JP2900307B2 - Fixing method of photocatalyst - Google Patents
Fixing method of photocatalystInfo
- Publication number
- JP2900307B2 JP2900307B2 JP8019010A JP1901096A JP2900307B2 JP 2900307 B2 JP2900307 B2 JP 2900307B2 JP 8019010 A JP8019010 A JP 8019010A JP 1901096 A JP1901096 A JP 1901096A JP 2900307 B2 JP2900307 B2 JP 2900307B2
- Authority
- JP
- Japan
- Prior art keywords
- photocatalyst
- titanium oxide
- oxide photocatalyst
- fixing
- sheet
- 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.)
- Expired - Lifetime
Links
- 239000011941 photocatalyst Substances 0.000 title claims description 162
- 238000000034 method Methods 0.000 title claims description 33
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 152
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 152
- 230000001699 photocatalysis Effects 0.000 claims description 40
- 239000000126 substance Substances 0.000 claims description 27
- 239000004065 semiconductor Substances 0.000 claims description 15
- -1 polytetrafluoroethylene Polymers 0.000 claims description 14
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 11
- 230000004931 aggregating effect Effects 0.000 claims description 7
- 239000004113 Sepiolite Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 239000011164 primary particle Substances 0.000 claims description 6
- 229910052624 sepiolite Inorganic materials 0.000 claims description 6
- 235000019355 sepiolite Nutrition 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 229910021536 Zeolite Inorganic materials 0.000 claims description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 5
- 229920001296 polysiloxane Polymers 0.000 claims description 5
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- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- 239000010457 zeolite Substances 0.000 claims description 5
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 102
- 239000007789 gas Substances 0.000 description 51
- 238000000354 decomposition reaction Methods 0.000 description 34
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000011521 glass Substances 0.000 description 12
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 10
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- 239000000701 coagulant Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
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- 229920001155 polypropylene Polymers 0.000 description 3
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
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- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- HXVJQEGYAYABRY-UHFFFAOYSA-N 1-ethenyl-4,5-dihydroimidazole Chemical compound C=CN1CCN=C1 HXVJQEGYAYABRY-UHFFFAOYSA-N 0.000 description 1
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- 244000198134 Agave sisalana Species 0.000 description 1
- 235000011624 Agave sisalana Nutrition 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 241000609240 Ambelania acida Species 0.000 description 1
- 244000099147 Ananas comosus Species 0.000 description 1
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- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
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- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 244000182625 Dictamnus albus Species 0.000 description 1
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- 108010010803 Gelatin Proteins 0.000 description 1
- 229920002907 Guar gum Polymers 0.000 description 1
- 240000000797 Hibiscus cannabinus Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
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- 101100258086 Postia placenta (strain ATCC 44394 / Madison 698-R) STS-01 gene Proteins 0.000 description 1
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- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 1
- 125000004103 aminoalkyl group Chemical group 0.000 description 1
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- LZBIYPIDWSGLOV-UHFFFAOYSA-N dimethyl(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C[NH+](C)CC=C LZBIYPIDWSGLOV-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Catalysts (AREA)
- Paper (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】この発明は光照射下での防
臭、防汚、抗菌の効果を持った微細な半導体光触媒の定
着方法に係り、特に、その担体自体が光触媒作用によっ
て劣化されないようにできる方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for fixing a fine semiconductor photocatalyst having an effect of deodorizing, antifouling, and antibacterial under light irradiation, and in particular, it can prevent the carrier itself from being deteriorated by the photocatalytic action. It is about the method.
【０００２】[0002]
【従来の技術】生活環境に対する関心が集まるなか、環
境汚染物質の社会的排出抑制や自助努力による生活改善
の気運が高まっている。そのため、防臭、防汚、抗菌な
どの環境浄化方法、システムが要求されている。2. Description of the Related Art With an increasing interest in the living environment, there is an increasing tendency to control social emissions of environmental pollutants and improve life through self-help efforts. Therefore, environmental purification methods and systems such as deodorization, antifouling, and antibacterial are required.
【０００３】このような要求に対し、半導体光触媒が注
目されている。その中で特に、酸化チタン光触媒が注目
されている。酸化チタンは、適度な硬度と無毒性から歯
磨剤などに利用され、また、卓越した着色性および隠蔽
力を有する白色顔料として、古くから塗料などに利用さ
れているほか、紫外線吸収剤として化粧品等に利用され
ている。また、酸化チタンの光触媒能力も古くから知ら
れており、特開昭61-135669 号公報では硫化物の分解、
特開平2-62297 号公報では窒素酸化物の光分解などが開
示されている。[0003] In response to such demands, semiconductor photocatalysts have attracted attention. Among them, a titanium oxide photocatalyst has attracted particular attention. Titanium oxide has been used in dentifrices due to its moderate hardness and non-toxicity, has been used as a white pigment with outstanding coloring and hiding power since ancient times in paints, etc. It is used for Also, the photocatalytic ability of titanium oxide has been known for a long time, and JP-A-61-135669 discloses decomposition of sulfide,
JP-A-2-62297 discloses photodecomposition of nitrogen oxides and the like.
【０００４】日常生活における脱臭剤としては、活性炭
に代表される吸着剤などが挙げられる。しかし、脱臭剤
としてのガス吸着剤は、悪臭物質などの吸着が飽和に達
すると吸着能力が失活してしまう。殺菌剤には強酸性物
質や強塩基性物質などが挙げられる。しかし、これらは
程度の差こそあれ劇毒性を有しており、人体に対して悪
影響を及ぼす。これに対し、酸化チタン光触媒は効果の
即時性には劣るものの、効果は失活することなく、永久
的に続くものであり、無毒性であるという利点を有す
る。[0004] Examples of deodorants in daily life include adsorbents represented by activated carbon. However, the gas adsorbent as a deodorant loses its adsorption capacity when the adsorption of malodorous substances reaches saturation. Fungicides include strongly acidic substances and strongly basic substances. However, they are more or less toxic, and adversely affect the human body. On the other hand, although the titanium oxide photocatalyst is inferior in the immediate effect, the effect does not deactivate, lasts forever, and has the advantage of being non-toxic.
【０００５】酸化チタンに代表される光触媒は、紫外線
照射下で酸化力の強い正孔を作り、空気中の水蒸気や酸
素と反応して、ＯＨラジカルやＯ2 - 等の活性酸素等の
反応活性種を発生し、防臭、防汚、抗菌の効果を出すこ
とが知られている。[0005] photocatalyst typified by titanium oxide, making a strong positive hole oxidizing power under UV irradiation, reacts with water vapor or oxygen in the air, OH radicals and O 2 - such as the reaction activity of the active oxygen etc. It is known to produce seeds and to have deodorant, antifouling and antibacterial effects.
【０００６】[0006]
【発明が解決しようとする課題】しかし、酸化チタン光
触媒を担体に担持させると、紫外線照射により悪臭物質
や汚れ物質の分解および細菌殺菌とともに担体の分解が
起こり、担体の強度低下が起きる。このように微細な酸
化チタン光触媒を担体と一緒に定着、凝集させる方法で
は、実用的な使用は不可能である。However, when a titanium oxide photocatalyst is supported on a carrier, the carrier is decomposed by ultraviolet irradiation, as well as decomposition of malodorous substances and dirt substances and sterilization of bacteria, and the strength of the carrier is reduced. Such a method of fixing and coagulating the fine titanium oxide photocatalyst together with the carrier cannot be practically used.
【０００７】特開平3-69695 号公報では、酸化チタン光
触媒などを紙類にコーティングして脱臭性、抗菌性など
を有するものの記載がある。また、特開平2-280818号お
よび同3-94814 号公報では、この担体の崩壊防止の一方
法として、セラミック繊維等を使用している。しかし、
この方法はセラミック繊維シートの後加工であるため製
造装置が特殊であること、素材に柔軟性がないことなど
課題が多い。また、特開平1-111100号および同1-156576
号公報では、紙または不織布に光触媒を内添または塗工
し、その表面をエッチングすることにより光触媒を露出
させる方法がある。これについては、エッチングの特殊
な加工が必要であり一般的な製造技術とはいえない。ま
た、通常製紙で使用される湿潤および乾燥紙力増強剤だ
けの添加では光触媒反応による劣化を防止することがで
きず、紫外線照射により極端に強度が低下し、実用に耐
えられるものではない。[0007] Japanese Patent Application Laid-Open No. 3-69695 describes that a titanium oxide photocatalyst or the like is coated on paper to have a deodorizing property and an antibacterial property. In Japanese Patent Application Laid-Open Nos. 2-280818 and 3-94814, ceramic fibers or the like are used as a method for preventing the carrier from collapsing. But,
Since this method is a post-processing of the ceramic fiber sheet, there are many problems such as a special manufacturing apparatus and a lack of flexibility of the material. Also, JP-A Nos. 1-111100 and 1-156576
In the publication, there is a method in which a photocatalyst is internally added or coated on paper or a nonwoven fabric, and the surface is etched to expose the photocatalyst. This requires special processing of etching and cannot be said to be a general manufacturing technique. Further, the addition of only a wet and dry paper strength enhancer usually used in papermaking cannot prevent deterioration due to a photocatalytic reaction, and the strength is extremely lowered by irradiation with ultraviolet rays, which is not practical.
【０００８】このように、光触媒を用いて、防臭、防
汚、抗菌効果を持たせた担体は、光触媒作用により、劣
化崩壊を起こす。そこで、この担体の劣化防止技術を開
発が必要である。[0008] As described above, a carrier having a deodorant, antifouling, and antibacterial effect by using a photocatalyst is degraded and collapsed by the photocatalytic action. Therefore, it is necessary to develop a technology for preventing the deterioration of the carrier.
【０００９】本発明は、上述の背景のもとでなされたも
のであり、半導体光触媒を担体、例えばシートに担持さ
せ、担体の劣化崩壊を抑制しつつ、防臭、防汚、抗菌効
果を発揮させることができる光触媒の定着方法を提供す
ることを目的とする。The present invention has been made in view of the above background, and has a semiconductor photocatalyst carried on a carrier, for example, a sheet, and exhibits deodorant, antifouling, and antibacterial effects while suppressing deterioration and collapse of the carrier. It is an object of the present invention to provide a method for fixing a photocatalyst that can be used.
【００１０】[0010]
【課題を解決するための手段】上記課題を解決するため
に本発明に係る光触媒の定着方法は、（構成１） 半導
体又は金属を含有する半導体の粉末又はゾルからなる光
触媒を、核となる物質に定着させた後に、凝集剤により
凝集させ、担体に担持させることにより、光触媒作用に
よって担体が劣化するのを防止するようにしたことを特
徴とする構成とし、この構成１の態様として、（構成
２) 構成1 の光触媒の定着方法において、前記半導体
又は金属を担持した半導体の粉末またはゾルからなる光
触媒として、一次粒子径が5 ｎｍ〜0.1 μｍの酸化チタ
ンの粉末またはゾルを用いることを特徴とする構成と
し、構成１または２の態様として、（構成３) 構成1
又は2 の光触媒の定着方法において、前記凝集剤によっ
て凝集した凝集体の大きさが、200nm 以上、望ましく
は、5μm 〜１cmであることを特徴とする構成とし、構
成１ないし３のいずれかの態様として、（構成４) 構
成1 ないし3 のいずれかの光触媒の定着方法において、
前記光触媒の配合量として、担体に対して重量比で1%〜
50% 、望ましくは5%〜30% であることを特徴とする構成
とし、構成１ないし４のいずれかの態様として、（構成
５) 構成1 ないし4 のいずれかの光触媒の定着方法に
おいて、前記核となる物質として、ポリテトラフルオロ
エチレン、ゼオライト、ホワイトカーボン、セピオライ
ト、活性炭、水酸化アルミニウム、シリコーンの単独ま
たは複数を用いることを特徴とする構成とした。According to the present invention, there is provided a method for fixing a photocatalyst according to the present invention. (Constitution 1) A photocatalyst comprising a semiconductor or metal-containing semiconductor powder or sol is used as a core material. After fixing to the carrier, the carrier is coagulated with a coagulant and supported on a carrier to prevent the carrier from deteriorating due to the photocatalytic action. 2) The method for fixing a photocatalyst according to the configuration 1, wherein a titanium oxide powder or a sol having a primary particle diameter of 5 nm to 0.1 μm is used as the photocatalyst comprising the semiconductor or the metal-carrying semiconductor powder or the sol. As an aspect of Configuration 1 or 2, (Configuration 3) Configuration 1
Or the photocatalyst fixing method according to item 2, wherein the size of the aggregate aggregated by the coagulant is 200 nm or more, preferably 5 μm to 1 cm. (Configuration 4) In the fixing method of the photocatalyst according to any one of Configurations 1 to 3,
As the blending amount of the photocatalyst, 1% by weight to the carrier
50%, desirably 5% to 30%, and in any one of the constitutions 1 to 4, (constitution 5) the method for fixing a photocatalyst according to any one of constitutions 1 to 4, The structure is characterized in that polytetrafluoroethylene, zeolite, white carbon, sepiolite, activated carbon, aluminum hydroxide, and silicone are used alone or in combination as a core substance.
【００１１】[0011]
【実施の形態】例えば、酸化チタン光触媒をスラリーと
混合して定着及び凝集させ、シートにすると、酸化チタ
ン光触媒の配合量が多くなる程、シートの強度保持が困
難となり、紫外線照射による光触媒反応によってさらに
強度の低下が起きる。DESCRIPTION OF THE PREFERRED EMBODIMENTS For example, when a titanium oxide photocatalyst is mixed with a slurry and fixed and aggregated to form a sheet, as the amount of the titanium oxide photocatalyst increases, it becomes more difficult to maintain the strength of the sheet. Further reduction in strength occurs.
【００１２】そこで、本願発明では、酸化チタン等の光
触媒の微粒子を、まず、核となる物質に定着させ、次
に、これらを凝集させて凝集体にし、次いで、スラリー
等の担体に担持させ、しかる後に必要に応じてシート等
の所定の構造体に形成するようにしたものである。これ
により、光触媒を担体と混合して定着と凝集を同時に行
うようにした従来の場合に比較して、光触媒作用による
担体自体の劣化を極めて効果的に防止できるようにした
ものである。Therefore, in the present invention, fine particles of a photocatalyst such as titanium oxide are first fixed to a substance serving as a nucleus, and then they are aggregated to form an aggregate, and then the aggregate is carried on a carrier such as a slurry. Thereafter, it is formed in a predetermined structure such as a sheet, if necessary. As a result, the deterioration of the carrier itself due to the photocatalytic action can be extremely effectively prevented as compared with the conventional case in which the photocatalyst is mixed with the carrier to simultaneously perform fixing and aggregation.
【００１３】本発明における光触媒としては、一次粒子
径が5nm 〜0.1 μm の半導体機能を持つ酸化チタン単
体、あるいは、半導体機能を持つ、金属を含有した酸化
チタン等を用いることができる。酸化チタンに含有され
る金属としては、例えば、パラジウム、亜鉛、インジウ
ム等がある。As the photocatalyst in the present invention, a titanium oxide having a primary particle diameter of 5 nm to 0.1 μm having a semiconductor function alone, a metal-containing titanium oxide having a semiconductor function, or the like can be used. Examples of the metal contained in titanium oxide include palladium, zinc, and indium.
【００１４】また、核となる物質としては、微粒子状の
光触媒を定着させることができる化学的性質や粒径を備
えたものであればよく、例えば、ポリテトラフルオロエ
チレンディスパージョン、ゼオライト、ホワイトカーボ
ン、セピオライト、活性炭、水酸化アルミニウムの単独
または混合したものがあげられる。The substance serving as a nucleus may be any substance having a chemical property and a particle size capable of fixing a particulate photocatalyst. Examples thereof include polytetrafluoroethylene dispersion, zeolite, and white carbon. , Sepiolite, activated carbon, and aluminum hydroxide alone or in combination.
【００１５】また、そのほかに核となる物質としては、
活性白土、ハロイサイト、酸化亜鉛、カオリンクレー、
炭酸カルシウム、サチンホワイト、プラスチック顔料等
があり、これらと酸化チタン光触媒を混合して定着さ
せ、凝集させてもよい。[0015] In addition, other core substances include:
Activated clay, halloysite, zinc oxide, kaolin clay,
There are calcium carbonate, satin white, plastic pigments and the like, and these may be mixed with a titanium oxide photocatalyst, fixed and aggregated.
【００１６】さらに、他の核となる物質としては、シリ
コーンディスパージョンのほかにポリ酢酸ビニルエマル
ジョン、酢酸ビニルコポリマーエマルジョン、アクリル
酸エステルコポリマーエマルジョン、塩化ビニリデンコ
ポリマーエマルジョン、塩化ビニルコポリマーエマルジ
ョン、ポリエチレンエマルジョン、エポキシ樹脂、ブタ
ジエンスチレンラテックス、ブタジエンアクリロニトリ
ルラテックスのほかに、スターチ、マンナンなどの水溶
性ポリマーなどを用いてもよい。Further, other core substances include, in addition to silicone dispersion, polyvinyl acetate emulsion, vinyl acetate copolymer emulsion, acrylate ester copolymer emulsion, vinylidene chloride copolymer emulsion, vinyl chloride copolymer emulsion, polyethylene emulsion, epoxy emulsion. In addition to resin, butadiene styrene latex and butadiene acrylonitrile latex, water-soluble polymers such as starch and mannan may be used.
【００１７】これら核となる物質の粒径は、5nm 〜100
μm であればよい。The particle size of these core materials is from 5 nm to 100
μm is sufficient.
【００１８】本発明における定着とは光触媒と核となる
物質とを繋ぎとめることをいい、その定着作用を行なわ
せる定着剤としては、例えば、ポリ塩化アルミニウム、
硫酸第一鉄、硫酸第二鉄、塩化第二鉄、硫酸アルミニウ
ム、アルミン酸ソーダ、ポリ酸化アルミニウムなどがあ
る。In the present invention, fixing means binding a photocatalyst to a substance serving as a nucleus. Examples of a fixing agent for performing the fixing action include polyaluminum chloride and the like.
There are ferrous sulfate, ferric sulfate, ferric chloride, aluminum sulfate, sodium aluminate, and polyaluminum oxide.
【００１９】本発明における凝集とは、光触媒を定着さ
せた状態の核となる物質同志を凝集させることをいい、
この凝集作用を行なわせる凝集剤としては、例えば、ポ
リアクリルアミド系、ポリアクリル酸ナトリウム、ポリ
アクリル酸アミノアルキルエステル系、キトサン、ジメ
チルアリルアンモニウムクロライド、アルキルアミンエ
ピクロルヒドリン縮合物、ポリエチレンイミン、アルキ
レンジクロライドとポリアルキレンポリアミンの縮合
物、ジシアンジアミドホルマリン縮合物、ビニルラクタ
ムアクリルアミド共重合体、ポリビニルピリジン、ビニ
ルイミダゾリン重合体、ジアルキルアミノエチルアクリ
レート、グアーガム、アルギン酸ソーダ、デンプン、ゼ
ラチン等であり、本発明はこれらを一種または複数種使
用することができる。In the present invention, the term "aggregation" refers to aggregating the core substances in a state where the photocatalyst is fixed.
Examples of the coagulant for performing this coagulation action include polyacrylamide, sodium polyacrylate, aminoalkyl polyacrylate, chitosan, dimethylallylammonium chloride, alkylamine epichlorohydrin condensate, polyethyleneimine, alkylene dichloride and Condensates of alkylene polyamines, dicyandiamide formalin condensates, vinyl lactam acrylamide copolymers, polyvinyl pyridine, vinyl imidazoline polymers, dialkylaminoethyl acrylate, guar gum, sodium alginate, starch, gelatin, etc. Multiple types can be used.
【００２０】また、本発明における担体としては、例え
ば、凝集体を担持させる工程においてはスラリー状態に
あって、担持後にシート等の多孔質構造体に形成できる
ものが望ましい。Further, as the carrier in the present invention, for example, a carrier which is in a slurry state in the step of supporting the aggregate and which can be formed into a porous structure such as a sheet after the supporting is desirable.
【００２１】スラリーとしては、例えば、化学パルプ、
砕木パルプ、楮、三椏、雁皮、亜麻、大麻、ケナフ、マ
ニラ麻、サイザル麻、藁、竹、バガス、葦、エスパル
ト、リンター、パインアップル等の非木材繊維等の単独
または混合したものを水に分散させたものが挙げられ
る。また、レーヨン、ビニロン、ポリエステル、ポリエ
チレン、ポリプロピレン、アクリル、アラミド、ポリ塩
化ビニル、ポリアクリロニトリル、ポリビニルアルコー
ル、ナイロン、ポリアミド、ポリウレタンなどの化学繊
維または合成繊維、クリソタイルアスベスト、アモサイ
ト、クロシドライト、アンソフィライト、アクチノライ
ト、セピオライト等の鉱物繊維および炭素繊維、ガラス
繊維、金属繊維、セラミック繊維、ウィスカーなどの単
独または複数をスラリーに配合してもよい。As the slurry, for example, chemical pulp,
Single or mixed non-wood fibers such as groundwood pulp, mulberry, mitsumata, ganpi, flax, hemp, kenaf, manila hemp, sisal hemp, straw, bamboo, bagasse, reed, esparto, linter, pineapple, etc. dispersed in water What was made is mentioned. In addition, rayon, vinylon, polyester, polyethylene, polypropylene, acrylic, aramid, polyvinyl chloride, polyacrylonitrile, polyvinyl alcohol, nylon, polyamide, polyurethane and other synthetic or synthetic fibers, chrysotile asbestos, amosite, crocidolite, anthophilite, Mineral fibers such as actinolite and sepiolite and carbon fibers, glass fibers, metal fibers, ceramic fibers and whiskers may be used alone or in combination with the slurry.
【００２２】このスラリーを多孔質構造体に形成する方
法としては、従来公知の抄紙方法によって抄造する方法
を用いることができる。抄造するに当たっては、必要に
応じてスラリーに乾燥紙力増強剤、湿潤紙力増強剤、サ
イズ剤、染料、填料、顔料、粘剤、スライムコントロー
ル剤、歩留向上剤、消泡剤等の各種添加剤を配合しても
良い。As a method of forming this slurry into a porous structure, a method of paper making by a conventionally known paper making method can be used. In making the paper, various kinds of slurry such as a dry paper strength agent, a wet paper strength agent, a sizing agent, a dye, a filler, a pigment, a sticky agent, a slime control agent, a retention improver, a defoaming agent, etc. Additives may be blended.
【００２３】本発明の方法によれば、光触媒を核となる
物質に定着させた後、それ自身を凝集させ、担体に担持
させる。このため光触媒は担体一面に分散固定されてい
るのではなく、凝集体が分散した状態で固定されている
ため担体の劣化を抑制することが可能となった。According to the method of the present invention, after the photocatalyst is fixed to the substance serving as a nucleus, the photocatalyst itself is aggregated and carried on a carrier. For this reason, the photocatalyst is not fixed to the entire surface of the carrier, but is fixed in a state where the aggregates are dispersed, so that the deterioration of the carrier can be suppressed.
【００２４】すなわち、本発明の方法によって得た光触
媒構造体は、比較的大きな粒径の核となる粒子の表面に
比較的小さな粒径の光触媒が多数定着され、この光触媒
の定着された核物質同志が凝集されてさらに大きな凝集
体を形成し、さらにこの凝集体が担体であるスラリーの
各々の繊維等の表面に多数担持され、そして、この多数
の凝集体を担持した多数の繊維等がシート状等の多孔質
構造体に形成されたものである。このため、光触媒の全
表面積に比較してその光触媒が繊維等の担体自体の表面
に接触する面積が著しく小さいものとなっている。それ
ゆえ、被処理物に対しては光触媒作用を行うに必要な十
分な接触面積を確保しつつ、この光触媒作用によって損
傷を受けやすい担体自体に対する光触媒の接触面積を小
さくすることを可能にしている。That is, in the photocatalyst structure obtained by the method of the present invention, a large number of photocatalysts having a relatively small particle size are fixed on the surface of particles serving as nuclei having a relatively large particle size. The agglomerates aggregate to form larger aggregates, and the aggregates are supported on the surface of each fiber or the like of the slurry as a carrier, and a large number of fibers or the like supporting the aggregates are formed on a sheet. It is formed in a porous structure such as a shape. For this reason, the area where the photocatalyst contacts the surface of the carrier itself such as a fiber is significantly smaller than the total surface area of the photocatalyst. Therefore, it is possible to reduce the contact area of the photocatalyst with the carrier itself, which is easily damaged by the photocatalysis, while securing a sufficient contact area necessary for performing the photocatalysis on the object to be processed. .
【００２５】なお、本発明にいたる契機の１つは、担体
として最適な条件（例えば製造が容易でかつ多孔質構造
体に形成でき、しかも光触媒構造体として汎用性に富む
等の条件）を満たせる材料（例えば繊維等）が、一般に
光触媒によって損傷を受けやすいものであるという事
実、逆に、光触媒に損傷を受けにくい材料は上記担体に
最適な条件を満たすものは少ないが、核物質となる粒子
状のものであればいくらでもあるという事実に着目した
点にある。また、他の１つは、担体の劣化を少なくする
には、被処理物に対しては光触媒作用を行うに必要な十
分な接触面積を確保しつつ、この光触媒作用によって損
傷を受けやすい担体自体に対する光触媒の接触面積を小
さくすればよいという発想をなした点にある。そして、
このような事実及び発想を基礎にして、光触媒を光触媒
作用に耐性のある核物質に定着させ、次にこれらを凝集
させて比較的大きな粒子状の凝集体を形成し、しかる後
にこの凝集体を担体に担持させるというアイデアを創出
して本発明をなすに至ったものである。One of the motives leading to the present invention is to satisfy the optimum conditions as a carrier (for example, conditions that are easy to produce, can be formed into a porous structure, and are versatile as a photocatalyst structure). The fact that materials (e.g., fibers) are generally susceptible to damage by photocatalysts. The point is to pay attention to the fact that there are many shapes. On the other hand, in order to reduce the deterioration of the carrier, the carrier itself is easily damaged by the photocatalysis while securing a sufficient contact area necessary for performing the photocatalysis on the object to be treated. The idea is to reduce the contact area of the photocatalyst with the photocatalyst. And
On the basis of these facts and ideas, the photocatalyst is fixed to nuclear materials resistant to photocatalysis, which are then agglomerated to form relatively large particulate agglomerates, which are then agglomerated. The present invention has been accomplished by creating an idea of being supported on a carrier.
【００２６】[0026]
（比較例１）本発明の実施例を掲げる前に、まず、本発
明の方法を用いた場合と比較するために、本発明の方法
を用いずに酸化チタン光触媒を試作し、その性能を試験
した比較例１を説明する。(Comparative Example 1) Before listing examples of the present invention, first, a titanium oxide photocatalyst was produced without using the method of the present invention, and its performance was tested for comparison with the case of using the method of the present invention. Comparative Example 1 will be described.
【００２７】酸化チタン光触媒と木材パルプを水に分散
させスラリーとし、定着剤として硫酸アルミニウムを添
加し、水酸化ナトリウムで中和し、発生する水酸化アル
ミニウムで酸化チタン光触媒を木材パルプに担持させた
後、ポリアクリルアミドで凝集させた。このときのパル
プ坪量は100g/m2 で、酸化チタン光触媒はパルプに対し
て5 ，10，15各重量% を内添し、タッピスタンダードシ
ートマシンにより比較例１の酸化チタン光触媒担持シー
トＡを試作した。このときの配合を表１に示す。The titanium oxide photocatalyst and the wood pulp were dispersed in water to form a slurry, aluminum sulfate was added as a fixing agent, neutralized with sodium hydroxide, and the titanium oxide photocatalyst was carried on the wood pulp with the generated aluminum hydroxide. Thereafter, the particles were aggregated with polyacrylamide. At this time, the pulp basis weight was 100 g / m 2 , and the titanium oxide photocatalyst was prepared by internally adding 5, 10, and 15% by weight to the pulp, and the titanium oxide photocatalyst supporting sheet A of Comparative Example 1 was applied by a tappi standard sheet machine. Prototype made. The composition at this time is shown in Table 1.
【００２８】[0028]
【表１】 なお、表1 における酸化チタンゾル（石原産業株式会社
製：ＳＴＳー０１）の一次粒径は７nmである。また、後
述する酸化チタンゾル（石原産業株式会社製：ＳＴー０
１）の一次粒径は２０nm であり、ＳＴー３１の一次粒
径は７nmである。[Table 1] The primary particle diameter of the titanium oxide sol (STS-01 manufactured by Ishihara Sangyo Co., Ltd.) in Table 1 is 7 nm. Also, a titanium oxide sol described below (ST-0 manufactured by Ishihara Sangyo Co., Ltd.)
1) The primary particle size is 20 nm, and the primary particle size of ST-31 is 7 nm.
【００２９】比較例１の酸化チタン光触媒担持シートＡ
の光触媒活性試験 アセトアルデヒドガスを充満させた密封ガラス容器（容
積：1.6 ｌ）に、比較例１の方法を用いて作製した酸化
チタン光触媒担持シートＡを入れ、光触媒活性を検討し
た。紫外線強度0.1mW/cm2 の白色蛍光灯を照射したとき
の悪臭物質であるアセトアルデヒドガスの分解の測定結
果を図1 に示す。このときのアセトアルデヒドガス初期
濃度は10ppm である。 Titanium oxide photocatalyst supporting sheet A of Comparative Example 1
Photocatalytic Activity Test The titanium oxide photocatalyst-supporting sheet A produced by the method of Comparative Example 1 was placed in a sealed glass container (volume: 1.6 l) filled with acetaldehyde gas, and the photocatalytic activity was examined. FIG. 1 shows the measurement results of the decomposition of acetaldehyde gas, which is a malodorous substance, when irradiated with a white fluorescent lamp having an ultraviolet intensity of 0.1 mW / cm 2 . At this time, the initial concentration of acetaldehyde gas is 10 ppm.
【００３０】図１から明らかなように、酸化チタン光触
媒が配合されていないパルプシートではアセトアルデヒ
ドガスは分解されないが、酸化チタン光触媒担持シート
Ａは紫外線を照射するとアセトアルデヒドが分解され、
酸化チタン光触媒量が多くなるほどアセトアルデヒドガ
スの分解量が多くなる。これは酸化チタン光触媒担持シ
ートが微弱光で高い光触媒活性を持つことを示してい
る。As is clear from FIG. 1, acetaldehyde gas is not decomposed in a pulp sheet containing no titanium oxide photocatalyst, but acetaldehyde is decomposed in the titanium oxide photocatalyst carrying sheet A when irradiated with ultraviolet light.
As the amount of the titanium oxide photocatalyst increases, the amount of decomposition of the acetaldehyde gas increases. This indicates that the titanium oxide photocatalyst-carrying sheet has high photocatalytic activity under weak light.
【００３１】また、アセトアルデヒドガスを充満させた
密封ガラス容器（容積：1.6 ｌ）に酸化チタン光触媒担
持シートＡを入れ、光触媒活性を検討した。紫外線強度
0.44mW/cm 2 の紫外線を照射したときの悪臭物質である
アセトアルデヒドガスの分解を測定した。このときのア
セトアルデヒドガス初期濃度は1000ppm である。このと
きのアセトアルデヒドガスの50分後の分解率を表2 に示
す。表2 に示されるように十分な光触媒活性を有してい
ることがわかる。The titanium oxide photocatalyst supporting sheet A was placed in a sealed glass container (volume: 1.6 l) filled with acetaldehyde gas, and the photocatalytic activity was examined. UV intensity
The decomposition of acetaldehyde gas, which is a malodorous substance, when irradiated with ultraviolet rays of 0.44 mW / cm 2 was measured. The initial concentration of acetaldehyde gas at this time is 1000 ppm. Table 2 shows the decomposition rate of the acetaldehyde gas at this time after 50 minutes. As shown in Table 2, it can be seen that it has a sufficient photocatalytic activity.
【００３２】[0032]
【表２】 比較例１の酸化チタン光触媒担持シートＡの破裂強さ試
験 紫外線強度1.6mW/cm2 の紫外線を連続照射し、酸化チタ
ン光触媒担持シートＡの破裂強さを測定した。この結果
を表3 に示す。[Table 2] Burst strength test of titanium oxide photocatalyst supporting sheet A of Comparative Example 1
The UV test UV intensity 1.6 mW / cm 2 was continuously irradiated to measure the bursting strength of the titanium oxide photocatalyst carrying sheet A. Table 3 shows the results.
【００３３】[0033]
【表３】 表３から明らかなように、酸化チタン光触媒をパルプス
ラリーに添加し、定着、凝集させるとシート強度が弱
く、酸化チタン光触媒の配合量が多い程、紫外光を照射
しなくても強度低下を起こす。また、光を照射すればこ
の傾向はさらに増幅され、悪臭物質の分解とともにシー
ト素材の崩壊も促進する。このように酸化チタン光触媒
は内添定着が可能であるが、強度低下が著しく製品化は
不可能であった。[Table 3] As is clear from Table 3, when the titanium oxide photocatalyst is added to the pulp slurry and fixed and aggregated, the sheet strength is weak, and the greater the blending amount of the titanium oxide photocatalyst, the lower the strength without irradiating ultraviolet light. . Further, when light is irradiated, this tendency is further amplified, and the decomposition of the malodorous substance and the collapse of the sheet material are promoted. As described above, the titanium oxide photocatalyst can be internally fixed and fixed, but its strength is remarkably reduced, and it has not been possible to commercialize it.
【００３４】（実施例１）次に、本発明の実施例１を説
明する。(Embodiment 1) Next, Embodiment 1 of the present invention will be described.
【００３５】酸化チタン光触媒を水中に分散させ、定着
剤として硫酸アルミニウムを添加後、水酸化ナトリウム
で中和し、発生する水酸化アルミニウムで酸化チタン光
触媒を定着させた後、ポリアクリルアミドで凝集させ
た。この時の凝集体の大きさは１００μｍ〜１ｃｍの塊
状集合体であった。この塊状集合体の一部を取り、光学
顕微鏡で観察するとさらに細かい粒子（５〜１０μｍ）
が結合していた。さらに別に用意したパルプスラリーに
混合後、パルプに担持させ、さらにポリアクリルアミド
で凝集させた。このときのパルプ坪量は100g/m2 、酸化
チタン光触媒はパルプに対して10重量% を内添し、タッ
ピスタンダードシートマシンにより実施例１の酸化チタ
ン光触媒担持シートＢを試作した。このときの配合を表
４に示す。The titanium oxide photocatalyst was dispersed in water, aluminum sulfate was added as a fixing agent, neutralized with sodium hydroxide, the titanium oxide photocatalyst was fixed with the generated aluminum hydroxide, and then coagulated with polyacrylamide. . The size of the aggregate at this time was a lump aggregate of 100 μm to 1 cm. When a part of this massive aggregate is taken and observed with an optical microscope, finer particles (5 to 10 μm) are obtained.
Was bound. After mixing with a separately prepared pulp slurry, the mixture was supported on pulp and further coagulated with polyacrylamide. At this time, the basis weight of the pulp was 100 g / m 2 , and the titanium oxide photocatalyst was internally added by 10% by weight with respect to the pulp, and a titanium oxide photocatalyst-carrying sheet B of Example 1 was prototyped by a tappi standard sheet machine. Table 4 shows the composition at this time.
【００３６】[0036]
【表４】 実施例１の酸化チタン光触媒担持シートＢの光触媒活性
試験 アセトアルデヒドガスを充満させた密封ガラス容器（容
積：1.6 ｌ）に酸化チタン光触媒担持シートＢを入れ、
光触媒活性を検討した。紫外線強度0.44mW/cm2 の紫外
線を照射したときの悪臭物質であるアセトアルデヒドガ
スの分解を測定した。このときのアセトアルデヒドガス
初期濃度は1000ppm である。このときのアセトアルデヒ
ドガスの50分後の分解率を表5 に示す。[Table 4] Photocatalytic activity of titanium oxide photocatalyst supporting sheet B of Example 1
The titanium oxide photocatalyst supporting sheet B is placed in a sealed glass container (volume: 1.6 l) filled with test acetaldehyde gas,
The photocatalytic activity was studied. Decomposition of acetaldehyde gas, which is a malodorous substance, when irradiated with ultraviolet light having an ultraviolet intensity of 0.44 mW / cm 2 was measured. The initial concentration of acetaldehyde gas at this time is 1000 ppm. Table 5 shows the decomposition rate of the acetaldehyde gas at this time after 50 minutes.
【００３７】[0037]
【表５】 表５から明らかなように、実施例１の酸化チタン光触媒
担持シートＢは、50分間で68.5％のアセトアルデヒドガ
スを分解し、十分な光触媒活性を示した。[Table 5] As is clear from Table 5, the titanium oxide photocatalyst-supporting sheet B of Example 1 decomposed 68.5% of acetaldehyde gas in 50 minutes, and showed sufficient photocatalytic activity.
【００３８】実施例１の酸化チタン光触媒担持シートＢ
の破裂強さ試験 紫外線強度1.6mW/cm2 の紫外線を連続照射し、酸化チタ
ン光触媒担持シートＢの破裂強さを測定した。この結果
を表6 に示す。 Titanium oxide photocatalyst supporting sheet B of Example 1
The rupture strength of the titanium oxide photocatalyst-carrying sheet B was measured by continuously irradiating an ultraviolet ray having an ultraviolet intensity of 1.6 mW / cm 2 . Table 6 shows the results.
【００３９】[0039]
【表６】 表6 から明らかなように、酸化チタン光触媒を予め定着
凝集させることにより、飛躍的に強度物性が向上し、担
体の劣化を防止することができた。[Table 6] As is clear from Table 6, by pre-fixing and aggregating the titanium oxide photocatalyst, the strength physical properties were dramatically improved, and the deterioration of the carrier could be prevented.
【００４０】（実施例２）次に実施例２を説明する。(Embodiment 2) Next, Embodiment 2 will be described.
【００４１】酸化チタン光触媒を水中に分散させ、化学
反応には極めて安定なポリテトラフルオロエチレン（粒
径：200 〜400nm ）に定着させ、水酸化ナトリウムで中
和させながら、ポリアクリルアミド及びポリアミンで凝
集させた。さらに別に用意したパルプスラリーに混合
後、パルプに担持させ、さらにポリアクリルアミド及び
ポリアミンで凝集させた。このときのパルプ坪量は100g
/m2 、酸化チタン光触媒はパルプに対して10重量% を内
添し、タッピスタンダードシートマシンにより実施例２
の酸化チタン光触媒担持シートＣを試作した。配合を表
７に示す。A titanium oxide photocatalyst is dispersed in water, fixed to polytetrafluoroethylene (particle diameter: 200 to 400 nm) which is extremely stable for chemical reaction, and coagulated with polyacrylamide and polyamine while neutralizing with sodium hydroxide. I let it. After mixing with a separately prepared pulp slurry, the mixture was supported on pulp, and further coagulated with polyacrylamide and polyamine. The pulp weight at this time is 100 g
/ m 2 , the titanium oxide photocatalyst was added internally by 10% by weight to the pulp, and the tapping standard sheet machine was used in Example 2
The titanium oxide photocatalyst supporting sheet C was produced as a trial. The formulations are shown in Table 7.
【００４２】[0042]
【表７】 実施例２の酸化チタン光触媒担持シートＣの光触媒活性
試験 アセトアルデヒドガスを充満させた密封ガラス容器（容
積：1.6 ｌ）に実施例２の酸化チタン光触媒担持シート
Ｃを入れ、光触媒活性を検討した。紫外線強度0.44mW/c
m 2 の紫外線を照射したときの悪臭物質であるアセトア
ルデヒドガスの分解を測定した。このときのアセトアル
デヒドガス初期濃度は1000ppm である。このときのアセ
トアルデヒドガスの50分後の分解率を表8 に示す。[Table 7] Photocatalytic activity of titanium oxide photocatalyst supporting sheet C of Example 2
The titanium oxide photocatalyst-carrying sheet C of Example 2 was placed in a sealed glass container (volume: 1.6 l) filled with test acetaldehyde gas, and the photocatalytic activity was examined. UV intensity 0.44mW / c
Decomposition of acetaldehyde gas, which is a malodorous substance, when irradiated with ultraviolet rays of m 2 was measured. The initial concentration of acetaldehyde gas at this time is 1000 ppm. Table 8 shows the decomposition rate of the acetaldehyde gas at this time after 50 minutes.
【００４３】[0043]
【表８】 実施例２の酸化チタン光触媒担持シートＣの破裂強さ試
験 紫外線強度1.6mW/cm2 の紫外線を連続照射し、実施例２
の酸化チタン光触媒担持シートＣの破裂強さを測定し
た。この結果を表9 に示す。[Table 8] Burst strength test of titanium oxide photocatalyst supporting sheet C of Example 2
The UV test UV intensity 1.6 mW / cm 2 was continuously irradiated, Example 2
Of the titanium oxide photocatalyst supporting sheet C was measured. Table 9 shows the results.
【００４４】[0044]
【表９】 表9 から明らかなように、酸化チタン光触媒をポリテト
ラフルオロエチレンと混合し、定着、凝集することによ
り、パルプの崩壊を防ぐことができ、酸化チタン光触媒
担持シートは飛躍的に安定性を増した。[Table 9] As is evident from Table 9, mixing the titanium oxide photocatalyst with polytetrafluoroethylene, fixing and agglomeration prevented the collapse of the pulp, and the titanium oxide photocatalyst-supported sheet dramatically increased its stability. .
【００４５】（実施例３，４，５，６，７）酸化チタン
光触媒を水中に分散させ、シリコーンディスパージョ
ン、ゼオライト、ホワイトカーボン、セピオライト、活
性炭をそれぞれ混合後、硫酸アルミニウムを添加し、水
酸化ナトリウムで中和させ発生する水酸化アルミニウム
で定着し、ポリアクリルアミド及びポリアミンで凝集さ
せた。これを別に用意したパルプスラリーに混合し、パ
ルプに担持させ、ポリアクリルアミド及びポリアミンで
凝集させた。このときのパルプ坪量は100g/m2 、酸化チ
タン光触媒はパルプに対して10重量% を内添し、タッピ
スタンダードシートマシンにより実施例３，４，５，
６，７の酸化チタン光触媒担持シートＤ、Ｅ、Ｆ、Ｇ、
Ｈを試作した。配合を表１０に示す。(Examples 3, 4, 5, 6, 7) A titanium oxide photocatalyst was dispersed in water, and silicone dispersion, zeolite, white carbon, sepiolite, and activated carbon were mixed. The resultant was fixed with aluminum hydroxide generated by neutralization with sodium, and agglomerated with polyacrylamide and polyamine. This was mixed with a separately prepared pulp slurry, supported on pulp, and agglomerated with polyacrylamide and polyamine. At this time, the pulp basis weight was 100 g / m 2 , and the titanium oxide photocatalyst was internally added to the pulp by 10% by weight.
6, 7 titanium oxide photocatalyst supporting sheets D, E, F, G,
H was prototyped. The formulations are shown in Table 10.
【００４６】[0046]
【表１０】 実施例３〜７の酸化チタン光触媒担持シートＤ〜Ｈの光
触媒活性試験 アセトアルデヒドガスを充満させたガラス容器（容積：
1.6 ｌ）に実施例３〜７の酸化チタン光触媒担持シート
Ｄ、Ｅ、Ｆ、Ｇ、Ｈを入れ、光触媒活性を検討した。紫
外線強度0.44mW/cm 2 の紫外線を照射したときの悪臭物
質であるアセトアルデヒドガスの分解を測定した。この
ときのアセトアルデヒドガス初期濃度は1000ppm であ
る。このときのアセトアルデヒドガスの50分後の分解率
を表11に示す。[Table 10] Light of titanium oxide photocatalyst supporting sheets D to H of Examples 3 to 7
Catalytic activity test Glass container filled with acetaldehyde gas (volume:
1.6 l) were loaded with the titanium oxide photocatalyst supporting sheets D, E, F, G, and H of Examples 3 to 7, and the photocatalytic activity was examined. Decomposition of acetaldehyde gas, which is a malodorous substance, when irradiated with ultraviolet light having an ultraviolet intensity of 0.44 mW / cm 2 was measured. The initial concentration of acetaldehyde gas at this time is 1000 ppm. Table 11 shows the decomposition rate of the acetaldehyde gas at this time after 50 minutes.
【００４７】[0047]
【表１１】 表11から明らかなように、実施例５，６のシートＦ、Ｇ
が良い光触媒活性を示した。[Table 11] As is clear from Table 11, sheets F and G of Examples 5 and 6 were used.
Showed good photocatalytic activity.
【００４８】実施例３〜７の酸化チタン光触媒担持シー
トＤ、Ｅ、Ｆ、Ｇ、Ｈの破裂強さ試験 紫外線強度1.6mW/cm2 の紫外線を連続照射し、実施例３
〜７の酸化チタン光触媒担持シートＤ、Ｅ、Ｆ、Ｇ、Ｈ
の破裂強さを測定した。この結果を表12に示す。The titanium oxide photocatalyst supporting sheets of Examples 3 to 7
DOO D, E, F, G, ultraviolet radiation burst strength test UV intensity 1.6 mW / cm 2 of H and continuous irradiation, Example 3
Titanium oxide photocatalyst supporting sheets D, E, F, G, H
Was measured for burst strength. Table 12 shows the results.
【００４９】[0049]
【表１２】 表12から明らかなように、酸化チタン光触媒をシリコー
ンディスパージョン、ゼオライト、ホワイトカーボン、
セピオライト、活性炭と混合し、定着凝集することによ
り、パルプの崩壊を防ぐことができた。[Table 12] As is clear from Table 12, the titanium oxide photocatalyst was used for silicone dispersion, zeolite, white carbon,
Mixing with sepiolite and activated carbon and fixing and agglomerating prevented pulp collapse.
【００５０】（実施例８，９，１０，１１）酸化チタン
光触媒を水中に分散させ、硫酸アルミニウムを添加後、
水酸化ナトリウムで中和し、発生する水酸化アルミニウ
ムで酸化チタン光触媒を定着させた後、ポリアクリルア
ミドで凝集させた。これを70重量% のパルプと30重量%
のレーヨン繊維、ポリエステル繊維、ポリエチレン繊維
およびポリプロピレン繊維をそれぞれ分散させたスラリ
ーに添加し、ポリアクリルアミドで繊維上に担持させ
た。この時のスラリーの抄紙坪量を100g/m2 、酸化チタ
ン光触媒はスラリーに対して10重量% を内添し、タッピ
スタンダードシートマシンにより、実施例８，９，１
０，１１の酸化チタン光触媒担持シートＩ、Ｊ、Ｋ、Ｌ
とした。配合を表13に示す。(Examples 8, 9, 10, and 11) A titanium oxide photocatalyst was dispersed in water, and aluminum sulfate was added.
After neutralizing with sodium hydroxide and fixing the titanium oxide photocatalyst with the generated aluminum hydroxide, the resultant was coagulated with polyacrylamide. 70% by weight pulp and 30% by weight
Was added to a slurry in which rayon fiber, polyester fiber, polyethylene fiber and polypropylene fiber were dispersed, respectively, and supported on the fiber with polyacrylamide. At this time, the papermaking basis weight of the slurry was 100 g / m 2 , and the titanium oxide photocatalyst was internally added by 10% by weight based on the slurry, and was subjected to Examples 8, 9, and 1 by a Tappi standard sheet machine.
0, 11 titanium oxide photocatalyst supporting sheets I, J, K, L
And The formulations are shown in Table 13.
【００５１】[0051]
【表１３】 実施例８〜１１の酸化チタン光触媒担持シートＩ〜Ｌの
光触媒活性試験 アセトアルデヒドガスを充満させた密封ガラス容器に、
実施例８〜１１の酸化チタン光触媒担持シートＩ、Ｊ、
Ｋ、Ｌを入れ、光触媒活性を検討した。紫外線強度0.44
mW/cm 2 の紫外線を照射したときの悪臭物質であるアセ
トアルデヒドガスの分解を測定した。このときのアセト
アルデヒドガス初期濃度は1000ppm である。このときの
アセトアルデヒドガスの50分後の分解率を表14に示す。[Table 13] Of titanium oxide photocatalyst supporting sheets I to L of Examples 8 to 11
Photocatalytic activity test In a sealed glass container filled with acetaldehyde gas,
The titanium oxide photocatalyst supporting sheets I and J of Examples 8 to 11,
K and L were added, and the photocatalytic activity was examined. UV intensity 0.44
Decomposition of acetaldehyde gas, which is a malodorous substance when irradiated with ultraviolet light of mW / cm 2 , was measured. The initial concentration of acetaldehyde gas at this time is 1000 ppm. Table 14 shows the decomposition rate of the acetaldehyde gas at this time after 50 minutes.
【００５２】[0052]
【表１４】 表14から明らかなように、サンプルＩはポリビニルアル
コールの造膜により酸化チタン光触媒を被覆しているた
め、分解率が悪いがその他は良い光触媒活性を示した。[Table 14] As is clear from Table 14, Sample I covered the titanium oxide photocatalyst with a film of polyvinyl alcohol, and thus exhibited good photocatalytic activity except for the low decomposition rate.
【００５３】実施例８〜１１の酸化チタン光触媒担持シ
ートＩ、Ｊ、Ｋ、Ｌの破裂強さ試験 実施例８〜１１の酸化チタン光触媒担持シートＩ、Ｊ、
Ｋ、Ｌの紫外線照射下での安定性をみるため、紫外線強
度1.6mW/cm2 の紫外線の連続照射を行い、破裂強さ試験
を行った。これを表15に示す。The titanium oxide photocatalyst supporting systems of Examples 8 to 11
Burst strength test of sheets I, J, K, L The titanium oxide photocatalyst supporting sheets I, J, of Examples 8 to 11
In order to check the stability of K and L under irradiation of ultraviolet rays, continuous irradiation of ultraviolet rays having an ultraviolet intensity of 1.6 mW / cm 2 was performed, and a burst strength test was performed. This is shown in Table 15.
【００５４】[0054]
【表１５】 表15から明らかなように、サンプルＪ、Ｋは酸化チタン
光触媒を予め定着凝集することにより、酸化チタン光触
媒がパルプ等の繊維との接触を少なくしたことのほか
に、繊維による強度物性が強いためより安定的な酸化チ
タン光触媒担持シートができた。[Table 15] As is clear from Table 15, Samples J and K were prepared by pre-aggregating and aggregating the titanium oxide photocatalyst to reduce the contact between the titanium oxide photocatalyst and fibers such as pulp. A more stable titanium oxide photocatalyst-carrying sheet was obtained.
【００５５】（実施例１２）酸化チタン光触媒を水中に
分散させ、硫酸アルミニウムを添加後、水酸化ナトリウ
ムで中和し、発生する水酸化アルミニウムで酸化チタン
光触媒を定着させた後、ポリアクリルアミドで凝集させ
た。さらにこれを紙力増強剤であるアクリル及びポリア
ミドエピクロルヒドリンを配合したパルプスラリーに添
加し、ポリアクリルアミド及びポリアミンで担持させ
た。このときのパルプ坪量は100g/m2 、酸化チタン光触
媒はパルプに対して10重量% を内添し、タッピスタンダ
ードシートマシンにより実施例１２の酸化チタン光触媒
担持シートＭを試作した。このときの配合を表16に示
す。Example 12 A titanium oxide photocatalyst was dispersed in water, aluminum sulfate was added, neutralized with sodium hydroxide, the titanium oxide photocatalyst was fixed with the generated aluminum hydroxide, and then coagulated with polyacrylamide. I let it. Further, this was added to a pulp slurry containing acrylic and polyamide epichlorohydrin, which were paper strength agents, and supported by polyacrylamide and polyamine. At this time, the basis weight of the pulp was 100 g / m 2 , and the titanium oxide photocatalyst was internally added at 10% by weight to the pulp, and a titanium oxide photocatalyst-supporting sheet M of Example 12 was prototyped by a tappi standard sheet machine. Table 16 shows the composition at this time.
【００５６】[0056]
【表１６】 実施例１２の酸化チタン光触媒担持シートＭの光触媒活
性試験 アセトアルデヒドガスを充満させた密封ガラス容器に、
実施例１２の酸化チタン光触媒担持シートＭを入れ、光
触媒活性を検討した。紫外線強度0.44mW/cm 2の紫外線
を照射したときの悪臭物質であるアセトアルデヒドガス
の分解を測定した。このときのアセトアルデヒドガス初
期濃度は1000ppm である。このときのアセトアルデヒド
ガスの50分後の分解率を表17に示す。[Table 16] Photocatalytic activity of titanium oxide photocatalyst supporting sheet M of Example 12
In a sealed glass container filled with acetaldehyde gas,
The titanium oxide photocatalyst supporting sheet M of Example 12 was inserted, and the photocatalytic activity was examined. Decomposition of acetaldehyde gas, which is a malodorous substance, when irradiated with ultraviolet light having an ultraviolet intensity of 0.44 mW / cm 2 was measured. The initial concentration of acetaldehyde gas at this time is 1000 ppm. Table 17 shows the decomposition rate of the acetaldehyde gas at this time after 50 minutes.
【００５７】[0057]
【表１７】 表17から明らかなように、酸化チタン光触媒担持シート
Ｍは、50分間で53.6%のアセトアルデヒドガスを分解
し、光触媒活性を示した。[Table 17] As is clear from Table 17, the titanium oxide photocatalyst-carrying sheet M decomposed 53.6% of acetaldehyde gas in 50 minutes and exhibited photocatalytic activity.
【００５８】実施例１２の酸化チタン光触媒担持シート
Ｍの破裂強さ試験 紫外線強度1.6mW/cm2 の紫外線を連続照射し、酸化チタ
ン光触媒担持シートＭの破裂強さを測定した。この結果
を表18に示す。 Titanium oxide photocatalyst supporting sheet of Example 12
M Burst Strength Test The rupture strength of the titanium oxide photocatalyst-carrying sheet M was measured by continuously irradiating ultraviolet light having an ultraviolet intensity of 1.6 mW / cm 2 . Table 18 shows the results.
【００５９】[0059]
【表１８】 表18から明らかなように、酸化チタン光触媒担持シート
Ｍは、紫外線照射下において、担体の強度劣化を抑制す
ることができた。[Table 18] As is clear from Table 18, the titanium oxide photocatalyst-carrying sheet M was able to suppress the strength deterioration of the carrier under ultraviolet irradiation.
【００６０】（実施例１３）酸化チタン光触媒を水中に
分散させ、硫酸アルミニウムを添加後、水酸化ナトリウ
ムで中和し、発生する水酸化アルミニウムで酸化チタン
光触媒を定着させた後、ポリアクリルアミドで凝集させ
た。さらにこれを紙力増強剤であるアクリル及びポリア
ミドエピクロルヒドリンを配合したパルプスラリーに添
加し、ポリアクリルアミド及びポリアミンで担持させ
た。このときのパルプ坪量は100g/m2 、酸化チタン光触
媒はパルプに対して10重量% を内添し、シートマシンに
より連続抄紙を行い、実施例１３の酸化チタン光触媒担
持シートＮを試作した。このときの配合を表19に示す。Example 13 A titanium oxide photocatalyst was dispersed in water, aluminum sulfate was added, neutralized with sodium hydroxide, the titanium oxide photocatalyst was fixed with the generated aluminum hydroxide, and then coagulated with polyacrylamide. I let it. Further, this was added to a pulp slurry containing acrylic and polyamide epichlorohydrin, which were paper strength agents, and supported by polyacrylamide and polyamine. At this time, the basis weight of the pulp was 100 g / m 2 , and the titanium oxide photocatalyst was internally added with 10% by weight based on the pulp, and continuous papermaking was performed by a sheet machine. Table 19 shows the composition at this time.
【００６１】[0061]
【表１９】 実施例１３の酸化チタン光触媒担持シートＮの光触媒活
性試験 アセトアルデヒドガスを充満させた密封ガラス容器（容
積：1.6 ｌ）に、実施例１３の酸化チタン光触媒担持シ
ートＮを入れ、光触媒活性を検討した。紫外線強度0.44
mW/cm 2 の紫外線を照射したときの悪臭物質であるアセ
トアルデヒドガスの分解を測定した。このときのアセト
アルデヒドガス初期濃度は1000ppm である。このときの
アセトアルデヒドガスの50分後の分解率を表20に示す。[Table 19] Photocatalytic activity of titanium oxide photocatalyst supporting sheet N of Example 13
The titanium oxide photocatalyst-supporting sheet N of Example 13 was placed in a sealed glass container (volume: 1.6 l) filled with acetaldehyde gas, and the photocatalytic activity was examined. UV intensity 0.44
Decomposition of acetaldehyde gas, which is a malodorous substance when irradiated with ultraviolet light of mW / cm 2 , was measured. The initial concentration of acetaldehyde gas at this time is 1000 ppm. Table 20 shows the decomposition rate of the acetaldehyde gas at this time after 50 minutes.
【００６２】[0062]
【表２０】 表20から明らかなように、酸化チタン光触媒担持シート
Ｎは、50分間で42.8%のアセトアルデヒドガスを分解
し、光触媒活性を示した。[Table 20] As is clear from Table 20, the titanium oxide photocatalyst-supporting sheet N decomposed 42.8% of acetaldehyde gas in 50 minutes and exhibited photocatalytic activity.
【００６３】実施例１３の酸化チタン光触媒担持シート
Ｎの破裂強さ試験 紫外線強度1.6mW/cm2 の紫外線を連続照射し、酸化チタ
ン光触媒担持シートＮの破裂強さを測定した。この結果
を表21に示す。 Titanium oxide photocatalyst supporting sheet of Example 13
N burst strength test The burst strength of the titanium oxide photocatalyst-carrying sheet N was measured by continuously irradiating ultraviolet rays having an ultraviolet intensity of 1.6 mW / cm 2 . Table 21 shows the results.
【００６４】[0064]
【表２１】 表21から明らかなように、酸化チタン光触媒担持シート
Ｎは、紫外線照射下において、担体の強度劣化を抑制す
ることができた。[Table 21] As is clear from Table 21, the titanium oxide photocatalyst-carrying sheet N was able to suppress the strength deterioration of the carrier under ultraviolet irradiation.
【００６５】実施例１２の酸化チタン光触媒担持シート
Ｍによるタバコのヤニの分解試験 実施例１２の酸化チタン光触媒担持シートＭにタバコ
（日本たばこ産業社製：MILD SEVEN Super Lights)のヤ
ニを付着させ紫外線照射によるヤニの分解実験を行っ
た。酸化チタン光触媒担持シートＭを入れた50cm×50cm
×50cmの箱に火をつけたタバコを入れ、煙を充満させ、
タバコのヤニをシートに付着させた。そして酸化チタン
光触媒担持シートＭを取り出し紫外線強度3.0mw/cm2 の
紫外線を照射し、ヤニの分解を行った。The titanium oxide photocatalyst supporting sheet of Example 12
Decomposition test of cigarette tar by M. Tobacco (MILD SEVEN Super Lights) tar was adhered to the titanium oxide photocatalyst supporting sheet M of Example 12, and a tar decomposition test was performed by ultraviolet irradiation. 50cm x 50cm with titanium oxide photocatalyst supporting sheet M
Put a lit cigarette in a box of 50 cm, fill with smoke,
Tobacco tar was adhered to the sheet. Then, the titanium oxide photocatalyst-carrying sheet M was taken out and irradiated with ultraviolet light having an ultraviolet intensity of 3.0 mw / cm 2 to decompose the tar.
【００６６】タバコのヤニの付着量を色差で測定した。
タバコ３本分を付着させた酸化チタン光触媒担持シート
Ｍ及び酸化チタン光触媒を担持していないパルプシート
に、紫外線を照射し酸化チタン標準白板との色差の経時
変化を測定した。この結果を表22に示す。The amount of the tar on the tobacco was measured by color difference.
The titanium oxide photocatalyst-carrying sheet M to which three cigarettes were attached and the pulp sheet not carrying the titanium oxide photocatalyst were irradiated with ultraviolet rays, and the time-dependent changes in the color difference from the titanium oxide standard white plate were measured. Table 22 shows the results.
【００６７】[0067]
【表２２】 表22から明らかなように、酸化チタン光触媒が配合され
ていないパルプシートはヤニが付着したままであった
が、酸化チタン光触媒担持シートＭは光触媒反応により
6 時間で完全にヤニが分解された。[Table 22] As is clear from Table 22, the pulp sheet in which the titanium oxide photocatalyst was not blended was still attached to the pulp, but the titanium oxide photocatalyst-carrying sheet M was subjected to the photocatalytic reaction.
In 6 hours, the tar was completely decomposed.
【００６８】実施例１３の酸化チタン光触媒担持シート
Ｎによるタバコのヤニの分解試験 実施例１３の酸化チタン光触媒担持シートＮにタバコ
（日本たばこ産業社製：MILD SEVEN Super Lights)のヤ
ニを付着させ紫外線照射によるヤニの分解実験を行っ
た。酸化チタン光触媒担持シートを入れた50cm×50cm×
50cmの箱に火をつけたタバコを入れ、煙を充満させ、タ
バコのヤニを付着させた。そして酸化チタン光触媒担持
シートを取り出し紫外線強度3.0mW/cm2 のブラックライ
ト及び0.08mW/cm 2 白色蛍光灯の紫外線を照射し、ヤニ
の分解を行った。白色蛍光灯照射によるヤニ未吸着の酸
化チタン光触媒担持シートとの色差の変化を図２に、ブ
ラックライト照射によるヤニ未吸着の酸化チタン光触媒
担持シートとの色差の変化を図３に示す。The titanium oxide photocatalyst supporting sheet of Example 13
Decomposition test of tobacco tar by N. A tobacco (MILD SEVEN Super Lights) tar was attached to the titanium oxide photocatalyst-supporting sheet N of Example 13, and a tar decomposition test was performed by ultraviolet irradiation. 50cm x 50cm x with titanium oxide photocatalyst carrying sheet
A lit cigarette was placed in a 50 cm box, filled with smoke, and the cigarette tar attached. The UV black light ultraviolet intensity 3.0 mW / cm 2 is taken out of the titanium oxide photocatalyst carrying sheet and 0.08mW / cm 2 white fluorescent lamp was irradiated, were decomposition of tar. FIG. 2 shows a change in the color difference between the titanium oxide photocatalyst-carrying sheet not adsorbed by the white fluorescent lamp and the titanium oxide photocatalyst sheet not adsorbed by the black light, and FIG.
【００６９】図２，３から明らかなように、紫外線照射
により色差が減少していくため、タバコのヤニが分解さ
れる。さらに、照射時間をもっと長くすればヤニは完全
に分解される。以上のように、酸化チタン担持シートは
タバコのヤニの分解ができ、防汚効果が認められた。As is clear from FIGS. 2 and 3, since the color difference is reduced by the irradiation of the ultraviolet rays, the cigarette tar is decomposed. Furthermore, if the irradiation time is made longer, the tar is completely decomposed. As described above, the titanium oxide-carrying sheet was able to decompose tobacco tar, and an antifouling effect was recognized.
【００７０】実施例１３の酸化チタン光触媒担持シート
Ｎを用いた大腸菌抗菌試験 酸化チタン光触媒担持シートＮを用いて大腸菌（Escher
ichia coli）の抗菌試験を行った。酸化チタン光触媒担
持シートＮに1200個/cm 2 の大腸菌を蒔き、紫外線照射
時間を変化させて生存菌数を測定した。紫外線強度1.0m
W/cm2 のブラックライトと0.03mW/cm 2 の白色蛍光灯を
用いた。The titanium oxide photocatalyst supporting sheet of Example 13
E. coli antibacterial test using N. Escherichia coli (Escher) using titanium oxide photocatalyst supporting sheet N
(ichia coli). Escherichia coli at 1200 cells / cm 2 were sown on the titanium oxide photocatalyst-supporting sheet N, and the number of surviving bacteria was measured by changing the ultraviolet irradiation time. UV intensity 1.0m
A W / cm 2 black light and 0.03 mW / cm 2 white fluorescent lamp were used.
【００７１】まず、大腸菌の菌液を酸化チタン光触媒担
持シートＮに滴下し、滅菌カバーガラスで鋏み、所定時
間の光照射の後に菌を回収する。光照射しない場合は暗
所に放置する。回収の際には滅菌ガーゼを用い、酸化チ
タン光触媒担持シートＮ及びガラス上の菌液を拭き取
る。その滅菌ガーゼに含まれている菌を生理食塩水中で
洗い落とし、その溶液を回収菌液とし寒天培地で一昼夜
培養する。このときの結果を図４に示す。First, a bacterial solution of Escherichia coli is dropped on the titanium oxide photocatalyst-carrying sheet N, scissors with a sterile cover glass, and the bacteria are collected after irradiation with light for a predetermined time. If not irradiated, leave in a dark place. At the time of recovery, the bacteria liquid on the titanium oxide photocatalyst supporting sheet N and the glass is wiped off using sterile gauze. The bacteria contained in the sterilized gauze are washed off in a physiological saline solution, and the solution is used as a recovered bacterial solution and cultured on an agar medium all day and night. FIG. 4 shows the result at this time.
【００７２】図４から明らかなように、光照射なしで大
腸菌は40% 程死滅するが、ブラックライトを照射するこ
とにより90% 以上の大腸菌が死滅した。また、同じよう
な実験を酸化チタン光触媒を担持してないパルプシート
にも行った結果を図５に示す。 図５から明らかなよう
に、紫外線を照射することにより、パルプシートでも30
% 程の大腸菌は死滅するが、酸化チタン光触媒担持シー
トＮはほとんどの大腸菌を死滅させた。酸化チタン光触
媒担持シートは抗菌効果があることが証明できた。As is clear from FIG. 4, E. coli was killed by about 40% without light irradiation, but 90% or more of E. coli was killed by irradiation with black light. FIG. 5 shows the results of a similar experiment performed on a pulp sheet not supporting the titanium oxide photocatalyst. As is clear from FIG. 5, irradiation of ultraviolet light allows pulp sheets to be 30
% Of the E. coli was killed, but the titanium oxide photocatalyst-carrying sheet N killed most of the E. coli. It was proved that the titanium oxide photocatalyst supporting sheet had an antibacterial effect.
【００７３】（比較例２）酸化チタン光触媒パウダーと
木材パルプを水に分散させスラリーとし、定着剤として
硫酸アルミニウムを添加し、水酸化ナトリウムで中和
し、発生する水酸化アルミニウムで酸化チタン光触媒を
木材パルプに担持させた後、ポリアクリルアミドで凝集
させた。このときのパルプ坪量は100g/m2 で、酸化チタ
ン光触媒はパルプに対し10重量% を内添し、タッピスタ
ンダードシートマシンにより、比較例２の酸化チタン光
触媒担持シートＯを試作した。このときの配合を表23に
示す。(Comparative Example 2) A titanium oxide photocatalyst powder and wood pulp were dispersed in water to form a slurry, aluminum sulfate was added as a fixing agent, neutralized with sodium hydroxide, and the titanium oxide photocatalyst was generated with aluminum hydroxide generated. After being supported on wood pulp, it was agglomerated with polyacrylamide. At this time, the basis weight of the pulp was 100 g / m 2 , and the titanium oxide photocatalyst was internally added with 10% by weight of the pulp, and a titanium oxide photocatalyst-supporting sheet O of Comparative Example 2 was prototyped by a tappi standard sheet machine. Table 23 shows the composition at this time.
【００７４】[0074]
【表２３】 比較例２の酸化チタン光触媒担持シートＯの光触媒活性
試験 アセトアルデヒドガスを充満させた密封ガラス容器（容
積：0.5 ｌ）に酸化チタン光触媒担持シートＯを入れ、
光触媒活性を検討した。紫外線強度0.5mW/cm2の紫外線
を照射したときのアセトアルデヒドガスの分解を測定し
た。このときのアセトアルデヒドガス初期濃度は1000pp
m である。このときのアセトアルデヒドガスの50分後の
分解率を表24に示す。[Table 23] Photocatalytic activity of titanium oxide photocatalyst supporting sheet O of Comparative Example 2
Place the titanium oxide photocatalyst supporting sheet O in a sealed glass container (volume: 0.5 l) filled with test acetaldehyde gas,
The photocatalytic activity was studied. The decomposition of acetaldehyde gas upon irradiation with ultraviolet light having an ultraviolet intensity of 0.5 mW / cm 2 was measured. The initial concentration of acetaldehyde gas at this time is 1000pp
m. Table 24 shows the decomposition rate of the acetaldehyde gas at this time after 50 minutes.
【００７５】[0075]
【表２４】 比較例２の酸化チタン光触媒担持シートＯの破裂強さ試
験 紫外線強度1.6mW/cm2 の紫外線を連続照射し、酸化チタ
ン光触媒担持シートＯの破裂強さを測定した。この結果
を表25に示す。[Table 24] Burst strength test of titanium oxide photocatalyst supporting sheet O of Comparative Example 2
The UV test UV intensity 1.6 mW / cm 2 was continuously irradiated to measure the bursting strength of the titanium oxide photocatalyst carrying sheet O. Table 25 shows the results.
【００７６】[0076]
【表２５】 （実施例１４）酸化チタン光触媒パウダーを水中に分散
させ、定着剤として硫酸アルミニウムを添加後、水酸化
ナトリウムで中和し、発生する水酸化アルミニウムで酸
化チタン光触媒パウダーを定着させた後、ポリアクリル
アミドで凝集させた。さらに別に用意したパルプスラリ
ーに混合後、パルプに担持させ、さらにポリアクリルア
ミドで凝集させた。このときのパルプ坪量は100g/m2 、
酸化チタン光触媒はパルプに対して10重量% を内添し、
タッピスタンダードシートマシンにより、実施例１４の
酸化チタン光触媒担持シートＰを試作した。このときの
配合を表26に示す。[Table 25] (Example 14) A titanium oxide photocatalyst powder was dispersed in water, aluminum sulfate was added as a fixing agent, neutralized with sodium hydroxide, and the titanium oxide photocatalyst powder was fixed with the generated aluminum hydroxide, followed by polyacrylamide. For aggregation. After mixing with a separately prepared pulp slurry, the mixture was supported on pulp and further coagulated with polyacrylamide. The pulp weight at this time is 100 g / m 2 ,
Titanium oxide photocatalyst adds 10% by weight to pulp internally,
A titanium oxide photocatalyst-carrying sheet P of Example 14 was prototyped by a tappi standard sheet machine. The composition at this time is shown in Table 26.
【００７７】[0077]
【表２６】 実施例１４の酸化チタン光触媒担持シートＰの光触媒活
性試験 アセトアルデヒドガスを充満させた密封ガラス容器に実
施例１４の酸化チタン光触媒担持シートＰを入れ、光触
媒活性を検討した。紫外線強度0.5mW/cm2 の紫外線を照
射したときの悪臭物質であるアセトアルデヒドガスの分
解を測定した。このときのアセトアルデヒドガス初期濃
度は1000ppm である。アセトアルデヒドガスの50分後の
分解率を表27に示す。[Table 26] Photocatalytic activity of titanium oxide photocatalyst supporting sheet P of Example 14
The titanium oxide photocatalyst supporting sheet P of Example 14 was placed in a sealed glass container filled with acetaldehyde gas, and the photocatalytic activity was examined. The decomposition of acetaldehyde gas, which is a malodorous substance, when irradiated with ultraviolet light having an ultraviolet intensity of 0.5 mW / cm 2 was measured. The initial concentration of acetaldehyde gas at this time is 1000 ppm. Table 27 shows the decomposition rate of the acetaldehyde gas after 50 minutes.
【００７８】[0078]
【表２７】 表27から明らかなように、酸化チタン光触媒担持シート
Ｐは、50分間で11.3％のアセトアルデヒドガスを分解
し、光触媒活性を示した。[Table 27] As is clear from Table 27, the titanium oxide photocatalyst-carrying sheet P decomposed 11.3% of acetaldehyde gas in 50 minutes and exhibited photocatalytic activity.
【００７９】実施例１４の酸化チタン光触媒担持シート
Ｐの破裂強さ試験 紫外線強度1.6mW/cm 2の紫外線を連続照射し、酸化チタ
ン光触媒担持シートＰの破裂強さを測定した。この結果
を表28に示す。The sheet carrying the titanium oxide photocatalyst of Example 14
Burst strength test of P The ultraviolet ray having an ultraviolet intensity of 1.6 mW / cm 2 was continuously irradiated, and the burst strength of the titanium oxide photocatalyst supporting sheet P was measured. Table 28 shows the results.
【００８０】[0080]
【表２８】 表28から明らかなように、酸化チタン光触媒を予め定着
凝集させることにより、強度物性が向上し、担体の劣化
を防止することができた。[Table 28] As is evident from Table 28, by pre-fixing and aggregating the titanium oxide photocatalyst, the strength physical properties were improved, and the deterioration of the carrier was prevented.
【００８１】（実施例１５，１６，１７，１８，１９）
酸化チタン光触媒を水中に分散させ、硫酸アルミニウム
を添加後、水酸化ナトリウムで中和し、発生する水酸化
アルミニウムで酸化チタン光触媒を定着させた後、ポリ
アクリルアミドで凝集させた。これを90重量% のレーヨ
ン繊維、ポリエステル繊維、ポリエチレン繊維、ポリプ
ロピレン繊維及びマイクロガラス繊維と10重量% の低融
点熱可塑性繊維をそれぞれ分散させたスラリーに添加
し、担持させた。この時のスラリーの抄紙坪量を100g/m
2 、酸化チタン光触媒はスラリーに対して10重量% を内
添し、タッピスタンダードシートマシンにより、実施例
１５，１６，１７，１８，１９の酸化チタン光触媒担持
シートＱ、Ｒ、Ｓ、Ｔ、Ｕとした。配合を表29に示す。(Examples 15, 16, 17, 18, and 19)
The titanium oxide photocatalyst was dispersed in water, aluminum sulfate was added, neutralized with sodium hydroxide, the titanium oxide photocatalyst was fixed with the generated aluminum hydroxide, and then coagulated with polyacrylamide. This was added to and supported by a slurry in which 90% by weight of rayon fiber, polyester fiber, polyethylene fiber, polypropylene fiber, micro glass fiber and 10% by weight of low melting thermoplastic fiber were dispersed. The papermaking basis weight of the slurry at this time is 100 g / m
2. 10% by weight of titanium oxide photocatalyst was internally added to the slurry, and the titanium oxide photocatalyst-supporting sheets Q, R, S, T, and U of Examples 15, 16, 17, 18, and 19 were applied by a Tappi standard sheet machine. And The formulations are shown in Table 29.
【００８２】[0082]
【表２９】 実施例１５〜１９の酸化チタン光触媒担持シートＱ〜Ｕ
の光触媒活性試験 アセトアルデヒドガスを充満させた密封ガラス容器に酸
化チタン光触媒担持シートＱ、Ｒ、Ｓ、Ｔ、Ｕを入れ、
光触媒活性を検討した。紫外線強度0.5mW/cm2の紫外線
を照射したときのアセトアルデヒドガスの分解を測定し
た。このときのアセトアルデヒドガス初期濃度は1000pp
m である。アセトアルデヒドガスの50分後の分解率を表
30に示す。[Table 29] Titanium oxide photocatalyst supporting sheets Q to U of Examples 15 to 19
Photocatalytic activity test of Titanium oxide photocatalyst carrying sheets Q, R, S, T, U in a sealed glass container filled with acetaldehyde gas,
The photocatalytic activity was studied. The decomposition of acetaldehyde gas upon irradiation with ultraviolet light having an ultraviolet intensity of 0.5 mW / cm 2 was measured. The initial concentration of acetaldehyde gas at this time is 1000pp
m. Shows the decomposition rate of acetaldehyde gas after 50 minutes.
Shown at 30.
【００８３】[0083]
【表３０】 実施例１５〜１９の酸化チタン光触媒担持シートＱ〜Ｕ
の破裂強さ試験 紫外線強度4.0mW/cm2 の紫外線の連続照射を行い、酸化
チタン光触媒担持シートＱ、Ｒ、Ｓ、Ｔ、Ｕの破裂強さ
試験を測定した。これを表31に示す。[Table 30] Titanium oxide photocatalyst supporting sheets Q to U of Examples 15 to 19
Performs the burst strength continuous irradiation of ultraviolet rays of the test UV intensity 4.0 mW / cm 2, titanium oxide photocatalyst carrying sheet Q, R, S, T, the burst strength test of the U was measured. This is shown in Table 31.
【００８４】[0084]
【表３１】 表31から明らかなようにサンプルＵシートは保持強度は
あったが、破裂強さ試験器で測定できる程の強度は無
く、安定したデータは得られなかった。[Table 31] As is clear from Table 31, the sample U sheet had a holding strength, but was not strong enough to be measured by a burst strength tester, and stable data could not be obtained.
【００８５】（実施例２０）亜鉛を含有する酸化チタン
光触媒パウダーを水中に分散させ、定着剤として硫酸ア
ルミニウムを添加後、水酸化ナトリウムで中和し、発生
する水酸化アルミニウムで酸化チタン光触媒を定着させ
た後、ポリアクリルアミドで凝集させた。さらに別に用
意したパルプスラリーに混合後、パルプに担持させ、さ
らにポリアクリルアミドで凝集させた。このときのパル
プ秤量は１００ｇ／ｍ2 、酸化チタン光触媒はパルプに
対して１０重量％内添し、タッピスタンダードシートマ
シンにより、実施例２０の酸化チタン光触媒担持シート
Ｖを試作した。このときの配合を表32に示す。(Example 20) A titanium oxide photocatalyst powder containing zinc was dispersed in water, aluminum sulfate was added as a fixing agent, neutralized with sodium hydroxide, and the titanium oxide photocatalyst was fixed with the generated aluminum hydroxide. After that, it was aggregated with polyacrylamide. After mixing with a separately prepared pulp slurry, the mixture was supported on pulp and further coagulated with polyacrylamide. At this time, the weight of the pulp was 100 g / m 2 , and the titanium oxide photocatalyst was internally added at 10% by weight to the pulp. The composition at this time is shown in Table 32.
【００８６】[0086]
【表３２】 実施例２０の酸化チタン光触媒担持シートＶの光触媒活
性試験 紫外線強度１．６ｍＷ／ｃｍ2 の紫外線を連続照射し、
酸化チタン光触媒担持シートＶの破裂強さを測定した。
この結果を表33に示す。[Table 32] Photocatalytic activity of titanium oxide photocatalyst supporting sheet V of Example 20
Ultraviolet sexual test UV intensity 1.6 mW / cm 2 irradiated continuously,
The burst strength of the titanium oxide photocatalyst supporting sheet V was measured.
The results are shown in Table 33.
【００８７】[0087]
【表３３】 [Table 33]
【００８８】[0088]
【発明の効果】以上詳述したように、本発明によれば、
紫外線照射下で極めて安定でかつ脱臭、消臭、防汚、抗
菌の機能を持った担体、例えば紙類で言えば、障子紙な
どの安定化が図れる。As described in detail above, according to the present invention,
Carriers that are extremely stable under ultraviolet irradiation and have deodorizing, deodorizing, antifouling, and antibacterial functions, such as paper for paper, can be used to stabilize shoji paper.
【図１】酸化チタン光触媒担持シートＡのアセトアルデ
ヒドガス分解の測定結果を示すグラフである。FIG. 1 is a graph showing measurement results of acetaldehyde gas decomposition of a titanium oxide photocatalyst supporting sheet A.
【図２】酸化チタン光触媒担持シートＮの白色螢光灯照
射によるタバコヤニ分解の測定結果を示すグラフであ
る。FIG. 2 is a graph showing the results of measuring the decomposition of cigarette tar on a titanium oxide photocatalyst-carrying sheet N by irradiation with a white fluorescent lamp.
【図３】酸化チタン光触媒担持シートＮのブラックライ
ト照射によるタバコヤニ分解の測定結果を示すグラフで
ある。FIG. 3 is a graph showing the results of measuring the decomposition of tobacco tar on the titanium oxide photocatalyst-carrying sheet N by irradiation with black light.
【図４】酸化チタン光触媒担持シートＮの殺菌効果の測
定結果を示すグラフである。FIG. 4 is a graph showing the measurement results of the sterilization effect of the titanium oxide photocatalyst-carrying sheet N.
【図５】各種の光照射による光触媒担持シートＮの殺菌
効果の測定結果を示すグラフである。FIG. 5 is a graph showing measurement results of a sterilization effect of the photocatalyst-carrying sheet N by various types of light irradiation.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｄ２１Ｈ 21/36 Ｄ２１Ｈ 3/78 5/22 Ｃ (72)発明者 藤嶋 昭 神奈川県川崎市中原区中丸子710番地５ (72)発明者 橋本 和仁 神奈川県横浜市栄区小菅ケ谷町2000番地 の10 南小菅ケ谷住宅２棟506号 (72)発明者 高田 誠 岐阜県関市西本郷通り６丁目10番５号 (72)発明者 神山 真一 岐阜県岐阜市折立679 (72)発明者 松原 弘一 東京都荒川区荒川５丁目39番６号 第２ エステートイケダ203号 (56)参考文献 特開 昭63−200838（ＪＰ，Ａ) 特開 平８−257360（ＪＰ，Ａ) 特開 平９−156919（ＪＰ，Ａ) (58)調査した分野(Int.Cl.6，ＤＢ名) B01J 21/00 - 38/00 D21H 17/67 ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 6 Identification code FI D21H 21/36 D21H 3/78 5/22 C (72) Inventor Akira Fujishima 710-5 Nakamaruko Nakahara-ku, Kawasaki City, Kanagawa Prefecture (72) Inventor Kazuhito Hashimoto 2nd 506, Minami Kosugaya House, 2000, Kosugaya-cho, Sakae-ku, Yokohama, Kanagawa Prefecture (72) Inventor Koichi Matsubara 5-39-6 Arakawa-ku, Arakawa-ku, Tokyo 2nd Estate Ikeda 203 (56) References JP-A-63-200838 (JP, A) JP-A-8- 257360 (JP, A) JP-A-9-156919 (JP, A) (58) Fields investigated (Int. Cl. 6 , DB name) B01J 21/00-38/00 D21H 17/67
Claims (6)
又はゾルからなる光触媒を、核となる物質に定着させた
後に、凝集剤により凝集させ、担体に担持させることに
より、光触媒作用によって担体が劣化するのを防止する
ようにしたことを特徴とする光触媒の定着方法。1. A photocatalyst comprising a semiconductor or a metal-containing semiconductor powder or sol is fixed to a nucleus substance, then agglomerated by an aggregating agent and carried on the carrier, whereby the carrier is degraded by the photocatalytic action A method for fixing a photocatalyst, wherein the fixing is prevented.
いて、 前記半導体又は金属を担持した半導体の粉末またはゾル
からなる光触媒として、一次粒子径が5nm 〜0.1 μｍの
酸化チタンの粉末またはゾルを用いることを特徴とする
光触媒の定着方法。2. The method for fixing a photocatalyst according to claim 1, wherein the photocatalyst comprising a semiconductor or metal-supported semiconductor powder or sol is a titanium oxide powder or sol having a primary particle diameter of 5 nm to 0.1 μm. A method for fixing a photocatalyst, which is used.
法において、 前記凝集剤によって凝集した凝集体の大きさが、200nm
以上であることを特徴とする光触媒の定着方法。3. The method for fixing a photocatalyst according to claim 1, wherein the size of the aggregate aggregated by the aggregating agent is 200 nm.
A method for fixing a photocatalyst characterized by the above .
触媒の定着方法において、前記光触媒の配合量として、
担体に対して重量比で1%〜50% であることを特徴とする
光触媒の定着方法。4. The method for fixing a photocatalyst according to claim 1, wherein the amount of the photocatalyst is as follows:
A method for fixing a photocatalyst, which is 1% to 50% by weight based on a carrier.
触媒の定着方法において、 前記核となる物質として、ポリテトラフルオロエチレ
ン、ゼオライト、ホワイトカーボン、セピオライト、活
性炭、水酸化アルミニウム、シリコーンの単独または複
数を用いることを特徴とする光触媒の定着方法。5. The method for fixing a photocatalyst according to claim 1, wherein the substance serving as a nucleus is polytetrafluoroethylene, zeolite, white carbon, sepiolite, activated carbon, aluminum hydroxide, or silicone alone. Alternatively, a method for fixing a photocatalyst, comprising using a plurality of photocatalysts.
又はゾルからなる光触媒が核となる物質に定着されておAlternatively, if a photocatalyst consisting of a sol is
り、これらが凝集剤により凝集されて担体に担持されてThese are agglomerated by a flocculant and supported on a carrier.
なる光触媒構造体であって、請求項１ないし５のいずれ6. A photocatalyst structure comprising:
かに記載の光触媒の定着方法を用いて製造されたものでIt is manufactured using the photocatalyst fixing method described in
あることを特徴とする光触媒構造体。A photocatalyst structure, which is characterized in that:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8019010A JP2900307B2 (en) | 1995-02-03 | 1996-02-05 | Fixing method of photocatalyst |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3934595 | 1995-02-03 | ||
| JP7-39345 | 1995-02-03 | ||
| JP8019010A JP2900307B2 (en) | 1995-02-03 | 1996-02-05 | Fixing method of photocatalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09206602A JPH09206602A (en) | 1997-08-12 |
| JP2900307B2 true JP2900307B2 (en) | 1999-06-02 |
Family
ID=26355799
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8019010A Expired - Lifetime JP2900307B2 (en) | 1995-02-03 | 1996-02-05 | Fixing method of photocatalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2900307B2 (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3557747B2 (en) * | 1995-08-23 | 2004-08-25 | 日板パッケージ株式会社 | Corrugated cardboard and deodorizing element using titanium oxide containing paper |
| JPH09291232A (en) * | 1996-04-24 | 1997-11-11 | Suzuki Sogyo Co Ltd | Material for preventing adhesion of aquatic organism |
| JPH10128066A (en) * | 1996-10-29 | 1998-05-19 | Nhk Spring Co Ltd | Deodorizing device using photocatalyst and carrier for photocatalyst |
| JPH11216276A (en) * | 1998-02-02 | 1999-08-10 | Matsushita Electric Ind Co Ltd | Manufacture of edge tool |
| JP2000110064A (en) * | 1998-07-31 | 2000-04-18 | Toray Ind Inc | Fiber structure having functional property |
| GB2356858A (en) * | 1999-07-21 | 2001-06-06 | Procter & Gamble | Combined photocatalytic and ultrasonic degradation of orgainc contaminants |
| JP5002864B2 (en) * | 2001-03-02 | 2012-08-15 | 独立行政法人国立高等専門学校機構 | Oxide photocatalyst materials using organometallic compounds and their applications |
| JP4901034B2 (en) * | 2001-09-05 | 2012-03-21 | 住化エンビロサイエンス株式会社 | Industrial antibacterial composition and antibacterial method |
| KR100482649B1 (en) * | 2002-04-25 | 2005-04-13 | 한국화학연구원 | Direct adhesion method of photocatalyst on substrate |
| JP5052067B2 (en) * | 2006-08-09 | 2012-10-17 | 日本曹達株式会社 | Photocatalytic liquid composition |
| JP2009256111A (en) * | 2006-08-10 | 2009-11-05 | Mitsui Chemicals Inc | Method for producing photosemiconductor particle |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3701984A1 (en) * | 1987-01-23 | 1988-08-04 | Siemens Ag | METHOD FOR PRODUCING TITANOXIDE CATALYSTS |
| JPH08257360A (en) * | 1995-03-24 | 1996-10-08 | Mitsubishi Paper Mills Ltd | Photoreactive material for removing harmful substance |
-
1996
- 1996-02-05 JP JP8019010A patent/JP2900307B2/en not_active Expired - Lifetime
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|---|---|
| JPH09206602A (en) | 1997-08-12 |
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