JPH10265586A - Photocatalyst sheet - Google Patents
Photocatalyst sheetInfo
- Publication number
- JPH10265586A JPH10265586A JP9071164A JP7116497A JPH10265586A JP H10265586 A JPH10265586 A JP H10265586A JP 9071164 A JP9071164 A JP 9071164A JP 7116497 A JP7116497 A JP 7116497A JP H10265586 A JPH10265586 A JP H10265586A
- Authority
- JP
- Japan
- Prior art keywords
- photocatalyst
- microbial cellulose
- sheet
- support
- forming component
- 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.)
- Pending
Links
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- 238000003756 stirring Methods 0.000 claims description 17
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- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000010893 paper waste Substances 0.000 description 1
- 239000011087 paperboard Substances 0.000 description 1
- 150000002972 pentoses Chemical class 0.000 description 1
- 235000019319 peptone Nutrition 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229920001289 polyvinyl ether Polymers 0.000 description 1
- 229920006215 polyvinyl ketone Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- CDAISMWEOUEBRE-UHFFFAOYSA-N scyllo-inosotol Natural products OC1C(O)C(O)C(O)C(O)C1O CDAISMWEOUEBRE-UHFFFAOYSA-N 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000011218 seed culture Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011122 softwood Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- DPJRMOMPQZCRJU-UHFFFAOYSA-M thiamine hydrochloride Chemical compound Cl.[Cl-].CC1=C(CCO)SC=[N+]1CC1=CN=C(C)N=C1N DPJRMOMPQZCRJU-UHFFFAOYSA-M 0.000 description 1
- 229960000344 thiamine hydrochloride Drugs 0.000 description 1
- 235000019190 thiamine hydrochloride Nutrition 0.000 description 1
- 239000011747 thiamine hydrochloride Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、光触媒反応を利用
し、臭気物質や汚れ物質などの有害物質を分解し得る光
触媒シートに関し、更に詳しくは微生物セルロースを用
いて光触媒を効率良く支持体上に保持された防汚効果に
優れた光触媒シートに関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photocatalyst sheet capable of decomposing harmful substances such as odorous substances and dirt substances by utilizing a photocatalytic reaction. More specifically, the present invention relates to a method for efficiently depositing a photocatalyst on a support by using microbial cellulose. The present invention relates to a retained photocatalyst sheet having an excellent antifouling effect.
【０００２】[0002]
【従来の技術】近年、環境問題に対する関心の高まりに
伴い、工業排気及び排水等工業レベルでの低濃度有害物
質の除去だけでなく、日常生活の中に於ても悪臭除去の
要求が増加している。低濃度有害物の除去には、特に日
常生活に於ける悪臭除去材としては一般的に活性炭やシ
リカ、アルミナ、及び金属酸化物等の複合化された無機
吸着剤等が使用されているが、吸着剤に有害物が吸着さ
れるに従い、次第に吸収能力が低下して行くなど、使用
上の数々の問題点があった。2. Description of the Related Art In recent years, with increasing interest in environmental issues, there has been an increasing demand for not only the removal of low-concentration harmful substances such as industrial exhaust and wastewater on an industrial level, but also the removal of offensive odors in daily life. ing. For the removal of low-concentration harmful substances, activated carbon, silica, alumina, and composite inorganic adsorbents such as metal oxides and the like are generally used as a malodor removing material in daily life, As the harmful substances are adsorbed on the adsorbent, there are a number of problems in use, such as the absorption capacity gradually decreasing.
【０００３】これに対し、近年光触媒を用いた有害物の
除去方法が開発された。特開昭６１−１３５６６９号公
報には、酸化亜鉛等の光触媒に紫外光を照射して、悪臭
物質である硫黄化合物を分解する方法が開示されてい
る。また、特公平２−６２２９７号公報には、酸化チタ
ンと活性炭混合物により低濃度窒素酸化物を除去する方
法が開示されている。酸化チタンや酸化亜鉛等の光触媒
による悪臭物質の分解は、これらの活性線励起による接
触悪臭物質の光触媒的酸化作用によるため、光触媒は悪
臭物質の分解で消費及び劣化を被らず、その能力は光曝
露されている限り基本的に低下しないため、吸着剤のみ
を使用する場合に比べて大きな利点を有する。On the other hand, in recent years, a method for removing harmful substances using a photocatalyst has been developed. JP-A-61-135669 discloses a method in which a photocatalyst such as zinc oxide is irradiated with ultraviolet light to decompose a sulfur compound as a malodorous substance. Further, Japanese Patent Publication No. 2-62297 discloses a method for removing low-concentration nitrogen oxides using a mixture of titanium oxide and activated carbon. The decomposition of malodorous substances by photocatalysts such as titanium oxide and zinc oxide is due to the photocatalytic oxidation of contact malodorous substances by the excitation of these actinic rays. Since it does not decrease basically as long as it is exposed to light, it has a great advantage as compared with the case where only the adsorbent is used.
【０００４】悪臭物質の分解による永続的な脱臭作用に
加えて、光触媒には、有機物系の汚れ物質を分解して、
その付着を防ぐ防汚作用や大腸菌などの細菌の繁殖を防
ぐ抗菌作用があることが知られており、かかる光触媒を
含有する光触媒シートは多方面の用途で使用されるもの
である。[0004] In addition to the permanent deodorizing effect due to the decomposition of malodorous substances, the photocatalyst also decomposes organic contaminants,
It is known that it has an antifouling action to prevent the adhesion and an antibacterial action to prevent the growth of bacteria such as Escherichia coli. A photocatalyst sheet containing such a photocatalyst is used in various applications.
【０００５】光触媒シートを得る方法として、特開平７
−２９９３５４号公報に光触媒を担持した担体を通気性
シートに内包する方法が、特開平８−２６６６０１号公
報に微細繊維を用いて光触媒を強固に保持する方法が開
示されている。中でも、微細繊維を用いて光触媒を強固
に保持した光触媒シートは、臭気物質の除去能に加えて
後加工性にも優れたものであるが、防汚効果がやや劣る
点が問題であった。A method for obtaining a photocatalyst sheet is disclosed in
Japanese Patent Application Laid-Open No. Hei 8-266601 discloses a method for enclosing a carrier supporting a photocatalyst in a gas permeable sheet and a method for firmly holding a photocatalyst using fine fibers. Above all, a photocatalyst sheet in which a photocatalyst is firmly held by using fine fibers is excellent in post-processability in addition to the ability to remove odorous substances, but has a problem in that the antifouling effect is slightly inferior.
【０００６】[0006]
【発明が解決しようとする課題】本発明の課題は、臭気
物質や汚れ物質などの有害物質の分解性に優れ、且つ後
加工性が優れ、更には難燃性に優れた光触媒シートを提
供することである。SUMMARY OF THE INVENTION An object of the present invention is to provide a photocatalyst sheet which is excellent in decomposability of harmful substances such as odorous substances and dirt substances, is excellent in post-processing properties, and is also excellent in flame retardancy. That is.
【０００７】[0007]
【課題を解決するための手段】本発明者らは上記課題を
解決すべく鋭意検討の結果、下記の発明を考案するに至
った。Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and as a result, have devised the following invention.
【０００８】光触媒、微生物セルロースおよび支持体形
成成分からなる光触媒シート。A photocatalyst sheet comprising a photocatalyst, microbial cellulose and a support-forming component.
【０００９】光触媒、微生物セルロースおよび支持体形
成成分からなる水性懸濁液を湿式抄造してなる光触媒シ
ート。A photocatalyst sheet obtained by wet-making an aqueous suspension comprising a photocatalyst, microbial cellulose and a support-forming component.
【００１０】光触媒、微生物セルロースおよび支持体形
成成分からなる水性懸濁液を湿式抄造してなる光触媒シ
ートにおいて、該水性懸濁液が更に凝集剤を含有するこ
とを特徴とする光触媒シート。[0010] A photocatalyst sheet obtained by wet-making an aqueous suspension comprising a photocatalyst, microbial cellulose and a support-forming component, wherein the aqueous suspension further contains a flocculant.
【００１１】光触媒、微生物セルロースおよび支持体形
成成分からなる水性懸濁液において、微生物セルロース
の光触媒保持指標（Ａ）と微生物セルロースの添加量
（Ｂ）の積に対する光触媒の添加量（Ｃ）の重量比（Ｃ
／（Ａ×Ｂ））が、０．５〜２であることを特徴とする
水性懸濁液を湿式抄造してなる光触媒シート。In an aqueous suspension comprising a photocatalyst, microbial cellulose and a support-forming component, the weight of the photocatalyst addition amount (C) to the product of the microbial cellulose photocatalyst retention index (A) and the microbial cellulose addition amount (B) Ratio (C
/ (A × B)) is 0.5 to 2, a photocatalyst sheet obtained by wet-paper-making an aqueous suspension.
【００１２】光触媒、微生物セルロースおよび支持体形
成成分からなる光触媒シートにおいて、該微生物セルロ
ースが撹拌培養法により生産されたセルロース性物質で
あることを特徴とする光触媒シート。A photocatalyst sheet comprising a photocatalyst, microbial cellulose and a support-forming component, wherein the microbial cellulose is a cellulosic substance produced by a stirring culture method.
【００１３】光触媒、微生物セルロースおよび支持体形
成成分からなる水性懸濁液を湿式抄造してなる光触媒シ
ートにおいて、該微生物セルロースが撹拌培養法により
生産されたセルロース性物質であることを特徴とする光
触媒シート。A photocatalyst sheet obtained by wet-making an aqueous suspension comprising a photocatalyst, microbial cellulose and a support-forming component, wherein the microbial cellulose is a cellulosic substance produced by a stirring culture method. Sheet.
【００１４】光触媒、微生物セルロースおよび支持体形
成成分からなる光触媒シートにおいて、該支持体形成成
分が難燃性物質であることを特徴とする光触媒シート。A photocatalyst sheet comprising a photocatalyst, microbial cellulose and a support-forming component, wherein the support-forming component is a flame-retardant substance.
【００１５】光触媒、微生物セルロースおよび支持体形
成成分からなる水性懸濁液を湿式抄造してなる光触媒シ
ートにおいて、該支持体形成成分が難燃性物質であるこ
とを特徴とする光触媒シート。A photocatalyst sheet obtained by wet-making an aqueous suspension comprising a photocatalyst, microbial cellulose and a support-forming component, wherein the support-forming component is a flame-retardant substance.
【００１６】[0016]
【発明の実施の形態】以下に本発明の光触媒シートに係
わる構成要素、次いでその製造方法を詳細に説明する。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The components relating to the photocatalyst sheet of the present invention and the method for producing the same will be described below in detail.
【００１７】本発明に係わる光触媒とは、０．５〜５ｅ
Ｖ、好ましくは１〜４ｅＶの禁止帯幅を有する、光触媒
反応をもたらす光反応性半導体である。本発明に係わる
このような光触媒としては、酸化亜鉛、酸化タングステ
ン、酸化チタン、及び酸化セリウム等の金属酸化物粒子
が挙げられるが、殊に酸化チタンはその構造安定性、光
反応性有害物除去能、更には取扱い上の安全性等から生
活空間において使用するには最も適しており、本発明に
係わる光触媒として有利に用いられる。The photocatalyst according to the present invention is 0.5 to 5 e
V, preferably a photoreactive semiconductor that provides a photocatalytic reaction with a band gap of 1-4 eV. Examples of such a photocatalyst according to the present invention include metal oxide particles such as zinc oxide, tungsten oxide, titanium oxide, and cerium oxide. In particular, titanium oxide has structural stability and photoreactive harmful substance removal. The photocatalyst according to the present invention is most suitable for use in a living space because of its performance and safety in handling, and is advantageously used as a photocatalyst according to the present invention.
【００１８】光触媒として有利に用いられる酸化チタン
は、白色顔料として用いる汎用の二酸化チタンの他、メ
タチタン酸、オルトチタン酸、含水酸化チタン、水和酸
化チタン、及び水酸化チタン等のチタン酸化物やチタン
水酸化物等が挙げられる。これらの酸化チタンは、四塩
化チタンや硫酸チタン、あるいは酸化硫酸チタンを原料
として、気相燃焼法、加水分解法、あるいは加熱分解法
等によって工業的に製造される。これらの中でも、１０
ｎｍ以下の大きさを中心とするアナターゼ構造を持つ微
粒子酸化チタンは、優れた光触媒である。更に、これら
の製造方法の他に有機チタネートを用いる方法があり、
この方法は均一性が高く透明性のある光反応性膜が得ら
れる。また、これらの酸化チタンの表面に、Ｐｔ、Ａ
ｕ、Ａｇ、Ｃｕ、Ｐｄ、Ｎｉ、Ｒｈ、Ｎｂ、Ｓｎ、Ｃｒ
及びＲｕ等の金属を担持あるいはドーピングさせたり、
酸化ルテニウム、酸化ニッケル、酸化マンガン、及び酸
化鉄等の他の金属酸化物を担持させても良い。Titanium oxide which is advantageously used as a photocatalyst includes titanium oxide such as metatitanic acid, orthotitanic acid, hydrous titanium oxide, hydrated titanium oxide and titanium hydroxide, in addition to general-purpose titanium dioxide used as a white pigment. Titanium hydroxide and the like can be mentioned. These titanium oxides are produced industrially by a gas phase combustion method, a hydrolysis method, a thermal decomposition method, or the like using titanium tetrachloride, titanium sulfate, or titanium oxide as a raw material. Among these, 10
Fine particle titanium oxide having an anatase structure centered on the size of nm or less is an excellent photocatalyst. Furthermore, there is a method using an organic titanate other than these production methods,
This method provides a highly uniform and transparent photoreactive film. In addition, Pt, A
u, Ag, Cu, Pd, Ni, Rh, Nb, Sn, Cr
And doping or doping metals such as Ru,
Other metal oxides such as ruthenium oxide, nickel oxide, manganese oxide, and iron oxide may be supported.
【００１９】光触媒における有害物分解機構は、光触媒
が活性光を受けるとその表面にフリーラジカルを生成
し、このフリーラジカルが光触媒の表面と接触した有害
物を攻撃して有害物を分解する。この過程を充分に発揮
させるには、光触媒の比表面積を大きくし、フリーラジ
カルの生成点を増加させることが効果的である。加え
て、比表面積を大きくすると、光触媒の単位量当りの有
害物との接触面積も増大することから、有害物を分解す
るためには、その比表面積が大きいほど効果的である。The mechanism for decomposing harmful substances in a photocatalyst generates free radicals on the surface of the photocatalyst when the photocatalyst receives active light, and the free radicals attack harmful substances in contact with the surface of the photocatalyst to decompose the harmful substances. In order to sufficiently exhibit this process, it is effective to increase the specific surface area of the photocatalyst and increase the free radical generation point. In addition, when the specific surface area is increased, the contact area with the harmful substance per unit amount of the photocatalyst is also increased. Therefore, in order to decompose the harmful substance, the larger the specific surface area is, the more effective.
【００２０】しかし、光触媒の比表面積を大きくしてい
くと、光触媒自体安定性が低下するし、凝集力が強くな
って分散が困難になり、実質的に有害物の接触の向上が
図れない。そこで、本発明に係わる光触媒の比表面積は
５０〜５００ｍ2/ｇ程度が好ましく、更には１００〜５
００ｍ2/ｇ程度が良い。また、特に酸化チタンの場合
は、比表面積は５０〜４００ｍ2/ｇ程度が好ましく、更
には１５０〜３５０ｍ2/ｇ程度が良い。However, as the specific surface area of the photocatalyst is increased, the stability of the photocatalyst itself is reduced, the cohesion is increased, and the dispersion is difficult, and the contact of harmful substances cannot be substantially improved. Therefore, the specific surface area of the photocatalyst according to the present invention is preferably about 50 to 500 m 2 / g, more preferably 100 to 5 m 2 / g.
About 00 m 2 / g is good. In particular, in the case of titanium oxide, the specific surface area is preferably about 50 to 400 m 2 / g, and more preferably about 150 to 350 m 2 / g.
【００２１】本発明の微生物セルロースとは、微生物に
より生産されたセルロース性物質であり、セルロースの
他にセルロースを主鎖としたヘテロ多糖、β−１，３、
β−１，２等のグルカンを含むものである。ヘテロ多糖
の場合のセルロース以外の構成成分は、マンノース、フ
ラクトース、ガラクトース、キシロース、アラビノー
ス、ラムノース、グルクロン酸等の６炭糖、５炭糖およ
び有機酸等である。The microbial cellulose of the present invention is a cellulosic substance produced by a microorganism, and in addition to cellulose, a heteropolysaccharide having cellulose as a main chain, β-1,3,
It contains glucans such as β-1, 2 and the like. The constituent components other than cellulose in the case of the heteropolysaccharide are hexoses, pentoses such as mannose, fructose, galactose, xylose, arabinose, rhamnose, and glucuronic acid, and organic acids.
【００２２】微生物セルロースを生産する微生物は、特
に限定されないが、アセトバクター・キシリナム（Acet
obactor xylinum）ＡＴＣＣ １０８２１、アセトバク
ター・キシリナム・サブスピーシーズ・シュクロファー
メンタンス（Acetobactor xylinum subsp. sucrofermen
tans）ＢＰＲ２００１株（ＦＥＲＭ ＢＰ−４５４
５）、アセトバクター・パストウリアヌス（A. pasteur
iunus）等の酢酸菌、その他に、アグロバクテリウム
属、リゾビウム属、サルシナ属、シュードモナス属、ア
クロモバクター属、アルカリゲネス属、アエロバクター
属、アゾトバクター属及びズーグレア属並びにそれらを
ニトロソグアニジン等を用いる処理や紫外線照射等の公
知の方法によって変異処理することにより創製される各
種変異株で、セルロース性物質を生産するものを利用す
ることができる。The microorganism producing cellulose is not particularly limited, but may be Acetobacter xylinum (Acetobacter).
obactor xylinum ATCC 10821, Acetobactor xylinum subsp. sucrofermentans
tans) BPR2001 strain (FERM BP-454)
5), Acetobacter pasteurianus (A. pasteur)
iunus) and other genus Agrobacterium, Rhizobium, Sarsina, Pseudomonas, Achromobacter, Alcaligenes, Aerobacter, Azotobacter and Zugrea, and treatment with nitrosoguanidine and the like. And various types of mutant strains that are created by performing a mutation treatment by a known method such as ultraviolet irradiation or the like, and that produce a cellulosic substance can be used.
【００２３】微生物セルロースを培養する方法として
は、静置培養、振とう培養、攪拌培養などを使用するこ
とができる。中でも、本発明で用いる微生物セルロース
は培養液を撹拌しながら行う撹拌培養法により生産され
たものが好ましい。撹拌培養法における撹拌手段として
は、例えばインペラー、エアリフト発酵槽、発酵ブロス
のポンプ駆動循環等を使用できる。As a method for culturing microbial cellulose, stationary culture, shaking culture, stirring culture and the like can be used. Among them, the microbial cellulose used in the present invention is preferably produced by a stirring culture method in which a culture solution is stirred. As a stirring means in the stirring culture method, for example, an impeller, an airlift fermenter, a pump-driven circulation of a fermentation broth and the like can be used.
【００２４】培養操作法としては、いわゆる回分発酵
法、流加回分発酵法、反復回分発酵法及び連続発酵法等
がある。撹拌培養を行うための槽としては、例えば、ジ
ャーファーメンター及びタンク等の撹拌槽、並びにバッ
フル付きフラスコ、坂口フラスコ及びエアリフト型の発
酵槽等が使用可能である。Examples of the culturing method include so-called batch fermentation, fed-batch batch fermentation, repeated batch fermentation, and continuous fermentation. As a tank for performing the stirring culture, for example, a stirring tank such as a jar fermenter and a tank, a flask with a baffle, a Sakaguchi flask, and an air-lift type fermenter can be used.
【００２５】本発明の撹拌培養においては、撹拌と同時
に、必要に応じて培養液に通気を行っても良い。例えば
嫌気性微生物を培養する場合には、酸素を含有しないア
ルゴン及び窒素等の不活性気体を通気することによっ
て、培養液を撹拌することができる。また、好気性微生
物を培養する場合には、酸素を含有する気体を通気する
ことによって、微生物の生育やセルロース性物質の生産
に必要な酸素を供給すると同時に、培養液を撹拌するこ
とができる。なお、この通気による撹拌とインペラー等
を用いた撹拌は併用することが可能である。なお、培養
に用いる微生物の種類と培養方法については、例えば、
酢酸菌においては、静置培養に向いた菌株と撹拌培養に
向いた菌株が存在することが知られており、培養法に応
じて菌株を選択することが好ましい。In the stirring culture of the present invention, the culture solution may be aerated as needed at the same time as the stirring. For example, when cultivating an anaerobic microorganism, the culture solution can be stirred by passing an inert gas such as argon and nitrogen containing no oxygen. In the case of culturing aerobic microorganisms, the culture solution can be agitated while supplying oxygen necessary for the growth of microorganisms and the production of cellulosic substances by aerating an oxygen-containing gas. The agitation by aeration and the agitation using an impeller or the like can be used in combination. In addition, about the type and culture method of the microorganism used for culture, for example,
It is known that acetic acid bacteria include a strain suitable for stationary culture and a strain suitable for stirring culture, and it is preferable to select the strain according to the culture method.
【００２６】本発明で用いる微生物セルロースは解繊処
理を施すことが好ましい。解繊処理は、特公平６−７２
３９４号公報等に記載されているミキサーなどの撹拌式
離解装置を用いる方法、ＰＣＴ／ＵＳ９２／０９６４２
号明細書に記載されている高圧式のホモジナイザ−を用
いる方法等を用いることができる。微生物セルロースの
解繊処理による変化は、例えば酢酸菌を静置培養して得
られる塊状の微生物セルロースは、水系で沈降性の低い
均質な繊維懸濁物となること、また、例えば酢酸菌を撹
拌培養して得られる水系で繊維懸濁状態の微生物セルロ
ースでは、特開平７−１１８３０３号公報に記載せれて
いる沈降性の低下、すなわち均質性の向上や特開平７−
１１９０６７号公報に記載せれている濾水性の低下等が
観察される。The microbial cellulose used in the present invention is preferably subjected to a defibration treatment. The defibration process is 6-72
No. 394, etc., using a stirring type disintegration apparatus such as a mixer, PCT / US92 / 09642.
A method using a high-pressure homogenizer described in the specification can be used. The change due to the fibrillation treatment of the microbial cellulose is, for example, that the bulk microbial cellulose obtained by static culturing of acetic acid bacteria becomes a homogeneous sediment with low sedimentation in an aqueous system, and, for example, stirring of the acetic acid bacteria In the case of microbial cellulose in a fiber suspension in an aqueous system obtained by culturing, the sedimentation property described in JP-A-7-118303 is reduced, that is, the homogeneity is improved.
A decrease in drainage and the like described in 119067 are observed.
【００２７】微生物セルロースの光触媒保持指標とは、
単位重量の微生物セルロースが保持し得る光触媒の重量
を表す比であり、無次元の量である。微生物セルロース
の光触媒保持指標を求めるには、微生物セルロース、微
生物セルロースに対して充分多量の光触媒、支持体形成
成分、および所望により凝集剤からなる水性懸濁液を調
整し、ＴＡＰＰＩ標準法Ｔ２６１ｐｍ−７９「ウェット
スクリーニングによる紙料の微細繊維分」におけるリテ
ンション操作に準拠した試験を行う。この試験結果から
得られる光触媒の留まった量（Ｄ）、微生物セルロース
を添加しない試験結果から得られる支持体形成成分によ
って光触媒の留まった量（Ｅ）および微生物セルロース
の留まった量（Ｆ）から数式１で表される式によって光
触媒保持指標（Ａ）が求まる。The photocatalyst retention index of microbial cellulose is as follows:
It is a ratio indicating the weight of the photocatalyst that can be held by a unit weight of microbial cellulose, and is a dimensionless amount. To determine the photocatalyst retention index of microbial cellulose, an aqueous suspension comprising microbial cellulose, a photocatalyst, a support-forming component and, if desired, an aggregating agent for microbial cellulose is prepared, and the TAPPI standard method T261 pm-79 is used. A test based on the retention operation in "fine fiber content of stock by wet screening" is performed. The amount of photocatalyst retained (D) obtained from the test results, the amount of photocatalyst retained by the support-forming component (E) and the amount of microbial cellulose retained (F) obtained from the test results without the addition of microbial cellulose were calculated from the following formula. The photocatalyst retention index (A) is determined by the equation represented by 1.
【００２８】[0028]
【数１】（数式１） 光触媒保持指標（Ａ）＝（Ｄ−Ｅ）／Ｆ(Equation 1) Photocatalyst retention index (A) = (DE) / F
【００２９】光触媒の添加量を固定して、微生物セルロ
ースの添加量を０から少しづつ増やしていくと、光触媒
の留まった量はほぼ直線的に増加して行き、その後飽和
してほぼ一定値となることが確認されるが、上記の微生
物セルロースに対して充分多量の光触媒という量関係
は、光触媒の留まった量がほぼ直線的に増えて飽和に達
するまでの、微生物セルロースの量が光触媒の量に対し
て少ない範囲のことである。また、微生物セルロースの
留まった量を求める場合に、このように微生物セルロー
スの添加量が相対的に少ない範囲では測定の誤差が大き
いため、例えば、微生物セルロースの添加量を支持体形
成成分に対して０〜１０重量％程度まで段階的に振って
試験を行い、微生物セルロースの添加量に対して微生物
セルロースの留まった量をプロットし、その一次回帰の
結果から、該当する微生物セルロース添加量における微
生物セルロースの留まった量を求める等のが補正を加え
る必要がある。When the addition amount of the photocatalyst is fixed and the addition amount of the microbial cellulose is gradually increased from 0, the remaining amount of the photocatalyst increases almost linearly, and then saturates to a substantially constant value. Although it is confirmed that the amount of the photocatalyst is sufficiently large with respect to the microbial cellulose, the amount of the microbial cellulose increases until the amount of the photocatalyst increases almost linearly and reaches saturation. Is a small range. In addition, when determining the amount of microbial cellulose retained, since the measurement error is large in such a range where the amount of microbial cellulose is relatively small, for example, the amount of microbial cellulose added to the support-forming component The test is performed by shaking stepwise to about 0 to 10% by weight, and the amount of microbial cellulose remaining is plotted against the amount of microbial cellulose added. It is necessary to add a correction, for example, to obtain the amount of remaining.
【００３０】光触媒、微生物セルロースおよび支持体形
成成分からなる水性懸濁液、好ましくは更に凝集剤を含
有する水性懸濁液を湿式抄造してなる光触媒シートにお
いては、微生物セルロースの光触媒保持指標（Ａ）と微
生物セルロースの添加量（Ｂ）の積に対する光触媒の添
加量（Ｃ）の重量比（Ｃ／（Ａ×Ｂ））が、０．５〜２
であることが好ましい。An aqueous suspension comprising a photocatalyst, microbial cellulose and a support-forming component, preferably an aqueous suspension further containing a flocculant, is wet-processed to form a photocatalyst sheet. ) And the amount of photocatalyst added (C) to the product of the amount of microbial cellulose added (B) is 0.5 to 2 (C / (A × B)).
It is preferred that
【００３１】上記の重量比（Ｃ／（Ａ×Ｂ））が０．５
より小さいと、加工時のシートからの粉落ちが問題とな
り、更に、湿式抄造時に光触媒がシート中に留まり難
く、排水が悪化する場合、及び充分な脱臭性が得られな
い場合等がある。また、上記の重量比（Ｃ／（Ａ×
Ｂ））が２より大きいと、防汚性が低下し、また、光触
媒がシート中に留まる量がかえって低下する場合があ
り、更に、難燃性の光触媒シートを得るために支持体形
成成分として難燃性物質を用いても、充分な難燃性が得
られない。The weight ratio (C / (A × B)) is 0.5
When the particle size is smaller than the above range, powder drops from the sheet during processing become a problem, and further, the photocatalyst hardly stays in the sheet during wet papermaking, drainage is deteriorated, and sufficient deodorizing properties may not be obtained. In addition, the weight ratio (C / (A ×
When B)) is larger than 2, the antifouling property is reduced, and the amount of the photocatalyst remaining in the sheet may be rather reduced. Further, in order to obtain a flame-retardant photocatalyst sheet, it is used as a support-forming component. Even if a flame retardant is used, sufficient flame retardancy cannot be obtained.
【００３２】本発明の支持体形成成分とは、光触媒シー
トを形成するに当たり、その形態を保持するために必要
な成分である。支持体形成成分としては、合成樹脂及び
天然繊維等を用いることができる。The support-forming component of the present invention is a component necessary for maintaining the form when forming the photocatalyst sheet. As the support-forming component, synthetic resins, natural fibers, and the like can be used.
【００３３】支持体形成成分に用いる合成樹脂として
は、ポリエチレンやポリプロピレン等のポリオレフィン
系樹脂、ポリエステル系樹脂、ポリ酢酸ビニル樹脂、エ
チレン酢酸ビニル共重合体樹脂、ナイロン等のポリアミ
ド系樹脂、アクリル系樹脂、ポリ塩化ビニル樹脂、ポリ
塩化ビニリデン樹脂、ポリビニルエーテル樹脂、ポリビ
ニルケトン樹脂、ポリエーテル樹脂、ポリビニルアルコ
ール系樹脂、ジエン系樹脂、及びポリウレタン系樹脂等
の熱可塑性合成樹脂、フェノール樹脂、メラミン樹脂、
フラン樹脂、尿素樹脂、アニリン樹脂、不飽和ポリエス
テル樹脂、アルキド樹脂、及びエポキシ樹脂等の熱硬化
性合成樹脂の他、シリコン系樹脂及びフッ素系樹脂等が
挙げられる。Examples of the synthetic resin used for the support-forming component include polyolefin resins such as polyethylene and polypropylene, polyester resins, polyvinyl acetate resins, ethylene vinyl acetate copolymer resins, polyamide resins such as nylon, and acrylic resins. , Polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl ether resin, polyvinyl ketone resin, polyether resin, polyvinyl alcohol resin, diene resin, thermoplastic synthetic resin such as polyurethane resin, phenol resin, melamine resin,
In addition to a thermosetting synthetic resin such as a furan resin, a urea resin, an aniline resin, an unsaturated polyester resin, an alkyd resin, and an epoxy resin, a silicon-based resin and a fluorine-based resin are included.
【００３４】これらの合成樹脂を繊維形態、いわゆる合
成樹脂繊維として用いる場合には、その断面形状は特に
制限はなく、円形のみならず楕円形、三角形、星形、Ｔ
型、Ｙ型、及び葉状等のいわゆる異型断面形状のもので
も良い。更に、繊維表面に空隙を有するもの、枝別れし
た構造、及び芯鞘構造を有するものも使用できる。これ
らの合成樹脂繊維の中でも、支持体あるいは光触媒シー
トとした際の繊維間結合強度、柔軟性（腰）、及び加工
性等を適度に制御できる点から主に軟化点の異なる芯鞘
構造を有するものが好適である。芯鞘構造を有する合成
樹脂繊維としては、芯部分がポリエステル、鞘部分がポ
リエステル共重合体からなる繊維や、芯部分がポリエス
テル、鞘部分がポリオレフィンからなる繊維等がある。When these synthetic resins are used in the form of a fiber, that is, as a so-called synthetic resin fiber, the cross-sectional shape is not particularly limited.
A so-called irregular cross-sectional shape such as a shape, a Y shape, and a leaf shape may be used. Further, those having voids on the fiber surface, those having a branched structure, and those having a core-sheath structure can also be used. Among these synthetic resin fibers, they have a core-sheath structure having a different softening point mainly from the viewpoint that the fiber-to-fiber bond strength, flexibility (elasticity), workability, and the like when used as a support or a photocatalyst sheet can be appropriately controlled. Those are preferred. Examples of the synthetic resin fiber having a core-sheath structure include a fiber whose core portion is made of polyester and a sheath portion made of a polyester copolymer, and a fiber whose core portion is made of polyester and whose sheath portion is made of polyolefin.
【００３５】また、特に第１の発明に係わる支持体形成
成分においては、フィルム状の形態のいわゆる合成樹脂
フィルムを用いることも可能である。In particular, as the support-forming component according to the first invention, a so-called synthetic resin film in the form of a film can be used.
【００３６】支持体形成成分に用いる天然繊維として
は、針葉樹材及び広葉樹材からのクラフトパルプ、亜硫
酸パルプ、及びアルカリパルプ等のケミカルパルプ、セ
ミケミカルパルプ、サーモメカニカルパルプ、メカニカ
ルパルプ、グランドパルプ等の木材繊維、楮、ミツマ
タ、稲や小麦等の藁、麻、ケナフ、竹、木綿、木綿リン
ター、バガス、及びエスパルト等の植物性非木材繊維を
挙げられる。また、これらは、古紙を原料とした再生パ
ルプ、脱墨パルプ等でも良い。The natural fibers used as the support-forming component include chemical pulp such as kraft pulp, sulfite pulp, and alkali pulp from softwood and hardwood, semi-chemical pulp, thermomechanical pulp, mechanical pulp, ground pulp and the like. Examples include wood fiber, mulberry, mulberry, straw such as rice and wheat, hemp, kenaf, bamboo, cotton, cotton linter, bagasse, and vegetable non-wood fibers such as espart. These may be recycled pulp or deinked pulp made from waste paper.
【００３７】支持体に用いる合成繊維樹脂及び天然繊維
以外の繊維としては、レーヨン等の再生繊維、セルロー
ス誘導体繊維等の天然物加工繊維、スチールウール及び
ステンレスウール等の金属繊維、炭素繊維、セラミック
繊維、及び各種ガラス繊維等を挙げられる。The fibers other than the synthetic fiber resin and the natural fiber used for the support include regenerated fibers such as rayon, processed natural fibers such as cellulose derivative fibers, metal fibers such as steel wool and stainless wool, carbon fibers, and ceramic fibers. And various glass fibers.
【００３８】支持体形成成分に用いる難燃性物質として
は、本質的に難燃性のアラミド樹脂、本質的に不燃性の
金属、ガラス、アルミナ等酸化物等の無機物のほかに、
合成樹脂、及び天然繊維等の中に難燃剤を化学的に組み
込んだり、物理的に配合した複合物を挙げることができ
る。特に第１の発明においては、支持体を形成した後に
難燃剤で表面処理する等、後加工で難燃性を付与した支
持体を用いることもできる。Examples of the flame-retardant substance used as the support-forming component include inorganic substances such as essentially flame-retardant aramid resin, essentially non-flammable metal, glass, and oxides such as alumina.
Examples include composites in which a flame retardant is chemically incorporated into a synthetic resin, natural fiber, or the like, or physically blended. In particular, in the first invention, it is possible to use a support provided with flame retardancy by post-processing such as surface treatment with a flame retardant after forming the support.
【００３９】本発明の凝集剤としては、アラム等の無機
化合物、及びポリアクリルアミド等の高分子化合物等が
ある。中でも、電解質高分子化合物が好ましく、カチオ
ン化ポリアクリルアミド、カチオン化澱粉、及びカチオ
ン化グアーガム等のカチオン性電解質高分子化合物が特
に好ましい。Examples of the flocculant of the present invention include inorganic compounds such as alum and high molecular compounds such as polyacrylamide. Among them, electrolyte polymer compounds are preferable, and cationic electrolyte polymer compounds such as cationized polyacrylamide, cationized starch, and cationized guar gum are particularly preferable.
【００４０】本発明の光触媒、微生物セルロースおよび
支持体形成成分からなる光触媒シートを製造するには、
光触媒、微生物セルロースおよび支持体形成成分からな
る原料混合物をシート化する方法、及び支持体形成成分
から予めシート状の支持体を形成した後に、この支持体
に光触媒および微生物セルロースからなる原料混合物を
含有させる方法等がある。To produce a photocatalyst sheet comprising the photocatalyst of the present invention, microbial cellulose and a support-forming component,
A method for forming a raw material mixture comprising a photocatalyst, a microbial cellulose and a support-forming component into a sheet, and a raw material mixture comprising a photocatalyst and a microbial cellulose contained in the support after forming a sheet-like support from the support-forming component in advance There is a method to make it.
【００４１】光触媒、微生物セルロースおよび支持体形
成成分からなる原料混合物をシート化する光触媒シート
の製造方法の具体例としては、光触媒、微生物セルロー
スおよび支持体形成成分からなる水性懸濁液を湿式抄造
する方法、及び光触媒、微生物セルロースおよび支持体
形成成分からなる原料を乾式抄造する方法等が挙げられ
る。中でも、湿式抄造による光触媒シートの製造方法が
好ましく、凝集剤、好ましくはカチオン性電解質高分子
化合物を更に含有する水性懸濁液を湿式抄造する製造方
法が特に好ましい。As a specific example of a method for producing a photocatalyst sheet in which a raw material mixture comprising a photocatalyst, microbial cellulose and a support-forming component is formed into a sheet, an aqueous suspension comprising a photocatalyst, microbial cellulose and a support-forming component is wet-processed. And a method of dry-papermaking a raw material comprising a photocatalyst, microbial cellulose and a support-forming component. Above all, a method for producing a photocatalyst sheet by wet papermaking is preferred, and a production method for wet-papering an aqueous suspension further containing a coagulant, preferably a cationic electrolyte polymer compound, is particularly preferred.
【００４２】湿式抄造には、円網抄紙機、長網抄紙機、
フォードリニヤー抄紙機、ツインワイヤー抄紙機、オン
トップ抄紙機等、及び複数の抄紙機を組み合わせたいわ
ゆるコンビネーションフォーマー等を用いることができ
る。また、水性懸濁液を調整するには、支持体形成成分
を予め水性液に分散させ、必要に応じて叩解等の処理を
施した後に、光触媒、微生物セルロース、及び所望によ
り凝集剤等と混合することが好ましい。For wet papermaking, a round paper machine, a fourdrinier paper machine,
Ford linear paper machines, twin wire paper machines, on-top paper machines, etc., and so-called combination formers combining a plurality of paper machines can be used. To prepare an aqueous suspension, the support-forming component is dispersed in an aqueous liquid in advance, and after treatment such as beating is performed, if necessary, mixed with a photocatalyst, microbial cellulose, and, if desired, a flocculant. Is preferred.
【００４３】支持体形成成分から予めシート状支持体を
形成した後に、この支持体に光触媒および微生物セルロ
ースからなる原料混合物を含有させる光触媒シートの製
造方法の具体例としては、支持体形成成分からなる繊維
状シート、及びフィルム等の支持体に光触媒および微生
物セルロースからなる水性塗液を塗設する方法等が挙げ
られる。A specific example of a method for producing a photocatalyst sheet in which a sheet-like support is formed in advance from the support-forming component, and the support is then mixed with a raw material mixture comprising a photocatalyst and microbial cellulose, comprises a support-forming component. A method of coating an aqueous coating solution comprising a photocatalyst and microbial cellulose on a support such as a fibrous sheet or a film may be used.
【００４４】塗設方法としては、水性塗液に繊維状シー
ト等の支持体を浸漬する含浸、及び繊維状シート、及び
フィルム等の支持体の表面への塗布が挙げられる。本発
明に係わる含浸及び塗布の方法として、２ロールタイプ
のコンベンショナルサイズプレス、タブサイズプレス、
ゲートロールサイズプレス、及びフィルムトランファー
方式のサイズプレス等や、ロールコーター、エアドクタ
ーコーター、ロッド（バー）コーター、ブレードコータ
ー、スプレーコーター、グラビアコーター、マイクログ
ラビアコーター、ダイコーター、及びカーテンコーター
を用いた方法等が挙げられる。Examples of the coating method include impregnation in which a support such as a fibrous sheet is immersed in an aqueous coating solution, and application to the surface of a support such as a fibrous sheet and a film. As a method of impregnation and coating according to the present invention, a two-roll type conventional size press, a tab size press,
For gate roll size press, film transfer type size press, roll coater, air doctor coater, rod (bar) coater, blade coater, spray coater, gravure coater, micro gravure coater, die coater, and curtain coater And the like.
【００４５】含浸及び塗布等の塗設に際しては、グロー
放電処理、火焔処理、プラズマ処理、電子線照射処理、
紫外線照射処理、及びオゾン処理等により、支持体表面
を処理した後に塗設することも好ましい方法である。こ
れら表面処理は二種以上の方法を組み合わせて用いても
良く、支持体の一方の面と他方の面で異なる処理を施し
ても良い。塗設は支持体の一方の面だけでも差し支えな
いので、表面処理は塗設面だけ行なっても良い。For coating such as impregnation and coating, glow discharge treatment, flame treatment, plasma treatment, electron beam irradiation treatment,
It is also a preferable method to coat the support after treating the surface of the support by ultraviolet irradiation treatment, ozone treatment or the like. These surface treatments may be used in combination of two or more methods, and different treatments may be performed on one surface and the other surface of the support. Since the coating may be performed on only one surface of the support, the surface treatment may be performed only on the coated surface.
【００４６】本発明の光触媒シートにおいては、微生物
セルロースは微視的には数十ｎｍの微細なリボン状繊維
が比較的粗な網目構造を形成しており、光触媒の吸着性
に優れ、且つ、微生物セルロースの微細な繊維は解繊処
理によって著しく均質な状態となるため、かかる微生物
セルロースに保持された光触媒は、支持体中に均質に分
散し、光触媒シートの表面においても汚れ物質を分解す
る光触媒が偏在せずに均質に存在することによって、著
しく優れた汚れ物質除去効果、いわゆる防汚効果が得ら
れるものである。In the photocatalyst sheet of the present invention, microbial cellulose is microscopically composed of fine ribbon-like fibers of several tens of nanometers forming a relatively coarse network structure, and has excellent photocatalytic adsorption properties, and Since the fine fibers of microbial cellulose become extremely homogenous by the fibrillation treatment, the photocatalyst held in such microbial cellulose is homogeneously dispersed in the support, and the photocatalyst that decomposes contaminants even on the surface of the photocatalyst sheet Is not unevenly distributed but is homogeneously present, whereby a remarkably excellent effect of removing dirt substances, that is, a so-called antifouling effect can be obtained.
【００４７】[0047]
【実施例】以下、実施例により更に本発明を詳細に説明
するが、本発明はその主旨を越えない限り、これらに限
定されるものではない。EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto unless it exceeds the gist of the invention.
【００４８】調製例１ 次の方法で微生物セルロースを調製した。 （１） シード菌液の調製（菌体の増殖） フラクトース４０ｇ／Ｌ、硫安３ｇ／Ｌ、リン酸水素カ
リウム１．０ｇ／Ｌ、硫酸マグネシウム（ＭｇＳＯ4・
７Ｈ2Ｏ）０．３ｇ／Ｌ、バクト−ペプトン５ｇ／Ｌ、
乳酸１．４ｍｌ／Ｌ、初発ｐＨ５．０の組成の基本培地
１００ｍｌを張り込んだ容量７５０ｍｌのＲｏｕｘフラ
スコに、アセトバクター・キシリナム・サブスピーシー
ズ・シュクロファーメンタンスＢＰＲ２００１株（ＦＥ
ＲＭ ＢＰ−４５４５）の凍結保存菌液１ｍｌを植菌
し、２８℃で３日間静置培養した。このシード培養後、
前記Ｒｏｕｘフラスコをよく振とうした後、無菌条件下
で内容物をガーゼ濾過し、シード菌液を得た。Preparation Example 1 Microbial cellulose was prepared by the following method. (1) Preparation of seed bacterial solution (growth of bacterial cells) Fructose 40 g / L, ammonium sulfate 3 g / L, potassium hydrogen phosphate 1.0 g / L, magnesium sulfate (MgSO 4.
7H 2 O) 0.3g / L, bacto - peptone 5 g / L,
Acetobacter xylinum subspecies schlofermentans BPR2001 strain (FE) was placed in a 750 ml Roux flask filled with 100 ml of a basic medium having a composition of lactic acid 1.4 ml / L and an initial pH of 5.0.
1 ml of a cryopreserved bacterial solution of RM BP-4545) was inoculated and cultured at 28 ° C. for 3 days. After this seed culture,
After thoroughly shaking the Roux flask, the contents were subjected to gauze filtration under aseptic conditions to obtain a seed bacterial solution.
【００４９】（２） 撹拌培養による微生物セルロース
の調製 フラクトース４０ｇ／Ｌ、硫安３．３ｇ／Ｌ、リン酸水
素カリウム１．０ｇ／Ｌ、硫酸マグネシウム（ＭｇＳＯ
4・７Ｈ2Ｏ）０．２５ｇ／Ｌ、コーン・スティープ・リ
カー４０ｇ／Ｌ、ビタミン混合液１０ｇ／Ｌ、及び塩類
混合液１０ｇ／Ｌからなる組成の滅菌済みの培地５４０
ｍｌを張り込んだ小型ジャーファーメンター（全容量１
０００ｍｌ）に上記シード菌液６０ｍｌを無菌的に植菌
し、３０℃で７２時間、ｐＨを１Ｎ ＮａＯＨと１Ｎ
Ｈ2ＳＯ4を用いて５．０に調整しながら、また、撹拌回
転数を初発４００ｒｐｍで、溶存酸素が３．０〜２１．
０％内に入るように回転数を制御しながらジャーファー
メンターで撹拌培養した。ここで、上記のビタミン混合
液とは、イノシトール２００ｍｇ／Ｌ、ナイアシン４０
ｍｇ／Ｌ、ヒリドキシン塩酸４０ｍｇ／Ｌ、チアミン塩
酸４０ｍｇ／Ｌ、パントテン酸カルシウム２０ｍｇ／
Ｌ、リポフラビン２０ｍｇ／Ｌ、ｐ−アミノ安息香酸２
０ｍｇ／Ｌ、葉酸０．２ｍｇ／Ｌ、ビオチン０．２ｍｇ
／Ｌからなる組成の液であり、また、上記の塩類混合液
とは、ＦｅＳＯ4・７Ｈ2Ｏ３６０ｍｇ／Ｌ、ＣａＣｌ2
・２Ｈ2Ｏ１４７０ｍｇ／Ｌ、Ｎａ2ＭｏＯ2・２Ｈ2Ｏ２
４２ｍｇ／Ｌ、ＺｎＳＯ4・７Ｈ2Ｏ１７３ｍｇ／Ｌ、Ｍ
ｎＳＯ4・５Ｈ2Ｏ１３９ｍｇ／Ｌ、ＣｕＳＯ4・５Ｈ2Ｏ
５ｍｇ／Ｌからなる組成の液である。(2) Preparation of microbial cellulose by stirring culture Fructose 40 g / L, ammonium sulfate 3.3 g / L, potassium hydrogen phosphate 1.0 g / L, magnesium sulfate (MgSO 4)
4 · 7H 2 O) 0.25g / L, corn steep liquor 40 g / L, vitamin mixture 10 g / L, and salts mixture sterile medium 540 a composition consisting of 10 g / L
ml jar fermenter (total volume 1)
000 ml) is aseptically inoculated with 60 ml of the above seed bacterial solution, and the pH is adjusted to 1N NaOH and 1N at 30 ° C. for 72 hours.
While adjusting to 5.0 using H 2 SO 4 , the stirring rotation speed was initially 400 rpm, and the dissolved oxygen was 3.0 to 21.
The mixture was stirred and cultured with a jar fermenter while controlling the number of revolutions so as to fall within 0%. Here, the above-mentioned vitamin mixture refers to inositol 200 mg / L, niacin 40
mg / L, hydridoxine hydrochloride 40 mg / L, thiamine hydrochloride 40 mg / L, calcium pantothenate 20 mg / L
L, lipoflavin 20 mg / L, p-aminobenzoic acid 2
0 mg / L, folic acid 0.2 mg / L, biotin 0.2 mg
/ L is the liquid composition consisting of, also, the above-mentioned salts mixture, FeSO 4 · 7H 2 O360mg / L, CaCl 2
· 2H 2 O1470mg / L, Na 2 MoO 2 · 2H 2 O2
42mg / L, ZnSO 4 · 7H 2 O173mg / L, M
nSO 4 · 5H 2 O139mg / L , CuSO 4 · 5H 2 O
This is a liquid having a composition of 5 mg / L.
【００５０】培養終了後、ジャーファーメンター内の固
形物を集積し、水洗した後に、１％ＮａＯＨ水溶液中で
１１０℃、２０分間処理し、更に洗浄液が中性付近にな
るまで生成セルロースを水洗して微生物セルロースを得
た。次いで乾燥重量に対して２００倍の水を加え、ブレ
ンダー（オースター社製）を用いて最高回転数（電源周
波数５０Ｈｚ）で２分間解繊処理し、０．５％の懸濁液
を調製し、調製例１の微生物セルロースとした。After the cultivation, the solid matter in the jar fermenter was collected, washed with water, treated in a 1% aqueous solution of NaOH at 110 ° C. for 20 minutes, and the resulting cellulose was washed with water until the washing solution became nearly neutral. To obtain microbial cellulose. Then, 200 times water based on the dry weight was added, and the mixture was defibrated at a maximum rotation speed (power frequency: 50 Hz) for 2 minutes using a blender (manufactured by Auster) to prepare a 0.5% suspension. And the microbial cellulose of Preparation Example 1.
【００５１】予備操作１ 調整例１の微生物セルロースの光触媒保持指標を以下の
方法により求めた。未叩解のＬＢＫＰからＴＡＰＰＩ標
準法Ｔ２６１ｐｍ−７９「ウェットスクリーニングによ
る紙料の微細繊維分」におけるふるい分け操作に従って
微細繊維分を除去したＬＢＫＰの長繊維分と調整例１の
微生物セルロースとの乾燥重量の合計１００部に対し
て、調整例１の微生物セルロースの置換量を、０、１、
２、４、及び８部と５水準に変化させ、酸化チタン（石
原産業製、ＳＴ−３１）を１００部およびカチオン化ポ
リアクリルアミド（アライドコロイド社製、パーコール
５７）を０．５部添加して濃度０．５％の水性懸濁液を
５００ｍｌ調整し、ＴＡＰＰＩ標準法Ｔ２６１ｐｍ−７
９「ウェットスクリーニングによる紙料の微細繊維分」
におけるリテンション操作に準拠して、酸化チタンの留
まった量および微生物セルロースの留まった量を求め
た。なお、スクリーンは１００メッシュの金網を使用
し、ダイナミック・ドレネージ・ジャーの回転数は５０
０ｒｐｍに設定した。この試験の結果、微生物セルロー
スの置換量が２部の場合に、微生物セルロースの留まっ
た量の補正値が０．８２部、酸化チタンの留まった量が
２３．１部、また、微生物セルロース未添加（置換量が
０部）の場合に酸化チタンの留まった量が９．２部であ
った。従って、凝集剤としてカチオン化ポリアクリルア
ミド（アライドコロイド社製、パーコール５７）を適量
添加した場合の調整例１の微生物セルロースの光触媒保
持指標は、１７．０である。なお、微生物セルロースの
留まった量の補正値は、微生物セルロースの置換量０、
１、２、４、及び８部に対して微生物セルロースの留ま
った量をプロットし、その一次回帰の結果から、微生物
セルロースの置換量２部における微生物セルロースの留
まった量を求めたものである。Preliminary Operation 1 The photocatalyst retention index of the microbial cellulose of Preparation Example 1 was determined by the following method. The sum of the dry weight of the long fiber of LBKP and the microbial cellulose of Preparation Example 1 from which fine fibers were removed from unbeaten LBKP by sieving operation in TAPPI standard method T261pm-79 "Fine fibers of stock by wet screening" For 100 parts, the replacement amount of the microbial cellulose of Preparation Example 1 was 0, 1,
2, 4, and 8 parts were changed to 5 levels, and 100 parts of titanium oxide (manufactured by Ishihara Sangyo, ST-31) and 0.5 part of cationized polyacrylamide (manufactured by Allied Colloids, Percoll 57) were added. An aqueous suspension having a concentration of 0.5% was adjusted to 500 ml, and TAPPI standard method T261pm-7 was prepared.
9 "fine fiber content of stock by wet screening"
The retention amount of the titanium oxide and the retention amount of the microbial cellulose were determined based on the retention operation in. The screen is made of 100 mesh wire mesh, and the rotation speed of the dynamic drainage jar is 50.
It was set to 0 rpm. As a result of this test, when the replacement amount of microbial cellulose was 2 parts, the correction value of the amount of microbial cellulose retained was 0.82 parts, the amount of retained titanium oxide was 23.1 parts, and no microbial cellulose was added. When the substitution amount was 0 parts, the remaining amount of titanium oxide was 9.2 parts. Therefore, the photocatalyst retention index of the microbial cellulose of Preparation Example 1 when a suitable amount of cationized polyacrylamide (Percoll 57, manufactured by Allied Colloids) was added as a flocculant was 17.0. In addition, the correction value of the remaining amount of microbial cellulose is 0,
The remaining amount of microbial cellulose was plotted against 1, 2, 4, and 8 parts, and the amount of microbial cellulose retained in 2 parts of the replacement amount of microbial cellulose was determined from the result of the primary regression.
【００５２】予備操作２ 予備操作１において、カチオン化ポリアクリルアミド
（アライドコロイド社製、パーコール５７）を０．５部
を添加しない以外は、全て予備操作１と同様にして試験
を行った。この試験の結果、微生物セルロースの置換量
が４部の場合に、微生物セルロースの留まった量の補正
値が１．６０部、酸化チタンの留まった量が２４．１
部、また、微生物セルロース未添加（置換量が０部）の
場合に酸化チタンの留まった量が８．８部であった。従
って、凝集剤を併用しない場合の調整例１の微生物セル
ロースの光触媒保持指標は、９．６である。Preliminary operation 2 The test was carried out in the same manner as in Preliminary operation 1, except that 0.5 parts of cationized polyacrylamide (manufactured by Allied Colloids, Percoll 57) was not added. As a result of this test, when the replacement amount of microbial cellulose was 4 parts, the correction value of the amount of microbial cellulose retained was 1.60 parts, and the amount of retained titanium oxide was 24.1 parts.
In addition, when microbial cellulose was not added (substitution amount was 0 part), the amount of titanium oxide retained was 8.8 parts. Therefore, the photocatalyst retention index of the microbial cellulose of Preparation Example 1 when no coagulant is used is 9.6.
【００５３】調製例２ 次の方法で微生物セルロースを調製した。シュークロー
ス５０ｇ／Ｌ、酵母エキス５ｇ／Ｌ、硫安５ｇ／Ｌ、リ
ン酸水素カリウム３ｇ／Ｌ、硫酸マグネシウム（ＭｇＳ
Ｏ4・７Ｈ2Ｏ）０．５ｇ／Ｌからなる組成の培地（ｐＨ
５．０）５０ｍｌを容量２００ｍｌの三角フラスコに張
り込み、１２０℃で２０分間蒸気殺菌して培養液を作成
した。次に、この培養液に酵母エキス５ｇ／Ｌ、ペプト
ン３ｇ／Ｌ、マンニトール２５ｇ／Ｌからなる組成の試
験管斜面寒天培地（ｐＨ６．０）で３０℃、３日間生育
させたアセトバクター・キシリナム（ＡＴＣＣ １０８
２１）を１白金耳ずつ接種し、３０℃で３０日間培養し
たところ、培養液の上層に白色の微生物セルロース性多
糖類を含むゲル状の膜が形成された。このゲル状の膜を
水洗した後に、１％ＮａＯＨ水溶液中で１１０℃、３０
分間処理し、更に洗浄液が中性付近になるまで生成セル
ロースを水洗して微生物セルロースを得た。次いで乾燥
重量に対して２００倍の水を加え、ブレンダー（オース
ター社製）を用いて最高回転数（電源周波数５０Ｈｚ）
で３分間解繊処理し、０．５％の懸濁液を調製し、調製
例２の微生物セルロースとした。Preparation Example 2 Microbial cellulose was prepared by the following method. Sucrose 50 g / L, yeast extract 5 g / L, ammonium sulfate 5 g / L, potassium hydrogen phosphate 3 g / L, magnesium sulfate (MgS
O 4 · 7H 2 O) medium composition consisting of 0.5 g / L (pH
5.0) 50 ml was placed in a 200 ml Erlenmeyer flask, and sterilized with steam at 120 ° C. for 20 minutes to prepare a culture solution. Next, Acetobacter xylinum (30 ml) grown on a test tube slant agar medium (pH 6.0) composed of 5 g / L of yeast extract, 3 g / L of peptone, and 25 g / L of mannitol in this culture solution at 30 ° C. ATCC 108
21) was inoculated one loop at a time and cultured at 30 ° C. for 30 days. As a result, a gel-like film containing white microbial cellulosic polysaccharide was formed on the upper layer of the culture solution. After washing this gel-like film with water, it is heated in a 1% NaOH aqueous solution at 110 ° C. for 30 minutes.
For a minute, and the resulting cellulose was washed with water until the washing solution was near neutral to obtain microbial cellulose. Next, water 200 times the dry weight was added, and the maximum number of revolutions (power frequency: 50 Hz) was performed using a blender (Auster).
For 3 minutes to prepare a 0.5% suspension, which was designated as Microbial Cellulose of Preparation Example 2.
【００５４】予備操作３ 予備操作１において、調製例１の微生物セルロースに代
えて調製例２の微生物セルロースとする以外は、全て予
備操作１と同様にして試験を行った。この試験の結果、
微生物セルロースの置換量が４部の場合に、微生物セル
ロースの留まった量の補正値が３．８３部、酸化チタン
の留まった量が４０．１部、また、微生物セルロース未
添加（置換量が０部）の場合に酸化チタンの留まった量
が９．２部であった。従って、凝集剤としてカチオン化
ポリアクリルアミド（アライドコロイド社製、パーコー
ル５７）を適量添加した場合の調整例２の微生物セルロ
ースの光触媒保持指標は、８．１である。Preliminary operation 3 The test was performed in the same manner as in Preparative operation 1 except that the microbial cellulose of Preparative example 1 was replaced with the microbial cellulose of Preparative example 2. As a result of this test,
When the replacement amount of the microbial cellulose is 4 parts, the correction value of the amount of the remaining microbial cellulose is 3.83 parts, the amount of the remaining titanium oxide is 40.1 parts, and no addition of the microbial cellulose (the replacement amount is 0). Parts), the amount of titanium oxide retained was 9.2 parts. Therefore, the photocatalyst retention index of microbial cellulose of Preparation Example 2 in the case where an appropriate amount of cationized polyacrylamide (Percoll 57, manufactured by Allied Colloid Co., Ltd.) was added as an aggregating agent was 8.1.
【００５５】調製例３ 支持体形成成分として塩化ビニル−酢酸ビニル共重合繊
維（三菱レイヨン社製、ＶＦ、繊度３デニール、繊維長
６ｍｍ）７５重量％、及びバインダー繊維として熱溶融
性ポリエステル繊維（ユニチカ社製、メルティ４０８
０、繊度２デニール、繊維長５ｍｍ）２５重量％を水中
に添加混合して水性スラリーを調製し、円網抄紙機を用
いて坪量５０ｇ／ｍ2の難燃性支持体を調製した。Preparation Example 3 75% by weight of vinyl chloride-vinyl acetate copolymer fiber (manufactured by Mitsubishi Rayon Co., Ltd., VF, fineness: 3 denier, fiber length: 6 mm) as a support-forming component, and a heat-fusible polyester fiber (Unitika) as a binder fiber Made by Melty 408
An aqueous slurry was prepared by adding and mixing 25% by weight of water, 0 denier, 2 denier, and fiber length of 5 mm) in water to prepare a flame-retardant support having a basis weight of 50 g / m 2 using a circular web paper machine.
【００５６】実施例１ クニミネ工業製スメクトンＳＡを水中で分散し、これに
光触媒として酸化チタン（日本アエロジル社製、Ｐ２５
Ｓ６）と調整例１の微生物セルロースとを、固形分比で
１：５：２となるように混合して塗液を調製し、この塗
液の塗布量が乾燥重量で１０ｇ／ｍ2となるように調製
例３の難燃性支持体を含浸させて、筒型ドライヤーで乾
燥し、実施例１の光触媒シートを得た。Example 1 Smecton SA manufactured by Kunimine Industries was dispersed in water, and titanium oxide (P25, manufactured by Nippon Aerosil Co., Ltd.) was used as a photocatalyst.
S6) and the microbial cellulose of Preparation Example 1 were mixed at a solid content ratio of 1: 5: 2 to prepare a coating solution, and the coating amount of the coating solution was 10 g / m 2 in dry weight. Thus, the flame-retardant support of Preparation Example 3 was impregnated and dried with a cylindrical dryer to obtain a photocatalyst sheet of Example 1.
【００５７】実施例２ 調整例１の微生物セルロースと、支持体形成成分として
予め水に分散した未叩解のＬＢＫＰを重量比で１：９９
に混合した原料１００部に対し、光触媒として酸化チタ
ン（石原産業製、ＳＴ−３１）を５１部および凝集剤と
してカチオン化ポリアクリルアミド（アライドコロイド
社製、パーコール５７）を０．２５部添加して水性懸濁
液を調製し、標準角型手抄きシートマシン（熊谷理機工
業社製）で坪量６０ｇ／ｍ2のシートを抄造し、筒型ド
ライヤーで乾燥し、実施例２の光触媒シートを得た。Example 2 The microbial cellulose of Preparation Example 1 and unbeaten LBKP previously dispersed in water as a support-forming component were mixed in a weight ratio of 1:99.
To 100 parts of the raw material mixed in, was added 51 parts of titanium oxide (manufactured by Ishihara Sangyo, ST-31) as a photocatalyst and 0.25 parts of cationized polyacrylamide (manufactured by Allied Colloids, Percoll 57) as a flocculant. An aqueous suspension was prepared, and a sheet having a basis weight of 60 g / m 2 was formed using a standard square-shaped sheet-making sheet machine (manufactured by Kumagaya Riki Kogyo Co., Ltd.), and dried using a cylindrical dryer. I got
【００５８】実施例３〜７ 実施例２において、微生物セルロースと未叩解のＬＢＫ
Ｐの重量比を１：９９に代えて１．５：９８．５、３：
９７、６：９４、８：９２、及び１０：９０で混合した
原料１００部とする以外は、すべて実施例２と同一の方
法で光触媒シートを製造した。これらの試料を、微生物
セルロースの混合比の少ないものから順に、実施例３、
実施例４、実施例５、実施例６、及び実施例７の光触媒
シートとした。Examples 3-7 In Example 2, microbial cellulose and unbeaten LBK were used.
1.5: 98.5 instead of 1:99 by weight of P, 3:
A photocatalyst sheet was produced in the same manner as in Example 2 except that 100 parts of the raw materials were mixed at 97, 6:94, 8:92, and 10:90. These samples were prepared in the order of Example 3,
The photocatalyst sheets of Examples 4, 5, 6, and 7 were obtained.
【００５９】実施例８ 実施例２において、凝集剤を添加せず、微生物セルロー
スと未叩解のＬＢＫＰの重量比を１：９９に代えて５：
９５で混合した原料１００部とする以外は、すべて実施
例２と同一の方法で光触媒シートを製造した。この試料
を、実施例８の光触媒シートとした。Example 8 In Example 2, the coagulant was not added and the weight ratio of microbial cellulose to unbeaten LBKP was changed to 1:99 and the ratio was changed to 5:
A photocatalyst sheet was produced in the same manner as in Example 2 except that 100 parts of the raw materials were mixed at 95. This sample was used as the photocatalyst sheet of Example 8.
【００６０】実施例９ 実施例５において、調整例１の微生物セルロースに代え
て調整例２の微生物セルロースとする以外は、すべて実
施例５と同一の方法で光触媒シートを製造した。この試
料を、実施例９の光触媒シートとした。Example 9 A photocatalyst sheet was produced in the same manner as in Example 5, except that the microbial cellulose of Preparation Example 2 was replaced with the microbial cellulose of Preparation Example 1. This sample was used as the photocatalyst sheet of Example 9.
【００６１】実施例１０及び１１ 実施例３及び４において、未叩解のＬＢＫＰに代えて、
塩化ビニル−酢酸ビニル共重合繊維（三菱レイヨン社
製、ＶＦ、繊度３デニール、繊維長６ｍｍ）とする以外
は、すべて実施例３及び４と同一の方法で光触媒シート
を製造した。これらの試料を、微生物セルロースの混合
比の少ないものから順に、実施例１０、及び１１の光触
媒シートとした。Examples 10 and 11 In Examples 3 and 4, instead of unbeaten LBKP,
Except for using vinyl chloride-vinyl acetate copolymer fiber (manufactured by Mitsubishi Rayon Co., Ltd., VF, fineness: 3 denier, fiber length: 6 mm), a photocatalyst sheet was produced in the same manner as in Examples 3 and 4. These samples were used as photocatalyst sheets of Examples 10 and 11 in ascending order of the mixing ratio of microbial cellulose.
【００６２】比較例１ 実施例１において、微生物セルロースに代えて微小繊維
化セルロース（ダイセル工業製、セリッシュＫＹ−１０
０Ｓ）とする以外は、すべて実施例１と同一の方法で光
触媒シートを製造した。この試料を、比較例１の光触媒
シートとした。Comparative Example 1 In Example 1, microfibrillated cellulose (manufactured by Daicel Industries, Selish KY-10) was used instead of microbial cellulose.
A photocatalyst sheet was produced in the same manner as in Example 1 except that the photocatalyst sheet was set to 0S). This sample was used as a photocatalyst sheet of Comparative Example 1.
【００６３】比較例２ 実施例２において、微生物セルロースに代えて微小繊維
化セルロース（ダイセル工業製、セリッシュＫＹ−１０
０Ｓ）とする以外は、すべて実施例２と同一の方法で光
触媒シートを製造した。この試料を、比較例２の光触媒
シートとした。Comparative Example 2 In Example 2, microfibrillated cellulose (Selice KY-10, manufactured by Daicel Industries) was used instead of microbial cellulose.
A photocatalyst sheet was produced in the same manner as in Example 2 except that the photocatalyst sheet was set to 0S). This sample was used as a photocatalyst sheet of Comparative Example 2.
【００６４】比較例３〜７ 実施例３〜７において、微生物セルロースに代えて微小
繊維化セルロース（ダイセル工業製、セリッシュＫＹ−
１００Ｓ）とする以外は、すべて実施例２と同一の方法
で光触媒シートを製造した。これらの試料を、微小繊維
化セルロースの混合比の少ないものから順に、比較例
３、比較例４、比較例５、比較例６、及び比較例７の光
触媒シートとした。Comparative Examples 3 to 7 In Examples 3 to 7, microfibrillated cellulose (manufactured by Daicel Industries, Cellish KY-
A photocatalyst sheet was produced in the same manner as in Example 2 except that the photocatalyst sheet was changed to 100S). These samples were used as photocatalyst sheets of Comparative Example 3, Comparative Example 4, Comparative Example 5, Comparative Example 6, and Comparative Example 7 in order of decreasing mixing ratio of microfibrillated cellulose.
【００６５】比較例８ 比較例７において、未叩解のＬＢＫＰに代えて、塩化ビ
ニル−酢酸ビニル共重合繊維（三菱レイヨン社製、Ｖ
Ｆ、繊度３デニール、繊維長６ｍｍ）とする以外は、す
べて比較例７と同一の方法で光触媒シートを製造した。
この試料を、比較例８の光触媒シートとした。Comparative Example 8 In Comparative Example 7, a vinyl chloride-vinyl acetate copolymer fiber (manufactured by Mitsubishi Rayon Co., Ltd., V) was used instead of unbeaten LBKP.
F, a fineness of 3 denier and a fiber length of 6 mm), except that a photocatalyst sheet was produced in the same manner as in Comparative Example 7.
This sample was used as a photocatalyst sheet of Comparative Example 8.
【００６６】以上、実施例及び比較例で得られた光触媒
シートは、以下の方法で試験を行い、その結果を表１に
示した。The photocatalyst sheets obtained in Examples and Comparative Examples were tested by the following methods, and the results are shown in Table 1.
【００６７】［防汚性］防汚性の試験は以下のようにし
て行った。まず、防汚性試験前の光触媒シートの色差を
色差計（ミノルタ製、Ｌａｂ型）で測定した。次に、
０．１ｍ3の密閉容器中に、実施例及び比較例の光触媒
シートを１枚ずつ設置し、ポンプを用いてタバコ（マイ
ルドセブン）１０本分の煙を容器内に導入した。次い
で、光触媒シートを取り出し、タバコ煙導入直後の光触
媒シートの色差を色差計で測定した後、容器内に光触媒
シートを戻して容器内に照明装置を設置し蛍光灯を５０
時間点灯、点灯後の光触媒シートの色差を色差計で測定
した。各光触媒シートの色差計の測定値の内、黄色みを
示すｂ値の変動で防汚性を判定した。すなわち、防汚性
試験前の光触媒シートのｂ値をｂ0、タバコ煙導入直後
の光触媒シートのｂ値をｂ1、蛍光灯５０時間点灯後の
光触媒シートのｂ値をｂ2とし、ｂ0〜ｂ1までの汚染負
荷を与えた場合、ｂ2の時に汚染負荷がどの程度除去さ
れているのかを百分率で表示した。該値が０％では汚染
負荷が全く低減していない状態を示し、１００％では汚
染負荷が完全に取り除かれている状態を示す。[Stain resistance] The stain resistance test was carried out as follows. First, the color difference of the photocatalyst sheet before the antifouling test was measured with a color difference meter (Lab type, manufactured by Minolta). next,
One photocatalyst sheet of each of Examples and Comparative Examples was placed in a 0.1 m 3 closed container, and smoke for 10 cigarettes (mild seven) was introduced into the container using a pump. Next, the photocatalyst sheet was taken out, and the color difference of the photocatalyst sheet immediately after the introduction of cigarette smoke was measured with a color difference meter. Then, the photocatalyst sheet was returned to the container, the lighting device was set in the container, and the fluorescent lamp was turned on.
The color difference of the photocatalyst sheet after lighting for a while and after lighting was measured by a color difference meter. Of the measured values of the color difference meter of each photocatalyst sheet, the antifouling property was determined by a change in the b value indicating yellowishness. That is, the b value of the photocatalyst sheet before the antifouling test was b0, the b value of the photocatalyst sheet immediately after the introduction of tobacco smoke was b1, the b value of the photocatalyst sheet after lighting the fluorescent lamp for 50 hours was b2, and b0 to b1 When a contamination load was applied, the percentage of the contamination load removed at the time of b2 was displayed. If the value is 0%, it indicates that the contamination load has not been reduced at all, and if it is 100%, it indicates that the contamination load has been completely removed.
【００６８】［脱臭性］０．１ｍ3の密閉容器中に実施
例及び比較例の光触媒シートを各１枚ずつ設置し、ポン
プを用いてタバコ（マイルドセブン）１０本分の煙を導
入した後、蛍光灯を点灯した。タバコ煙導入直後より、
容器内のアセトアルデヒド（タバコの臭気の主成分の一
つ）濃度をガスクロマトグラフで測定、１５分後のアセ
トアルデヒド減少量が、ブランク（光触媒シートを装着
せずに蛍光灯を点灯した場合の１５分後）のアセトアル
デヒド減少量の５倍よりも大である場合を脱臭性が優、
２〜５倍の場合を脱臭性が良、２倍より小さく１倍以上
の場合を脱臭性が並、１倍より小さい場合を脱臭性が劣
で判定した。[Deodorizing property] One photocatalyst sheet of each of Examples and Comparative Examples was placed in a 0.1 m 3 closed container, and smoke for 10 cigarettes (mild seven) was introduced using a pump. The fluorescent light was turned on. Immediately after the introduction of tobacco smoke,
The concentration of acetaldehyde (one of the main components of the odor of tobacco) in the container was measured by gas chromatography, and the amount of acetaldehyde decreased after 15 minutes was blank (after 15 minutes when the fluorescent lamp was turned on without installing a photocatalyst sheet). )) When the acetaldehyde reduction amount is more than 5 times, the deodorization is excellent,
The case of 2 to 5 times was judged to have good deodorizing property, the case of less than 2 times and 1 time or more was judged to have good deodorizing property, and the case of less than 1 time was judged to be poor for deodorizing property.
【００６９】［光触媒の定着率］支持体形成成分が難燃
性物質である光触媒シートを除いて、光触媒シートの灰
分を、ＪＩＳ−Ｐ−８１２８記載の紙及び板紙の灰分試
験法に準拠して、電気炉を用いて５００℃に加熱して灰
化し、測定した。また、光触媒シートを抄造する前の水
性懸濁液の一部を定量分析用濾紙を用いて濾過、乾燥
し、光触媒シートと同様にして灰分を測定した。実施例
および比較例における光触媒シートは、光触媒以外の無
機成分の含有量が微量であるため、灰分は光触媒シート
および水性懸濁液中の光触媒の含有率を表している。そ
こで、光触媒シートの灰分（Ｇ％）および水性懸濁液濾
過物の灰分（Ｈ％）から、下記の数式２で表される式に
よって、光触媒シート抄造時の光触媒の定着率（Ｉ）を
求めた。[Fixation rate of photocatalyst] Except for the photocatalyst sheet whose support-forming component is a flame-retardant substance, the ash content of the photocatalyst sheet was determined in accordance with the ash test method for paper and paperboard described in JIS-P-8128. Then, the sample was heated to 500 ° C. using an electric furnace, incinerated, and measured. Further, a part of the aqueous suspension before forming the photocatalyst sheet was filtered using a filter paper for quantitative analysis and dried, and the ash content was measured in the same manner as in the photocatalyst sheet. Since the photocatalyst sheets in Examples and Comparative Examples have a small content of inorganic components other than the photocatalyst, the ash indicates the content of the photocatalyst in the photocatalyst sheet and the aqueous suspension. Then, from the ash content (G%) of the photocatalyst sheet and the ash content (H%) of the aqueous suspension filtrate, the fixing rate (I) of the photocatalyst at the time of photocatalyst sheet papermaking is determined by the following equation (2). Was.
【００７０】[0070]
【数２】（数式２） Ｉ（％）＝１００×｛Ｇ／（１００−Ｇ）｝／｛Ｈ／
（１００−Ｈ）｝(Equation 2) I (%) = 100 × {G / (100−G)} / ｛H /
(100-H)｝
【００７１】［加工性］実施例および比較例の光触媒シ
ートを、同一側の面が接触して折り目が付くように１８
０度折り曲げ、次いで元に戻した後に反対の向きに同様
にして１８０度折り曲げる操作を１回として、この折り
曲げを１０回行った後に、最初に折り曲げた時の内側、
いわゆる谷折り側の折り目に市販のセロハン粘着テープ
を貼り付け、これを剥離した時にテープに付着した汚れ
の程度を観察した。光触媒シートの加工性は、汚れが全
くないものを優、僅かに汚れたものを良、普通に汚れた
ものを並、および著しく汚れたものを劣として判定し
た。[Workability] The photocatalyst sheets of the example and the comparative example were folded in such a manner that the surfaces on the same side were in contact with each other and creased.
The operation of bending at 0 degree, then returning to the original state, and then bending in the opposite direction in the same manner as 180 degrees is performed once, and after performing this bending 10 times, the inside when the first bending is performed,
A commercially available cellophane adhesive tape was attached to the fold on the so-called valley fold side, and the degree of dirt attached to the tape when the tape was peeled was observed. The workability of the photocatalyst sheet was evaluated as excellent when there was no stain at all, good when slightly soiled, good when ordinary soiled, and poor when significantly soiled.
【００７２】［難燃性］支持体形成成分が難燃性物質で
ある光触媒シートについて、ＪＩＳ−Ｌ−１０９１のＡ
−１法に従って難燃性を試験した。区分３とは、着炎３
秒後、残炎時間が３秒以下等の項目を満たすものであっ
て、類焼の恐れがある可燃物が近接しない場合等、高い
難燃性を特に必要とする場合に要求されるレベルであ
り、区分２とは、着炎３秒後、残炎時間が１０秒以下等
の項目を満たすものであって、通常の難燃性を必要とす
る場合に必要なレベルであり、区分１とは、難燃性が低
く、加熱、着炎の恐れがある場合には使用できないレベ
ルである。[Flame Retardancy] Regarding the photocatalyst sheet whose support-forming component is a flame retardant substance, A of JIS-L-1091
The flame retardancy was tested according to the -1 method. Category 3 is flame 3
After 2 seconds, it is a level that is required when high flame retardancy is particularly required, such as when the after-flame time is 3 seconds or less and flammables that may be burnt are not in close proximity. , Category 2 is a level that satisfies items such as after-flame time of 10 seconds or less after igniting 3 seconds, and is a necessary level when ordinary flame retardancy is required. It has low flame retardancy and cannot be used when there is a risk of heating or flame.
【００７３】以上の試験項目の結果を表１に示す。Table 1 shows the results of the above test items.
【００７４】[0074]
【表１】 [Table 1]
【００７５】表中の光触媒重量比とは、微生物セルロー
スの光触媒保持指標（Ａ）と微生物セルロースの添加量
（Ｂ）の積に対する光触媒の添加量（Ｃ）の重量比（Ｃ
／（Ａ×Ｂ））である。本発明では、０．５〜２である
ことが好ましい。The photocatalyst weight ratio in the table means the weight ratio (C) of the photocatalyst addition amount (C) to the product of the photocatalyst retention index (A) of microbial cellulose and the addition amount (B) of microbial cellulose.
/ (A × B)). In the present invention, it is preferably 0.5 to 2.
【００７６】[0076]
【発明の効果】以上の如く、本発明の光触媒シートは、
光触媒、微生物セルロースおよび支持体形成成分からな
る光触媒シート、または、光触媒、微生物セルロースお
よび支持体形成成分からなる水性懸濁液を湿式抄造して
なる光触媒シートであって、臭気物質や汚れ物質などの
有害物質の分解性に優れ、且つ、シートの後加工性に優
れた光触媒シートを提供するものである。As described above, the photocatalyst sheet of the present invention is
A photocatalyst, a photocatalyst sheet comprising microbial cellulose and a support-forming component, or a photocatalyst sheet obtained by wet-making an aqueous suspension comprising a photocatalyst, microbial cellulose and a support-forming component, such as an odorous substance or a soil substance. An object of the present invention is to provide a photocatalyst sheet having excellent decomposability of harmful substances and excellent post-processing properties of the sheet.
【００７７】特に、光触媒、微生物セルロースおよび支
持体形成成分からなる水性懸濁液を湿式抄造してなる光
触媒シートにおいては、水性懸濁液が更に凝集剤を含有
することが好ましく、光触媒の定着率、脱臭性が更に優
れた光触媒シートを提供するものである。In particular, in a photocatalyst sheet obtained by wet-making an aqueous suspension comprising a photocatalyst, microbial cellulose and a support-forming component, the aqueous suspension preferably further contains a flocculant, and the fixing rate of the photocatalyst is increased. Another object of the present invention is to provide a photocatalyst sheet having even better deodorization properties.
【００７８】加えて、光触媒、微生物セルロースおよび
支持体形成成分からなる水性懸濁液、好ましくは更に凝
集剤を含有する水性懸濁液を湿式抄造してなる光触媒シ
ートにおいては、微生物セルロースの光触媒保持指標
（Ａ）と微生物セルロースの添加量（Ｂ）の積に対する
光触媒の添加量（Ｃ）の重量比（Ｃ／（Ａ×Ｂ））を
０．５〜２の範囲とすることが好ましい。つまり、上記
の重量比が０．５より小さいと、光触媒の定着率および
後加工性が低下し、２より大きいと、光触媒の定着率が
飽和するのみならず、かえって低下し、且つ防汚性が明
らかに低下する。一方、本発明の光触媒シートにおいて
は、微生物セルロースが撹拌培養法により生産されたセ
ルロース性物質であることが好ましく、防汚性が特に優
れた光触媒シートを提供するものである。In addition, an aqueous suspension comprising a photocatalyst, microbial cellulose and a support-forming component, preferably an aqueous suspension further containing a flocculant, is wet-processed to form a photocatalyst sheet. The weight ratio (C / (A × B)) of the photocatalyst addition amount (C) to the product of the index (A) and the microbial cellulose addition amount (B) is preferably in the range of 0.5 to 2. That is, if the weight ratio is less than 0.5, the fixing rate and post-processability of the photocatalyst decrease. If it is greater than 2, the fixing rate of the photocatalyst not only saturates, but also decreases, and Is clearly reduced. On the other hand, in the photocatalyst sheet of the present invention, microbial cellulose is preferably a cellulosic substance produced by a stirring culture method, and provides a photocatalyst sheet with particularly excellent antifouling properties.
【００７９】更に、支持体形成成分が難燃性物質である
ことを特徴とする本発明の光触媒シートは、有害物質の
分解性、及びシートの後加工性に加えて、微生物セルロ
ースが光触媒の保持性に著しく優れるため、可燃性であ
るセルロース性物質の含有量を極少量に抑えることがで
き、難燃性に優れた光触媒シートを提供するものであ
り、この難燃性に優れた光触媒シートは、発熱を伴う光
触媒励起光源、及び放電発火の恐れがある光源や送風機
など電気機器の接点と近接して使用し得るものであり、
例えば空気清浄機のフィルター部材等として非常に有用
性の高いものである。Further, the photocatalyst sheet of the present invention, wherein the support-forming component is a flame-retardant substance, is characterized in that, in addition to the decomposability of harmful substances and the post-processing property of the sheet, the microbial cellulose holds the photocatalyst. Because of its remarkable excellent properties, the content of the flammable cellulosic substance can be suppressed to an extremely small amount, and a photocatalyst sheet with excellent flame retardancy is provided. , Which can be used in close proximity to the contacts of electrical equipment such as a photocatalyst-excited light source with heat generation, and a light source or blower that may cause discharge ignition,
For example, it is very useful as a filter member of an air purifier.
Claims (6)
形成成分からなる光触媒シート。1. A photocatalyst sheet comprising a photocatalyst, microbial cellulose and a support-forming component.
形成成分からなる水性懸濁液を湿式抄造してなる光触媒
シート。2. A photocatalyst sheet obtained by wet-making an aqueous suspension comprising a photocatalyst, microbial cellulose and a support-forming component.
を特徴とする請求項２記載の光触媒シート。3. The photocatalyst sheet according to claim 2, wherein the aqueous suspension further contains a flocculant.
（Ａ）と微生物セルロースの添加量（Ｂ）の積に対する
光触媒の添加量（Ｃ）の重量比（Ｃ／（Ａ×Ｂ））が、
０．５〜２であることを特徴とする請求項２および３記
載の光触媒シート。4. The weight ratio (C / (A × B)) of the photocatalyst addition amount (C) to the product of the photocatalyst retention index (A) of microbial cellulose and the microbial cellulose addition amount (B),
The photocatalyst sheet according to claim 2, wherein the ratio is 0.5 to 2. 5.
産されたセルロース性物質であることを特徴とする請求
項１、２、３および４記載の光触媒シート。5. The photocatalyst sheet according to claim 1, wherein the microbial cellulose is a cellulosic substance produced by a stirring culture method.
を特徴とする請求項１、２、３、４および５記載の光触
媒シート。6. The photocatalyst sheet according to claim 1, wherein the support-forming component is a flame-retardant substance.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9071164A JPH10265586A (en) | 1997-03-25 | 1997-03-25 | Photocatalyst sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9071164A JPH10265586A (en) | 1997-03-25 | 1997-03-25 | Photocatalyst sheet |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH10265586A true JPH10265586A (en) | 1998-10-06 |
Family
ID=13452738
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9071164A Pending JPH10265586A (en) | 1997-03-25 | 1997-03-25 | Photocatalyst sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH10265586A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015206156A (en) * | 2012-08-10 | 2015-11-19 | 王子ホールディングス株式会社 | Microfibrous cellulose aggregate |
| JP2018111888A (en) * | 2017-01-06 | 2018-07-19 | 日本精工株式会社 | Production method of purification paper for water treatment |
-
1997
- 1997-03-25 JP JP9071164A patent/JPH10265586A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015206156A (en) * | 2012-08-10 | 2015-11-19 | 王子ホールディングス株式会社 | Microfibrous cellulose aggregate |
| US9932461B2 (en) | 2012-08-10 | 2018-04-03 | Oji Holdings Corporation | Microfibrous cellulose-containing substance |
| JP2019065454A (en) * | 2012-08-10 | 2019-04-25 | 王子ホールディングス株式会社 | Process for producing fine fibrous cellulose aggregate |
| US10875988B2 (en) | 2012-08-10 | 2020-12-29 | Oji Holdings Corporation | Microfibrous cellulose-containing substance |
| US11702532B2 (en) | 2012-08-10 | 2023-07-18 | Oji Holdings Corporation | Microfibrous cellulose-containing substance |
| JP2018111888A (en) * | 2017-01-06 | 2018-07-19 | 日本精工株式会社 | Production method of purification paper for water treatment |
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