JP5688631B2 - Catalyst body supporting method, catalyst body supporting substrate and catalyst body supporting liquid preparation kit - Google Patents
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本発明は、触媒体担持方法、触媒体担持基材及び触媒体担持液調製用キットに関するものである。 The present invention relates to a catalyst body supporting method, a catalyst body supporting base material, and a catalyst body supporting liquid preparation kit.
従来、太陽光等の光線の照射により光触媒活性を発揮することができ、当該光触媒活性に基づく消臭効果、抗菌効果等を発揮することのできる光触媒が知られており、このような光触媒として、酸化チタンを例示することができる。 Conventionally, photocatalyst activity can be exhibited by irradiation of light such as sunlight, and a photocatalyst capable of exhibiting a deodorizing effect, an antibacterial effect, and the like based on the photocatalytic activity is known. As such a photocatalyst, Titanium oxide can be exemplified.
酸化チタンは、紫外線の照射により光触媒活性を発揮することのできる光触媒（紫外線応答型光触媒）であって、可視光線が照射されたとしても光触媒活性を発揮することができないものであるため、室内のように紫外線強度が微弱な環境下においては、光触媒活性を十分に発揮することができない。 Titanium oxide is a photocatalyst that can exhibit photocatalytic activity when irradiated with ultraviolet rays (ultraviolet-responsive photocatalyst) and cannot exhibit photocatalytic activity even when irradiated with visible light. Thus, in an environment where the ultraviolet intensity is weak, the photocatalytic activity cannot be sufficiently exhibited.
そこで、このような問題を解決すべく、従来、可視光線の照射により光触媒活性を発揮することのできる光触媒（可視光応答型光触媒）等が提案されている（特許文献１）。 Thus, in order to solve such problems, conventionally, a photocatalyst (visible light responsive photocatalyst) that can exhibit photocatalytic activity by irradiation with visible light has been proposed (Patent Document 1).
そして、このような紫外線や可視光線の照射により光触媒活性を発揮し得る光触媒体は、例えば、繊維又は繊維製品等の各種基材に光触媒活性に基づく消臭機能等を付与することを目的として繊維等に固着されて使用されており、従来、当該光触媒体を固着させてなる繊維又は繊維製品や、当該光触媒体を練り込んでなる繊維等が提案されている（特許文献２、３）。 And the photocatalyst which can exhibit photocatalytic activity by irradiation of such an ultraviolet-ray or visible light is a fiber for the purpose of providing the deodorizing function etc. based on photocatalytic activity to various base materials, such as a fiber or a textile product, for example Conventionally, a fiber or a fiber product in which the photocatalyst is fixed, a fiber in which the photocatalyst is kneaded, and the like have been proposed (Patent Documents 2 and 3).
しかしながら、特許文献２に記載されている繊維製品等は、光触媒体を含有する繊維処理剤に繊維製品を浸漬させることで、繊維に一定量の光触媒体が固着されてなるものであるが、得られる繊維製品等が、光触媒体の光触媒活性に基づく消臭機能等を十分に発揮し得ないという問題がある。 However, the fiber product described in Patent Document 2 is obtained by immersing the fiber product in a fiber treatment agent containing a photocatalyst, so that a certain amount of the photocatalyst is fixed to the fiber. There is a problem that the fiber product or the like obtained cannot sufficiently exhibit the deodorizing function based on the photocatalytic activity of the photocatalyst.
また、特許文献３に記載されている繊維は、光触媒体が練り込まれてなるものであるが、この繊維においても同様に光触媒体の光触媒活性に基づく消臭機能等を十分に発揮し得ないという問題がある。 Moreover, although the fiber described in Patent Document 3 is formed by kneading a photocatalyst body, this fiber cannot exhibit a deodorizing function or the like based on the photocatalytic activity of the photocatalyst body in the same manner. There is a problem.
このような課題に鑑みて、本発明は、繊維製品等を含む基材に、光触媒活性が十分に発揮され得るように触媒体を担持させることのできる触媒体担持方法、当該担持方法により触媒体が担持されてなる触媒体担持基材及び当該担持方法に使用し得る触媒体担持液調製用キットを提供することを目的とする。 In view of such a problem, the present invention provides a catalyst body supporting method capable of supporting a catalyst body on a substrate including a fiber product or the like so that the photocatalytic activity can be sufficiently exhibited, and the catalyst body by the supporting method. An object of the present invention is to provide a catalyst body-supporting base material on which catalyst is supported and a catalyst body-supporting liquid preparation kit that can be used in the supporting method.
上記課題を解決するために、本発明は、光線の照射により光触媒活性を発揮し得る触媒体を基材に担持させる方法であって、前記触媒体及び酸若しくはその塩又は２〜１０質量％の尿素と、前記基材とを接触させることで、前記基材に前記触媒体を担持させる担持工程を含むことを特徴とする触媒体担持方法を提供する（発明１）。 In order to solve the above-mentioned problems, the present invention is a method for supporting a catalyst body capable of exhibiting photocatalytic activity by irradiation of light on a substrate, the catalyst body and an acid or a salt thereof, or 2 to 10% by mass. There is provided a catalyst body supporting method characterized by including a supporting step of supporting the catalyst body on the base material by bringing urea into contact with the base material ( Invention 1).
上記発明（発明１）によれば、触媒体を担持させる対象である基材に触媒体とともに酸若しくはその塩又は尿素を接触させることで、基材に担持された触媒体が十分な光触媒活性を発揮することができる。したがって、上記発明（発明１）に係る方法により触媒体が担持された基材が、触媒体の光触媒活性に基づく消臭機能等の各種機能を十分に発揮することができる。 According to the above invention ( Invention 1), the catalyst body supported on the base material has sufficient photocatalytic activity by contacting the catalyst body with an acid or a salt thereof or urea together with the base material on which the catalyst body is supported. It can be demonstrated. Therefore, the base material on which the catalyst body is supported by the method according to the invention ( Invention 1) can sufficiently exhibit various functions such as a deodorizing function based on the photocatalytic activity of the catalyst body.
上記発明（発明１）においては、前記担持工程において、前記触媒体及び酸若しくはその塩又は尿素を含有する触媒体担持液に前記基材を浸漬させてもよい（発明２）。かかる発明（発明２）によれば、基材に略均一に触媒体を担持させることができる。 In the said invention ( invention 1), in the said carrying | support process, you may immerse the said base material in the said catalyst body and the catalyst body carrying | support liquid containing an acid or its salt, or urea ( invention 2). According to this invention ( Invention 2), the catalyst body can be supported substantially uniformly on the substrate.
上記発明（発明１）においては、前記担持工程が、前記触媒体を含有する第１の液体に前記基材を浸漬させる工程と、前記酸若しくはその塩又は尿素を含有する第２の液体に前記基材を浸漬させる工程とを含むものであってもよい（発明３）。 In the above invention ( Invention 1), the supporting step includes the step of immersing the substrate in the first liquid containing the catalyst body, and the second liquid containing the acid or a salt thereof or urea. And a step of immersing the substrate ( Invention 3).
触媒体の種類によっては、酸等と混合すると当該触媒体が沈殿してしまい、基材に触媒体を担持させるのが困難となるおそれがあるが、上記発明（発明３）のように触媒体を基材に接触させる工程と、酸等を基材に接触させる工程とを別工程とすることで、酸等と混合させることにより沈殿を生じてしまうような触媒体であっても、効果的に基材に担持させることができる。 Depending on the type of catalyst body, when mixed with an acid or the like, the catalyst body may precipitate, making it difficult to support the catalyst body on the substrate. However, as in the above invention ( Invention 3), Even if it is a catalyst body which precipitates by mixing with an acid etc. by making the process which makes a base material contact the process, and the process which makes an acid etc. contact a base material, it is effective Can be supported on a substrate.
上記発明（発明１〜３）においては、前記酸が、クエン酸、リンゴ酸、シュウ酸、アジピン酸、酢酸、コハク酸、乳酸、酒石酸、塩酸、硝酸、リン酸及び炭酸からなる群より選択される少なくとも１種であるのが好ましい（発明４）。 In the above inventions ( Inventions 1 to 3), the acid is selected from the group consisting of citric acid, malic acid, oxalic acid, adipic acid, acetic acid, succinic acid, lactic acid, tartaric acid, hydrochloric acid, nitric acid, phosphoric acid and carbonic acid. At least one of these is preferable ( Invention 4).
さらに、本発明は、基材に、上記発明（発明１〜４）に係る触媒体担持方法により前記触媒体が担持されてなることを特徴とする触媒体担持基材を提供する（発明５）。かかる発明（発明５）によれば、光触媒活性を十分に発揮し得る触媒体担持基材を提供することができる。 Furthermore, the present invention provides a catalyst body-supporting base material, wherein the catalyst body is supported on the base material by the catalyst body support method according to the above inventions ( Inventions 1 to 4) ( Invention 5). . According to this invention ( invention 5), it is possible to provide a catalyst body-supporting substrate that can sufficiently exhibit photocatalytic activity.
さらにまた、本発明は、光線の照射により光触媒活性を発揮し得る触媒体を基材に担持させるために用いられる触媒体担持液の調製用キットであって、前記触媒体が収容されている第１の容器と、少なくとも酸若しくはその塩又は尿素が収容されている第２の容器とを備えることを特徴とする触媒体担持液調製用キットを提供する（発明６）。 Furthermore, the present invention is a kit for preparing a catalyst body-supporting liquid used for supporting a catalyst body capable of exhibiting photocatalytic activity by irradiation of light on a substrate, wherein the catalyst body is contained in the first kit. There is provided a kit for preparing a catalyst-supporting liquid, characterized in that it comprises one container and a second container containing at least an acid or a salt thereof or urea ( Invention 6).
本発明によれば、繊維製品等を含む基材に、光触媒活性が十分に発揮され得るように触媒体を担持させることのできる触媒体担持方法、当該担持方法により触媒体が担持されてなる触媒体担持基材及び当該担持方法に使用し得る触媒体担持液調製用キットを提供することができる。 According to the present invention, a catalyst body supporting method capable of supporting a catalyst body on a substrate including a fiber product or the like so that the photocatalytic activity can be sufficiently exhibited, and a catalyst in which the catalyst body is supported by the supporting method. It is possible to provide a medium carrying substrate and a catalyst body carrying liquid preparation kit that can be used in the carrying method.
以下、本発明の実施形態について説明する。
本実施形態に係る触媒体担持方法は、光線の照射により光触媒活性を発揮し得る触媒体及び酸若しくはその塩又は２〜１０質量％の尿素と、基材とを接触させることで、基材に触媒体を担持させる担持工程を含むものである。
Hereinafter, embodiments of the present invention will be described.
The catalyst body carrying | support method which concerns on this embodiment makes the base material contact the catalyst body which can exhibit photocatalytic activity by irradiation of light, an acid or its salt, or 2-10 mass% urea, and a base material. It includes a supporting step for supporting the catalyst body.
上記基材としては、特に限定されるものではなく、例えば、綿、ウール、麻、絹、セルロース系繊維等の繊維；それらの繊維のうちの少なくとも１種の繊維から構成される織布、不織布等の繊維集合体等が挙げられるが、これらのうち綿布が好適に用いられる。本実施形態に係る方法により綿布に触媒体を担持させることで、当該綿布を、触媒体の光触媒活性に基づく消臭機能等の各種機能に極めて優れたものとすることができる。 The substrate is not particularly limited, and examples thereof include cotton, wool, hemp, silk, cellulosic fibers, and the like; woven fabrics and nonwoven fabrics composed of at least one of these fibers Among these, a cotton cloth is preferably used. By carrying a catalyst body on a cotton cloth by the method according to this embodiment, the cotton cloth can be made extremely excellent in various functions such as a deodorizing function based on the photocatalytic activity of the catalyst body.
上記触媒体は、可視光線の照射により光触媒活性を発揮せず、紫外線の照射により光触媒活性を発揮し得る粉末状（粒子状）の光触媒体（いわゆる「紫外線応答型光触媒（従来型光触媒）」、以下「第１の触媒体」という場合がある。）であってもよいし、少なくとも可視光線の照射により光触媒活性を発揮し得る粉末状（粒子状）の光触媒体（いわゆる「可視光応答型光触媒（可視光型光触媒）」、以下「第２の触媒体」という場合がある。）であってもよいし、これらの混合物であってもよい。 The above-mentioned catalyst body does not exhibit photocatalytic activity when irradiated with visible light, but is a powdery (particulate) photocatalyst body that can exhibit photocatalytic activity when irradiated with ultraviolet rays (so-called “ultraviolet-responsive photocatalyst (conventional photocatalyst)”), Hereinafter, it may be referred to as “first catalyst body”), or at least a powdered (particulate) photocatalyst that can exhibit photocatalytic activity by irradiation with visible light (so-called “visible light responsive photocatalyst”). (Visible light photocatalyst) ", hereinafter may be referred to as" second catalyst body "), or a mixture thereof.
第１の触媒体としては、例えば、酸化チタン（ＴｉＯ２）、酸化亜鉛（ＺｎＯ）、チタン酸ストロンチウム（ＳｒＴｉＯ３）等の金属酸化物；硫化亜鉛（ＺｎＳ）等の金属硫化物等が挙げられ、第２の触媒体としては、例えば、酸化タングステン（ＷＯ３）；酸化チタン又は酸化タングステンに白金（Ｐｔ）、金（Ａｕ）、鉄（Ｆｅ）、銅（Ｃｕ）等の金属のうちの少なくとも１種を担持させた金属担持酸化チタン又は金属担持酸化タングステン；酸化チタンに窒素、炭素、硫黄等のうちの少なくとも１種をドープしたドープ酸化チタン；二酸化チタンの結晶から部分的に酸素原子を引き抜いた酸素欠損型酸化チタン等が挙げられる。 Examples of the first catalyst body include metal oxides such as titanium oxide (TiO 2 ), zinc oxide (ZnO) and strontium titanate (SrTiO 3 ); metal sulfides such as zinc sulfide (ZnS) and the like. As the second catalyst body, for example, tungsten oxide (WO 3 ); at least one of metals such as titanium oxide or tungsten oxide and platinum (Pt), gold (Au), iron (Fe), copper (Cu), etc. Metal-supported titanium oxide or metal-supported tungsten oxide supporting one species; doped titanium oxide doped with at least one of nitrogen, carbon, sulfur, etc. on titanium oxide; partially extracting oxygen atoms from titanium dioxide crystals And oxygen deficient titanium oxide.
第１の触媒体及び第２の触媒体として酸化チタン（第２の触媒体としての酸化チタンは、金属が担持され、窒素等がドープされ、又は部分的に酸素原子が引き抜かれる対象としての酸化チタン）を用いる場合、当該酸化チタンの結晶構造としては、アナターゼ型、ルチル型、ブルッカイト型等が挙げられ、当該酸化チタンは、これらのうち１種の結晶構造を有するもののみであってもよいし、２種以上の結晶構造を有するものの混合物であってもよい。当該酸化チタンは、これらのうち、光触媒活性が比較的高いとされるアナターゼ型の結晶構造を有する酸化チタンを少なくとも含んでいるのが好ましい。 Titanium oxide as the first catalyst body and the second catalyst body (titanium oxide as the second catalyst body is oxidized as a target on which a metal is supported, nitrogen is doped, or oxygen atoms are partially extracted. In the case of using (titanium), examples of the crystal structure of the titanium oxide include anatase type, rutile type, brookite type, etc., and the titanium oxide may have only one type of crystal structure. A mixture of two or more crystal structures may be used. Of these, the titanium oxide preferably contains at least titanium oxide having an anatase-type crystal structure that has a relatively high photocatalytic activity.
酸化チタンの結晶構造は、例えば、Ｘ線回折スペクトルのピーク位置に基づいて同定することができる。また、このときのピーク位置とその半価幅から、結晶子径を求めることができる。例えば、アナターゼ型の結晶構造を有する酸化チタンを用いる場合、その結晶子径は、通常１０ｎｍ以上であり、そのような光触媒であれば、光の照射に対して高い光触媒活性を示すものとなる。 The crystal structure of titanium oxide can be identified based on, for example, the peak position of the X-ray diffraction spectrum. Further, the crystallite diameter can be obtained from the peak position at this time and the half width thereof. For example, when titanium oxide having an anatase type crystal structure is used, the crystallite diameter is usually 10 nm or more, and such a photocatalyst exhibits high photocatalytic activity against light irradiation.
酸又はその塩としては、特に限定されるものではなく、例えば、クエン酸、リンゴ酸、シュウ酸、アジピン酸、酢酸、コハク酸、乳酸、酒石酸等の有機酸、塩酸、硝酸、リン酸、炭酸等の無機酸等、又はそれらのナトリウム塩、カルシウム塩等を用いることができる。 The acid or salt thereof is not particularly limited, and examples thereof include citric acid, malic acid, oxalic acid, adipic acid, acetic acid, succinic acid, lactic acid, tartaric acid and other organic acids, hydrochloric acid, nitric acid, phosphoric acid, carbonic acid, and the like. Inorganic acids such as these, or their sodium salts, calcium salts, and the like can be used.
本実施形態に係る触媒体担持方法につき、以下具体的な実施形態を説明する。
〔第１の実施形態〕
第１の実施形態に係る触媒体担持方法は、触媒体及び酸若しくはその塩又は２〜１０質量％の尿素と、基材とを接触させるべく、触媒体及び酸若しくはその塩又は２〜１０質量％の尿素を含有する触媒体担持液に基材を浸漬させる。
Specific embodiments of the catalyst body carrying method according to the present embodiment will be described below.
[First Embodiment]
The catalyst body carrying | support method which concerns on 1st Embodiment is a catalyst body, an acid, its salt, or 2-10 mass in order to make a catalyst body, an acid or its salt, or 2-10 mass% urea and a base material contact. The substrate is immersed in a catalyst support liquid containing 1% urea.
触媒体担持液における触媒体の含有量は、特に限定されるものではなく、０．０５〜２質量％であるのが好ましく、０．０５〜１質量％であるのがより好ましく、０．０５〜０．５質量％であるのが特に好ましい。０．０５質量％未満であると基材への触媒体の担持量が少なくなり、所望とする光触媒活性が発揮されないおそれがあり、２質量％を超えると触媒体担持基材の製造コストが増大してしまう。 The content of the catalyst body in the catalyst body support liquid is not particularly limited and is preferably 0.05 to 2% by mass, more preferably 0.05 to 1% by mass, It is particularly preferable that the content be ˜0.5% by mass. If the amount is less than 0.05% by mass, the amount of the catalyst body supported on the substrate decreases, and the desired photocatalytic activity may not be exhibited. If the amount exceeds 2% by mass, the production cost of the catalyst body-supported substrate increases. Resulting in.
触媒体担持液は、触媒体の他、当該触媒体を分散させるための分散媒がさらに含まれるものである。このような分散媒としては、例えば、水；エチルアルコール、イソプロピルアルコール等の有機溶媒等が挙げられ、これらのうち水を分散媒として用いるのが好ましい。 In addition to the catalyst body, the catalyst body supporting liquid further includes a dispersion medium for dispersing the catalyst body. Examples of such a dispersion medium include water; organic solvents such as ethyl alcohol and isopropyl alcohol. Among these, water is preferably used as the dispersion medium.
触媒体担持液における分散媒の配合量は、触媒体担持液中に触媒体が好適に分散し得る範囲内であれば特に限定されず、担持工程における作業性等に応じて適宜設定することができる。 The amount of the dispersion medium in the catalyst body supporting liquid is not particularly limited as long as the catalyst body can be suitably dispersed in the catalyst body supporting liquid, and can be set as appropriate according to workability in the supporting process. it can.
触媒体担持液には、バインダー成分がさらに含まれていてもよい。バインダー成分としては、例えば、アクリル系樹脂、ポリエステル樹脂、メラミン樹脂、ウレタン系樹脂、フッ素系樹脂等を用いることができる。 The catalyst support liquid may further contain a binder component. As the binder component, for example, an acrylic resin, a polyester resin, a melamine resin, a urethane resin, a fluorine resin, or the like can be used.
触媒体担持液におけるバインダー成分の配合量は、特に限定されるものではなく、例えば、基材に触媒体を担持させる際に、当該触媒体が基材に効果的に担持され得るように適宜調整すればよい。 The blending amount of the binder component in the catalyst body supporting liquid is not particularly limited. For example, when the catalyst body is supported on the base material, it is appropriately adjusted so that the catalyst body can be effectively supported on the base material. do it.
なお、触媒体担持液には、さらに任意成分として、ジ−２−エチルヘキシルスルホコハク酸ナトリウム等の界面活性剤（浸透剤）；ゼオライト、シリカ等の消臭剤；イソプロピルアルコール、エチルアルコール等のアルコール類等が含まれていてもよい。 In addition, the catalyst support liquid further includes, as optional components, surfactants (penetrating agents) such as sodium di-2-ethylhexylsulfosuccinate; deodorants such as zeolite and silica; alcohols such as isopropyl alcohol and ethyl alcohol Etc. may be included.
触媒体担持液が酸又はその塩を含有するものである場合、当該触媒体担持液における酸又はその塩の含有量は、０．０１質量％以上であるのが好ましく、０．０５〜０．３質量％であるのがより好ましい。０．０１質量％未満であると、基材に担持された触媒体の光触媒活性が発揮され難いおそれがあり、０．３質量％を超えると、上記担持工程を行うための装置が錆びたり、基材の酸性度が強くなったりするおそれがある。また、触媒体担持基材の製造コストが増大してしまう。 In the case where the catalyst body supporting liquid contains an acid or a salt thereof, the content of the acid or salt thereof in the catalyst body supporting liquid is preferably 0.01% by mass or more, and 0.05 to 0.00. More preferably, it is 3% by mass. If it is less than 0.01% by mass, the photocatalytic activity of the catalyst supported on the substrate may be difficult to be exhibited, and if it exceeds 0.3% by mass, the apparatus for performing the above-described supporting process may rust, There is a possibility that the acidity of the substrate becomes strong. In addition, the manufacturing cost of the catalyst body-supporting substrate increases.
また、触媒体担持液が尿素を含有するものである場合、当該触媒体担持液における尿素の含有量は、２〜１０質量％であり、４〜８質量％であるのが好ましい。２質量％未満であると、基材に担持された触媒体の光触媒活性が発揮されず、１０質量％を超えても、基材に担持された触媒体による光触媒活性のさらなる向上が見込めないばかりか、触媒体担持基材の製造コストが増大してしまう。 Moreover, when the catalyst body supporting liquid contains urea, the urea content in the catalyst body supporting liquid is 2 to 10% by mass, and preferably 4 to 8% by mass. If it is less than 2% by mass, the photocatalytic activity of the catalyst body supported on the substrate cannot be exhibited, and even if it exceeds 10% by mass, further improvement of the photocatalytic activity due to the catalyst body supported on the substrate cannot be expected. Or the manufacturing cost of a catalyst body support base material will increase.
触媒体担持液は、触媒体担持液を構成する各成分（触媒体、酸若しくはその塩又は尿素、分散媒、バインダー成分等）を所望含有量となるように混合することで調製することができるが、後述する触媒体担持液調製用キットを用いることにより、容易に調製することができる。 The catalyst body supporting liquid can be prepared by mixing each component (catalyst body, acid or salt thereof, urea, dispersion medium, binder component, etc.) constituting the catalyst body supporting liquid so as to have a desired content. However, it can be easily prepared by using a catalyst body supporting liquid preparation kit described later.
第１の実施形態において、触媒体担持液に基材を浸漬させる時間は、基材に所望とする量の触媒体を担持させることができる限り特に制限はなく、基材の種類等（基材として繊維集合体を用いる場合、繊維集合体を構成する繊維の種類、目付量、厚さ等）に応じて適宜設定することができる。 In the first embodiment, the time for immersing the base material in the catalyst body supporting liquid is not particularly limited as long as the desired amount of the catalyst body can be supported on the base material. In the case of using a fiber assembly, it can be appropriately set according to the type of fibers constituting the fiber assembly, the basis weight, the thickness, and the like.
そして、触媒体担持液に浸漬させた基材を取り出し、触媒体担持液から取り出した基材を乾燥させる。基材の乾燥は、常温で行ってもよいし、乾燥機等を用いて常法により行ってもよい。 And the base material immersed in the catalyst body supporting liquid is taken out, and the base material taken out from the catalyst body supporting liquid is dried. The substrate may be dried at room temperature or by a conventional method using a dryer or the like.
このようにして第１の実施形態により得られる触媒体担持基材における触媒体の担持量は、０．０５〜１ｇ／ｍ２であるのが好ましく、特に０．１〜０．５ｇ／ｍ２であるのが好ましい。基材における触媒体の担持量が上記範囲内であれば、光触媒活性に基づく優れた消臭機能等の各種機能を触媒体担持基材に付与することができる。 Supported amount of the catalytic body in this way, the first embodiment by the catalyst-supported substrate obtained is preferably from 0.05 to 1 g / m 2, in particular 0.1 to 0.5 g / m 2 Is preferred. If the amount of the catalyst body supported on the substrate is within the above range, various functions such as an excellent deodorizing function based on the photocatalytic activity can be imparted to the catalyst body-supported substrate.
上述したように、第１の実施形態に係る触媒体担持方法によれば、基材に担持された触媒体が十分な光触媒活性を発揮することができるため、光触媒活性に基づく消臭機能等の各種機能に優れた触媒体担持基材を製造することができる。 As described above, according to the catalyst body supporting method according to the first embodiment, since the catalyst body supported on the base material can exhibit sufficient photocatalytic activity, the deodorizing function based on the photocatalytic activity, etc. A catalyst body-supporting substrate excellent in various functions can be produced.
〔第２の実施形態〕
第２の実施形態に係る触媒体担持方法は、触媒体を含有する第１の液体に基材を浸漬させる工程（第１の工程）と、酸若しくはその塩又は２〜１０質量％の尿素を含有する第２の液体に基材を浸漬させる工程（第２の工程）とを含む。
[Second Embodiment]
The catalyst body supporting method according to the second embodiment includes a step of immersing the substrate in the first liquid containing the catalyst body (first step), an acid or a salt thereof, or 2 to 10% by mass of urea. And a step of immersing the base material in the second liquid to be contained (second step).
第１の実施形態に係る方法のように触媒体と酸等とを混合させて触媒体担持液を調製したとしても、触媒体の種類によっては、当該触媒体担持液において触媒体が沈殿してしまうものもある。触媒体が沈殿してしまうと、触媒体担持液に基材を浸漬させたとしても、基材と触媒体とを接触させることが困難となり、結果として基材に触媒体を担持させることが困難となってしまう。そこで、第２の実施形態に係る方法のように、基材に触媒体を接触させる第１の工程と基材に酸等を接触させる第２の工程との別工程とすることで、酸等と混合すると沈殿してしまうような触媒体であっても効果的に基材に担持させることができる。 Even if the catalyst body supporting liquid is prepared by mixing the catalyst body and acid as in the method according to the first embodiment, depending on the type of the catalyst body, the catalyst body is precipitated in the catalyst body supporting liquid. Some will end up. If the catalyst body is precipitated, even if the substrate is immersed in the catalyst body supporting liquid, it is difficult to bring the substrate and the catalyst body into contact with each other, and as a result, it is difficult to support the catalyst body on the substrate. End up. Therefore, as in the method according to the second embodiment, the first step of bringing the catalyst body into contact with the base material and the second step of bringing the acid or the like into contact with the base material make it possible to use acid or the like. Even a catalyst body that precipitates when mixed with can be effectively supported on a substrate.
第１の液体における触媒体の含有量及び第２の液体における酸若しくはその塩又は尿素の含有量は、第１の実施形態の触媒体担持液におけるそれらの含有量と同様であればよい。 The content of the catalyst body in the first liquid and the content of the acid or salt thereof or urea in the second liquid may be the same as those contents in the catalyst body support liquid of the first embodiment.
第１の液体には、第１の実施形態の触媒体担持液と同様に分散媒が含まれ、また、バインダー成分、浸透剤、消臭剤、アルコール類等が含まれていてもよい。なお、第１の液体におけるそれらの含有量も第１の実施形態の触媒体担持液と同様であればよい。 The first liquid contains a dispersion medium in the same manner as the catalyst body supporting liquid of the first embodiment, and may contain a binder component, a penetrant, a deodorant, alcohols, and the like. Note that the content of the first liquid may be the same as that of the catalyst-supporting liquid of the first embodiment.
さらに、第１の液体に含まれる触媒体としては、第１の実施形態の触媒体担持液に含まれる触媒体と同様のものを用いることができるが、酸等と混合した際に沈殿を生じてしまうおそれのある触媒体を好適に用いることができ、第２の液体に含まれる酸又はその塩としては、第１の実施形態の触媒体担持液に含まれる酸又はその塩と同様のものを用いることができる。 Furthermore, as the catalyst body contained in the first liquid, the same catalyst body as that contained in the catalyst body supporting liquid of the first embodiment can be used, but precipitation occurs when mixed with an acid or the like. The acid or the salt thereof contained in the second liquid is preferably the same as the acid or the salt contained in the catalyst-body-supporting liquid of the first embodiment. Can be used.
第２の実施形態において、第１の工程と第２の工程とを行う順序は、特に限定されるものではないが、第１の工程を第２の工程よりも先に行うのが好ましい。第１の工程を第２の工程よりも先に行った方が、触媒体の光触媒活性に基づく、より優れた消臭機能等を有する触媒体担持基材を得ることができる。 In the second embodiment, the order in which the first step and the second step are performed is not particularly limited, but it is preferable to perform the first step before the second step. When the first step is performed before the second step, a catalyst body-supporting substrate having a more excellent deodorizing function and the like based on the photocatalytic activity of the catalyst body can be obtained.
第１の液体は、第１の液体を構成する各成分（触媒体、分散媒、バインダー成分等）を所望の含有量となるように混合することで得ることができ、第２の液体は、第２の液体を構成する各成分（酸若しくはその塩又は尿素）を所望の含有量となるように混合することで得ることができるが、後述する触媒体担持液調製用キットを用いることにより、容易に調製することができる。 The first liquid can be obtained by mixing each component (catalyst, dispersion medium, binder component, etc.) constituting the first liquid so as to have a desired content, and the second liquid is Although it can be obtained by mixing each component (acid or salt thereof or urea) constituting the second liquid so as to have a desired content, by using a catalyst body supporting liquid preparation kit described later, It can be easily prepared.
第１及び第２の工程における基材の第１及び第２の液体への浸漬時間は、基材に所望とする量の触媒体を担持させることができる限り特に制限はなく、基材の種類等（基材として繊維集合体を用いる場合、繊維集合体を構成する繊維の種類、目付量、厚さ等）に応じて適宜設定することができる。 The immersion time of the base material in the first and second liquids in the first and second steps is not particularly limited as long as the desired amount of the catalyst body can be supported on the base material. Etc. (when a fiber assembly is used as the substrate, it can be appropriately set according to the type of fibers constituting the fiber assembly, the basis weight, the thickness, etc.).
第１又は第２の工程後、第２又は第１の工程に移行する前に、基材を乾燥させてもよい。特に、第１の工程後に第２の工程を行う場合には、第１の工程後に基材を乾燥させるのが好ましい。基材を乾燥させることなく第１の工程から第２の工程に移行すると、第２の工程において第２の液体中に基材から触媒体が流出してしまうおそれがある。 After the first or second step, the substrate may be dried before moving to the second or first step. In particular, when the second step is performed after the first step, it is preferable to dry the substrate after the first step. If the process shifts from the first step to the second step without drying the substrate, the catalyst body may flow out from the substrate into the second liquid in the second step.
このようにして得られる触媒体担持基材は、基材に担持された触媒体が十分な光触媒活性を発揮することができるため、光触媒活性に基づく消臭機能等の各種機能に優れたものとなる。 The catalyst body-supporting base material obtained in this way is excellent in various functions such as a deodorizing function based on the photocatalytic activity because the catalyst body supported on the base material can exhibit sufficient photocatalytic activity. Become.
第２の実施形態により得られる触媒体担持基材における触媒体の担持量は、０．０５〜１ｇ／ｍ２であるのが好ましく、特に０．１〜０．５ｇ／ｍ２であるのが好ましい。基材における触媒体の担持量が上記範囲内であれば、光触媒活性に基づく優れた消臭機能等の各種機能を触媒体担持基材に付与することができる。 Supported amount of the catalytic body according to a second embodiment the catalyst-supported substrate obtained by the form is preferably from 0.05 to 1 g / m 2, and even in particular 0.1 to 0.5 g / m 2 preferable. If the amount of the catalyst body supported on the substrate is within the above range, various functions such as an excellent deodorizing function based on the photocatalytic activity can be imparted to the catalyst body-supported substrate.
上述したように、第２の実施形態に係る触媒体担持方法によれば、基材に担持された触媒体が十分な光触媒活性を発揮することができるため、光触媒活性に基づく消臭機能等の各種機能に優れた触媒体担持基材を製造することができる。特に、第２の実施形態に係る触媒体担持方法によれば、酸等と混合すると沈澱を生じてしまうような触媒体であっても効果的に基材に担持させることができる。 As described above, according to the catalyst body supporting method according to the second embodiment, since the catalyst body supported on the base material can exhibit sufficient photocatalytic activity, the deodorizing function based on the photocatalytic activity, etc. A catalyst body-supporting substrate excellent in various functions can be produced. In particular, according to the catalyst body supporting method according to the second embodiment, even a catalyst body that causes precipitation when mixed with an acid or the like can be effectively supported on a substrate.
〔触媒体担持液調製用キット〕
触媒体担持液調製用キットは、少なくとも触媒体を含有する第１の原液を収容する第１の容器と、少なくとも酸若しくはその塩又は尿素を含有する第２の原液を収容する第２の容器とを備える。
[Catalyst support liquid preparation kit]
A kit for preparing a catalyst body-supporting liquid includes a first container that contains a first stock solution containing at least a catalyst body, and a second container that contains a second stock solution containing at least an acid, a salt thereof, or urea. Is provided.
上記触媒体担持液調製用キットを用いることで、上記第１の実施形態の担持工程において使用される触媒体担持液又は上記第２の実施形態の第１の工程及び第２の工程において使用される第１の液体及び第２の液体を極めて容易に調製することができる。 By using the catalyst body supporting liquid preparation kit, the catalyst body supporting liquid used in the supporting process of the first embodiment or the first process and the second process of the second embodiment is used. The first liquid and the second liquid can be prepared very easily.
第１の実施形態における触媒体担持液は、第１の容器に収容されている第１の原液を水（純水等）で希釈して得られる第１の希釈液と第２の容器に収容されている第２の原液とを混合することにより調製することができる。なお、第１の原液中の触媒体含有量や第２の原液中の酸若しくはその塩又は尿素含有量によっては、第１の原液と、第２の原液又は第２の原液を純水等の水で希釈して得られる第２の希釈液とを混合して触媒体担持液を調製してもよい。 The catalyst body supporting liquid in the first embodiment is stored in the first container and the second container obtained by diluting the first stock solution stored in the first container with water (pure water or the like). It can be prepared by mixing the second stock solution. Depending on the catalyst body content in the first stock solution and the acid or salt thereof or urea content in the second stock solution, the first stock solution, the second stock solution or the second stock solution may be purified water or the like. A catalyst support liquid may be prepared by mixing with a second diluent obtained by diluting with water.
第２の実施形態における第１の液体としては、第１の液体中の触媒体含有量が所定の含有量となる限り、第１の原液中の触媒体含有量に応じて、第１の原液をそのまま使用してもよいいし、第１の原液を水（純水等）で希釈して得られる第１の希釈液を使用してもよい。 As a 1st liquid in 2nd Embodiment, as long as the catalyst body content in a 1st liquid turns into predetermined content, according to the catalyst body content in a 1st stock solution, the 1st stock solution May be used as they are, or a first diluted solution obtained by diluting the first stock solution with water (pure water or the like) may be used.
第２の実施形態における第２の液体としては、第２の液体中の酸若しくはその塩又は尿素含有量が所定の含有量となる限り、第２の原液中のそれらの含有量に応じて、第２の原液をそのまま使用してもよいし、第２の原液を水（純水等）で希釈して得られる第２の希釈液を使用してもよい。 As the second liquid in the second embodiment, as long as the acid or salt thereof or urea content in the second liquid is a predetermined content, according to their content in the second stock solution, The second stock solution may be used as it is, or a second diluted solution obtained by diluting the second stock solution with water (pure water or the like) may be used.
上記希釈液（第１の希釈液、第２の希釈液）を調製する場合における希釈倍率（質量基準）は、基材の種類、第１の原液中の触媒体含有量、第２の原液中の酸若しくはその塩又は尿素含有量等に応じて適宜設定することができるが、例えば、基材として繊維集合体を使用する場合には、２０〜８０倍であるのが好ましく、３０倍〜５０倍程度であるのがより好ましい。 The dilution ratio (mass standard) in the case of preparing the dilution liquid (first dilution liquid, second dilution liquid) is the kind of base material, the content of the catalyst body in the first stock solution, and in the second stock solution. Although it can set suitably according to the acid or its salt of urea or urea content etc., when using a fiber assembly as a base material, it is preferable that it is 20-80 times, 30 times-50 times, for example. More preferably, it is about double.
上述したように、上記触媒体担持液調製用キットによれば、それぞれ別個の容器に収容されている第１の原液（又は第１の原液を希釈して得られる第１の希釈液）と第２の原液（又は第２の原液を希釈して得られる第２の希釈液）とを混合するだけで、触媒体担持液を極めて簡単に調製することができる。 As described above, according to the kit for preparing a catalyst body-supporting liquid, the first stock solution (or the first diluted solution obtained by diluting the first stock solution) and the first stock solution that are housed in separate containers, respectively. By simply mixing the two stock solutions (or the second diluted solution obtained by diluting the second stock solution), the catalyst body supporting solution can be prepared very easily.
以上説明した実施形態は、本発明の理解を容易にするために記載されたものであって、本発明を限定するために記載されたものではない。したがって、上記実施形態に開示された各要素は、本発明の技術的範囲に属する全ての設計変更や均等物をも含む趣旨である。 The embodiment described above is described for facilitating understanding of the present invention, and is not described for limiting the present invention. Therefore, each element disclosed in the above embodiment is intended to include all design changes and equivalents belonging to the technical scope of the present invention.
上記第１の実施形態又は第２の実施形態において、基材を触媒体担持液、又は第１の液体及び第２の液体に浸漬させることにより基材に触媒体を担持させているが、これに限定されるものではなく、基材表面に触媒体担持液、又は第１の液体及び第２の液体を噴霧する方法により、基材に触媒体を担持させるようにしてもよい。この場合において、基材に噴霧される触媒体担持液又は第１の液体中の触媒体含有量は、０．５〜５質量％であるのが好ましい。 In the first embodiment or the second embodiment, the substrate is supported on the substrate by immersing the substrate in the catalyst support liquid, or the first liquid and the second liquid. However, the catalyst body may be supported on the base material by a method of spraying the catalyst body supporting liquid or the first liquid and the second liquid on the surface of the base material. In this case, the catalyst body content in the catalyst body-supporting liquid or the first liquid sprayed on the base material is preferably 0.5 to 5% by mass.
また、上記方法以外にも、ロールコーター、ナイフコーター、ロールナイフコーター、エアナイフコーター、ダイコーター、バーコーター、グラビアコーター、カーテンコーター等の塗工機を用いて基材表面に触媒体担持液、又は第１の液体及び第２の液体を塗布し乾燥する方法により基材に触媒体を担持させるようにしてもよい。 In addition to the above method, a catalyst carrier-supporting liquid on the substrate surface using a coating machine such as a roll coater, knife coater, roll knife coater, air knife coater, die coater, bar coater, gravure coater, curtain coater, or You may make it carry | support a catalyst body on a base material by the method of apply | coating and drying a 1st liquid and a 2nd liquid.
上記触媒体担持液調製用キットにおける第１の容器には第１の原液が収容されているが、これに限定されるものではなく、例えば、第１の容器に触媒体（粉末状等）のみが収容されており、触媒体を分散させるための分散媒、バインダー等が収容された別個の容器をさらに備えるものであってもよい。 The first container in the catalyst body supporting liquid preparation kit contains the first stock solution. However, the present invention is not limited to this. For example, only the catalyst body (powder or the like) is contained in the first container. And a separate container in which a dispersion medium, a binder, and the like for dispersing the catalyst body are accommodated.
以下、実施例及び比較例を挙げて本発明をさらに詳細に説明するが、本発明は下記の実施例に何ら限定されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated further in detail, this invention is not limited to the following Example at all.
〔比較例１〕
紫外線応答型光触媒（Ｆ６−ＡＰＳ，昭和電工社製）と飽和共重合ポリエステル樹脂エマルジョン（ガラス転移温度（Ｔｇ）：−１０℃）とを混合し、水で希釈して、酸化チタン固形分７質量％、ポリエステル樹脂固形分３．０質量％の第１の原液を調製した。得られた第１の原液を水で４０倍（質量基準）に希釈した希釈液に綿ブロード布（目付量：１１５ｇ／ｍ２）を浸漬させ、その後乾燥させて、触媒体担持基材を得た。
[Comparative Example 1]
A UV-responsive photocatalyst (F6-APS, Showa Denko KK) and a saturated copolymerized polyester resin emulsion (glass transition temperature (Tg): −10 ° C.) are mixed, diluted with water, and a solid content of titanium oxide of 7 mass. %, A first stock solution having a polyester resin solid content of 3.0% by mass was prepared. A cotton broad cloth (weight per unit area: 115 g / m 2 ) was immersed in a diluted solution obtained by diluting the obtained first stock solution 40 times (mass basis) with water, and then dried to obtain a catalyst body-supporting substrate. It was.
〔比較例２〕
第１の原液を希釈した希釈液における尿素含有量が０．１質量％となるように尿素を添加した以外は、比較例１と同様にして触媒体担持基材を得た。
[Comparative Example 2]
A catalyst body-supporting substrate was obtained in the same manner as in Comparative Example 1 except that urea was added so that the urea content in the diluted solution obtained by diluting the first stock solution was 0.1% by mass.
〔比較例３〕
第１の原液を希釈した希釈液における尿素含有量が０．５質量％となるように尿素を添加した以外は、比較例１と同様にして触媒体担持基材を得た。
[Comparative Example 3]
A catalyst body-supporting substrate was obtained in the same manner as in Comparative Example 1 except that urea was added so that the urea content in the diluted solution obtained by diluting the first stock solution was 0.5 mass%.
〔実施例１〕
第１の原液を希釈した希釈液における尿素含有量が４質量％となるように尿素を添加した以外は、比較例１と同様にして触媒体担持基材を得た。
[Example 1]
A catalyst body-supporting substrate was obtained in the same manner as in Comparative Example 1 except that urea was added so that the urea content in the diluted solution obtained by diluting the first stock solution was 4% by mass.
〔実施例２〕
第１の原液を希釈した希釈液における尿素含有量が８質量％となるように尿素を添加した以外は、比較例１と同様にして触媒体担持基材を得た。
[Example 2]
A catalyst body-supporting substrate was obtained in the same manner as in Comparative Example 1 except that urea was added so that the urea content in the diluted solution obtained by diluting the first stock solution was 8% by mass.
〔比較例４〕
綿ブロード布に代えてウール（目付量：２００ｇ／ｍ２）を用い、第１の原液を希釈した希釈液における浸透剤含有量が０．０５質量％となるように浸透剤（アニオン性界面活性剤，ＡＯＴ）を添加した以外は、比較例１と同様にして触媒体担持基材を得た。
[Comparative Example 4]
Instead of cotton broad cloth, wool (weight per unit area: 200 g / m 2 ) was used, and the penetrant (anionic surfactant) was adjusted so that the penetrant content in the diluted solution obtained by diluting the first stock solution was 0.05% by mass. A catalyst-supporting base material was obtained in the same manner as in Comparative Example 1 except that the agent, AOT) was added.
〔実施例３〕
第１の原液を希釈した希釈液における浸透剤含有量が０．０４質量％となるように浸透剤を添加し、当該希釈液における尿素含有量が４質量％となるように尿素を添加した以外は、比較例４と同様にして触媒体担持基材を得た。
Example 3
Except for adding penetrant so that the penetrant content in the diluted solution obtained by diluting the first stock solution is 0.04% by mass, and adding urea so that the urea content in the diluted solution is 4% by mass Obtained a catalyst body-supporting substrate in the same manner as in Comparative Example 4.
〔比較例５〕
紫外線応答型光触媒（ＭＰＴ−４２２，石原産業社製）とアニオン性アクリル樹脂エマルジョン（ガラス転移温度（Ｔｇ）：−７℃）とを混合し、水で希釈して、酸化チタン固形分７質量％、アクリル樹脂固形分３．０質量％の第１の原液を調製した。得られた第１の原液を水で４０倍（質量基準）に希釈した希釈液に綿ブロード布（目付量：１１５ｇ／ｍ２）を浸漬させ、その後乾燥させて、触媒体担持基材を得た。
[Comparative Example 5]
A UV-responsive photocatalyst (MPT-422, manufactured by Ishihara Sangyo Co., Ltd.) and an anionic acrylic resin emulsion (glass transition temperature (Tg): −7 ° C.) are mixed, diluted with water, and a solid content of titanium oxide of 7% by mass. A first stock solution having an acrylic resin solid content of 3.0% by mass was prepared. A cotton broad cloth (weight per unit area: 115 g / m 2 ) was immersed in a diluted solution obtained by diluting the obtained first stock solution 40 times (mass basis) with water, and then dried to obtain a catalyst body-supporting substrate. It was.
〔実施例４〕
第１の原液を希釈した希釈液におけるクエン酸含有量が０．０２質量％となるようにクエン酸を添加した以外は、比較例５と同様にして触媒体担持基材を得た。
Example 4
A catalyst body-supporting substrate was obtained in the same manner as in Comparative Example 5 except that citric acid was added so that the citric acid content in the diluted solution obtained by diluting the first stock solution was 0.02% by mass.
〔実施例５〕
第１の原液を希釈した希釈液におけるクエン酸含有量が０．０５質量％となるようにクエン酸を添加した以外は、比較例５と同様にして触媒体担持基材を得た。
Example 5
A catalyst body-supporting substrate was obtained in the same manner as in Comparative Example 5 except that citric acid was added so that the citric acid content in the diluted solution obtained by diluting the first stock solution was 0.05 mass%.
〔実施例６〕
第１の原液を希釈した希釈液におけるクエン酸含有量が０．１質量％となるようにクエン酸を添加した以外は、比較例５と同様にして触媒体担持基材を得た。
Example 6
A catalyst body-supporting substrate was obtained in the same manner as in Comparative Example 5 except that citric acid was added so that the citric acid content in the diluted solution obtained by diluting the first stock solution was 0.1% by mass.
〔実施例７〕
第１の原液を希釈した希釈液におけるクエン酸含有量が０．２質量％となるようにクエン酸を添加した以外は、比較例５と同様にして触媒体担持基材を得た。
Example 7
A catalyst body-supporting substrate was obtained in the same manner as in Comparative Example 5 except that citric acid was added so that the citric acid content in the diluted solution obtained by diluting the first stock solution was 0.2% by mass.
〔実施例８〕
第１の原液を希釈した希釈液におけるクエン酸含有量が０．５質量％となるようにクエン酸を添加した以外は、比較例５と同様にして触媒体担持基材を得た。
Example 8
A catalyst body-supporting substrate was obtained in the same manner as in Comparative Example 5 except that citric acid was added so that the citric acid content in the diluted solution obtained by diluting the first stock solution was 0.5 mass%.
〔比較例６〕
紫外線応答型光触媒（ＭＰＴ−４２２，石原産業社製）とアニオン性アクリル樹脂エマルジョン（ガラス転移温度（Ｔｇ）：−７℃）とを混合し、水で希釈して、酸化チタン固形分７質量％、アクリル樹脂固形分３質量％の第１の原液を調製した。得られた第１の原液を水で５０倍（質量基準）に希釈した希釈液に１１号帆布（目付量：２６０ｇ／ｃｍ２）を浸漬させ、その後乾燥させて、触媒体担持基材を得た。
[Comparative Example 6]
A UV-responsive photocatalyst (MPT-422, manufactured by Ishihara Sangyo Co., Ltd.) and an anionic acrylic resin emulsion (glass transition temperature (Tg): −7 ° C.) are mixed, diluted with water, and a solid content of titanium oxide of 7% by mass. A first stock solution having an acrylic resin solid content of 3% by mass was prepared. No. 11 canvas (weight per unit area: 260 g / cm 2 ) was immersed in a diluted solution obtained by diluting the obtained first stock solution 50 times (mass basis) with water, and then dried to obtain a catalyst body-supporting substrate. It was.
〔実施例９〕
第１の原液がクエン酸２質量％を含有する以外は、比較例６と同様にして触媒体担持基材を得た。
Example 9
A catalyst-supporting substrate was obtained in the same manner as in Comparative Example 6 except that the first stock solution contained 2% by mass of citric acid.
〔比較例７〕
１１号帆布に代えて綿シーチング（目付量：１４０ｇ／ｃｍ２）を用いた以外は、比較例６と同様にして触媒体担持基材を得た。
[Comparative Example 7]
A catalyst-supporting base material was obtained in the same manner as in Comparative Example 6 except that cotton sheeting (weight per unit area: 140 g / cm 2 ) was used in place of No. 11 canvas.
〔実施例１０〕
第１の原液がクエン酸２質量％を含有する以外は、比較例７と同様にして触媒体担持基材を得た。
Example 10
A catalyst-supporting substrate was obtained in the same manner as in Comparative Example 7, except that the first stock solution contained 2% by mass of citric acid.
〔比較例８〕
１１号帆布に代えて綿ブロード布（目付量：１１５ｇ／ｍ２）を用いた以外は、比較例６と同様にして触媒体担持基材を得た。
[Comparative Example 8]
A catalyst carrier-supporting substrate was obtained in the same manner as in Comparative Example 6 except that a cotton broad cloth (weight per unit area: 115 g / m 2 ) was used instead of No. 11 canvas.
〔実施例１１〕
第１の原液を希釈した希釈液におけるクエン酸ナトリウム含有量が０．２質量％となるようにクエン酸ナトリウム水溶液を添加した以外は、比較例８と同様にして触媒体担持基材を得た。
Example 11
A catalyst-supporting base material was obtained in the same manner as in Comparative Example 8, except that an aqueous sodium citrate solution was added so that the sodium citrate content in the diluted solution obtained by diluting the first stock solution was 0.2% by mass. .
〔実施例１２〕
第１の原液を希釈した希釈液に４質量％塩酸を添加して当該希釈液のｐＨを３．０に調整した以外は、比較例６と同様にして触媒体担持基材を得た。
Example 12
A catalyst body-supporting substrate was obtained in the same manner as in Comparative Example 6 except that 4% by mass hydrochloric acid was added to the diluted solution obtained by diluting the first stock solution to adjust the pH of the diluted solution to 3.0.
〔実施例１３〕
第１の原液を希釈した希釈液における酢酸含有量が０．２質量％となるように酢酸を添加した以外は、比較例６と同様にして触媒体担持基材を得た。
Example 13
A catalyst body-supporting substrate was obtained in the same manner as in Comparative Example 6 except that acetic acid was added so that the acetic acid content in the diluted solution obtained by diluting the first stock solution was 0.2% by mass.
〔実施例１４〕
第１の原液を希釈した希釈液におけるリンゴ酸含有量が０．１質量％となるようにリンゴ酸を添加した以外は、比較例６と同様にして触媒体担持基材を得た。
Example 14
A catalyst body-supporting substrate was obtained in the same manner as in Comparative Example 6 except that malic acid was added so that the malic acid content in the diluted solution obtained by diluting the first stock solution was 0.1% by mass.
〔実施例１５〕
第１の原液を希釈した希釈液におけるシュウ酸含有量が０．１質量％となるようにシュウ酸を添加した以外は、比較例６と同様にして触媒体担持基材を得た。
Example 15
A catalyst-supporting substrate was obtained in the same manner as in Comparative Example 6 except that oxalic acid was added so that the oxalic acid content in the diluted solution obtained by diluting the first stock solution was 0.1% by mass.
〔実施例１６〕
第１の原液を希釈した希釈液におけるアジピン酸含有量が０．１質量％となるようにアジピン酸を添加した以外は、比較例６と同様にして触媒体担持基材を得た。
Example 16
A catalyst-supporting base material was obtained in the same manner as in Comparative Example 6 except that adipic acid was added so that the adipic acid content in the diluted solution obtained by diluting the first stock solution was 0.1% by mass.
〔比較例９〕
紫外線応答型光触媒（Ｆ６−ＡＰＳ，昭和電工社製）と飽和共重合ポリエステル樹脂エマルジョン（ガラス転移温度（Ｔｇ）：−１０℃）とを混合し、水で希釈して、酸化チタン固形分７質量％、ポリエステル樹脂固形分３．０質量％の第１の原液を調製した。得られた第１の原液を水で４０倍（質量基準）に希釈した希釈液に綿ブロード布（目付量：１１５ｇ／ｍ２）を浸漬させ、その後乾燥させた。乾燥後の綿ブロード布を純水に浸漬させ、その後乾燥させて、触媒体担持基材を得た。
[Comparative Example 9]
A UV-responsive photocatalyst (F6-APS, Showa Denko KK) and a saturated copolymerized polyester resin emulsion (glass transition temperature (Tg): −10 ° C.) are mixed, diluted with water, and a solid content of titanium oxide of 7 mass. %, A first stock solution having a polyester resin solid content of 3.0% by mass was prepared. A cotton broad cloth (weight per unit area: 115 g / m 2 ) was immersed in a diluted solution obtained by diluting the obtained first stock solution 40 times (mass basis) with water, and then dried. The dried cotton broad cloth was immersed in pure water and then dried to obtain a catalyst body-supporting substrate.
〔実施例１７〕
第１の原液を希釈した希釈液に浸漬させ、乾燥させた後の綿ブロード布を純水に代えて０．２質量％クエン酸水溶液に浸漬させる以外は、比較例９と同様にして触媒体担持基材を得た。
Example 17
The catalyst body was made in the same manner as in Comparative Example 9 except that the cotton broad cloth after the first stock solution was immersed in a diluted diluent and then dried was immersed in a 0.2% by mass citric acid aqueous solution instead of pure water. A support substrate was obtained.
〔実施例１８〕
第１の原液を希釈した希釈液に浸漬させ、乾燥させた後の綿ブロード布を純水に代えて０．５質量％クエン酸水溶液に浸漬させる以外は、比較例９と同様にして触媒体担持基材を得た。
Example 18
A catalyst body in the same manner as in Comparative Example 9, except that the cotton broad cloth after the first undiluted solution was immersed in a diluted solution and then dried was immersed in a 0.5 mass% citric acid aqueous solution instead of pure water. A support substrate was obtained.
〔実施例１９〕
第１の原液を希釈した希釈液に浸漬させ、乾燥させた後の綿ブロード布を純水に代えて１質量％クエン酸水溶液に浸漬させる以外は、比較例９と同様にして触媒体担持基材を得た。
Example 19
A catalyst carrier-supporting group was prepared in the same manner as in Comparative Example 9 except that the cotton broad cloth after the first stock solution was immersed in a diluted diluent and dried, was immersed in a 1% by mass aqueous citric acid solution instead of pure water. The material was obtained.
〔実施例２０〕
第１の原液を希釈した希釈液に浸漬させ、乾燥させた後の綿ブロード布を純水に代えて２質量％クエン酸水溶液に浸漬させる以外は、比較例９と同様にして触媒体担持基材を得た。
Example 20
A catalyst carrier-supporting group was prepared in the same manner as in Comparative Example 9 except that the cotton broad cloth after the first stock solution was immersed in a diluted diluent and dried, was immersed in a 2% by mass aqueous citric acid solution instead of pure water. The material was obtained.
〔実施例２１〕
第１の原液を希釈した希釈液に浸漬させ、乾燥させた後の綿ブロード布を純水に代えて４質量％クエン酸水溶液に浸漬させる以外は、比較例９と同様にして触媒体担持基材を得た。
Example 21
The catalyst carrier-supporting group was the same as Comparative Example 9 except that the cotton broad cloth after the first stock solution was immersed in a diluted diluent and dried, was immersed in a 4% by mass citric acid aqueous solution instead of pure water. The material was obtained.
〔実施例２２〕
紫外線応答型光触媒（ＭＰＴ−４２２，石原産業社製）とアニオン性アクリル樹脂エマルジョン（ガラス転移温度（Ｔｇ）：−７℃）とを混合し、水で希釈して、酸化チタン固形分７質量％、アクリル樹脂固形分３．０質量％の第１の原液を調製した。０．１質量％クエン酸水溶液に綿ブロード布（目付量：１１５ｇ／ｍ２）を浸漬させ、その後乾燥させた。乾燥後の綿ブロード布を、第１の原液を水で４０倍（質量基準）に希釈した希釈液に浸漬させ、その後乾燥させて、触媒体担持基材を得た。
[Example 22]
A UV-responsive photocatalyst (MPT-422, manufactured by Ishihara Sangyo Co., Ltd.) and an anionic acrylic resin emulsion (glass transition temperature (Tg): −7 ° C.) are mixed, diluted with water, and a solid content of titanium oxide of 7% by mass. A first stock solution having an acrylic resin solid content of 3.0% by mass was prepared. A cotton broad cloth (weight per unit area: 115 g / m 2 ) was immersed in a 0.1% by mass citric acid aqueous solution and then dried. The dried cotton broad cloth was immersed in a diluted solution obtained by diluting the first stock solution with water 40 times (mass basis), and then dried to obtain a catalyst-supporting substrate.
〔比較例１０〕
紫外線応答型光触媒（ＭＰＴ−４２２，石原産業社製）とアニオン性アクリル樹脂エマルジョン（ガラス転移温度（Ｔｇ）：−７℃）とを混合し、水で希釈して、酸化チタン固形分７質量％、アクリル樹脂固形分３．０質量％の第１の原液を調製した。得られた第１の原液を水で４０倍（質量基準）に希釈した希釈液にキュプラ布（目付量：６０ｇ／ｍ２）を浸漬させ、その後乾燥させて、触媒体担持基材を得た。
[Comparative Example 10]
A UV-responsive photocatalyst (MPT-422, manufactured by Ishihara Sangyo Co., Ltd.) and an anionic acrylic resin emulsion (glass transition temperature (Tg): −7 ° C.) are mixed, diluted with water, and a solid content of titanium oxide of 7% by mass. A first stock solution having an acrylic resin solid content of 3.0% by mass was prepared. A cupra cloth (weight per unit area: 60 g / m 2 ) was immersed in a diluted solution obtained by diluting the obtained first stock solution 40 times (mass basis) with water, and then dried to obtain a catalyst body-supporting substrate. .
〔実施例２３〕
第１の原液を希釈した希釈液におけるクエン酸含有量が０．１質量％となるようにクエン酸を添加した以外は、比較例１０と同様にして触媒体担持基材を得た。
Example 23
A catalyst-supporting substrate was obtained in the same manner as in Comparative Example 10 except that citric acid was added so that the citric acid content in the diluted solution obtained by diluting the first stock solution was 0.1% by mass.
〔アセトアルデヒド消臭試験〕
実施例１〜２３及び比較例１〜１０の触媒体担持基材について、下記のようにしてアセトアルデヒド消臭試験を行った。
[Acetaldehyde deodorization test]
About the catalyst body carrying | support base material of Examples 1-23 and Comparative Examples 1-10, the acetaldehyde deodorization test was done as follows.
触媒体担持基材（実施例１〜２３，比較例１〜１０）を５×５ｃｍに切断し、試料とした。ブラックライト（型式：ＦＬ４０Ｓ・ＢＬＢ−Ａ，東芝ライテック社製）を用い、試料表面での紫外線強度が１ｍＷ／ｃｍ２となるようにブラックライトと試料との距離を調整し、前処理として紫外線を所定時間（表１参照）照射した。 Catalyst body-supporting substrates (Examples 1 to 23, Comparative Examples 1 to 10) were cut to 5 × 5 cm to obtain samples. Using a black light (model: FL40S · BLB-A, manufactured by Toshiba Lighting & Technology Corp.), adjusting the distance between the black light and the sample so that the ultraviolet intensity on the sample surface is 1 mW / cm 2 , Irradiated for a predetermined time (see Table 1).
容量１Ｌのテドラーバックの中に上記前処理を施した試料を収容した後、空気を抜いてから２０ｐｐｍのアセトアルデヒド１Ｌを注入した。 After storing the pretreated sample in a 1 L capacity Tedlar bag, the air was evacuated and then 1 L of acetaldehyde of 20 ppm was injected.
ブラックライト（型式：ＦＬ４０Ｓ・ＢＬＢ−Ａ，東芝ライテック社製）を用い、テドラーバック内の試料に紫外線を所定時間（表１を参照）照射し（試料表面での紫外線強度が１ｍＷ／ｃｍ２）、その後、テドラーバック内のアセトアルデヒド濃度を、アセトアルデヒド用検知管（ガステック社製）を用いて測定した。 Using a black light (model: FL40S / BLB-A, manufactured by Toshiba Lighting & Technology Co., Ltd.), the sample in the Tedlar bag was irradiated with ultraviolet rays for a predetermined time (see Table 1) (UV intensity on the sample surface was 1 mW / cm 2 ), Thereafter, the acetaldehyde concentration in the Tedlar bag was measured using an acetaldehyde detector tube (manufactured by Gastec).
コントロールとして光触媒を担持させていない基材（綿ブロード布、ウール、１１号帆布、綿シーチング、キュプラ布）のみについても上記と同様の操作を行ってアセトアルデヒド濃度を測定し、下記式によりアセトアルデヒド除去率（％）を算出した。 For the base material (cotton broad cloth, wool, No. 11 canvas, cotton sheeting, cupra cloth) not carrying a photocatalyst as a control, the acetaldehyde concentration was measured by the same operation as above, and the acetaldehyde removal rate was calculated according to the following formula. (%) Was calculated.
アセトアルデヒド除去率(％)＝(Ｂ−Ａ)／Ｂ×１００
式中、Ａは「試料のアセトアルデヒド濃度」を表し、Ｂは「コントロールのアセトアルデヒド濃度」を表す。
結果を表１〜３に示す。
Acetaldehyde removal rate (%) = (BA) / B × 100
In the formula, A represents “sample acetaldehyde concentration”, and B represents “control acetaldehyde concentration”.
The results are shown in Tables 1-3.
表１に示すように、尿素を所定量（４質量％，８質量％）含有する触媒体担持液に浸漬させて得られた触媒体担持基材（実施例１，２）は、尿素を含有しない触媒体担持液に浸漬させて得られた触媒体担持基材（比較例１）よりも消臭性能に優れることが確認された。また、尿素含有量を低減させた触媒体担持液に浸漬させて得られた触媒体担持基材（比較例２，３）の消臭性能は、尿素を含有しない触媒体担持液に浸漬させて得られた触媒体担持基材（比較例１）と略同等であった。この結果から、所定量の尿素と触媒体とを含有する触媒体担持液に基材を浸漬させることで、基材に担持された触媒体の光触媒活性に基づく消臭機能等の各種機能に優れた触媒体担持基材が得られることが判明した。 As shown in Table 1, catalyst body-supporting substrates (Examples 1 and 2) obtained by immersing in a catalyst body-supporting liquid containing urea in a predetermined amount (4% by mass, 8% by mass) contain urea. It was confirmed that the catalyst body-supporting substrate (Comparative Example 1) obtained by immersing in the catalyst body-supporting liquid is superior in deodorizing performance. In addition, the deodorizing performance of the catalyst body-supporting base material (Comparative Examples 2 and 3) obtained by immersing in the catalyst body-supporting liquid with a reduced urea content was immersed in the catalyst body-supporting liquid not containing urea. The obtained catalyst body-supporting substrate (Comparative Example 1) was substantially equivalent. From this result, it is excellent in various functions such as a deodorizing function based on the photocatalytic activity of the catalyst body supported on the base material by immersing the base material in a catalyst body support liquid containing a predetermined amount of urea and the catalyst body. It was found that a catalyst-supporting substrate was obtained.
また、実施例３及び比較例４の試験結果から明らかなように、基材として綿布に代えてウールを用いても、尿素を含有する触媒体担持液に基材を浸漬させることで、基材に担持された触媒体の光触媒活性に基づく消臭機能等の各種機能に優れた触媒体担持基材が得られることが確認された。 Further, as is clear from the test results of Example 3 and Comparative Example 4, even when wool was used as the base material instead of cotton, the base material was immersed in the catalyst-supporting liquid containing urea. It was confirmed that a catalyst body-supporting substrate excellent in various functions such as a deodorizing function based on the photocatalytic activity of the catalyst body supported on the catalyst body was obtained.
さらに、実施例４〜１６及び比較例５〜８の試験結果（表２を参照）から明らかなように、酸又はその塩を含有する触媒体担持液に基材を浸漬させることで、基材に担持された触媒体の光触媒活性に基づく消臭機能等の各種機能に優れた触媒体担持基材が得られることが確認された。 Further, as is clear from the test results of Examples 4 to 16 and Comparative Examples 5 to 8 (see Table 2), the base material was immersed in the catalyst support liquid containing acid or a salt thereof. It was confirmed that a catalyst body-supporting substrate excellent in various functions such as a deodorizing function based on the photocatalytic activity of the catalyst body supported on the catalyst body was obtained.
さらにまた、実施例１７〜２３及び比較例９の試験結果（表３を参照）から明らかなように、触媒体を含有する第１の液体に基材を浸漬させる工程（第１の工程）と、酸若しくはその塩又は所定量の尿素を含有する第２の液体に基材を浸漬させる工程（第２の工程）との別工程にて触媒体及び酸若しくはその塩又は尿素と基材とを接触させることによっても、基材に担持された触媒体の光触媒活性に基づく消臭機能等の各種機能に優れた触媒体担持基材が得られることが確認された。 Furthermore, as is clear from the test results of Examples 17 to 23 and Comparative Example 9 (see Table 3), a step of immersing the base material in the first liquid containing the catalyst body (first step); The catalyst body and the acid or salt thereof or urea and the substrate in a separate step from the step of immersing the substrate in the second liquid containing acid or a salt thereof or a predetermined amount of urea (second step) It was confirmed that a catalyst-supporting base material excellent in various functions such as a deodorizing function based on the photocatalytic activity of the catalyst body supported on the base material can also be obtained by contacting them.
なお、実施例１７〜２２の試験結果から、第１及び第２の工程を行う順序にかかわらず、基材に担持された触媒体の光触媒活性に基づく消臭機能等の各種機能に優れた触媒体担持基材が得られることが確認された。 From the test results of Examples 17 to 22, regardless of the order in which the first and second steps are performed, the touch excellent in various functions such as a deodorizing function based on the photocatalytic activity of the catalyst supported on the base material. It was confirmed that a medium carrying substrate was obtained.
実施例２３及び比較例１０の試験結果（表３を参照）から明らかなように、セルロース系繊維であるキュプラ布を基材として使用した場合であっても、酸若しくはその塩を含有する触媒体担持液に基材を浸漬させることで、基材に担持された触媒体の光触媒活性に基づく消臭機能等の各種機能に優れた触媒体担持基材が得られることが確認された。 As is clear from the test results of Example 23 and Comparative Example 10 (see Table 3), even when a cupra cloth that is a cellulosic fiber is used as a base material, a catalyst body containing an acid or a salt thereof. It was confirmed that by immersing the base material in the support liquid, a catalyst body-supporting base material excellent in various functions such as a deodorizing function based on the photocatalytic activity of the catalyst body supported on the base material was obtained.
このことから、セルロース系繊維材料である木材等を基材として使用しても、基材に担持された触媒体の光触媒活性に基づく消臭機能等の各種機能に優れた触媒体担持基材を得ることができると推察される。 Therefore, even when wood or the like which is a cellulosic fiber material is used as a base material, a catalyst body-supporting base material excellent in various functions such as a deodorizing function based on the photocatalytic activity of the catalyst body supported on the base material. It is speculated that it can be obtained.
本発明の触媒体担持方法は、光線の照射により光触媒活性を発揮し得る触媒体を担持させ、当該触媒体の光触媒活性に基づく消臭機能等の各種機能に優れた触媒体担持基材を製造する方法として有用である。 The catalyst body carrying method of the present invention produces a catalyst body carrying substrate excellent in various functions such as a deodorizing function based on the photocatalytic activity of the catalyst body by carrying a catalyst body that can exhibit photocatalytic activity by irradiation of light. It is useful as a method to
Claims (4)
前記触媒体と有機酸又はその塩とを、前記基材に接触させることで、前記基材に前記触媒体を担持させる担持工程を含み、
前記有機酸がクエン酸、リンゴ酸又はシュウ酸であることを特徴とする触媒体担持方法。 A method of supporting a catalyst body capable of exhibiting photocatalytic activity by irradiation of light on a substrate,
And said catalyst and an organic acid or a salt thereof, by contacting said substrate, seen including a supporting step of supporting the catalyst on the substrate,
A method for supporting a catalyst body , wherein the organic acid is citric acid, malic acid or oxalic acid .
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