylic acid such as naphthalene dicarboxylic acid, an aliphatic dicarboxylic acid such as oxalic acid, adipic acid, sebacic acid, succinic acid and undecadicarboxylic acid, an aliphatic dicarboxylic acid such as hexahydroterephthalic acid, or 2 of these Zikaru selected from more than one kind Amorphous resin in the polyester formed from the phosphate unit is applicable.
非晶性ポリエステルの製造方法は、特に限定されるものではなく、周知慣用の方法で製造することができる。非晶性ポリエステルとして容易入手し得る市販銘柄としては、イーストマン・コダック社の製品である「KODAR PETG」或いは「PCTA」等が適用可能である。 The method for producing the amorphous polyester is not particularly limited, and can be produced by a well-known conventional method. As a commercial brand that can be easily obtained as an amorphous polyester, “KODAR PETG” or “PCTA”, which is a product of Eastman Kodak Company, is applicable.
また、上記本発明の光透過性樹脂には、必要に応じて軟質重合体を添加しても良い。例えば、α−オレフィンからなるオレフィン系軟質重合体、イソブチレンからなるイソブチレン系軟質重合体、ブタジエン、イソプレン等の共役ジエンからなるジエン系軟質重合体、ノルボルネン、シクロペンテン等の環状オレフィンからなる環状オレフィン系軟質重合体、有機ポリシロキサン系軟質重合体、α、β−不飽和酸とその誘導体からなる軟質重合体、不飽和アルコール及びアミン又はそのアシル誘導体又はアセタールからなる軟質重合体、エポキシ化合物の重合体、フッ素系ゴム等が適用できる。 Moreover, you may add a soft polymer to the light transmissive resin of the said invention as needed. For example, an olefin-based soft polymer composed of α-olefin, an isobutylene-based soft polymer composed of isobutylene, a diene-based soft polymer composed of conjugated dienes such as butadiene and isoprene, and a cyclic olefin-based soft composed of a cyclic olefin such as norbornene and cyclopentene. Polymer, organopolysiloxane-based soft polymer, soft polymer composed of α, β-unsaturated acid and its derivative, soft polymer composed of unsaturated alcohol and amine or acyl derivative or acetal thereof, polymer of epoxy compound, Fluorine rubber or the like can be applied.
本発明において光散乱剤として適用可能な材料としては、炭酸カルシウム、硫酸バリウム、アルミナ、二酸化チタン、二酸化ケイ素、ガラスビーズ等の無機微粒子、スチレン架橋ビーズ、MS架橋ビーズ、シロキサン系架橋ビーズ等の有機微粒子等が挙げられる。また、メタクリル系樹脂、ポリカーボネート系樹脂、MS樹脂、環状オレフィン樹脂等の透明性の高い樹脂材料からなる中空架橋微粒子及びガラスからなる中空微粒子等も光散乱剤として適用可能である。尚、光散乱剤は前記第1の光透過性樹脂及び第2の光透過性樹脂にそれぞれ分散されていることが好ましい。 Examples of materials that can be used as a light scattering agent in the present invention include inorganic fine particles such as calcium carbonate, barium sulfate, alumina, titanium dioxide, silicon dioxide, and glass beads, and organic materials such as styrene crosslinked beads, MS crosslinked beads, and siloxane crosslinked beads. Examples thereof include fine particles. Moreover, hollow cross-linked fine particles made of highly transparent resin materials such as methacrylic resin, polycarbonate resin, MS resin, and cyclic olefin resin, hollow fine particles made of glass, and the like are also applicable as the light scattering agent. The light scattering agent is preferably dispersed in each of the first light transmitting resin and the second light transmitting resin.
また、面発光体に分散される光散乱剤の形状は特に限定されるものではなく、例えば、真球状、球状、平面扇形状、キュービック状、平面菱形状、六方晶状、不定形状等の光散乱剤が適用可能である。 In addition, the shape of the light scattering agent dispersed in the surface light emitter is not particularly limited. For example, light having a spherical shape, a spherical shape, a flat fan shape, a cubic shape, a flat rhombus shape, a hexagonal shape, an indefinite shape, or the like. Scattering agents are applicable.
本発明に用いられる面発光体は、好ましくは、光散乱剤濃度の低い基材層と、光散乱剤濃度の高い皮膜層とを、特定の厚さ比で有する。具体的には、基材層の厚さに対する皮膜層の厚さの比が1/300〜1/7であり、且つ、基材層の光散乱剤濃度に対する皮膜層の光散乱剤濃度の比が100/1〜2000/1である。 The surface light emitter used in the present invention preferably has a base material layer having a low light scattering agent concentration and a coating layer having a high light scattering agent concentration at a specific thickness ratio. Specifically, the ratio of the thickness of the coating layer to the thickness of the base material layer is 1/300 to 1/7, and the ratio of the light scattering agent concentration of the coating layer to the light scattering agent concentration of the base material layer Is 100/1 to 2000/1.
尚、以下では、基材層の厚さに対する皮膜層の厚さの比を「皮膜層/基材層の厚さ比」と記し、基材層の光散乱剤濃度に対する皮膜層の光散乱剤濃度の比を「皮膜層/基材層の光散乱剤濃度比」と記す。 In the following, the ratio of the thickness of the coating layer to the thickness of the base layer is referred to as “the thickness ratio of the coating layer / base layer”, and the light scattering agent of the coating layer with respect to the light scattering agent concentration of the base layer. The concentration ratio is referred to as “film layer / base material layer light scattering agent concentration ratio”.
尚、本発明において、光散乱剤濃度とは、光透過性樹脂中に含まれる光散乱剤の重量分率をppmで定義した値である。 In the present invention, the light scattering agent concentration is a value in which the weight fraction of the light scattering agent contained in the light transmitting resin is defined in ppm.
本発明において、皮膜層/基材層の厚さ比が1/200〜1/15で、且つ、皮膜層/基材層の光散乱剤の濃度比が200/1〜1500/1の範囲であることが好ましく、更に好ましくは、皮膜層/基材層の厚さ比が1/100〜1/25で、且つ、皮膜層/基材層の光散乱剤の濃度比が300/1〜1000/1の範囲である。 In the present invention, the thickness ratio of the coating layer / base material layer is 1/200 to 1/15, and the concentration ratio of the light scattering agent of the coating layer / base material layer is in the range of 200/1 to 1500/1. Preferably, the thickness ratio of the coating layer / base material layer is 1/100 to 1/25, and the concentration ratio of the light scattering agent of the coating layer / base material layer is 300/1 to 1000. / 1 range.
以下に、本発明に用いられる面発光体の製造方法について記す。 Below, the manufacturing method of the surface light-emitting body used for this invention is described.
本発明では、光透過性樹脂中に光散乱剤を分散させ、その組成物を基材層及び皮膜層として用いることが好ましい。尚、上記したように、本発明においては、光透過性樹脂として熱可塑性の樹脂を用いることが好ましい。 In this invention, it is preferable to disperse | distribute a light-scattering agent in light transmissive resin, and to use the composition as a base material layer and a membrane | film | coat layer. As described above, in the present invention, it is preferable to use a thermoplastic resin as the light transmissive resin.
ここで、光透過性樹脂と光散乱剤とを有する光透過性樹脂組成物において、光散乱剤の微粒子が透明熱可塑性樹脂中に均一に分散しているのであれば、光透過性樹脂組成物の製造方法は、特に限定されない。但し、光散乱剤の微粒子を予め有機液体中に均一に分散させ、得られた分散液を用いて光透過性樹脂組成物を製造することが好ましい。 Here, in the light transmissive resin composition having the light transmissive resin and the light scattering agent, if the light scattering agent fine particles are uniformly dispersed in the transparent thermoplastic resin, the light transmissive resin composition. The manufacturing method is not particularly limited. However, it is preferable that the light scattering agent fine particles are uniformly dispersed in advance in an organic liquid, and a light-transmitting resin composition is produced using the obtained dispersion.
面発光体を構成する光透過性樹脂組成物の製造方法としては、光散乱剤の微粒子を予め有機液体中に分散させることにより、光散乱剤の微粒子を光透過性樹脂中に均一に分散させることが好ましい。また、光散乱剤の微粒子を有機液体中に均一に分散させるのは、超音波発生装置を用いることが好ましい。 As a method for producing the light-transmitting resin composition constituting the surface light emitter, the light scattering agent fine particles are dispersed in advance in the organic liquid so that the light scattering agent fine particles are uniformly dispersed in the light transmitting resin. It is preferable. Further, it is preferable to use an ultrasonic generator to uniformly disperse the fine particles of the light scattering agent in the organic liquid.
尚、ここでいう有機液体には、一般有機液体の他、光透過性樹脂を構成する重合性単量体等も含まれ、光散乱剤の微粒子が溶解、膨潤等を起こし難く、また均一に分散するものであれば特に限定されるものではない。また、光散乱剤の微粒子の分散状態により数種類の有機液体を任意の割合で混合して使用しても良い。 The organic liquid referred to here includes not only general organic liquids but also polymerizable monomers constituting the light-transmitting resin, so that the light scattering agent particles hardly dissolve, swell, etc., and are uniform. If it disperses | distributes, it will not specifically limit. Moreover, you may mix and use several types of organic liquids in arbitrary ratios by the dispersion state of the microparticles | fine-particles of a light-scattering agent.
一般有機液体としては、アセトン、メチルエチルケトン等のケトン類、キシレン、トルエン等の芳香族類、メタノール、エタノール等のアルコール類を適用することができる。また、重合性単量体としては、例えば光透過性樹脂がメタクリル樹脂の場合、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸プロピル、メタクリル酸ブチル、メタクリル酸シクロヘキシル、メタクリル酸フェニル、メタクリル酸2−エチルヘキシル等のメタクリル酸エステル類、アクリル酸メチル、アクリル酸エチル、アクリル酸ブチル、アクリル酸シクロヘキシル、アクリル酸フェニル、アクリル酸2−エチルヘキシル等のアクリル酸エステル類、メタクリル酸、アクリル酸等の不飽和酸類等が適用できる。 As the general organic liquid, ketones such as acetone and methyl ethyl ketone, aromatics such as xylene and toluene, and alcohols such as methanol and ethanol can be applied. As the polymerizable monomer, for example, when the light-transmitting resin is a methacrylic resin, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, 2-ethylhexyl methacrylate Methacrylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, phenyl acrylate, acrylic acid esters such as 2-ethylhexyl acrylate, unsaturated acids such as methacrylic acid and acrylic acid, etc. Is applicable.
面発光体の基材層及び皮膜層となる光透過性樹脂及び光散乱剤の微粒子を含む光透過性樹脂組成物を製造する場合、光散乱剤の微粒子を光透過性樹脂中に均一分散させる方法として、例えば、以下の〔1〕或いは〔2〕の方法を適用することができる。 When producing a light-transmitting resin composition containing a light-transmitting resin and a light-scattering agent fine particles as a base layer and a coating layer of a surface light emitter, the light-scattering agent fine particles are uniformly dispersed in the light-transmitting resin. As a method, for example, the following method [1] or [2] can be applied.
〔1〕押出機で、基材層及び皮膜層となる光透過性樹脂と光散乱剤の微粒子とを溶融混練する方法。 [1] A method of melt-kneading a light-transmitting resin to be a base material layer and a coating layer and fine particles of a light scattering agent with an extruder.
この場合には、光散乱剤の微粒子を有機液体中に、好ましくは超音波発生装置を用いて分散させ、光散乱剤分散液を作製する。作製した光散乱剤分散液と光透過性樹脂とを混合し、その混合物を押出機で溶融混練する。その際、使用する有機液体は上述の通り、光散乱剤の微粒子が溶解、膨潤等を起こすことなく、且つ均一に分散するものであれば何ら限定されるものではない。また分散状態により数種類の有機液体を任意の割合で混合して使用することができる。 In this case, the light scattering agent dispersion is prepared by dispersing the light scattering agent fine particles in the organic liquid, preferably using an ultrasonic generator. The produced light scattering agent dispersion and the light transmissive resin are mixed, and the mixture is melt-kneaded with an extruder. In this case, the organic liquid to be used is not limited as long as the fine particles of the light scattering agent are not dissolved, swelled, or the like and uniformly dispersed as described above. Depending on the dispersion state, several kinds of organic liquids can be mixed and used at an arbitrary ratio.
ここで、光散乱剤の微粒子と有機液体との混合比は、光散乱剤の微粒子の分散性を考慮して任意に決定することができるが、有機液体100重量部に対して光散乱剤の微粒子を0.001〜80重量部の範囲で混合することが好ましい。 Here, the mixing ratio of the light scattering agent fine particles to the organic liquid can be arbitrarily determined in consideration of the dispersibility of the light scattering agent fine particles. It is preferable to mix the fine particles in the range of 0.001 to 80 parts by weight.
また、光散乱剤と微粒子と有機液体とからなる光拡散剤分散液と、面発光体の基材となる光透過性樹脂との混合比も混合押し出し工程でのハンドリング性を考慮して任意に決定することができるが、面発光体の基材となる光透過性樹脂100重量部に対して分散液を0.001〜10重量部の範囲で混合することが好ましい。 Also, the mixing ratio of the light diffusing agent dispersion composed of a light scattering agent, fine particles, and an organic liquid and the light-transmitting resin that is the base material of the surface light emitter is arbitrarily determined in consideration of the handling property in the mixing extrusion process. Although it can determine, it is preferable to mix a dispersion liquid in 0.001-10 weight part with respect to 100 weight part of light transmissive resin used as the base material of a surface light-emitting body.
光散乱剤分散液の光透過性樹脂への混合方法は、特に限定されるものではなく、例えば、ヘンシェルミキサーによる混合、スーパーフローターによる混合、タンブラーによる混合といった周知慣用の混合方法で混合することができる。 The method of mixing the light scattering agent dispersion into the light-transmitting resin is not particularly limited, and for example, mixing by a well-known and conventional mixing method such as mixing with a Henschel mixer, mixing with a super floater, or mixing with a tumbler. it can.
また、上記混合物の溶融混練に用いられる押出機についても必ずしも特異なものを用いる必要はなく、通常の単軸又は二軸の押出機等であれば良い。但し、分散に使用した有機液体の揮発成分除去の観点からベントロで好ましくは40kPa以下の減圧脱揮が可能な押出機が好ましい。更に、ダイスとしては、皮膜厚さを制御可能な多層ダイスを用いる。 Also, the extruder used for melt kneading the above mixture does not necessarily need to be a unique one, and any ordinary single-screw or twin-screw extruder may be used. However, from the viewpoint of removing volatile components from the organic liquid used for dispersion, an extruder capable of devolatilization under reduced pressure of 40 kPa or less is preferable with Bentro. Further, as the die, a multilayer die capable of controlling the film thickness is used.
また、光散乱剤の微粒子の二次凝集防止の観点から二軸押出機を使用することが製造上好ましい。押出機の温度は使用する光透過性樹脂の種類によって任意に設定することができる。例えば、光透過性樹脂がメタクリル樹脂を用いる場合には、180℃〜260℃前後である。 From the viewpoint of preventing secondary aggregation of the light scattering agent fine particles, it is preferable in production to use a twin screw extruder. The temperature of the extruder can be arbitrarily set depending on the type of light transmissive resin to be used. For example, when the light transmissive resin uses a methacrylic resin, the temperature is about 180 ° C. to 260 ° C.
〔2〕キャスト法により重合し、面発光体を得る方法。 [2] A method of obtaining a surface light emitter by polymerization by a casting method.
この場合には、光散乱剤の微粒子を、基材となる光透過樹脂の原料単量体、又はこの単量体と共重合可能な単量体中に、好ましくは超音波発生装置を用いて分散させる方法が適用できる。この場合、光散乱剤の微粒子を原材料モノマーの一部に予め分散させ、その後、部分重合したポリマー溶液等に混合して使用することが好ましい。光散乱剤の微粒子とそれを分散する原料モノマーとの量比は、分散性、仕込み時の粘度、ハンドリング性等から任意に決定できる。 In this case, the light scattering agent fine particles are preferably used in a raw material monomer of a light-transmitting resin as a base material or a monomer copolymerizable with this monomer, preferably using an ultrasonic generator. A method of dispersing can be applied. In this case, the light scattering agent particles are preferably dispersed in advance in a part of the raw material monomer, and then mixed with a partially polymerized polymer solution or the like. The amount ratio between the light scattering agent fine particles and the raw material monomer in which the light scattering agent is dispersed can be arbitrarily determined from the dispersibility, the viscosity at the time of preparation, the handling property, and the like.
また、キャスト法における重合温度、重合時間、重合開始剤量等の重合条件や面発光体となるキャスト板の形成方法についても特に限定されるものではない。キャスト板の形成方法としては、例えば、ガラスセルキャスト法、連続キャスト法等が適用できる。 Also, there are no particular limitations on the polymerization conditions such as the polymerization temperature, polymerization time, and amount of polymerization initiator in the casting method, and the method of forming the cast plate that will be the surface light emitter. As a method for forming the cast plate, for example, a glass cell casting method, a continuous casting method, or the like can be applied.
尚、粒子の分散に使用される超音波発生装置は、特に限定されるものではなく、市販の超音波洗浄機や超音波スターラー等を使用することができる。例えば、超音波周波数が28kHz〜100kHzの超音波洗浄機が一般的に使用される。超音波発生装置による照射時間は、光散乱剤の微粒子の分散状態により任意に設定できるが、一般的には1分〜60分程度照射することが好ましい。 In addition, the ultrasonic generator used for dispersion | distribution of particle | grains is not specifically limited, A commercially available ultrasonic cleaner, an ultrasonic stirrer, etc. can be used. For example, an ultrasonic cleaner having an ultrasonic frequency of 28 kHz to 100 kHz is generally used. Although the irradiation time by the ultrasonic generator can be arbitrarily set according to the dispersion state of the light scattering agent fine particles, it is generally preferable to irradiate for about 1 to 60 minutes.
本方法で得られる多層面発光体は輝度比L10/L210を向上することができ、発光輝度の優れた面発光体を得ることができる。 The multilayer surface light emitter obtained by this method can improve the luminance ratio L 10 / L 210, and a surface light emitter excellent in light emission luminance can be obtained.
尚、本発明において、輝度比L10/L210は、光源からの距離が10mmの位置における面発光体の輝度をL10、光源からの距離が210mmの位置における面発光体の輝度をL210とした時の両者の比を表している。1に近い輝度比を有する面発光体は発光体としての均一性に優れている。
In the present invention, the luminance ratio L 10 / L 210 means that the luminance of the surface light emitter at a
本発明に係る光触媒層は、光触媒(A)及びバインダー成分(B)を含む光触媒組成物(C)からなり、特に、光触媒層中における光触媒(A)の濃度が、光透過性材料側から他方の露出面に向かって高くなることが望ましい。 The photocatalyst layer according to the present invention comprises a photocatalyst composition (C) containing a photocatalyst (A) and a binder component (B). In particular, the concentration of the photocatalyst (A) in the photocatalyst layer is the other from the light transmissive material side. It is desirable that the height increases toward the exposed surface.
この際、全光触媒層中の光触媒含有量(濃度)100に対し、露出面と接する表面側近傍の相対濃度が120以上であることが光触媒能力や親水化能力の向上効果を発現し、防汚効果が大きくなるために好ましい。より好ましくは150以上、更に好ましくは200以上である。また、面発光体に接する側の相対濃度が50以下であると界面劣化防止効果の点で好ましい。該面発光体に接する面近傍の相対濃度はより好ましくは10以下、更に好ましくは0であると良い。 At this time, when the relative concentration in the vicinity of the surface side in contact with the exposed surface is 120 or more with respect to the photocatalyst content (concentration) of 100 in the total photocatalyst layer, the effect of improving the photocatalytic ability and the hydrophilization ability is exhibited, and the antifouling property is exhibited. It is preferable because the effect is increased. More preferably, it is 150 or more, More preferably, it is 200 or more. Moreover, it is preferable from the point of the interface deterioration prevention effect that the relative density | concentration of the side in contact with a surface light emitter is 50 or less. The relative concentration in the vicinity of the surface in contact with the surface light emitter is more preferably 10 or less, and even more preferably 0.
また、本発明における光触媒層中における光触媒(A)の濃度は、該面発光体に接する面から他方の露出面に向かって徐々に高くなっても良いし、単に該面発光体に接する面での光触媒濃度が低く、他方の露出面における光触媒濃度が高く、その間の変化が不連続であっても良い。 In the present invention, the concentration of the photocatalyst (A) in the photocatalyst layer may gradually increase from the surface in contact with the surface light emitter toward the other exposed surface, or simply on the surface in contact with the surface light emitter. The photocatalyst concentration may be low, the photocatalyst concentration on the other exposed surface may be high, and the change therebetween may be discontinuous.
更に、かかる光触媒層中において、保護層の上に光触媒層を塗布した場合に生じる様な明確な膜界面が存在しない方が好ましい。光触媒層中にこのような明確な膜界面が存在しない場合、光触媒(A)は強固に光触媒層中に固定化され、光触媒層の剥離等の問題が発生しなくなる。 Further, in such a photocatalyst layer, it is preferable that there is no clear film interface that occurs when a photocatalyst layer is applied on the protective layer. When such a clear film interface does not exist in the photocatalyst layer, the photocatalyst (A) is firmly fixed in the photocatalyst layer, and problems such as peeling of the photocatalyst layer do not occur.
本発明において、光触媒層を光触媒活性及び/又は親水性にするのに有用に使用できる光触媒(A)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、Ta3N5等、更には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号公報等参照)や、窒素ドープ酸化チタン(特開平13−278625号公報、特開平13−278627号公報、特開平13−335321号公報、特開平14−029750号公報、特開平13−207082号公報等参照)や、酸素欠陥型の酸化チタン(特開平13−212457号公報参照)の如き、可視光応答型酸化チタン光触媒も好適に使用することができる。また、TaON、LaTiO2N、CaNbO2N、LaTaON2、CaTaO2N等のオキシナイトライド化合物やSm2Ti2S2O7等のオキシサルファイド化合物は可視光による光触媒活性が大きく、好適に使用することができる。
In the present invention, the photocatalyst layer as the photocatalyst (A) which can be usefully employed to the photocatalyst activity and / or hydrophilicity, for example TiO 2, ZnO, SrTiO 3, CdS, GaP, InP, GaAs,
更に、これらの光触媒材料に、Pt、Rh、Ru、Nb、Cu、Sn、Ni、Feなどの金属及び/又はこれらの酸化物を添加或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材料(特開平10−244166号公報参照)等を使用することもできる。 Further, these photocatalytic materials were coated with a metal such as Pt, Rh, Ru, Nb, Cu, Sn, Ni, Fe and / or an oxide thereof added or immobilized, porous calcium phosphate, or the like. A photocatalytic material (see JP-A-10-244166) or the like can also be used.
上記光触媒(A)の結晶粒子径(1次粒子径)は1〜400nmであることが好ましく、より好ましくは1〜50nmの光触媒が好適に選択される。 The crystal particle size (primary particle size) of the photocatalyst (A) is preferably 1 to 400 nm, and more preferably a photocatalyst of 1 to 50 nm is suitably selected.
これらの光触媒材料のうち、酸化チタンは無毒であり、化学的安定性にも優れると共に、光照射により、酸化チタン自体の親水性が非常に高まるため好ましい。該酸化チタンとしては、アナターゼ型、ルチル型、ブルッカイト型のうち、いずれの結晶形を使用してもよい。また、可視光応答性である上記窒素ドープ酸化チタンや酸素欠陥型の酸化チタンも、該酸化チタンとして好適に使用できる。 Of these photocatalytic materials, titanium oxide is preferable because it is non-toxic and excellent in chemical stability, and the hydrophilicity of titanium oxide itself is greatly enhanced by light irradiation. As the titanium oxide, any crystal form of anatase type, rutile type and brookite type may be used. Further, the above nitrogen-doped titanium oxide and oxygen-deficient titanium oxide that are responsive to visible light can be suitably used as the titanium oxide.
本発明においては、上記光触媒(A)を、後述する少なくとも1種の変性剤化合物(b)を用いて変性処理した変性光触媒(A1)を用いることが好ましい。 In the present invention, it is preferable to use a modified photocatalyst (A1) obtained by modifying the photocatalyst (A) with at least one modifier compound (b) described later.
本発明において光触媒(A)の変性とは、後述する少なくとも1種の変性剤化合物(b)を、光触媒(A)粒子の表面に固定化することを意味する。変性剤化合物(b)の光触媒(A)粒子の表面への固定化は、ファン・デル・ワールス力(物理吸着)やクーロン力又は化学結合によるものと考えられる。特に、化学結合を利用した変性は、変性剤化合物(b)と光触媒(A)との相互作用が強く、変性剤化合物(b)が光触媒(A)粒子の表面に強固に固定化されるので好ましい。 In the present invention, the modification of the photocatalyst (A) means that at least one modifier compound (b) described later is immobilized on the surface of the photocatalyst (A) particles. The immobilization of the modifier compound (b) on the surface of the photocatalyst (A) particles is considered to be due to van der Waals force (physical adsorption), Coulomb force or chemical bonding. In particular, modification using chemical bonds has a strong interaction between the modifier compound (b) and the photocatalyst (A), and the modifier compound (b) is firmly immobilized on the surface of the photocatalyst (A) particles. preferable.
本発明においては、光触媒(A)を変性光触媒(A1)とすることにより、面発光体上に、上記光触媒(A)を含む光触媒層を形成する場合に、該光触媒層中における光触媒(A)の濃度が、面発光体に接する側から他方の露出面に向かって高くなる構造の形成が、特に後述するバインダー成分(B)と組み合わせた場合に容易になるため、非常に好ましい。 In the present invention, when the photocatalyst (A) is the modified photocatalyst (A1) to form a photocatalyst layer containing the photocatalyst (A) on the surface light emitter, the photocatalyst (A) in the photocatalyst layer is formed. It is very preferable to form a structure in which the concentration of the light source increases from the side in contact with the surface light emitter toward the other exposed surface, particularly when combined with the binder component (B) described later.
本発明においては、変性に用いる光触媒(A)の性状が、変性光触媒(A1)の分散安定性、成膜性、及び種々の機能の発現にとって重要な因子となる。即ち、変性に使用される光触媒(A)としては、一次粒子と二次粒子との混合物の数平均分散粒子径が400nm以下の光触媒が変性後の光触媒の表面特性を有効に利用できるために好ましい。特に数平均分散粒子径が100nm以下の光触媒を使用した場合、生成する変性光触媒(A1)と後述するバインダー成分(B)を含む光触媒組成物(C)から形成された光触媒層では、変性光触媒(A1)を効率的に光触媒層の表面(露出面)に存在させることができるため非常に好ましい。より好ましくは80nm以下3nm以上、更に好ましくは50nm以下3nm以上の光触媒(A)が好適に選択される。 In the present invention, the properties of the photocatalyst (A) used for modification are important factors for the dispersion stability of the modified photocatalyst (A1), film-forming properties, and expression of various functions. That is, as the photocatalyst (A) used for modification, a photocatalyst having a number average dispersed particle size of a mixture of primary particles and secondary particles of 400 nm or less is preferable because the surface characteristics of the modified photocatalyst can be effectively used. . In particular, when a photocatalyst having a number average dispersed particle size of 100 nm or less is used, in the photocatalyst layer formed from the photocatalyst composition (C) containing the modified photocatalyst (A1) to be generated and the binder component (B) described later, the modified photocatalyst ( A1) can be efficiently present on the surface (exposed surface) of the photocatalyst layer, which is very preferable. More preferably, the photocatalyst (A) having a thickness of 80 nm or less and 3 nm or more, and more preferably 50 nm or less and 3 nm or more is suitably selected.
これらの光触媒(A)としては、以下の理由から、光触媒粉体ではなく光触媒ゾルを使用することが好ましい。 As these photocatalysts (A), it is preferable to use a photocatalyst sol instead of a photocatalyst powder for the following reasons.
一般に微細な粒子からなる粉体は、単結晶粒子(一次粒子)が強力に凝集した二次粒子を形成するため、無駄にする表面特性が多いが、一次粒子にまで分散させるのは非常に困難である。これに対して、光触媒ゾルの場合、光触媒粒子は溶解せずに一次粒子に近い形で存在しているため表面特性を有効に利用でき、それから生成する変性光触媒は分散安定性、成膜性等に優れるばかりか、種々の機能を有効に発現するので好ましく使用することができる。ここで、本発明に用いる光触媒ゾルとは、光触媒(A)粒子が水及び/又は有機溶媒中に0.01〜70質量%、好ましくは0.1〜50質量%で一次粒子及び/又は二次粒子として分散されたものである。 In general, powders composed of fine particles form secondary particles in which single crystal particles (primary particles) are strongly agglomerated, so there are many surface properties that are wasted, but it is very difficult to disperse to primary particles. It is. On the other hand, in the case of a photocatalyst sol, the photocatalyst particles do not dissolve but exist in a form close to primary particles, so that the surface characteristics can be used effectively. It can be preferably used because it effectively exhibits various functions. Here, the photocatalyst sol used in the present invention means that the photocatalyst (A) particles are 0.01 to 70% by mass, preferably 0.1 to 50% by mass in water and / or an organic solvent, and primary particles and / or secondary particles. Dispersed as secondary particles.
ここで、上記光触媒ゾルに使用される上記有機溶媒としては、例えばエチレングリコール、ブチルセロソルブ、n−プロパノール、イソプロパノール、n−ブタノール、エタノール、メタノール等のアルコール類、トルエンやキシレン等の芳香族炭化水素類、ヘキサン、シクロヘキサン、ヘプタン等の脂肪族炭化水素類、酢酸エチル、酢酸n−ブチル等のエステル類、アセトン、メチルエチルケトン、メチルイソブチルケトン等のケトン類、テトラヒドロフラン、ジオキサン等のエーテル類、ジメチルアセトアミド、ジメチルホルムアミド等のアミド類、クロロホルム、塩化メチレン、四塩化炭素等のハロゲン化合物類、ジメチルスルホキシド、ニトロベンゼン等、更にはこれらの2種以上の混合物が挙げられる。 Here, examples of the organic solvent used in the photocatalyst sol include alcohols such as ethylene glycol, butyl cellosolve, n-propanol, isopropanol, n-butanol, ethanol and methanol, and aromatic hydrocarbons such as toluene and xylene. , Aliphatic hydrocarbons such as hexane, cyclohexane and heptane, esters such as ethyl acetate and n-butyl acetate, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, ethers such as tetrahydrofuran and dioxane, dimethylacetamide, dimethyl Examples include amides such as formamide, halogen compounds such as chloroform, methylene chloride, and carbon tetrachloride, dimethyl sulfoxide, nitrobenzene, and a mixture of two or more of these.
該光触媒ゾルとして酸化チタンのゾルを例にとると、例えば実質的に水を分散媒とし、その中に酸化チタン粒子が解膠された酸化チタンヒドロゾル等を挙げることができる。(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質量%程度以上含有されていることを意味する。)かかるゾルの調整は公知であり、容易に製造できる(特開昭63−17221号公報、特開平7−819号公報、特開平9−165218号公報、特開平11−43327号公報等参照)。例えば、硫酸チタンや四塩化チタンの水溶液を加熱加水分解して生成したメタチタン酸をアンモニア水で中和し、析出した含水酸化チタンを濾別、洗浄、脱水させると酸化チタン粒子の凝集物が得られる。この凝集物を、硝酸、塩酸、又はアンモニア等の作用の下に解膠させ水熱処理等を行うことにより酸化チタンヒドロゾルが得られる。また、酸化チタンヒドロゾルとしては、酸化チタン粒子を酸やアルカリの作用の下で解膠させたものや、酸やアルカリを使用せず、必要に応じてポリアクリル酸ソーダなどの分散安定剤を使用し、強力なせん断力の下で水中に分散させたゾルも用いることができる。更に、pHが中性付近の水溶液中においても分散安定性に優れる、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も特開平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。 Taking a titanium oxide sol as an example of the photocatalyst sol, for example, a titanium oxide hydrosol in which water is substantially used as a dispersion medium and titanium oxide particles are peptized therein can be exemplified. (Here, substantially using water as a dispersion medium means that water is contained in the dispersion medium in an amount of about 80% by mass or more.) Adjustment of such a sol is known and can be easily produced ( (See JP-A-63-17221, JP-A-7-819, JP-A-9-165218, JP-A-11-43327, etc.). For example, metatitanic acid produced by heating and hydrolyzing an aqueous solution of titanium sulfate or titanium tetrachloride is neutralized with aqueous ammonia, and the precipitated hydrous titanium oxide is filtered, washed, and dehydrated to obtain aggregates of titanium oxide particles. It is done. Titanium oxide hydrosol can be obtained by peptizing the agglomerates under the action of nitric acid, hydrochloric acid, ammonia or the like and performing hydrothermal treatment. In addition, as titanium oxide hydrosol, titanium oxide particles are peptized under the action of acid or alkali, or dispersion stabilizer such as sodium polyacrylate is used as required without using acid or alkali. Sols that are used and dispersed in water under strong shear forces can also be used. Furthermore, an anatase-type titanium oxide sol having excellent dispersion stability even in an aqueous solution having a pH near neutral and having a particle surface modified with a peroxo group can be easily obtained by the method proposed in JP-A-10-67516. it can.
上述した酸化チタンヒドロゾルはチタニアゾルとして市販されている(例えば、石原産業株式会社製「STS−02」、田中転写株式会社製「TO−240」等)。 The titanium oxide hydrosol described above is commercially available as a titania sol (for example, “STS-02” manufactured by Ishihara Sangyo Co., Ltd., “TO-240” manufactured by Tanaka Transcription Co., Ltd., etc.).
上記酸化チタンヒドロゾル中の酸化チタンは好ましくは50質量%以下、好ましくは30質量%以下である。更に好ましくは30質量%以下0.1質量%以上である。 The titanium oxide in the titanium oxide hydrosol is preferably 50% by mass or less, and preferably 30% by mass or less. More preferably, it is 30 mass% or less and 0.1 mass% or more.
このようなヒドロゾルの粘度(20℃)は比較的低い。本発明においては、ヒドロゾルの粘度は、0.5mPa・s〜2000mPa・s程度の範囲にあるのが好ましい。より好ましくは1mPa・s〜1000mPa・s、更に好ましくは1mPa・s〜500mPa・sである。 Such hydrosols have a relatively low viscosity (20 ° C.). In the present invention, the viscosity of the hydrosol is preferably in the range of about 0.5 mPa · s to 2000 mPa · s. More preferably, it is 1 mPa * s-1000 mPa * s, More preferably, it is 1 mPa * s-500 mPa * s.
また、例えば酸化セリウムゾル(特開平8−59235号公報参照)やTi、Nb、Ta、Vよりなる群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号公報等参照)等、様々な光触媒ゾルの製造方法についても酸化チタンゾルと同様に知られている。 Further, for example, a cerium oxide sol (see JP-A-8-59235) or a layered oxide sol having at least one element selected from the group consisting of Ti, Nb, Ta, and V (JP-A-9-25123). The manufacturing method of various photocatalytic sols such as JP-A-9-67124, JP-A-9-227122, JP-A-9-227123, JP-A-10-259023, etc.) is the same as that of titanium oxide sol. Known to.
また、実質的に有機溶媒を分散媒とし、その中に光触媒粒子が分散された光触媒オルガノゾルは、例えば上記光触媒ヒドロゾルをポリエチレングリコール類の如き相間移動活性を有する化合物(異なる第1の相と第2相との界面に第3の相を形成し、第1の相、第2の相、第3の相を相互に溶解及び/又は可溶化する化合物)で処理し有機溶媒で希釈したり(特開平10−167727号公報)、ドデシルベンゼンスルホン酸ナトリウム等の陰イオン界面活性剤で水に不溶性の有機溶剤中に分散移行させてゾルを調整する方法(特開昭58−29863号公報)やブチルセロソルブ等の水より高沸点のアルコール類を上記光触媒ヒドロゾルに添加した後、水を(減圧)蒸留等によって除去する方法等により得ることができる。また、実質的に有機溶媒を分散媒とし、その中に酸化チタン粒子が分散された酸化チタンオルガノゾルは市販されている(例えば、テイカ株式会社製「TKS−251」)。ここで、実質的に有機溶媒を分散媒とするとは、分散媒中に有機溶媒が80質量%程度以上含有されていることを意味する。 In addition, a photocatalyst organosol in which an organic solvent is substantially used as a dispersion medium and in which photocatalyst particles are dispersed is a compound having a phase transfer activity such as polyethylene glycol (for example, different first phase and second phase). A third phase is formed at the interface with the phase, the first phase, the second phase, the third phase are mutually dissolved and / or solubilized compounds) and diluted with an organic solvent (special (Kaihei 10-167727), a method of preparing a sol by dispersing and transferring it in an organic solvent insoluble in water using an anionic surfactant such as sodium dodecylbenzenesulfonate (Japanese Patent Laid-Open No. 58-29863) or butyl cellosolve After adding alcohols having a boiling point higher than water, such as water, to the photocatalyst hydrosol, the water can be obtained by a method of removing the water by (vacuum) distillation or the like. In addition, a titanium oxide organosol in which an organic solvent is substantially used as a dispersion medium and titanium oxide particles are dispersed therein is commercially available (for example, “TKS-251” manufactured by Teika Co., Ltd.). Here, substantially using an organic solvent as a dispersion medium means that the dispersion medium contains about 80% by mass or more of the organic solvent.
本発明において、変性光触媒(A1)を得るのに用いられる少なくとも1種の変性剤化合物(b)は、下記式(1)で表されるトリオルガノシラン単位、式(2)で表されるモノオキシジオルガノシラン単位、式(3)で表されるジオキシオルガノシラン単位、及びフッ化メチレン(−CF2−)単位よりなる群から選ばれる少なくとも1種の構造単位を有する化合物類よりなる群から選ばれる。 In the present invention, the at least one modifier compound (b) used to obtain the modified photocatalyst (A1) is a triorganosilane unit represented by the following formula (1), a monoorganism represented by the formula (2). A group consisting of compounds having at least one structural unit selected from the group consisting of an oxydiorganosilane unit, a dioxyorganosilane unit represented by formula (3), and a methylene fluoride (—CF 2 —) unit. Chosen from.
R3Si− (1)
−(R2SiO)− (2)
R 3 Si- (1)
- (R 2 SiO) - ( 2)
上述した構造単位を有する変性剤化合物(b)で光触媒粒子表面が変性処理された変性光触媒(A1)は、その粒子表面の表面エネルギーが非常に小さくなる。 In the modified photocatalyst (A1) in which the surface of the photocatalyst particle is modified with the modifier compound (b) having the structural unit described above, the surface energy of the particle surface becomes very small.
本発明において、光触媒(A)の変性剤化合物(b)による変性処理は、水及び/又は有機溶媒の存在下或いは非存在下において、前述した光触媒(A)と、同じく前述した変性剤化合物(b)を好ましくは質量比(A)/(b)=1/99〜99.9/0.1、より好ましくは(A)/(b)=10/90〜99/1の割合で混合し、好ましくは0〜200℃、より好ましくは10〜80℃にて加熱したり、(減圧)蒸留等により該混合物の溶媒組成を変化させる等の操作をすることにより得ることができる。 In the present invention, the modification treatment of the photocatalyst (A) with the modifier compound (b) is carried out in the presence or absence of water and / or an organic solvent in the same manner as the above-described photocatalyst (A) and the modifier compound ( b) is preferably mixed at a mass ratio (A) / (b) = 1/99 to 99.9 / 0.1, more preferably (A) / (b) = 10/90 to 99/1. It can be obtained by heating at 0 to 200 ° C., more preferably at 10 to 80 ° C., or by changing the solvent composition of the mixture by (reduced pressure) distillation or the like.
ここで、上記変性処理に使用できる有機溶媒としては、例えばトルエンやキシレン等の芳香族炭化水素類、ヘキサン、シクロヘキサン、ヘプタン等の脂肪族炭化水素類、酢酸エチル、酢酸n−ブチル等のエステル類、エチレングリコール、ブチルセロソルブ、イソプロパノール、n−ブタノール、エタノール、メタノール等のアルコール類、アセトン、メチルエチルケトン、メチルイソブチルケトン等のケトン類、テトラヒドロフラン、ジオキサン等のエーテル類、ジメチルアセトアミド、ジメチルホルムアミド等のアミド類、クロロホルム、塩化メチレン、四塩化炭素等のハロゲン化合物類、ジメチルスルホキシド、ニトロベンゼン等やこれらの2種以上の混合物が挙げられる。 Here, examples of the organic solvent that can be used for the modification treatment include aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as hexane, cyclohexane, and heptane, and esters such as ethyl acetate and n-butyl acetate. Alcohols such as ethylene glycol, butyl cellosolve, isopropanol, n-butanol, ethanol and methanol, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, ethers such as tetrahydrofuran and dioxane, amides such as dimethylacetamide and dimethylformamide, Examples include halogen compounds such as chloroform, methylene chloride, and carbon tetrachloride, dimethyl sulfoxide, nitrobenzene, and a mixture of two or more thereof.
本発明に用いられる変性光触媒(A1)を得るのに使用される上記変性剤化合物(b)としては、例えばSi−H基、加水分解性シリル基(アルコキシシリル基、ヒドロキシシリル基、ハロゲン化シリル基、アセトキシシリル基、アミノキシシリル基等)、エポキシ基、アセトアセチル基、チオール基、酸無水物基等の光触媒(A)粒子と反応性を有するケイ素化合物やフルオロアルキル化合物、フルオロオレフィン重合体等を挙げることができる。 Examples of the modifier compound (b) used to obtain the modified photocatalyst (A1) used in the present invention include Si—H groups, hydrolyzable silyl groups (alkoxysilyl groups, hydroxysilyl groups, silyl halides). Group, acetoxysilyl group, aminoxysilyl group, etc.), epoxy group, acetoacetyl group, thiol group, acid anhydride group and other photocatalyst (A) silicon compound, fluoroalkyl compound, fluoroolefin polymer having reactivity with particles Etc.
また、上記変性剤化合物(b)の他の例としては、例えばポリオキシアルキレン基等の光触媒(A)粒子とファン・デル・ワールス力、クーロン力等により相互作用する構造を有するケイ素化合物等やフルオロアルキル化合物、フルオロオレフィン重合体等を挙げることができる。 Other examples of the modifier compound (b) include, for example, silicon compounds having a structure that interacts with photocatalyst (A) particles such as polyoxyalkylene groups by van der Waals force, Coulomb force, etc. Examples thereof include a fluoroalkyl compound and a fluoroolefin polymer.
本発明において、上記変性剤化合物(b)として、下記式(4)で表されるSi−H基含有ケイ素化合物(b1)を用いると、非常に効率よく光触媒粒子表面を変性することができるため好ましい。 In the present invention, when the Si-H group-containing silicon compound (b1) represented by the following formula (4) is used as the modifier compound (b), the surface of the photocatalyst particles can be modified very efficiently. preferable.
HxRySiO(4-x-y)/2 (4)
〔上記式中、Rは各々独立に直鎖状又は分岐状の炭素数1〜30個のアルキル基、炭素数5〜20のシクロアルキル基、直鎖状又は分岐状の炭素数1〜30個のフルオロアルキル基、直鎖状又は分岐状の炭素数2〜30個のアルケニル基、フェニル基、炭素数1〜20のアルコキシ基、又は水酸基を表す。x及びyは、0<x<4、0<y<4であり、そして(x+y)≦4である。〕
H x R y SiO (4-xy) / 2 (4)
[In the above formula, each R is independently a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or a linear or branched carbon group having 1 to 30 carbon atoms. A fluoroalkyl group, a linear or branched alkenyl group having 2 to 30 carbon atoms, a phenyl group, an alkoxy group having 1 to 20 carbon atoms, or a hydroxyl group. x and y are 0 <x <4, 0 <y <4, and (x + y) ≦ 4. ]
上記式(4)で表されるSi−H基含有ケイ素化合物(b1)による光触媒(A)の変性処理は、水及び/又は有機溶媒の存在下或いは非存在下において、光触媒(A)と該Si−H基含有ケイ素化合物(b1)を好ましくは質量比(A)/(b1)=1/99〜99.9/0.1、より好ましくは(A)/(b1)=10/90〜99/1の割合で好ましくは0〜200℃にて混合することにより実施できる。この変性の操作により混合液からは水素ガスが発生すると共に、光触媒(A)として光触媒ゾルを用いた場合、その平均分散粒子径の増加が観察される。また、例えば光触媒(A)として酸化チタンを用いた場合、上記変性操作により、Ti−OH基の減少がIRスペクトルにおける3630〜3640cm-1の吸収の減少として観測される。 The modification treatment of the photocatalyst (A) with the Si—H group-containing silicon compound (b1) represented by the above formula (4) is carried out in the presence or absence of water and / or an organic solvent and the photocatalyst (A). The Si—H group-containing silicon compound (b1) is preferably a mass ratio (A) / (b1) = 1/99 to 99.9 / 0.1, more preferably (A) / (b1) = 10/90 to It can be carried out by mixing at a ratio of 99/1, preferably at 0 to 200 ° C. By this modification operation, hydrogen gas is generated from the mixed solution, and when the photocatalyst sol is used as the photocatalyst (A), an increase in the average dispersed particle size is observed. For example, when titanium oxide is used as the photocatalyst (A), a decrease in Ti—OH groups is observed as a decrease in absorption at 3630 to 3640 cm −1 in the IR spectrum by the above modification operation.
これらのことより、変性剤化合物(b)として上記式(4)で表されるSi−H基含有ケイ素化合物(b1)を選択した場合は、本発明の変性光触媒(A1)は、Si−H基含有ケイ素化合物(b1)と光触媒(A)との単なる混合物ではなく、両者の間には化学反応に伴う何らかの相互作用を生じていることが予測できるため非常に好ましい。実際、この様にして得られた変性光触媒(A1)は、有機溶媒に対する分散安定性や化学的安定性、耐久性等において非常に優れたものとなっている。 From these, when the Si-H group-containing silicon compound (b1) represented by the above formula (4) is selected as the modifier compound (b), the modified photocatalyst (A1) of the present invention is Si-H. This is very preferable because it is not a mere mixture of the group-containing silicon compound (b1) and the photocatalyst (A), but it can be predicted that some kind of interaction accompanying a chemical reaction occurs between the two. In fact, the modified photocatalyst (A1) thus obtained is very excellent in dispersion stability, chemical stability, durability and the like in an organic solvent.
また、上記式(4)で表されるSi−H基含有ケイ素化合物(b1)による光触媒(A)の変性処理は、Si−H基に対する脱水素縮合触媒を使用して好ましくは0〜150℃で実施することもできる。 Moreover, the modification treatment of the photocatalyst (A) with the Si—H group-containing silicon compound (b1) represented by the above formula (4) is preferably 0 to 150 ° C. using a dehydrogenative condensation catalyst for the Si—H group. Can also be implemented.
この場合、予め光還元法等の方法で脱水素縮合触媒を光触媒(A)に固定し、上記Si−H基含有ケイ素化合物(b1)で変性処理しても良いし、脱水素縮合触媒の存在下に上記Si−H基含有化合物ケイ素(b1)で光触媒(A)を変性処理しても良い。 In this case, the dehydrogenation condensation catalyst may be fixed to the photocatalyst (A) in advance by a method such as a photoreduction method and modified with the Si-H group-containing silicon compound (b1), or the presence of the dehydrogenation condensation catalyst. The photocatalyst (A) may be modified with the Si—H group-containing compound silicon (b1) below.
ここでSi−H基に対する脱水素縮合触媒とは、Si−H基と光触媒表面に存在する水酸基(酸化チタンの場合はTi−OH基)やチオール基、アミノ基、カルボキシル基等の活性水素基、更には水等との脱水素縮合反応を加速する物質を意味し、該脱水素縮合触媒を使用することにより温和な条件で光触媒(A)表面を変性することが可能となる。 Here, the dehydrogenative condensation catalyst for the Si-H group is an active hydrogen group such as a Si-H group and a hydroxyl group (Ti-OH group in the case of titanium oxide) existing on the photocatalyst surface, a thiol group, an amino group, or a carboxyl group. Furthermore, it means a substance that accelerates the dehydrogenation condensation reaction with water or the like, and the use of the dehydrogenation condensation catalyst makes it possible to modify the surface of the photocatalyst (A) under mild conditions.
該脱水素縮合触媒としては、例えば白金族触媒、即ちルテニウム、ロジウム、パラジウム、オスミウム、イリジウム、白金の単体及びその化合物や、銀、鉄、銅、コバルト、ニッケル、錫等の単体及びその化合物が挙げられる。これらの中で白金族触媒が好ましく、白金の単体及びその化合物が特に好ましい。 Examples of the dehydrogenative condensation catalyst include platinum group catalysts, that is, ruthenium, rhodium, palladium, osmium, iridium, platinum simple substance and compounds thereof, and simple substances such as silver, iron, copper, cobalt, nickel, tin and compounds thereof. Can be mentioned. Of these, platinum group catalysts are preferred, and platinum alone and its compounds are particularly preferred.
ここで、上記白金化合物としては、例えば塩化白金(II)、テトラクロロ白金酸(II)、塩化白金(IV)、ヘキサクロロ白金酸(IV)、ヘキサクロロ白金(IV)アンモニウム、ヘキサクロロ白金(IV)カリウム、水酸化白金(II)、二酸化白金(IV)、ジクロロ−ジシクロペンタジエニル−白金(II)、白金−ビニルシロキサン錯体、白金−ホスフィン錯体、白金−オレフィン錯体等を使用することができる。 Here, examples of the platinum compound include platinum chloride (II), tetrachloroplatinic acid (II), platinum chloride (IV), hexachloroplatinic acid (IV), hexachloroplatinum (IV) ammonium, and hexachloroplatinum (IV) potassium. Platinum (II) hydroxide, platinum (IV) dioxide, dichloro-dicyclopentadienyl-platinum (II), platinum-vinylsiloxane complex, platinum-phosphine complex, platinum-olefin complex, and the like can be used.
上記式(4)で表されるSi−H基含有ケイ素化合物において、Si−H基は光触媒(A)を穏和な条件で選択性良く変性するために好ましい官能基である。これに対し、加水分解性基は、同様に光触媒(A)の変性に利用することもできるが、副反応を抑制し、得られる変性光触媒(A1)の安定性を向上するためには、その含有量は少ない方が好ましい。 In the Si—H group-containing silicon compound represented by the above formula (4), the Si—H group is a preferred functional group for modifying the photocatalyst (A) with good selectivity under mild conditions. On the other hand, the hydrolyzable group can also be used for the modification of the photocatalyst (A), but in order to suppress side reactions and improve the stability of the resulting modified photocatalyst (A1), A smaller content is preferred.
本発明に好適に使用できる上記式(4)で表されるSi−H基含有ケイ素化合物(b1)としては、例えば下記式(5)で表されるモノSi−H基含有化合物、式(6)で表される両末端Si−H基含有化合物、式(7)で表されるHシリコーンよりなる群から選ばれる少なくとも1種の、加水分解性シリル基を有さないS−H基含有化合物を挙げることができる。 Examples of the Si—H group-containing silicon compound (b1) represented by the above formula (4) that can be suitably used in the present invention include a mono-Si—H group-containing compound represented by the following formula (5), a formula (6) At least one selected from the group consisting of Si-H group-containing compounds represented by formula (7) and H-silicone represented by formula (7), and having no hydrolyzable silyl groups Can be mentioned.
−O−(R4 2SiO)m−SiR4 3 (8)
(式中、R4はそれぞれ独立に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、直鎖状又は分岐状の炭素数が1〜30個のフルオロアルキル基、直鎖状又は分岐状の炭素数2〜30個のアルケニル基、又はフェニル基を表す。また、mは整数であり、0≦m≦1000である。)〕
H−(R3 2SiO)n−SiR3 2−H (6)
〔式中、R3は式(5)で定義した通りである。nは整数であり、0≦n≦1000である。〕
—O— (R 4 2 SiO) m —SiR 4 3 (8)
(In the formula, each R 4 is independently a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or a linear or branched carbon number of 1 to 1. 30 represents a fluoroalkyl group, a linear or branched alkenyl group having 2 to 30 carbon atoms, or a phenyl group, and m is an integer, and 0 ≦ m ≦ 1000.
H— (R 3 2 SiO) n —SiR 3 2 —H (6)
[Wherein R 3 is as defined in formula (5). n is an integer, and 0 ≦ n ≦ 1000. ]
(R3HSiO)a(R3 2SiO)b(R3 3SiO1/2)c (7)
〔式中、R3は式(5)で定義した通りである。aは1以上の整数であり、bは0以上の整数であり、(a+b)≦10000であり、そしてcは0又は2である。但し、(a+b)が2以上の整数であり且つc=0の場合、式(7)の該Hシリコーンは環状シリコーンであり、c=2の場合、式(7)の該Hシリコーンは鎖状シリコーンである。〕
(R 3 HSiO) a (R 3 2 SiO) b (R 3 3 SiO 1/2 ) c (7)
[Wherein R 3 is as defined in formula (5). a is an integer of 1 or more, b is an integer of 0 or more, (a + b) ≦ 10000, and c is 0 or 2. However, when (a + b) is an integer of 2 or more and c = 0, the H silicone of formula (7) is a cyclic silicone, and when c = 2, the H silicone of formula (7) is chain-like. Silicone. ]
本発明において、上記式(5)で表されるモノSi−H基含有化合物の具体例としては、例えばビス(トリメチルシロキシ)メチルシラン、ビス(トリメチルシロキシ)エチルシラン、ビス(トリメチルシロキシ)n−プロピルシラン、ビス(トリメチルシロキシ)i−プロピルシラン、ビス(トリメチルシロキシ)n−ブチルシラン、ビス(トリメチルシロキシ)n−ヘキシルシラン、ビス(トリメチルシロキシ)シクロヘキシルシラン、ビス(トリメチルシロキシ)フェニルシラン、ビス(トリエチルシロキシ)メチルシラン、ビス(トリエチルシロキシ)エチルシラン、トリス(トリメチルシロキシ)シラン、トリス(トリエチルシロキシ)シラン、ペンタメチルジシロキサン、1,1,1,3,3,5,5−ヘプタメチルトリシロキサン、1,1,1,3,3,5,5,6,6−ノナメチルテトラシロキサン、トリメチルシラン、エチルジメチルシラン、メチルジエチルシラン、トリエチルシラン、フェニルジメチルシラン、ジフェニルメチルシラン、シクロヘキシルジメチルシラン、t−ブチルジメチルシラン、ジ−t−ブチルメチルシラン、n−オクタデシルジメチルシラン、トリ−n−プロピルシラン、トリ−i−プロピルシラン、トリ−i−ブチルシラン、トリ−n−ヘキシルシラン、トリフェニルシラン、アリルジメチルシラン、1−アリル−1,1,3,3−テトラメチルジシロキサン、クロロメチルジメチルシラン、7−オクテニルジメチルシラン等を挙げることができる。
In the present invention, specific examples of the mono-Si—H group-containing compound represented by the above formula (5) include, for example, bis (trimethylsiloxy) methylsilane, bis (trimethylsiloxy) ethylsilane, bis (trimethylsiloxy) n-propylsilane. Bis (trimethylsiloxy) i-propylsilane, bis (trimethylsiloxy) n-butylsilane, bis (trimethylsiloxy) n-hexylsilane, bis (trimethylsiloxy) cyclohexylsilane, bis (trimethylsiloxy) phenylsilane, bis (triethylsiloxy) ) Methylsilane, bis (triethylsiloxy) ethylsilane, tris (trimethylsiloxy) silane, tris (triethylsiloxy) silane, pentamethyldisiloxane, 1,1,1,3,3,5,5-
これらのモノSi−H基含有化合物の中で、光触媒(A)の変性処理時におけるSi−H基の反応性(脱水素縮合反応)の良さや表面エネルギーの低さから、ビス(トリメチルシロキシ)メチルシラン、トリス(トリメチルシロキシ)シラン、ペンタメチルジシロキサン等の分子中にシロキシ基を有し、フェニル基を有さない下式(9)で表されるものが好ましい。 Among these mono-Si-H group-containing compounds, bis (trimethylsiloxy) has a good Si-H group reactivity (dehydrogenation condensation reaction) and low surface energy during the modification of the photocatalyst (A). Those represented by the following formula (9) having a siloxy group in the molecule, such as methylsilane, tris (trimethylsiloxy) silane, pentamethyldisiloxane and the like and having no phenyl group are preferable.
−O−(R4' 2SiO)m−SiR4' 3 (8b)
(式中、R4'はそれぞれ独立に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、又は直鎖状又は分岐状の炭素数が1〜30個のフルオロアルキル基を表す。また、mは整数であり、0≦m≦1000である。)〕
—O— (R 4 ′ 2 SiO) m —SiR 4 ′ 3 (8b)
(In the formula, each R 4 ′ is independently a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or a linear or branched carbon number. Represents 1 to 30 fluoroalkyl groups, m is an integer, and 0 ≦ m ≦ 1000.)]
本発明において、上記式(6)で表される両末端Si−H基含有化合物の具体例としては、例えば1,1,3,3−テトラメチルジシロキサン、1,1,3,3,5,5−ヘキサメチルトリシロキサン、1,1,3,3,5,5,7,7−オクタメチルテトラシロキサン等の数平均分子量50000以下のH末端ポリジメチルシロキサン類や、1,1,3,3−テトラエチルジシロキサン、1,1,3,3,5,5−ヘキサエチルトリシロキサン、1,1,3,3,5,5,7,7−オクタエチルテトラシロキサン等の数平均分子量50000以下のH末端ポリジエチルシロキサン類や、1,1,3,3−テトラフェニルジシロキサン、1,1,3,3,5,5−ヘキサフェニルトリシロキサン、1,1,3,3,5,5,7,7−オクタフェニルテトラシロキサン等の数平均分子量50000以下のH末端ポリジフェニルシロキサン類や、1,3−ジフェニル−1,3−ジメチル−ジシロキサン、1,3,5−トリメチル−1,3,5−トリフェニル−トリシロキサン、1,3,5,7−テトラメチル−1,3,5,7−テトラフェニル−テトラシロキサン等の数平均分子量50000以下のH末端ポリフェニルメチルシロキサン類や、ジメチルシラン、エチルメチルシラン、ジエチルシラン、フェニルメチルシラン、ジフェニルシラン、シクロヘキシルメチルシラン、t−ブチルメチルシラン、ジ−t−ブチルシラン、n−オクタデシルメチルシラン、アリルメチルシラン等を例示することができる。 In the present invention, specific examples of the both-terminal Si—H group-containing compound represented by the above formula (6) include 1,1,3,3-tetramethyldisiloxane, 1,1,3,3,5. , 5-hexamethyltrisiloxane, 1,1,3,3,5,5,7,7-octamethyltetrasiloxane and the like H-terminal polydimethylsiloxanes having a number average molecular weight of 50000 or less, Number average molecular weight of 50,000 or less such as 3-tetraethyldisiloxane, 1,1,3,3,5,5-hexaethyltrisiloxane, 1,1,3,3,5,5,7,7-octaethyltetrasiloxane H-terminal polydiethylsiloxanes, 1,1,3,3-tetraphenyldisiloxane, 1,1,3,3,5,5-hexaphenyltrisiloxane, 1,1,3,3,5,5 , 7,7-Octaf H-terminated polydiphenylsiloxanes having a number average molecular weight of 50000 or less such as nyltetrasiloxane, 1,3-diphenyl-1,3-dimethyl-disiloxane, 1,3,5-trimethyl-1,3,5-triphenyl -H-terminal polyphenylmethylsiloxanes having a number average molecular weight of 50000 or less, such as trisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetraphenyl-tetrasiloxane, dimethylsilane, ethylmethyl Examples thereof include silane, diethylsilane, phenylmethylsilane, diphenylsilane, cyclohexylmethylsilane, t-butylmethylsilane, di-t-butylsilane, n-octadecylmethylsilane, and allylmethylsilane.
これらの中で、光触媒(A)の変性処理時におけるSi−H基の反応性(脱水素縮合反応)の良さや表面エネルギーの低さから、数平均分子量が好ましくは10000以下、より好ましくは2000以下、更に好ましくは1000以下のH末端ポリジアルキルシロキサン(式(10))が両末端Si−H基含有化合物として好適に使用できる。 Among these, the number average molecular weight is preferably 10,000 or less, more preferably 2000 from the good reactivity of the Si—H group (dehydrogenation condensation reaction) and low surface energy during the modification treatment of the photocatalyst (A). Hereinafter, more preferably 1000 or less H-terminated polydialkylsiloxane (formula (10)) can be suitably used as the Si-H group-containing compound at both ends.
H−(R6 2SiO)d−SiR6 2−H (10)
〔式中、R6はそれぞれ独立に直鎖状又は分岐状の炭素数が1〜30個のアルキル基、直鎖状又は分岐状の炭素数が1〜30個のフルオロアルキル基を表す。dは整数であり、0≦d≦1000である。〕
H— (R 6 2 SiO) d —SiR 6 2 —H (10)
[In the formula, each R 6 independently represents a linear or branched alkyl group having 1 to 30 carbon atoms, or a linear or branched fluoroalkyl group having 1 to 30 carbon atoms. d is an integer, and 0 ≦ d ≦ 1000. ]
本発明に用いる上記式(7)で表されるHシリコーンとしては、光触媒(A)の変性処理時における分散安定性(光触媒粒子の凝集の防止)の点より、数平均分子量が好ましくは5000以下、より好ましくは2000以下、更に好ましくは1000以下のHシリコーンが好適に使用できる。 The H silicone represented by the above formula (7) used in the present invention preferably has a number average molecular weight of 5000 or less from the viewpoint of dispersion stability (prevention of aggregation of photocatalyst particles) during the modification treatment of the photocatalyst (A). More preferably, 2000 or less, and still more preferably 1000 or less H silicone can be suitably used.
また、本発明に用いられる変性光触媒(A1)の好ましい形態は、変性光触媒(A1)の一次粒子と二次粒子との混合物の数平均分散粒子径が400nm以下、更に好ましくは1nm以上100nm以下、特に好ましくは5nm以上80nm以下である。ゾルの状態であることが好ましい。 The modified photocatalyst (A1) used in the present invention preferably has a number average dispersed particle size of a mixture of primary particles and secondary particles of the modified photocatalyst (A1) of 400 nm or less, more preferably 1 nm to 100 nm. Especially preferably, they are 5 nm or more and 80 nm or less. A sol state is preferable.
また、特に数平均分散粒子径が100nm以下の変性光触媒ゾルを光触媒組成物(C)に用いると、変性光触媒(A1)粒子の濃度が面発光体と接する界面近傍では小さく、光触媒層の表面近傍では大きく分布するような表面方向に異方分布した光触媒層を形成するのに有利となり、光触媒作用による面発光体との界面劣化が無く、光触媒活性が大きい光触媒層を形成するため非常に好ましい。この様な変性光触媒ゾルは、上記変性剤化合物(b)で変性処理をする光触媒(A)として前述した光触媒ゾルを用いることにより得ることができる。 In particular, when a modified photocatalyst sol having a number average dispersed particle size of 100 nm or less is used for the photocatalyst composition (C), the concentration of the modified photocatalyst (A1) particles is small in the vicinity of the interface in contact with the surface light emitter, and in the vicinity of the surface of the photocatalyst layer. Then, it is advantageous to form a photocatalyst layer that is anisotropically distributed in the surface direction, which is widely distributed, and it is very preferable because a photocatalyst layer having high photocatalytic activity is formed without interfacial deterioration with a surface light emitter due to photocatalytic action. Such a modified photocatalyst sol can be obtained by using the above-mentioned photocatalyst sol as the photocatalyst (A) that is modified with the above modifier compound (b).
尚、従来、二酸化チタンなどで単に粒径として表示されている数値は、多くの場合一次粒子径(結晶子径)であり、凝集による二次粒子径を考慮した数値ではない。 Conventionally, a numerical value simply indicated as a particle size in titanium dioxide or the like is a primary particle diameter (crystallite diameter) in many cases, and is not a numerical value considering a secondary particle diameter due to aggregation.
本発明に係る光触媒層を形成する光触媒組成物(C)は、光触媒(A)(好ましくは変性光触媒(A1))とバインダー成分(B)を含むことを特徴とし、その質量比(A1)/(B)は0.1/99.9〜90/10であることが好ましく、(A1)/(B)が1/99〜50/50で含むことがより好ましい。 The photocatalyst composition (C) forming the photocatalyst layer according to the present invention comprises a photocatalyst (A) (preferably a modified photocatalyst (A1)) and a binder component (B), and its mass ratio (A1) / (B) is preferably 0.1 / 99.9 to 90/10, and more preferably (A1) / (B) is included at 1/99 to 50/50.
本発明に用いられる変性光触媒(A1)は、表面エネルギーの非常に小さい構造(前記式(1)〜(3))を有する変性剤化合物(b)で変性処理されているため、光触媒層を形成する際、空気と接する側の表面に移動しやすい性質を持っている。 Since the modified photocatalyst (A1) used in the present invention is modified with the modifier compound (b) having a structure having a very small surface energy (the above formulas (1) to (3)), a photocatalytic layer is formed. When moving, it has the property of easily moving to the surface on the side in contact with air.
ここで、本発明のバインダー成分(B)として、光触媒(A)、特に該変性光触媒(A1)より表面エネルギーが高いバインダー樹脂(B’)を用いることにより、変性光触媒(A1)の上記性質を助長するため、本発明に係る光触媒組成物(C)は、光触媒(A)、特に変性光触媒(A1)の分布について大きな自己傾斜性を有することが可能となる。ここで自己傾斜性とは、光触媒組成物(C)から光触媒層を形成する際、その形成過程において光触媒(A)、特に変性光触媒(A1)が、光触媒層が接する界面の性状(特に親水/疎水性)に対応して、光触媒(A)、特に変性光触媒(A1)の濃度勾配を有する構造を自律的に形成することを意味する。 Here, as the binder component (B) of the present invention, by using the photocatalyst (A), particularly the binder resin (B ′) having a surface energy higher than that of the modified photocatalyst (A1), the above properties of the modified photocatalyst (A1) can be obtained. In order to promote, the photocatalyst composition (C) according to the present invention can have a large self-gradient with respect to the distribution of the photocatalyst (A), particularly the modified photocatalyst (A1). Here, the self-grading property means that when the photocatalyst layer is formed from the photocatalyst composition (C), the photocatalyst (A), particularly the modified photocatalyst (A1) in the formation process, is the property of the interface (especially hydrophilic / Corresponding to (hydrophobic), it means that a structure having a concentration gradient of the photocatalyst (A), particularly the modified photocatalyst (A1) is autonomously formed.
本発明に用いられるバインダー成分(B)としては、光触媒(A)(好ましくは変性光触媒(A1))より、表面エネルギーが2mN/m以上、好ましくは5mN/m以上大きい樹脂を選択すると、上記自己傾斜性が大きくなり非常に好ましい。 As the binder component (B) used in the present invention, when a resin having a surface energy of 2 mN / m or more, preferably 5 mN / m or more larger than the photocatalyst (A) (preferably the modified photocatalyst (A1)) is selected, It is very preferable because the gradient is increased.
ここで、上記表面エネルギーや表面エネルギーの相対差は、例えばPolymer Handbook(米国,A Wiley−interscience publication出版)等を参照したり、以下の方法で測定したりすることにより求めることができる。 Here, the surface energy and the relative difference between the surface energies can be obtained by referring to, for example, Polymer Handbook (published by A Wiley-interscience publication) in the United States, or by measuring by the following method.
即ち、上記光触媒組成物(C)を構成する光触媒(A)、特に変性光触媒(A1)及びバインダー成分(B)から各々それらの層を有する基材を調整し、脱イオン水を滴下して20℃における接触角(θ)を測定し、下記のSellとNeumannの実験式により、各々の表面エネルギーを求めることができる。 That is, a substrate having these layers is prepared from the photocatalyst (A), particularly the modified photocatalyst (A1) and the binder component (B) constituting the photocatalyst composition (C), and deionized water is added dropwise to prepare 20 The contact angle (θ) at ° C. is measured, and the surface energy of each can be obtained by the following empirical formulas for Sell and Neumann.
本発明に用いられる光触媒組成物(C)において、バインダー成分(B)に使用できる化合物としては、上記条件を満たす表面エネルギーを有すればよく、特に制限されないが、各種単量体、合成樹脂及び天然樹脂等が挙げられ、また被膜の形成後に、乾燥、加熱、吸湿、光照射等により硬化するものも挙げることができる。また、その形態については、無溶媒の状態(ペレット、粉体、液体等)であっても溶媒に溶解或いは分散した形態であっても良く、特に制限はない。 In the photocatalyst composition (C) used in the present invention, the compound that can be used for the binder component (B) is not particularly limited as long as it has a surface energy that satisfies the above conditions. Examples thereof include natural resins, and examples thereof include those that are cured by drying, heating, moisture absorption, light irradiation, and the like after the formation of the film. Further, the form thereof may be in a solvent-free state (pellets, powder, liquid, etc.) or may be dissolved or dispersed in a solvent, and is not particularly limited.
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。 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.
また、上記天然高分子としては、ニトロセルロース等のセルロース系樹脂、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やでんぷん等を挙げることができる。 Examples of the natural polymer include cellulose resins such as nitrocellulose, isoprene resins such as natural rubber, protein resins such as casein, and starch.
本発明において、光触媒組成物(C)に使用するバインダー成分(B)としては、下記式(11)で表されるフェニル基含有シリコーン(BP)が、本発明の変性光触媒(A1)より表面エネルギーが高く、その骨格を成すシロキサン結合(−O−Si−)は光触媒作用による酸化分解が起こらないため、最も好適に使用できる。 In the present invention, as the binder component (B) used in the photocatalyst composition (C), the phenyl group-containing silicone (BP) represented by the following formula (11) is more surface energy than the modified photocatalyst (A1) of the present invention. Since the siloxane bond (—O—Si—) constituting the skeleton does not undergo oxidative decomposition due to photocatalysis, it can be most preferably used.
R1 pR2 qXrSiO(4-p-q-r)/2 (11)
〔式中、各R1はフェニル基を表し、R2は各々独立に直鎖状又は分岐状の炭素数1〜30のアルキル基、炭素数5〜20のシクロアルキル基、又は直鎖状又は分岐状の炭素数2〜30個のアルケニル基を表す。Xは、各々独立に水素原子、水酸基、炭素数1〜20のアルコキシ基、炭素数1〜20のアシロキシ基、アミノキシ基、炭素数1〜20のオキシム基、ハロゲン原子を表す。そしてp、q及びrは、0<p<4、0≦q<4、0≦r<4、及び0<(p+q+r)<4であり、そして0.05≦p/(p+q)≦1である。〕
R 1 p R 2 q X r SiO (4-pqr) / 2 (11)
[Wherein, each R 1 represents a phenyl group, and each R 2 independently represents a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or a linear or A branched alkenyl group having 2 to 30 carbon atoms is represented. X represents a hydrogen atom, a hydroxyl group, a C1-C20 alkoxy group, a C1-C20 acyloxy group, an aminoxy group, a C1-C20 oxime group, and a halogen atom each independently. And p, q and r are 0 <p <4, 0 ≦ q <4, 0 ≦ r <4, and 0 <(p + q + r) <4, and 0.05 ≦ p / (p + q) ≦ 1 is there. ]
上記式(11)で示されるフェニル基含有シリコーン(BP)としては、例えば一般式(12)、(13)、(14)及び(15)で表されるシロキサン結合の少なくとも1種の構造を含むシリコーンを挙げることができる。 Examples of the phenyl group-containing silicone (BP) represented by the above formula (11) include at least one structure of a siloxane bond represented by the general formulas (12), (13), (14), and (15). Mention may be made of silicone.
−(R7 2SiO)− (13) — (R 7 2 SiO) — (13)
上述した構造を含むシリコーンは、例えば一般式R7SiX3〔式中、R7は、フェニル基、直鎖状又は分岐状の炭素数1〜30のアルキル基、炭素数5〜20のシクロアルキル基を表す。各Xは、各々独立に水素原子、水酸基、炭素数1〜20のアルコキシ基、炭素数1〜20のアシロキシ基、アミノキシ基、炭素数1〜20のオキシム基、ハロゲン原子からなる群より選ばれる一つの反応性基を表す。以下同様。〕で表される3官能シラン誘導体及び/又は一般式R7 2SiX2で表される2官能シラン誘導体及び/又は一般式SiX4で表される4官能シラン誘導体を部分的に加水分解・縮重合させ、必要により一般式R7 3SiXで表される1官能シラン誘導体及び/又はアルコール類によって末端停止させることにより調製できる。この様にして得られるシラン誘導体モノマーの部分縮合物のポリスチレン換算重量平均分子量は、好ましくは100〜100,000、より好ましくは400〜50,000である。 The silicone containing the structure described above is, for example, a general formula R 7 SiX 3 [wherein R 7 is a phenyl group, a linear or branched alkyl group having 1 to 30 carbon atoms, or a cycloalkyl group having 5 to 20 carbon atoms. Represents a group. Each X is independently selected from the group consisting of a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, an acyloxy group having 1 to 20 carbon atoms, an aminoxy group, an oxime group having 1 to 20 carbon atoms, and a halogen atom. Represents one reactive group. The same applies below. ] Partially hydrolyzed / condensed trifunctional silane derivative and / or bifunctional silane derivative represented by general formula R 7 2 SiX 2 and / or tetrafunctional silane derivative represented by general formula SiX 4 It can be prepared by polymerizing and, if necessary, terminating with a monofunctional silane derivative represented by the general formula R 7 3 SiX and / or alcohols. The polystyrene-converted weight average molecular weight of the partial condensate of the silane derivative monomer thus obtained is preferably 100 to 100,000, more preferably 400 to 50,000.
これらの中で、上記式(11)で示されるフェニル基含有シリコーンとして、上記式(12)で表されるラダー構造を10モル%以上、好ましくは40モル%以上含むものを選択すると、本発明に係る光触媒組成物(C)から形成される光触媒層は、硬度、耐熱性、耐候性、耐汚染性、耐薬品性等の点で非常に優れたものとなるため好ましい。特に、上記ラダー構造としてフェニルラダー構造(式(12)におけるR7が全てフェニル基のもの)を有するものは上述した光触媒含有光触媒層の物性が非常に向上するため好ましい。この様なラダー構造は、例えば赤外線吸収スペクトルにおける1040cm-1と1160cm-1付近の2本のシロキサン結合に由来する吸収の存在により同定する事ができる(J.F.Brown.Jr.,etal.,:J.Am.Chem.Soc.,82,6194(1960)参照。)。 Among these, when the phenyl group-containing silicone represented by the above formula (11) is selected to contain a ladder structure represented by the above formula (12) of 10 mol% or more, preferably 40 mol% or more, the present invention The photocatalyst layer formed from the photocatalyst composition (C) according to the above is preferable because it is very excellent in terms of hardness, heat resistance, weather resistance, stain resistance, chemical resistance, and the like. In particular, the ladder structure having a phenyl ladder structure (all R 7 in Formula (12) is a phenyl group) is preferable because the physical properties of the photocatalyst-containing photocatalyst layer described above are greatly improved. Such ladder structure, for example can be identified by the presence of absorption derived from two siloxane bonds near 1040 cm -1 and 1160 cm -1 in the infrared absorption spectrum (J.F.Brown.Jr., Etal. ,: J. Am. Chem. Soc., 82, 6194 (1960)).
本発明に用いる上記式(11)で表されるフェニル基含有シリコーン(BP)は、Ph−Si結合(Ph:フェニル基)を有することが好ましい。 The phenyl group-containing silicone (BP) represented by the above formula (11) used in the present invention preferably has a Ph—Si bond (Ph: phenyl group).
即ち、本発明に係る光触媒組成物(C)において、表面エネルギーの非常に小さい構造(式(1)〜(3))を有する変性剤化合物(b)で変性処理されている変性光触媒(A1)のバインダーとして、該変性光触媒(A1)より表面エネルギーが高いフェニル基含有シリコーン(BP)を含むバインダー成分(B)を用いることにより、光触媒組成物(C)は変性光触媒(A1)の分布について高い自己傾斜性を有することが可能となる。 That is, in the photocatalyst composition (C) according to the present invention, the modified photocatalyst (A1) modified with the modifier compound (b) having a structure (formulas (1) to (3)) having a very small surface energy. By using the binder component (B) containing a phenyl group-containing silicone (BP) having a surface energy higher than that of the modified photocatalyst (A1) as the binder, the photocatalyst composition (C) has a high distribution of the modified photocatalyst (A1). It becomes possible to have a self-tilting property.
この様な表面エネルギーの高いフェニル基含有シリコーン(BP)による自己傾斜性の発現効果は、フェニル基(R1)を、フェニル基(R1)とR2〔R2は直鎖状又は分岐状の炭素数1〜30のアルキル基、炭素数5〜20のシクロアルキル基、炭素数2〜20のアルケニル基を表す。〕の合計{以下(R1+R2)と表す。}に対し5モル%以上有する上記式(11)で示されるフェニル基含有シリコーン(BP)を用いることによってより顕著に発揮することができるので、このようなフェニル基含有シリコーン(BP)を用いることは好ましい。 Such a self-gradient expression effect by the phenyl group-containing silicone (BP) having a high surface energy is obtained by converting the phenyl group (R 1 ) into the phenyl group (R 1 ) and R 2 [R 2 is linear or branched. Represents an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, and an alkenyl group having 2 to 20 carbon atoms. ] {Represented as (R 1 + R 2 ) below. }, A phenyl group-containing silicone (BP) represented by the above formula (11) having 5 mol% or more of Is preferred.
また、上述した自己傾斜性の発現効果は、フェニル基(R1)の(R1+R2)に対する割合が増えるに従い増大する。よって、本発明の光触媒組成物に使用するバインダー成分(B)のフェニル基含有シリコーンとしてより好ましいものは、(R1+R2)に対するフェニル基(R1)の割合が10モル%以上、更に好ましくは20モル%以上、更に好ましくは50モル%以上のものである。 In addition, the self-tilting effect described above increases as the ratio of the phenyl group (R 1 ) to (R 1 + R 2 ) increases. Therefore, a more preferable phenyl group-containing silicone of the binder component (B) used in the photocatalyst composition of the present invention has a ratio of phenyl group (R 1 ) to (R 1 + R 2 ) of 10 mol% or more, more preferably. Is 20 mol% or more, more preferably 50 mol% or more.
また、該フェニル基含有シリコーン(BP)は有機樹脂等の有機基材に対する密着性が良好であり、その骨格を成すシロキサン結合(−O−Si−)は光触媒作用による酸化分解がおこらないため、本発明の光触媒組成物(C)を面発光体にコーティングして得られる光触媒含有光触媒層は、非常に耐候性に優れたものになる。 In addition, the phenyl group-containing silicone (BP) has good adhesion to an organic substrate such as an organic resin, and the siloxane bond (—O—Si—) constituting the skeleton does not undergo oxidative decomposition due to photocatalysis, The photocatalyst-containing photocatalyst layer obtained by coating the photocatalyst composition (C) of the present invention on a surface light emitter has extremely excellent weather resistance.
本発明の光触媒組成物(C)において、バインダー成分(B)に使用するフェニル基含有シリコーン(BP)として、上述した効果を発揮するより好ましいものは、下記式(16)で表されるアルキル基を含有しないフェニル基含有シリコーン(BP1)である。 In the photocatalyst composition (C) of the present invention, the phenyl group-containing silicone (BP) used for the binder component (B) is more preferably an alkyl group represented by the following formula (16), which exhibits the above-described effects. It is a phenyl group-containing silicone (BP1) that does not contain.
R1 sXtSiO(4-s-t)/2 (16)
〔式中、R1はフェニル基を表し、Xは各々独立に水素原子、水酸基、炭素数1〜20のアルコキシ基、炭素数1〜20のアシロキシ基、アミノキシ基、炭素数1〜20のオキシム基、ハロゲン原子を表し、s及びtは、0<s<4、0≦t<4、そして0<(s+t)<4である。〕
R 1 s X t SiO (4-st) / 2 (16)
[Wherein, R 1 represents a phenyl group, and each X independently represents a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, an acyloxy group having 1 to 20 carbon atoms, an aminoxy group, or an oxime having 1 to 20 carbon atoms. Represents a group, a halogen atom, and s and t are 0 <s <4, 0 ≦ t <4, and 0 <(s + t) <4. ]
また、バインダー成分(B)が、下記式(17)で表されるアルキル基含有シリコーン(BA)を更に含有すると、本発明に係る光触媒組成物(C)から形成される光触媒層は、成膜性、硬度、耐熱性、耐汚染性、耐薬品性等の点で優れたものとなるため好ましい。 When the binder component (B) further contains an alkyl group-containing silicone (BA) represented by the following formula (17), the photocatalyst layer formed from the photocatalyst composition (C) according to the present invention is formed into a film. It is preferable because it is excellent in terms of properties, hardness, heat resistance, contamination resistance, chemical resistance and the like.
R2 uXvSiO(4-u-v)/2 (17)
〔式中、R2は各々独立に直鎖状又は分岐状の炭素数1〜30のアルキル基、炭素数5〜20のシクロアルキル基、又は直鎖状又は分岐状の炭素数2〜30個のアルケニル基を表す。Xは、各々独立に水素原子、水酸基、炭素数1〜20のアルコキシ基、炭素数1〜20のアシロキシ基、アミノキシ基、炭素数1〜20のオキシム基、ハロゲン原子を表す。u及びvは、0<u<4、0≦v<4、そして0<(u+v)<4である。〕
R 2 u X v SiO (4-uv) / 2 (17)
[In the formula, each R 2 is independently a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or a linear or branched carbon group having 2 to 30 carbon atoms. Represents an alkenyl group. X represents a hydrogen atom, a hydroxyl group, a C1-C20 alkoxy group, a C1-C20 acyloxy group, an aminoxy group, a C1-C20 oxime group, and a halogen atom each independently. u and v are 0 <u <4, 0 ≦ v <4, and 0 <(u + v) <4. ]
更に、上記フェニル基含有シリコーン(BP1)と混合する上記アルキル基含有シリコーン(BA)として、式(18)で表されるモノオキシジオルガノシラン単位(D)と式(19)で表されるジオキシオルガノシラン単位(T)を、モル比が好ましくは(D)/(T)=100/0〜5/95、より好ましくは90/10〜10/90の割合で有する構造のものを用いると、アルキル基含有シリコーン(BA)の応力緩和作用が増加し、本発明に係る光触媒組成物(C)から生成する光触媒層の耐クラック性が向上する結果、耐候性が非常に優れたものとなる。 Furthermore, as the alkyl group-containing silicone (BA) mixed with the phenyl group-containing silicone (BP1), the monooxydiorganosilane unit (D) represented by the formula (18) and the diester represented by the formula (19) are used. When the oxyorganosilane unit (T) has a structure having a molar ratio of preferably (D) / (T) = 100/0 to 5/95, more preferably 90/10 to 10/90. As a result, the stress relaxation action of the alkyl group-containing silicone (BA) is increased, and the crack resistance of the photocatalyst layer produced from the photocatalyst composition (C) according to the present invention is improved. As a result, the weather resistance is very excellent. .
−(R2 2SiO)− (18) — (R 2 2 SiO) — (18)
本発明において、長期の耐候性向上には、バインダー成分(B)が相分離構造を形成することが好ましく、特にミクロ相分離した構造を形成することが好ましい。 In the present invention, in order to improve long-term weather resistance, the binder component (B) preferably forms a phase separation structure, and particularly preferably forms a microphase separation structure.
例えば、バインダー成分(B)として、上述した光触媒(A)、特に該変性光触媒(A1)より表面エネルギーが高いバインダー樹脂(B’)と上記式(6)で表されるアルキル基含有シリコーン(BA)とを、好ましくは質量比(B’)/(BA)=5/95〜95/5、より好ましくは(B’)/(BA)=30/70〜90/10で混合したものを用いると、本発明に係る光触媒組成物(C)から形成される光触媒層は、表面エネルギーが高いバインダー樹脂(B’)とアルキル基含有シリコーン(BA)が相分離したバインダー中に光触媒(A)が分散した構造となり、長期の耐候性に優れたものとなるため好ましい。 For example, as the binder component (B), the above-described photocatalyst (A), particularly the binder resin (B ′) having a higher surface energy than the modified photocatalyst (A1) and the alkyl group-containing silicone (BA) represented by the above formula (6) ), Preferably in a mass ratio (B ′) / (BA) = 5/95 to 95/5, more preferably (B ′) / (BA) = 30/70 to 90/10 The photocatalyst layer formed from the photocatalyst composition (C) according to the present invention has a photocatalyst (A) in a binder in which a binder resin (B ′) and an alkyl group-containing silicone (BA) having a high surface energy are phase-separated. A dispersed structure is preferable because it has excellent long-term weather resistance.
ここで、表面エネルギーが高いバインダー成分(B’)とアルキル基含有シリコーン(BA)の相分離は、連続層でない相が好ましくは1nm3〜1μm3、より好ましくは10nm3〜0.1μm3、更に好ましくは10nm3〜0.001μm3の大きさのドメインを形成してミクロ相分離した場合に、より効果を奏する。 Here, the phase separation between the binder component (B ′) having a high surface energy and the alkyl group-containing silicone (BA) is preferably a phase that is not a continuous layer, preferably 1 nm 3 to 1 μm 3 , more preferably 10 nm 3 to 0.1 μm 3 , More preferably, it is more effective when a domain having a size of 10 nm 3 to 0.001 μm 3 is formed and microphase separation is performed.
また、光触媒(A)が、表面エネルギーの高いバインダー樹脂(B’)と相分離状態にあるアルキル基含有シリコーン(BA)相中に存在した状態は、光触媒層の表面により多く光触媒(A)が存在することができるため好ましい。 In addition, the state in which the photocatalyst (A) is present in the alkyl group-containing silicone (BA) phase in a phase-separated state with the binder resin (B ′) having a high surface energy is more likely to be present on the surface of the photocatalyst layer. Preferred because it can be present.
本発明におけるアルキル基含有シリコーン(BA)と相分離する表面エネルギーの高いバインダー樹脂(B’)としては、上述したフェニル基含有シリコーン(BP)が、その骨格を成すシロキサン結合(−O−Si−)は光触媒作用による酸化分解が起こらないため好ましく、アルキル基を含有しないフェニル基含有シリコーン(BP1)が特に好ましい。 As the binder resin (B ′) having a high surface energy that is phase-separated from the alkyl group-containing silicone (BA) in the present invention, the above-described phenyl group-containing silicone (BP) is a siloxane bond (—O—Si—) constituting the skeleton. ) Is preferable because oxidative degradation due to photocatalysis does not occur, and phenyl group-containing silicone (BP1) not containing an alkyl group is particularly preferable.
この際、上記フェニル基含有シリコーン(BP1)及び上記アルキル基含有シリコーン(BA)の各々の、GPCで測定したポリスチレン換算重量平均分子量が、好ましくは100〜10,000、より好ましくは500〜6,000、更に好ましくは700〜4,000であるものを使用すると、上述したバインダー成分(B)はミクロ相分離構造を容易に形成するため好ましい。 Under the present circumstances, the polystyrene conversion weight average molecular weights measured by GPC of each of the phenyl group-containing silicone (BP1) and the alkyl group-containing silicone (BA) are preferably 100 to 10,000, more preferably 500 to 6, 000, more preferably 700 to 4,000, is preferable because the above-described binder component (B) easily forms a microphase separation structure.
本発明において、光触媒組成物(C)に使用する前述したバインダー成分(B)は、溶剤に溶けたタイプ、溶媒に分散したタイプ、溶媒と混合されていないタイプ(液体、固体)のいずれであっても良い。 In the present invention, the binder component (B) used in the photocatalyst composition (C) is any of a type dissolved in a solvent, a type dispersed in a solvent, and a type not mixed with a solvent (liquid or solid). May be.
係る光触媒組成物(C)において上記式(11)で示されるフェニル基含有シリコーン(BP)は、反応性を有する基(式(11)中のX)を有しても、有さなくても良いが、反応性を有する基(式(11)中のX)を有する(即ち、式(4)において0<r)と、係る光触媒組成物(C)から得られる光触媒層は、硬度や耐熱性、耐薬品性、耐久性等に優れたものとなるため好ましい。また、同様の理由から、式(16)において0<t、式(17)において0<vが好ましい。 In the photocatalyst composition (C), the phenyl group-containing silicone (BP) represented by the above formula (11) may or may not have a reactive group (X in the formula (11)). The photocatalyst layer obtained from the photocatalyst composition (C) having a reactive group (X in the formula (11) (that is, 0 <r in the formula (4)) has a hardness and heat resistance. It is preferable because it has excellent properties, chemical resistance, durability and the like. Further, for the same reason, 0 <t in the formula (16) and 0 <v in the formula (17) are preferable.
本発明に係る光触媒組成物(C)において上記式(11)で示されるフェニル基含有シリコーン(BP)が反応性を有する基(式(11)中のX)として、水酸基及び/又は加水分解性基を有する場合、従来公知の加水分解触媒や硬化触媒を、フェニル基含有シリコーン(BP)に対し、好ましくは0.01〜20質量%、より好ましくは0.1〜5質量%の割合で添加することができる。 In the photocatalyst composition (C) according to the present invention, the phenyl group-containing silicone (BP) represented by the above formula (11) is reactive (X in the formula (11)) as a hydroxyl group and / or hydrolyzable. When it has a group, a conventionally known hydrolysis catalyst or curing catalyst is preferably added in a proportion of 0.01 to 20% by mass, more preferably 0.1 to 5% by mass with respect to the phenyl group-containing silicone (BP). can do.
該加水分解触媒としては、酸性のハロゲン化水素、カルボン酸、スルホン酸、酸性或いは弱酸性の無機塩、イオン交換樹脂などの固体酸などが好ましい。また、加水分解触媒の量は、ケイ素原子上の加水分解性基1モルに対して好ましくは0.001〜5モルの範囲内であることが好ましい。 The hydrolysis catalyst is preferably an acidic hydrogen halide, a carboxylic acid, a sulfonic acid, an acidic or weakly acidic inorganic salt, a solid acid such as an ion exchange resin, or the like. The amount of the hydrolysis catalyst is preferably in the range of 0.001 to 5 mol with respect to 1 mol of the hydrolyzable group on the silicon atom.
また上記硬化触媒としては、例えば水酸化ナトリウム、水酸化カリウム、ナトリウムメチラート、酢酸ナトリウム、テトラメチルアンモニウムクロライド、テトラメチルアンモニウムヒドロキシドの如き塩基性化合物類;トリブチルアミン、ジアザビシクロウンデセン、エチレンジアミン、ジエチレントリアミン、エタノールアミン類、γ−アミノプロピルトリメトキシシラン、γ−(2−アミノエチル)−アミノプロピルトリメトキシシランの如きアミン化合物;テトライソプロピルチタネート、テトラブチルチタネートのようなチタン化合物;アルミニウムトリイソプロポキシド、アルミニウムアセチルアセトナート、過塩素酸アルミニウム、塩化アルミニウムのようなアルミニウム化合物;錫アセチルアセトナート、ジブチル錫オクチレート、ジブチル錫ジラウレートのような錫化合物;コバルトオクチレート、コバルトアセチルアセトナート、鉄アセチルアセトナートの如き含金属化合物類;リン酸、硝酸、フタル酸、p−トルエンスルホン酸、トリクロル酢酸の如き酸性化合物類などが挙げられる。 Examples of the curing catalyst include basic compounds such as sodium hydroxide, potassium hydroxide, sodium methylate, sodium acetate, tetramethylammonium chloride, tetramethylammonium hydroxide; tributylamine, diazabicycloundecene, ethylenediamine. , Diethylenetriamine, ethanolamines, amine compounds such as γ-aminopropyltrimethoxysilane, γ- (2-aminoethyl) -aminopropyltrimethoxysilane; titanium compounds such as tetraisopropyl titanate, tetrabutyl titanate; aluminum triiso Aluminum compounds such as propoxide, aluminum acetylacetonate, aluminum perchlorate, aluminum chloride; tin acetylacetonate, dibutyltin octile And tin compounds such as dibutyltin dilaurate; metal-containing compounds such as cobalt octylate, cobalt acetylacetonate and iron acetylacetonate; such as phosphoric acid, nitric acid, phthalic acid, p-toluenesulfonic acid and trichloroacetic acid Examples include acidic compounds.
本発明の光触媒組成物(C)において上記式(11)で示されるフェニル基含有シリコーン(BP)がSi−H基を有する場合、多官能アルケニル化合物の如き架橋剤を、Si−H基に対しアルケニル基が好ましくは0.01〜2当量、より好ましくは0.1〜1当量となるように添加することが好ましい。該多官能アルケニル合物としては、アルケニル基を有しSi−H基と反応して硬化を促進するものであれば何でもよいが、ビニル基、アリル基、ヘキセニル基などの炭素数2〜30の1価不飽和炭化水素基を有するアルケニル基含有シリコーンが一般に用いられている。 In the photocatalyst composition (C) of the present invention, when the phenyl group-containing silicone (BP) represented by the above formula (11) has a Si—H group, a crosslinking agent such as a polyfunctional alkenyl compound is used for the Si—H group. The alkenyl group is preferably added so that the amount is preferably 0.01 to 2 equivalents, more preferably 0.1 to 1 equivalents. The polyfunctional alkenyl compound may be anything as long as it has an alkenyl group and reacts with the Si—H group to accelerate curing, but has 2 to 30 carbon atoms such as a vinyl group, an allyl group, or a hexenyl group. Alkenyl group-containing silicones having monounsaturated hydrocarbon groups are generally used.
また、Si−H基と該多官能アルケニル化合物の反応を促進する目的で、触媒をフェニル基含有シリコーン(BP)と多官能アルケニル化合物の総量に対し、好ましくは1〜10000ppm、より好ましくは1〜1000ppmの割合で添加しても良い。該触媒としては白金族触媒、即ちルテニウム、ロジウム、パラジウム、オスミウム、イリジウム、白金の化合物が適しているが、特に白金化合物とパラジウム化合物が好適である。白金化合物としては、例えば塩化白金(II)、テトラクロロ白金酸(II)、塩化白金(IV)、ヘキサクロロ白金酸(IV)、ヘキサクロロ白金(IV)アンモニウム、ヘキサクロロ白金(IV)カリウム、水酸化白金(II)、二酸化白金(IV)、ジクロロ−ジシクロペンタジエニル−白金(II)、白金−ビニルシロキサン錯体、白金−ホスフィン錯体、白金−オレフィン錯体や白金の単体、アルミナやシリカや活性炭に固体白金を担持させたものが挙げられる。パラジウム化合物としては、例えば塩化パラジウム(II)、塩化テトラアンミンパラジウム(II)酸アンモニウム、酸化パラジウム(II)等が挙げられる。該白金族触媒はSi−H基含有シリコーンと多官能アルケニル化合物の合計量に対し白金族金属の量で好ましくは5〜1000ppmの範囲内で使用されるが、これは反応性、経済性及び所望の硬化速度等に応じて増減させることができる。また、所望により白金族触媒の活性を抑制し、ポットライフを延長させる目的で、各種の有機窒素化合物、有機リン化合物、アセチレン系化合物などの活性抑制剤を添加してもよい。 Further, for the purpose of promoting the reaction between the Si—H group and the polyfunctional alkenyl compound, the catalyst is preferably from 1 to 10,000 ppm, more preferably from 1 to 10,000 ppm, based on the total amount of the phenyl group-containing silicone (BP) and the polyfunctional alkenyl compound. You may add in the ratio of 1000 ppm. As the catalyst, platinum group catalysts, that is, ruthenium, rhodium, palladium, osmium, iridium, and platinum compounds are suitable, and platinum compounds and palladium compounds are particularly suitable. Examples of platinum compounds include platinum chloride (II), tetrachloroplatinic acid (II), platinum chloride (IV), hexachloroplatinic acid (IV), hexachloroplatinum (IV) ammonium, hexachloroplatinum (IV) potassium, and platinum hydroxide. (II), platinum dioxide (IV), dichloro-dicyclopentadienyl-platinum (II), platinum-vinylsiloxane complex, platinum-phosphine complex, platinum-olefin complex and platinum alone, solid on alumina, silica and activated carbon The thing which carry | supported platinum is mentioned. Examples of the palladium compound include palladium chloride (II), ammonium tetraammine chloride (II) chloride, palladium oxide (II) and the like. The platinum group catalyst is preferably used in an amount of 5 to 1000 ppm in terms of platinum group metal based on the total amount of Si-H group-containing silicone and polyfunctional alkenyl compound. It can be increased / decreased according to the curing rate and the like. Moreover, you may add activity inhibitors, such as various organic nitrogen compounds, an organic phosphorus compound, and an acetylene type compound, for the purpose of suppressing the activity of a platinum group catalyst and extending pot life if desired.
また、本発明に用いられる光触媒組成物(C)には、それから形成される光触媒層の硬度や耐擦傷性、親水性を向上させる目的でシリカ、アルミナ、酸化ジルコニウム、酸化アンチモン、希土類酸化物等の金属酸化物微粒子を粉末或いはゾルの状態で添加しても良い。但し、これら金属酸化物微粒子は、本発明におけるバインダー成分(B)の様なバインダーとしての能力はなく、光触媒(A)と同様に光触媒層の柔軟性(耐屈曲性、耐衝撃性)を低下させる。よって、該金属酸化物の添加量は、光触媒組成物(C)から形成される光触媒層中において光触媒(A)と金属酸化物の総重量が50質量%以下とすることが好ましい。 The photocatalyst composition (C) used in the present invention includes silica, alumina, zirconium oxide, antimony oxide, rare earth oxide, etc. for the purpose of improving the hardness, scratch resistance and hydrophilicity of the photocatalyst layer formed therefrom. The metal oxide fine particles may be added in the form of powder or sol. However, these metal oxide fine particles do not have the ability as a binder like the binder component (B) in the present invention, and reduce the flexibility (flexibility, impact resistance) of the photocatalyst layer as with the photocatalyst (A). Let Therefore, the addition amount of the metal oxide is preferably such that the total weight of the photocatalyst (A) and the metal oxide is 50% by mass or less in the photocatalyst layer formed from the photocatalyst composition (C).
本発明に係る光触媒組成物(C)は、無溶媒の状態(液体、固体)であっても溶媒に溶解或いは分散した状態であっても良く、特に制限はないが、コーティング剤として用いる場合は、溶媒に対し溶解或いは分散した状態が好ましい。この際、該光触媒組成物(C)中の光触媒(A)とバインダー成分(B)の総量は、好ましくは0.01〜95質量%、より好ましくは0.1〜70質量%である。 The photocatalyst composition (C) according to the present invention may be in a solvent-free state (liquid, solid) or dissolved or dispersed in a solvent, and is not particularly limited, but when used as a coating agent A dissolved or dispersed state in a solvent is preferable. At this time, the total amount of the photocatalyst (A) and the binder component (B) in the photocatalyst composition (C) is preferably 0.01 to 95% by mass, more preferably 0.1 to 70% by mass.
本発明において、光触媒組成物(C)に用いる溶媒としては、例えば水やエチレングリコール、ブチルセロソルブ、イソプロパノール、n−ブタノール、エタノール、メタノール等のアルコール類、トルエンやキシレン等の芳香族炭化水素類、ヘキサン、シクロヘキサン、ヘプタン等の脂肪族炭化水素類、酢酸エチル、酢酸n−ブチル等のエステル類、アセトン、メチルエチルケトン、メチルイソブチルケトン等のケトン類、テトラヒドロフラン、ジオキサン等のエーテル類、ジメチルアセトアミド、ジメチルホルムアミド等のアミド類、クロロホルム、塩化メチレン、四塩化炭素等のハロゲン化合物類、ジメチルスルホキシド、ニトロベンゼン等が挙げられる。これらの溶媒は、単独で又は組み合わせて用いられる。 In the present invention, examples of the solvent used in the photocatalyst composition (C) include water, alcohols such as ethylene glycol, butyl cellosolve, isopropanol, n-butanol, ethanol and methanol, aromatic hydrocarbons such as toluene and xylene, hexane, and the like. , Aliphatic hydrocarbons such as cyclohexane and heptane, esters such as ethyl acetate and n-butyl acetate, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, ethers such as tetrahydrofuran and dioxane, dimethylacetamide, dimethylformamide and the like Amides, halogen compounds such as chloroform, methylene chloride, carbon tetrachloride, dimethyl sulfoxide, nitrobenzene and the like. These solvents are used alone or in combination.
また、本発明に係る光触媒組成物(C)には、必要により通常、塗料に添加配合される成分、例えば顔料、充填剤、分散剤、光安定剤、湿潤剤、増粘剤、レオロジーコントロール剤、消泡剤、可塑剤、成膜助剤、防錆剤、染料、防腐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。 In addition, the photocatalyst composition (C) according to the present invention usually contains components that are usually added and blended into the paint, for example, pigments, fillers, dispersants, light stabilizers, wetting agents, thickeners, rheology control agents. Antifoaming agents, plasticizers, film-forming aids, rust inhibitors, dyes, preservatives, and the like can be selected and combined according to their respective purposes.
本発明に係る光触媒組成物(C)において、自己傾斜性が非常に高い場合(即ち、光触媒層中の光触媒(A)含有量(濃度)100に対し、面発光体でない側である、露出面と接する表面近傍の相対濃度が好ましくは150以上、より好ましくは200以上である場合)、該光触媒組成物(C)において光触媒(A)とバインダー成分(B)の質量比が好ましくは(A)/(B)=0.1/99.9〜40/60、より好ましくは(A)/(B)=0.1/99.9〜30/70という光触媒(A)の含有量が非常に少ない範囲においてさえ、形成される光触媒層は、光照射による十分な親水化能力(超親水化能力:20℃における水の接触角が10゜以下)や優れた光触媒活性を有する。また、この様に光触媒(A)の含有量が少ない光触媒層はバインダー成分(B)本来の物性を発現するため、強度や柔軟性(耐屈曲性、耐衝撃性)等に優れたものとなる。 In the photocatalyst composition (C) according to the present invention, when the self-gradient is very high (that is, the exposed surface on the side that is not a surface light emitter with respect to the photocatalyst (A) content (concentration) of 100 in the photocatalyst layer) When the relative concentration in the vicinity of the surface in contact with the surface is preferably 150 or more, more preferably 200 or more), the mass ratio of the photocatalyst (A) to the binder component (B) is preferably (A) in the photocatalyst composition (C). /(B)=0.1/99.9 to 40/60, more preferably (A) / (B) = 0.1 / 99.9 to 30/70 Even in a small range, the formed photocatalyst layer has sufficient hydrophilization ability (superhydrophilicity ability: water contact angle at 20 ° C. of 10 ° or less) by light irradiation and excellent photocatalytic activity. In addition, since the photocatalyst layer having a small content of the photocatalyst (A) exhibits the original physical properties of the binder component (B), the photocatalyst layer has excellent strength and flexibility (flexibility, impact resistance) and the like. .
本発明における光触媒層は、該光触媒層中における光触媒(A)の濃度が面発光体の側から表面に向かって高くなることが望ましい。但し、本発明においては、本発明の効果を妨げない範囲で、光触媒層以外の部分に光触媒(A)及び/又はバインダー成分(B)を含むことができる。 In the photocatalyst layer in the present invention, it is desirable that the concentration of the photocatalyst (A) in the photocatalyst layer increases from the surface light emitter side to the surface. However, in this invention, a photocatalyst (A) and / or a binder component (B) can be included in parts other than a photocatalyst layer in the range which does not prevent the effect of this invention.
本発明における光触媒層を有する面発光体は、該光触媒層を皮膜状とし、面発光体の皮膜層上に光触媒(A)及びバインダー成分(B)を含む当該皮膜を備えた形態とすることができる。この様な形態とすることにより、面発光体と光触媒層で機能を分担した構造が可能となり好ましい。 The surface light emitter having a photocatalyst layer according to the present invention may have a form in which the photocatalyst layer is a film, and the film containing the photocatalyst (A) and the binder component (B) is provided on the film layer of the surface light emitter. it can. By adopting such a form, a structure in which functions are shared by the surface light emitter and the photocatalyst layer becomes possible, which is preferable.
また、光触媒層以外の部分例えば面発光体部に光触媒(A)及び/又はバインダー成分(B)を含むものは、成形を一度にすることが可能であり、また光触媒層の欠陥部を補うことができ好ましい。このような形態は、例えば薄膜状の部材とする場合に好ましい。 In addition, a part other than the photocatalyst layer, for example, the one containing the photocatalyst (A) and / or the binder component (B) in the surface light emitter part can be molded at once, and compensates for the defective part of the photocatalyst layer. This is preferable. Such a form is preferable when, for example, a thin film member is used.
本発明における光触媒層を有する面発光体は、皮膜層上に本発明の光触媒組成物(C)からなる光触媒層を形成する場合に限定されない。面発光体の基材層と皮膜層と光触媒組成層を同時に成形、例えば、一体成形、積層成形してもよい。また、光触媒組成物(C)と面発光体とを個別に成形後、接着、融着等により光触媒層を有する面発光体としてもよい。 The surface light emitter having the photocatalyst layer in the present invention is not limited to the case where the photocatalyst layer comprising the photocatalyst composition (C) of the present invention is formed on the coating layer. The substrate layer, the coating layer, and the photocatalyst composition layer of the surface light emitter may be simultaneously molded, for example, integrally molded or laminated. Moreover, it is good also as a surface light-emitting body which has a photocatalyst layer by adhesion | attachment, melt | fusion, etc., after shape | molding a photocatalyst composition (C) and a surface light-emitting body separately.
本発明における光触媒層を有する面発光体は、該光触媒層を皮膜状とする場合は、例えば上記光触媒組成物(C)を面発光体に塗布し、乾燥した後、所望により好ましくは20℃〜500℃、より好ましくは40℃〜250℃の熱処理や紫外線照射等を行い、皮膜を形成することにより得ることができる。上記塗布方法としては、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、キャスティング法、スポンジ塗り法等が挙げられる。 The surface light emitter having a photocatalyst layer in the present invention, when the photocatalyst layer is formed into a film, for example, after applying the photocatalyst composition (C) to the surface light emitter and drying, is preferably 20 ° C. to It can be obtained by forming a film by performing a heat treatment at 500 ° C., more preferably 40 ° C. to 250 ° C., or ultraviolet irradiation. Examples of the coating method include spray spraying, flow coating, roll coating, brush coating, dip coating, spin coating, casting, and sponge coating.
この際、光触媒組成物(C)から形成される皮膜の膜厚は、好ましくは0.1〜200μm、より好ましくは0.5〜20μm、更に好ましくは1.5〜10μmである。 Under the present circumstances, the film thickness of the membrane | film | coat formed from a photocatalyst composition (C) becomes like this. Preferably it is 0.1-200 micrometers, More preferably, it is 0.5-20 micrometers, More preferably, it is 1.5-10 micrometers.
尚、本明細書では、皮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。 In this specification, the expression “film” is used. However, the film is not necessarily a continuous film, and may be a discontinuous film, an island-shaped dispersion film, or the like.
また、本発明の光触媒層を有する面発光体の表面には、Ag、Cu、Znのような金属を添加することができる。前記金属を添加した光触媒層は、表面に付着した細菌や黴を暗所でも死滅させることができる。 Moreover, metals such as Ag, Cu, and Zn can be added to the surface of the surface light emitter having the photocatalyst layer of the present invention. The photocatalyst layer to which the metal is added can kill bacteria and sputum attached to the surface even in the dark.
本発明における光触媒層を有する面発光体は、光触媒層に含まれる光触媒(A)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(励起光)を照射することにより光触媒活性及び/又は親水性を示し、優れた防汚性能を発現する。 The surface light emitter having a photocatalyst layer in the present invention exhibits photocatalytic activity and / or hydrophilicity by irradiating light (excitation light) with energy higher than the band gap energy of the photocatalyst (A) contained in the photocatalyst layer, Exhibits excellent antifouling performance.
この際、光触媒(A)が、上述した式(1)で表されるトリオルガノシラン単位、式(2)で表されるモノオキシジオルガノシラン単位、式(3)で表されるジオキシオルガノシラン単位よりなる群から選ばれる少なくとも1種の構造単位を有する化合物類よりなる群から選ばれる少なくとも1種の変性剤化合物(b)で変性処理された変性光触媒(A1)である場合、励起光照射により光触媒(A)粒子の近傍に存在する該変性剤化合物(b)のケイ素原子に結合した有機基(R)の少なくとも一部は、光触媒(A)の分解作用により水酸基に置換される。その結果、光触媒層表面の親水性が高まると共に、生成した水酸基同士が脱水縮合反応してシロキサン結合が生成した場合には、該光触媒層の硬度が非常に高くなる。この様な状態は、本発明の様態において好ましい。 At this time, the photocatalyst (A) is a triorganosilane unit represented by the above formula (1), a monooxydiorganosilane unit represented by the formula (2), or a dioxyorgano represented by the formula (3). In the case of the modified photocatalyst (A1) modified with at least one modifier compound (b) selected from the group consisting of compounds having at least one structural unit selected from the group consisting of silane units, excitation light At least a part of the organic group (R) bonded to the silicon atom of the modifier compound (b) present in the vicinity of the photocatalyst (A) particles by irradiation is substituted with a hydroxyl group by the decomposition action of the photocatalyst (A). As a result, the hydrophilicity of the surface of the photocatalyst layer is increased, and when the generated hydroxyl groups are subjected to a dehydration condensation reaction to form a siloxane bond, the hardness of the photocatalyst layer becomes very high. Such a state is preferable in the aspect of the present invention.
また、バインダー成分(B)として上述したシリコーンを用いた時も同様に、励起光照射により光触媒(A)粒子の近傍に存在するシリコーンのケイ素原子に結合した有機基の少なくとも一部は、光触媒(A)の分解作用により水酸基に置換され、光触媒層表面の親水性が高まると共に、生成した水酸基同士の脱水縮合反応が進行しシロキサン結合が生成した場合には、該光触媒層の硬度が非常に高くなる。この様な状態は、本発明の様態において好ましい。 Similarly, when the above-mentioned silicone is used as the binder component (B), at least a part of the organic groups bonded to the silicon atoms of the silicone present in the vicinity of the photocatalyst (A) particles by irradiation with excitation light is photocatalyst ( When the hydroxyl group is substituted by the decomposition action of A) to increase the hydrophilicity of the surface of the photocatalyst layer and the dehydration condensation reaction between the generated hydroxyl groups proceeds to form a siloxane bond, the photocatalyst layer has a very high hardness. Become. Such a state is preferable in the aspect of the present invention.
本発明においては、LED光源と面発光体との間隔は特に規定されるものではないが、500mm以下がLED(1)による光触媒の光励起を効果的に発現させる上で好ましい。 In the present invention, the distance between the LED light source and the surface light emitter is not particularly defined, but 500 mm or less is preferable for effectively expressing photoexcitation of the photocatalyst by the LED (1).
また、本発明の表示体においては、面発光体と光触媒層との間、或いは、光触媒層を設けていない側の面発光体表面に適宜意匠を施すことができる。 Moreover, in the display body of this invention, a design can be suitably given between the surface light emitter and the photocatalyst layer, or the surface light emitter surface on the side where the photocatalyst layer is not provided.
本発明の表示体に意匠性を付与して用いる場合、意匠性の付与方法は特に制限されるものではなく面発光体の表面に写真やイラスト、文字等を転写したり、貼付したり、印刷したりして意匠性が付与される。また、彫刻によりイラスト、文字等を表示しても良い。更に、光透過性材料そのものを着色して使用しても良い。 In the case of using the display body of the present invention with designability, the designability imparting method is not particularly limited, and photographs, illustrations, characters, etc. are transferred, pasted, or printed on the surface of the surface light emitter. Or design properties are imparted. Also, illustrations, characters, etc. may be displayed by engraving. Further, the light transmissive material itself may be colored and used.
本発明の活用例として、棚、ショーケース、パーテーション、サイン等のディスプレイ装置、非常口やトイレ等の表示灯、意匠性を有した照明器具、パネル、パーテーション、ウォール等の建材、看板等に広く適用可能である。また、信号機や車載内外装照明、例えばインスツルメントパネル、室内灯、足元灯、ヘッドランプ、フォグランプ、リアコンビネーションランプ(テール、ストップ、ターン)ハイマウント・ストップランプ、ドアサイドターンランプ等に適用可能である。 As an application example of the present invention, it is widely applied to display devices such as shelves, showcases, partitions, signs, etc., indicator lights such as emergency exits and toilets, lighting fixtures with design, panels, partitions, building materials such as walls, signs, etc. Is possible. Also applicable to traffic lights and vehicle interior / exterior lighting such as instrument panels, interior lights, footlights, headlamps, fog lights, rear combination lamps (tail, stop, turn), high mount stop lamps, door side turn lamps, etc. It is.
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。 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.
以下の実施例、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。 In the following Examples, Reference Examples and Comparative Examples, various physical properties were measured by the following methods.
〈面発光体〉
(1)光線透過率
測定機器として東京電飾株式会社(TOKYO DENSHOKU CO.,LTD)製の「COLOR AND DEFFERENCE METER MODEL TC−1500MC」を用い、光源には標準光を使用し、視野角10°で220mm長試験片(8mm幅×30mm高さ×220mm長さ)を透過する光束の三刺激値XYZを測定した。そのY値を光線透過率として採用した。
<Surface emitter>
(1) Light transmittance The “COLOR AND DEFFERENCE METER MODEL TC-1500MC” manufactured by TOKYO DENSHOKU CO., LTD. Is used as a measuring instrument, standard light is used as a light source, and a viewing angle is 10 °. The tristimulus values XYZ of the light beam passing through a 220 mm long test piece (8 mm width × 30 mm height × 220 mm length) were measured. The Y value was adopted as the light transmittance.
(2)光散乱剤の平均粒径
散乱剤の微粒子を有機溶液中に超音波により分散させ、得られた分散液をマイクロトラック法を用いて測定し、50%累積粒径を平均粒径として採用した。
(2) Average particle size of light scattering agent Fine particles of scattering agent are dispersed in an organic solution by ultrasonic waves, and the resulting dispersion is measured using a microtrack method. The 50% cumulative particle size is taken as the average particle size. Adopted.
(3)輝度比L10/L210
図1に示すように試験片10の1端面の中央部に入光部巾5mmの冷陰極管(8mmφ:ハリソン電気製)(光源2)を配設し、直流電圧安定装置より12Vの電圧をかけ20分間点灯後に輝度計輝度測定装置として株式会社トプコン製BM−7を用いて、視野角1°、輝度計と試験片との離間距離50cmで試験片の上部表面の輝度を測定し、光源からの距離10mmの位置の輝度をL10、光源からの距離210mmの位置の輝度をL210とし、その比を輝度比L10/L210として採用した。
(3) Luminance ratio L 10 / L 210
As shown in FIG. 1, a cold cathode tube (8 mmφ: made by Harrison Electric) (light source 2) having a light incident width of 5 mm is disposed at the center of one end face of the
(4)視認性−1
面発光体の光触媒層で被覆されていない側(裏面)に1cm角の黒色格子模様(線幅1mm)を印刷し、光源を点灯し、格子の見え具合を4段階評価した。
◎:極めてきれいに格子模様が視認される。面発光体全体の出光が充分である。
○:きれいに格子模様が視認される。面発光体全体の出光が若干劣る。
△:格子模様がはっきり視認出来ない。面発光体の出光が不均一で出光が劣る。
×:格子模様が視認出来ない。面発光の出光が不十分。
(4) Visibility-1
A 1 cm square black grid pattern (line width: 1 mm) was printed on the side of the surface light emitter not covered with the photocatalyst layer (back surface), the light source was turned on, and the appearance of the grid was evaluated in four stages.
(Double-circle): A lattice pattern is visually recognized very beautifully. The light emission of the entire surface light emitter is sufficient.
○: The lattice pattern is clearly visible. The light output of the entire surface light emitter is slightly inferior.
Δ: The lattice pattern is not clearly visible. The light emission of the surface light emitter is uneven and the light output is inferior.
X: A lattice pattern cannot be visually recognized. Insufficient surface emission.
(5)視認性−2
面発光体の片面に1cm角の黒色格子模様(線幅1mm)を印刷し、その上に光触媒層を設け、光源を点灯し、格子の見え具合を視認性−1と同様に4段階評価した。
(5) Visibility-2
A 1 cm square black grid pattern (line width: 1 mm) was printed on one surface of the surface light emitter, a photocatalyst layer was provided thereon, the light source was turned on, and the appearance of the grid was evaluated in four stages in the same manner as in visibility-1. .
〈光触媒〉
(1)粒径分布及び数平均粒子径
試料中の光触媒含有量が1〜20重量%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。
<photocatalyst>
(1) Particle size distribution and number average particle size A solvent is appropriately added to dilute the photocatalyst content in the sample to 1 to 20% by weight, and a wet particle size analyzer (Nikkiso Microtrac UPA-9230) is used. It was measured.
(2)重量平均分子量
ポリスチレン標品を用いて作成した検量線を用い、ゲルパーミエーションクロマトグラフィー(GPC)によって求めた。GPCの条件は以下の通りである。
・装置:東ソー製HLC−8020 LC−3A型クロマトグラフ
・カラム:TSKgel G1000HXL、TSKgel G2000HXL及びTSKgel G4000HXL(いずれも東ソー製)を直列に接続して用いた。
・データ処理装置:島津製作所製CR−4A型データ処理装置
・移動相:テトラヒドロフラン(フェニル基含有シリコーンの分析に使用)
クロロホルム(フェニル基を含有しないシリコーンの分析に使用)
・流速:1.0ml/min.
・サンプル調製法:移動相に使用する溶媒で希釈(濃度は0.5〜2重量%の範囲で適宜調節した)して分析に供した。
(2) Weight average molecular weight It calculated | required by the gel permeation chromatography (GPC) using the analytical curve created using the polystyrene sample. The conditions for GPC are as follows.
Apparatus: Tosoh HLC-8020 LC-3A type chromatograph column: TSKgel G1000H XL , TSKgel G2000H XL and TSKgel G4000H XL (all manufactured by Tosoh) were used in series.
・ Data processor: CR-4A type data processor manufactured by Shimadzu Corporation ・ Mobile phase: Tetrahydrofuran (used for analysis of phenyl group-containing silicone)
Chloroform (used for analysis of silicones that do not contain phenyl groups)
-Flow rate: 1.0 ml / min.
Sample preparation method: The sample was diluted with a solvent used for the mobile phase (concentration was appropriately adjusted in the range of 0.5 to 2% by weight) and subjected to analysis.
(3)赤外線吸収スペクトル
日本分光製FT/IR−5300型赤外分光計を用いて測定した。
(3) Infrared absorption spectrum The infrared absorption spectrum was measured using an FT / IR-5300 type infrared spectrometer manufactured by JASCO.
(4)29Si核磁気共鳴の測定
日本電子製JNM−LA400を用いて測定した。
(4) Measurement of 29 Si nuclear magnetic resonance It measured using JEOL JNM-LA400.
(5)皮膜(光触媒層)表面に対する水の接触角
皮膜(光触媒層)の表面に脱イオン水の滴を乗せ、20℃で1分間放置した後、協和界面科学製CA−X150型接触角計を用いて測定した。
(5) Contact angle of water to the surface of the film (photocatalyst layer) After placing a drop of deionized water on the surface of the film (photocatalyst layer) and leaving it at 20 ° C. for 1 minute, CA-X150 type contact angle meter manufactured by Kyowa Interface Science It measured using.
皮膜に対する水の接触角が小さいほど、皮膜表面は親水性が高い。 The smaller the contact angle of water with the film, the higher the hydrophilicity of the film surface.
(6)皮膜(光触媒層)の光触媒活性
皮膜(光触媒層)表面にメチレンブルーの5重量%エタノール溶液を塗布した後、LED光源を30日間点灯し、その後、光触媒の作用によるメチレンブルーの分解の程度(皮膜表面の退色の程度に基づき、目視で評価)に基づき、光触媒の活性を以下の4段階で評価した。
◎:メチレンブルーが完全に分解。
○:メチレンブルーの青色が部分的にわずかに残る。
△:メチレンブルーの青色が残る。
×:メチレンブルーの分解はほとんど観測されず、青色がほとんど残る。
(6) Photocatalytic activity of the film (photocatalyst layer) After applying a 5% by weight ethanol solution of methylene blue to the surface of the film (photocatalyst layer), the LED light source is turned on for 30 days, and then the degree of decomposition of methylene blue by the action of the photocatalyst ( Based on the degree of fading on the surface of the film, the activity of the photocatalyst was evaluated based on the following four levels.
A: Methylene blue is completely decomposed.
○: A little blue of methylene blue remains.
Δ: Blue of methylene blue remains.
X: Methylene blue was hardly decomposed and blue color remained.
[参考例1]
面発光体−1の製造
デルペットLP−1(メタクリル樹脂:旭化成ケミカルズ株式会社製)に光散乱剤として平均粒径0.5μmのアルミナを2.5ppmブレンドし、基材層用樹脂を用意した。更に、デルペットLP−1に前記のアルミナを1000ppmブレンドし、皮膜層用樹脂を用意した。基材層用樹脂をスクリュウ径120mmφ、L/D(押し出し長さ/押し出し直径)=32の押出機にフィードし、更に皮膜層用樹脂をスクリュウ径40mmφ、L/D=32の押出機にフィードし、これら押出機を用いて、厚さ8mm、幅1000mmの積層シートを押出し成形し、面発光体−1を得た。皮膜層の厚さは200μmであった。
[Reference Example 1]
Manufacture of surface light emitter-1 Delpet LP-1 (methacrylic resin: manufactured by Asahi Kasei Chemicals Corporation) was blended with 2.5 ppm of alumina having an average particle size of 0.5 μm as a light scattering agent to prepare a resin for a base layer. . Furthermore, 1000 ppm of the above-mentioned alumina was blended with Delpet LP-1 to prepare a resin for the film layer. The base layer resin is fed to an extruder having a screw diameter of 120 mmφ and L / D (extruded length / extruded diameter) = 32, and the coating layer resin is fed to an extruder having a screw diameter of 40 mmφ and L / D = 32. Then, using these extruders, a laminated sheet having a thickness of 8 mm and a width of 1000 mm was extruded to obtain a surface light emitter-1. The thickness of the coating layer was 200 μm.
その積層シートから長さ220mm、巾30mm、厚さ8mmのサイズの試験片を切り出して、切断面を研磨した後、光線透過率を測定したところ、220mm光路長における光線透過率は42%であった。また、光源からの距離10mmの位置の輝度(L10)は75cd/m2、光源からの距離210mmの位置の輝度(L210)は42cd/m2であり、輝度比L10/L210は1.8であった。
A test piece having a length of 220 mm, a width of 30 mm, and a thickness of 8 mm was cut out from the laminated sheet, the cut surface was polished, and the light transmittance was measured. The light transmittance at a light path length of 220 mm was 42%. It was. Further, the luminance (L 10 ) at a
[参考例2]
面発光体−2の製造
基材層の光散乱剤の量を1.5ppmとした以外は前記参考例1と同様にして、積層シートを押出し成形し、面発光体−2を得た。光線透過率は60%で、L10は62cd/m2、L210は36cd/m2であり、輝度比L10/L210は1.7であった。
[Reference Example 2]
Manufacture of surface light emitter-2 A laminated sheet was extruded in the same manner as in Reference Example 1 except that the amount of the light scattering agent in the base material layer was 1.5 ppm to obtain surface light emitter-2. The light transmittance was 60%, L 10 was 62 cd / m 2 , L 210 was 36 cd / m 2 , and the luminance ratio L 10 / L 210 was 1.7.
[参考例3]
面発光体−3の製造
基材層の光散乱剤の量を5ppmとした以外は前記参考例1と同様にして、積層シートを押出し成形し、面発光体−3を得た。光線透過率は25%で、L10は98cd/m2、L210は43cd/m2であり、輝度比L10/L210は2.3であった。
[Reference Example 3]
Production of surface light emitter-3 Except that the amount of the light scattering agent in the base material layer was set to 5 ppm, the laminated sheet was extruded in the same manner as in Reference Example 1 to obtain a surface light emitter-3. The light transmittance was 25%, L 10 was 98 cd / m 2 , L 210 was 43 cd / m 2 , and the luminance ratio L 10 / L 210 was 2.3.
[参考例4]
面発光体−4の製造
皮膜層の厚さ100μm、皮膜層中の光散乱剤となるアルミナ濃度2000ppm、とした以外は前記参考例1と同様にして、積層シートを押出し成形し、面発光体−4を得た。光線透過率は41%で、L10は78cd/m2、L210は46cd/m2であり、輝度比L10/L210は1.7であった。
[Reference Example 4]
Manufacture of surface light emitter-4 A laminated sheet was extruded and formed in the same manner as in Reference Example 1 except that the thickness of the coating layer was 100 μm and the alumina concentration in the coating layer was 2000 ppm as the light scattering agent. -4 was obtained. The light transmittance was 41%, L 10 was 78 cd / m 2 , L 210 was 46 cd / m 2 , and the luminance ratio L 10 / L 210 was 1.7.
[参考例5]
面発光体−5の製造
皮膜層中の光散乱剤を平均粒径7.5μmの炭酸カルシウムとし、皮膜層の光散乱剤の量を3500ppmとした以外は前記参考例1と同様にして、積層シートを押出し成形し、面発光体−5を得た。光線透過率は40%で、L10は65cd/m2、L210は36cd/m2であり、輝度比L10/L210は1.8であった。
[Reference Example 5]
Manufacture of surface light emitter-5 The light scattering agent in the coating layer was calcium carbonate having an average particle size of 7.5 μm, and the lamination was performed in the same manner as in Reference Example 1 except that the amount of the light scattering agent in the coating layer was 3500 ppm. The sheet was extruded to obtain a surface light emitter-5. The light transmittance was 40%, L 10 was 65 cd / m 2 , L 210 was 36 cd / m 2 , and the luminance ratio L 10 / L 210 was 1.8.
[参考例6]
面発光体−6の製造
光散乱剤を含まない単層シートを押出し成形し、面発光体−6を得た。光線透過率は87%で、L10は3.1cd/m2、L210は0.13cd/m2であり、輝度比L10/L210は24であった。
[Reference Example 6]
Production of surface light emitter-6 A single layer sheet containing no light scattering agent was extruded to obtain a surface light emitter-6. The light transmittance was 87%, L 10 was 3.1 cd / m 2 , L 210 was 0.13 cd / m 2 , and the luminance ratio L 10 / L 210 was 24.
[参考例7]
面発光体−7の製造
光散乱剤の量を12ppmとした以外は前記参考例6と同様にして、単層シートを押出し成形し、面発光体−7を得た。光線透過率は13%で、L10は39cd/m2、L210は17cd/m2であり、輝度比L10/L210は2.3であった。
[Reference Example 7]
Manufacture of surface light emitter-7 Except that the amount of the light scattering agent was 12 ppm, a single layer sheet was extruded and formed to obtain a surface light emitter-7. The light transmittance was 13%, L 10 was 39 cd / m 2 , L 210 was 17 cd / m 2 , and the luminance ratio L 10 / L 210 was 2.3.
[参考例8]
面発光体−8の製造
光散乱剤の量を2ppmとした以外は前記参考例6と同様にして、単層シートを押出し成形し、面発光体−8を得た。光線透過率は45%で、L10は20cd/m2、L210は1.1cd/m2であり、輝度比L10/L210は18であった。
[Reference Example 8]
Production of surface light emitter-8 Except that the amount of the light scattering agent was 2 ppm, a single layer sheet was extruded and formed to obtain a surface light emitter-8. The light transmittance was 45%, L 10 was 20 cd / m 2 , L 210 was 1.1 cd / m 2 , and the luminance ratio L 10 / L 210 was 18.
[参考例9]
面発光体−9の製造
基材層に光散乱剤を含まない以外は前記参考例1と同様にして、積層シートを押出し成形し、面発光体−9を得た。光線透過率は82%で、L10は38cd/m2、L210は17cd/m2であり、輝度比L10/L210は2.4であった。
[Reference Example 9]
Production of surface light emitter-9 Except that the base material layer did not contain a light scattering agent, the laminate sheet was extruded and formed in the same manner as in Reference Example 1 to obtain a surface light emitter-9. The light transmittance was 82%, L 10 was 38 cd / m 2 , L 210 was 17 cd / m 2 , and the luminance ratio L 10 / L 210 was 2.4.
[参考例10]
フェニル基含有シリコーン(BP1−1)の合成。
[Reference Example 10]
Synthesis of phenyl group-containing silicone (BP1-1).
還流冷却器、温度計及び撹拌装置を有する反応器に入れたジオキサン78gにフェニルトリクロロシラン26.0gを添加した後、室温にて約10分間撹拌した。これに水3.2gとジオキサン12.9gからなる混合液を、反応液を10〜15℃に保ちながら約30分かけて滴下した後、更に10〜15℃で約30分撹拌し、続いて反応液を60℃に昇温させ3時間撹拌した。得られた反応液を25〜30℃に降温させ、392gのトルエンを約30分かけて滴下した後、再度反応液を60℃に昇温させ2時間撹拌した。 After adding 26.0 g of phenyltrichlorosilane to 78 g of dioxane placed in a reactor having a reflux condenser, a thermometer and a stirrer, the mixture was stirred at room temperature for about 10 minutes. A mixture of 3.2 g of water and 12.9 g of dioxane was added dropwise thereto over about 30 minutes while maintaining the reaction solution at 10 to 15 ° C., followed by further stirring at 10 to 15 ° C. for about 30 minutes, The reaction solution was heated to 60 ° C. and stirred for 3 hours. The resulting reaction solution was cooled to 25-30 ° C., 392 g of toluene was added dropwise over about 30 minutes, and then the reaction solution was again heated to 60 ° C. and stirred for 2 hours.
得られた反応液を10〜15℃に降温させ、メタノール19.2gを約30分かけて添加した。その後更に25〜30℃にて約2時間撹拌を続行し、続いて反応液を60℃に昇温させ2時間撹拌した。得られた反応液から60℃で減圧下に溶媒を溜去することにより重量平均分子量3600のラダー骨格を有するフェニル基含有シリコーン(BP1−1)を得た。得られたフェニル基含有シリコーン(BP1−1)には、IRスペクトルにおけるラダ−骨格の伸縮振動に由来する吸収(1130cm-1及び1037cm-1)が観測された。 The resulting reaction solution was cooled to 10 to 15 ° C., and 19.2 g of methanol was added over about 30 minutes. Thereafter, stirring was further continued at 25 to 30 ° C. for about 2 hours, and then the reaction solution was heated to 60 ° C. and stirred for 2 hours. By distilling off the solvent from the obtained reaction solution at 60 ° C. under reduced pressure, a phenyl group-containing silicone (BP1-1) having a ladder skeleton with a weight average molecular weight of 3600 was obtained. In the obtained phenyl group-containing silicone (BP1-1), absorptions (1130 cm −1 and 1037 cm −1 ) derived from the stretching vibration of the ladder skeleton in the IR spectrum were observed.
また、29Si核磁気共鳴の測定結果より求めた上記フェニル基含有シリコーン(BP1−1)の式は、(Ph)1(OCH3)0.58SiO1.21であった(ここでPhはフェニル基を表す。)。 Further, 29 wherein the Si-nuclear magnetic resonance measurement results from the phenyl group-containing silicone obtained (BP1-1) represents (Ph) 1 (OCH 3) 0.58 was SiO 1.21 (where Ph is phenyl .)
[参考例11]
アルキル基含有シリコーン(BA−1)の合成。
[Reference Example 11]
Synthesis of alkyl group-containing silicone (BA-1).
還流冷却器、温度計及び撹拌装置を有する反応器に入れたメタノール300gにメチルトリメトキシシラン136g(1モル)、及びジメチルジメトキシシラン120g(1モル)を添加した後、室温にて約10分間撹拌した。これに氷冷下で、0.05Nの塩酸水溶液12.6g(0.7モル)とメタノール63gからなる混合液を、約40分かけて滴下し、加水分解を行った。滴下終了後、更に10℃以下で約20分、室温で6時間それぞれ撹拌した。 After adding 136 g (1 mol) of methyltrimethoxysilane and 120 g (1 mol) of dimethyldimethoxysilane to 300 g of methanol in a reactor equipped with a reflux condenser, a thermometer and a stirrer, the mixture was stirred at room temperature for about 10 minutes. did. A mixture of 12.6 g (0.7 mol) of 0.05N aqueous hydrochloric acid and 63 g of methanol was added dropwise thereto over about 40 minutes under ice-cooling to carry out hydrolysis. After completion of dropping, the mixture was further stirred at 10 ° C. or lower for about 20 minutes and at room temperature for 6 hours.
その後、得られた反応液から60℃で減圧下に溶媒を溜去することにより重量平均分子量3600のアルキル基含有シリコーン(BA−1)を得た。得られたアルキル基含有シリコーン(BA−1)の構造を29Si核磁気共鳴によって測定したところ、T構造とD構造を示すシグナルが確認され、その比率はT構造:D構造=1:1であった。 Then, the alkyl group containing silicone (BA-1) of the weight average molecular weight 3600 was obtained by distilling a solvent off under reduced pressure at 60 degreeC from the obtained reaction liquid. When the structure of the obtained alkyl group-containing silicone (BA-1) was measured by 29 Si nuclear magnetic resonance, signals indicating T structure and D structure were confirmed, and the ratio was T structure: D structure = 1: 1. there were.
また、29Si核磁気共鳴の測定結果より求めた上記アルキル基含有シリコーン(BA−1)の平均組成式は、(CH3)1.5(OCH3)0.27SiO1.12であった。 The average composition formula of the alkyl group-containing silicone (BA-1) obtained from the measurement result of 29 Si nuclear magnetic resonance was (CH 3 ) 1.5 (OCH 3 ) 0.27 SiO 1.12 .
[参考例12]
シリコーン組成物(B−1)の調整。
[Reference Example 12]
Adjustment of silicone composition (B-1).
参考例10で合成したフェニル基含有シリコーン(BP1−1)6gと参考例11で合成したアルキル基含有シリコーン(BA−1)3gを混合したものに、トルエン14.7g、イソプロパノール29.8g、ブチルセロソルブ15.1gを添加し、室温で撹拌する事によりバインダー成分(B−1)の溶液を得た。 A mixture of 6 g of the phenyl group-containing silicone (BP1-1) synthesized in Reference Example 10 and 3 g of the alkyl group-containing silicone (BA-1) synthesized in Reference Example 11 was mixed with 14.7 g of toluene, 29.8 g of isopropanol, and butyl cellosolve. 15.1g was added and the solution of the binder component (B-1) was obtained by stirring at room temperature.
また、各々の組成物の平均組成式より、上記バインダー成分(B−1)の平均組成式は、(Ph)0.67(CH3)0.5(OCH3)0.47SiO1.18と計算できる(ここでPhはフェニル基を表す。)。 From the average composition formula of each composition, the average composition formula of the binder component (B-1) can be calculated as (Ph) 0.67 (CH 3 ) 0.5 (OCH 3 ) 0.47 SiO 1.18 (where Ph is Represents a phenyl group).
[参考例13]
還流冷却器、温度計及び撹拌装置を有する反応器に入れたTKS−251{酸化チタンオルガノゾルの商品名(テイカ製)、分散媒:トルエンとイソプロパノールの混合溶媒、TiO2濃度20重量%、平均結晶子径6nm(カタログ値)}40gにビス(トリメチルシロキシ)メチルシランの20重量%トルエン溶液40gを50℃にて約5分かけて添加し、更に50℃で12時間撹拌を続けることにより、非常に分散性の良好な変性光触媒オルガノゾル(A−1)を得た。この時、ビス(トリメチルシロキシ)メチルシランの反応に伴い生成した水素ガス量は23℃において718mlであった。また、得られた変性酸化チタンオルガノゾルをKBr板上にコーティングしIRスペクトルを測定したところ、Ti−OH基の吸収(3630〜3640cm-1)の消失が観測された。
[Reference Example 13]
TKS-251 {trade name of titanium oxide organosol (manufactured by Teica), dispersion medium: mixed solvent of toluene and isopropanol, TiO 2 concentration 20% by weight, average, placed in a reactor having a reflux condenser, a thermometer and a stirrer By adding 40 g of a 20 wt% toluene solution of bis (trimethylsiloxy) methylsilane to 40 g of
得られた変性光触媒オルガノゾル(A−1)の粒径分布は単一分散(数平均粒子径は25nm)であり、さらに変性処理前のTKS−251の単一分散(数平均粒子径は12nm)の粒径分布が完全に消失した。 The resulting modified photocatalyst organosol (A-1) has a single particle size distribution (number average particle size is 25 nm), and further a single dispersion of TKS-251 before the modification treatment (number average particle size is 12 nm). The particle size distribution completely disappeared.
続いて、参考例12で調整したシリコーン成分(B−1)の溶液68gに上記変性光触媒オルガノゾル(A−1)20gを室温にて撹拌下において添加し、さらに硬化触媒(ジラウリル酸ジブチル錫)0.5gを攪拌下に添加して光触媒組成物(C−1)を得た。 Subsequently, 20 g of the modified photocatalyst organosol (A-1) was added to 68 g of the solution of the silicone component (B-1) prepared in Reference Example 12 at room temperature with stirring, and a curing catalyst (dibutyltin dilaurate) 0 .5 g was added with stirring to obtain a photocatalyst composition (C-1).
[実施例1〜5、比較例1〜4]
参考例1〜9で成形した面発光体の裏面に視認性−1評価用印刷を施した後、参考例13で調整した光触媒組成物(C−1)を表面上に膜厚が約3μmとなるようにスプレー塗布した後、室温で2日間乾燥し、続いて50℃にて3日間加熱することにより平滑な光触媒含有皮膜を有する面発光体(D−1〜9)を得た。
[Examples 1 to 5, Comparative Examples 1 to 4]
After applying the visibility-1 evaluation printing on the back surface of the surface light emitters molded in Reference Examples 1 to 9, the photocatalyst composition (C-1) prepared in Reference Example 13 has a film thickness of about 3 μm on the surface. After spray coating as described above, the film was dried at room temperature for 2 days, and then heated at 50 ° C. for 3 days to obtain surface light emitters (D-1 to 9) having a smooth photocatalyst-containing film.
該面発光体を暗室内に設置された図2に示す表示体に組み込んだ。図2は当該表示体の断面模式図であり、図中、1は面発光体、3はLED光源、4はランプハウス、5は光触媒層、6は印刷層で1cm角の格子である。LED光源のLED(1)として日亜化学工業株式会社製NSHU590B(ピーク波長365nm)、LED(3)として日亜化学工業株式会社製NSPW500BS(白色)を交互に配設して使用した。 The surface light emitter was incorporated in a display body shown in FIG. 2 installed in a dark room. FIG. 2 is a schematic cross-sectional view of the display body, in which 1 is a surface light emitter, 3 is an LED light source, 4 is a lamp house, 5 is a photocatalyst layer, and 6 is a printed layer of 1 cm square lattice. NSHU590B (peak wavelength 365 nm) manufactured by Nichia Corporation was used as LED (1) of the LED light source, and NSPW500BS (white) manufactured by Nichia Corporation was used alternately as LED (3).
LED(1)の発光時間はLED(3)の単位発光時間当たり、50/100となるように発光時間を制御し(一時間当りLED(3)は常時発光、LED(1)は30分間発光し、残り30分間は発光させない)、30日間点灯した後、光触媒活性、水の接触角、視認性−1の評価を行った。結果を表1に示す。 The light emission time of LED (1) is controlled to be 50/100 per unit light emission time of LED (3) (LED (3) always emits light per hour, LED (1) emits light for 30 minutes The remaining 30 minutes were not allowed to emit light), and after lighting for 30 days, photocatalytic activity, water contact angle, and visibility-1 were evaluated. The results are shown in Table 1.
[比較例5]
実施例1のD−1を用い、LED(1)を発光させず、LED(3)のみを発光させる以外、実施例1と同様にして30日間点灯し、実施例1と同様の評価を行った。メチレンブルー塗布部位外の視認性−1は◎であったが、光触媒活性は×、水の接触角105°であり、防汚性に劣り、実用に供し得るものではなかった。
[Comparative Example 5]
Using D-1 of Example 1, the LED (1) is not emitted, and only the LED (3) is emitted, except that the LED (3) is lit for 30 days, and the same evaluation as in Example 1 is performed. It was. Visibility-1 outside the methylene blue application site was ◎, but the photocatalytic activity was x, the contact angle of water was 105 °, the antifouling property was inferior, and it was not practically usable.
[実施例6]
実施例1のLED(3)の代わりにLED(2)として日亜化学工業株式会社製NSPR510AS(赤色)を用いる以外、実施例1と同様にして30日間点灯し、実施例1と同様の評価を行った。光触媒活性は◎、水の接触角0°、視認性−1は◎であり、実用に供し得るものであった。
[Example 6]
It is lit for 30 days in the same manner as in Example 1 except that NSPR510AS (red) manufactured by Nichia Corporation is used as the LED (2) instead of the LED (3) in Example 1, and the same evaluation as in Example 1 Went. The photocatalytic activity was ◎, the water contact angle was 0 °, and the visibility-1 was ◎, which was practically usable.
[実施例7]
参考例1で成形した面発光体の表面に視認性−2評価用印刷を施した後、参考例13で調整した光触媒組成物(C−1)を該印刷面上に膜厚が約3μmとなるようにスプレー塗布した後、室温で2日間乾燥し、続いて50℃にて3日間加熱することにより平滑な光触媒層を有する面発光体(D−10)を得た。図3に本例の表示体の断面模式図を示す。図中の符号は図2と同様である。
[Example 7]
After performing the visibility-2 evaluation printing on the surface of the surface light emitter formed in Reference Example 1, the photocatalyst composition (C-1) prepared in Reference Example 13 has a film thickness of about 3 μm on the printed surface. After being spray-coated as such, it was dried at room temperature for 2 days, and then heated at 50 ° C. for 3 days to obtain a surface light emitter (D-10) having a smooth photocatalyst layer. FIG. 3 is a schematic sectional view of the display body of this example. The reference numerals in the figure are the same as those in FIG.
実施例1のD−1の代わりにD−10を用いる以外、実施例1と同様にして30日間点灯し、実施例1と同様の評価を行った。光触媒活性は◎、水の接触角0°、視認性−2は◎であり、実用に供し得るものであった。 Except that D-10 was used instead of D-1 in Example 1, it was lit for 30 days in the same manner as in Example 1, and the same evaluation as in Example 1 was performed. The photocatalytic activity was ◎, the water contact angle was 0 °, and the visibility-2 was ◎, which could be put to practical use.
[実施例8]
実施例1のLED(1)とLED(3)の発光時間比を10/100とする以外、実施例1と同様にして30日間点灯し、実施例1と同様の評価を行った。光触媒活性は○、水の接触角5°、視認性−1は◎であり、実用に供し得るものであった。
[Example 8]
The LED was turned on for 30 days in the same manner as in Example 1 except that the light emission time ratio of LED (1) and LED (3) in Example 1 was 10/100, and the same evaluation as in Example 1 was performed. The photocatalytic activity was ◯, the water contact angle was 5 °, and the visibility-1 was ◎, which could be put to practical use.
[実施例9]
実施例1のLED(1)とLED(3)の発光時間比を90/100とする以外、実施例1と同様にして30日間点灯し、実施例1と同様の評価を行った。光触媒活性は◎、水の接触角0°、視認性−1は○であり、実用に供し得るものであった。
[Example 9]
The LED was turned on for 30 days in the same manner as in Example 1 except that the light emission time ratio of LED (1) and LED (3) in Example 1 was 90/100, and the same evaluation as in Example 1 was performed. The photocatalytic activity was ◎, the water contact angle was 0 °, and visibility-1 was ◯, which could be put to practical use.
[実施例10]
実施例1のD−1を用い、LED(1)とLED(3)を常時発光させる以外、実施例1と同様にして30日間点灯し、実施例1と同様の評価を行った。光触媒活性は◎、水の接触角0°と防汚性は優れたものであったが、実用に供しうる範囲で面発光体自体に若干の濁りが生じた。
[Example 10]
Using D-1 of Example 1, the LED (1) and LED (3) were lit for 30 days in the same manner as in Example 1 except that the LED (1) and LED (3) were always lit, and the same evaluation as in Example 1 was performed. The photocatalytic activity was excellent, and the contact angle of water was 0 ° and the antifouling property was excellent. However, the surface light emitter itself was slightly turbid within a practical range.
1 面発光体
2 光源(冷陰極管)
3 LED光源
4 LED光源ランプハウス
5 光触媒層
6 印刷層(1cm角の格子)
7 LED(2)または(3)
8 LED(1)
10 試験片
1 Surface light emitter 2 Light source (cold cathode tube)
3 LED light source 4 LED light
7 LED (2) or (3)
8 LEDs (1)
10 test pieces
Claims (9)
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20090279019A1 (en) * | 2008-05-09 | 2009-11-12 | Funai Electric Co., Ltd. | Backlight Device and Liquid Crystal Display Apparatus |
WO2010074528A2 (en) * | 2008-12-24 | 2010-07-01 | Jang U In | Lighting apparatus with led for plant cultivation |
JP2010202733A (en) * | 2009-03-02 | 2010-09-16 | Idemitsu Technofine Co Ltd | Coating agent for signboard |
JP2013114875A (en) * | 2011-11-28 | 2013-06-10 | Inazuma Denki Koji:Kk | Lighting device |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001096167A (en) * | 1999-09-30 | 2001-04-10 | Toyoda Gosei Co Ltd | Photocatalyst component |
JP2003234005A (en) * | 2001-11-20 | 2003-08-22 | Asahi Kasei Corp | Light guide plate |
JP2003290664A (en) * | 2002-01-31 | 2003-10-14 | Toshiba Lighting & Technology Corp | Photocatalyst device, deodorizing device and refrigerator |
JP2005101458A (en) * | 2003-09-26 | 2005-04-14 | Sharp Corp | Semiconductor light emitting device |
JP2006012511A (en) * | 2004-06-24 | 2006-01-12 | Toshiba Lighting & Technology Corp | Lighting system and storage house |
-
2006
- 2006-03-31 JP JP2006098419A patent/JP2007273309A/en active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001096167A (en) * | 1999-09-30 | 2001-04-10 | Toyoda Gosei Co Ltd | Photocatalyst component |
JP2003234005A (en) * | 2001-11-20 | 2003-08-22 | Asahi Kasei Corp | Light guide plate |
JP2003290664A (en) * | 2002-01-31 | 2003-10-14 | Toshiba Lighting & Technology Corp | Photocatalyst device, deodorizing device and refrigerator |
JP2005101458A (en) * | 2003-09-26 | 2005-04-14 | Sharp Corp | Semiconductor light emitting device |
JP2006012511A (en) * | 2004-06-24 | 2006-01-12 | Toshiba Lighting & Technology Corp | Lighting system and storage house |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20090279019A1 (en) * | 2008-05-09 | 2009-11-12 | Funai Electric Co., Ltd. | Backlight Device and Liquid Crystal Display Apparatus |
US8773611B2 (en) * | 2008-05-09 | 2014-07-08 | Funai Electric Co., Ltd. | Angled backlight device and liquid crystal display apparatus |
WO2010074528A2 (en) * | 2008-12-24 | 2010-07-01 | Jang U In | Lighting apparatus with led for plant cultivation |
WO2010074528A3 (en) * | 2008-12-24 | 2010-10-21 | Jang U In | Lighting apparatus with led for plant cultivation |
JP2010202733A (en) * | 2009-03-02 | 2010-09-16 | Idemitsu Technofine Co Ltd | Coating agent for signboard |
JP2013114875A (en) * | 2011-11-28 | 2013-06-10 | Inazuma Denki Koji:Kk | Lighting device |
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