JP2006214044A - Photocatalyst paper-like article and method for producing the same - Google Patents

Photocatalyst paper-like article and method for producing the same Download PDF

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JP2006214044A
JP2006214044A JP2005029434A JP2005029434A JP2006214044A JP 2006214044 A JP2006214044 A JP 2006214044A JP 2005029434 A JP2005029434 A JP 2005029434A JP 2005029434 A JP2005029434 A JP 2005029434A JP 2006214044 A JP2006214044 A JP 2006214044A
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paper
binder
photocatalyst
sheet
heating roll
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JP4639270B2 (en
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Shunpei Ohashi
俊平 大橋
Hideaki Ichiura
英明 市浦
Masaaki Morikawa
政昭 森川
Hiroshi Miyazaki
宏 宮崎
Satoru Shimizu
悟 清水
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MARUSAN SEISHI KK
Fukusuke Kogyo Co Ltd
Ehime Prefecture
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MARUSAN SEISHI KK
Fukusuke Kogyo Co Ltd
Ehime Prefecture
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a photocatalyst paper-like article whose paper strength can be enhanced without deteriorating the activity of the photocatalyst, and to provide a method for producing the same. <P>SOLUTION: This method for producing the photocatalyst paper-like article is characterized by superposing a binder-free surface sheet 4 wet-prepared from a mixture of a photocatalyst-carrying material and fibers on a substrate sheet 5 wet-prepared from a mixture of fibers and a binder, and then drying the product with a drying means 3. The paper strength of the article is improved with the binder, and the employment of a peeling agent is not needed. Consequently, the photocatalyst is not covered with a binder and the peeling agent, and can therefore keep a good photocatalyst activity. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

本発明は、有害物質分解能および脱臭能等に優れた光触媒を担持した紙状体に関するものであり、特に生活環境を改善するのに好適に使用されるものである。   The present invention relates to a paper-like material carrying a photocatalyst excellent in toxic substance resolution and deodorizing ability, and is particularly suitable for improving the living environment.

近年、光触媒は、優れた有害物質分解能及び脱臭能等を有することから、環境浄化材として種々の製品への応用が検討されており、その一つとして、特許文献1に示すように、光触媒を担持させた無機繊維と基材繊維とを混抄してなる光触媒紙状体が知られている。
特開2003−236391号公報
In recent years, photocatalysts have excellent toxic substance resolution, deodorizing ability, etc., and therefore, application to various products as an environmental purification material has been studied. A photocatalytic paper-like body obtained by mixing a supported inorganic fiber and a base fiber is known.
JP 2003-236391 A

上記光触媒紙状体は、優れた耐久性を備えたものであるが、紙製品の用途によっては紙力強度を上げることが必要になる場合があり、このような場合には、繊維同士を固着させる目的で、ポリビニルアルコールなどのバインダーが使用されている。   The photocatalytic paper-like body has excellent durability, but depending on the application of the paper product, it may be necessary to increase the paper strength. In such a case, the fibers are fixed to each other. For this purpose, a binder such as polyvinyl alcohol is used.

しかしながら、上記光触媒紙状体においてバインダーを使用すると、溶融したバインダーが光触媒の表面を覆って、光触媒活性を低下させるという問題が生じていた。   However, when a binder is used in the photocatalytic paper-like material, there has been a problem that the melted binder covers the surface of the photocatalyst and the photocatalytic activity is lowered.

さらに、繊維とバインダーとを混抄して得られた湿紙を加熱ロールで乾燥させる場合、溶融して紙表面に滲み出たバインダーが加熱ロールに付着し、その結果、紙が加熱ロールに貼り付いて取れなくなるという問題があった。このような紙の貼り付きを防止するために、シリコーン系化合物、ポリオレフィン系化合物、アルキド樹脂あるいは長鎖アルキル基含有ポリマー等の剥離剤が一般的に使用されているが、剥離剤が光触媒に付着すると、光触媒活性を大幅に低下させてしまうといった問題も生じていた。   Furthermore, when the wet paper obtained by mixing the fiber and binder is dried with a heating roll, the binder that has melted and oozed out on the paper surface adheres to the heating roll, and as a result, the paper sticks to the heating roll. There was a problem that could not be removed. In order to prevent such sticking of paper, release agents such as silicone compounds, polyolefin compounds, alkyd resins or long chain alkyl group-containing polymers are generally used, but the release agent adheres to the photocatalyst. Then, the problem that photocatalytic activity will fall significantly has also arisen.

特にシリコーン系化合物は、剥離剤として優れた効果を有する反面、著しく光触媒活性を低下させるため、得られた光触媒紙状体はほとんど光触媒能を発揮しなくなるという問題があった。   In particular, the silicone-based compound has an excellent effect as a release agent, but has a problem that the photocatalytic paper-like body hardly exhibits photocatalytic activity because it significantly reduces the photocatalytic activity.

そこで、本発明においては、光触媒活性を低下させることなく、紙力強度を高めることが可能な光触媒紙状体及びその製造方法の提供を目的とする。   Accordingly, an object of the present invention is to provide a photocatalytic paper-like body capable of increasing the paper strength without reducing the photocatalytic activity and a method for producing the same.

上記課題を解決するために、本発明では、繊維と、バインダーとを混合して湿式抄造してなる基材シートと、光触媒担持体と、繊維とを混合して湿式抄造してなるノーバインダーの表面用シートとを重ねて乾燥手段により乾燥させることを特徴とする。   In order to solve the above-mentioned problems, in the present invention, a base sheet obtained by mixing a fiber and a binder to perform wet papermaking, a photocatalyst support, and a no-binder formed by mixing the fiber with wet papermaking. It is characterized in that the surface sheet is stacked and dried by a drying means.

上記構成によれば、多層抄きによって紙状体を多層構造とし、基材層を形成する基材シートにのみバインダーを含有させ、表面層を形成する表面用シートにのみ光触媒を含有させて乾燥手段により加熱乾燥することで、バインダーによって紙力強度が向上するとともに、光触媒がバインダーに覆われることなく、良好な光触媒活性を維持することが可能となる。   According to the above configuration, the paper-like body is made into a multilayer structure by multilayer papermaking, the binder is contained only in the base material sheet forming the base material layer, and the photocatalyst is contained only in the surface sheet forming the surface layer and dried. By heating and drying by means, the paper strength is improved by the binder, and the photocatalyst is not covered with the binder, and good photocatalytic activity can be maintained.

乾燥手段としては特に限定はないが、単筒式加熱ロール(いわゆるヤンキーロール)や多筒式加熱ロールを用いることができる。単筒式加熱ロールを使用する場合、基材シートと表面用シートとを重ね合せたシートを、表面用シート側が加熱ロールと接触するようにして加熱すれば、表面用シートの表面にバインダーが滲み出して加熱ロールに付着するおそれがない。   Although there is no limitation in particular as a drying means, a single cylinder heating roll (what is called a Yankee roll) and a multi cylinder heating roll can be used. When a single cylinder heating roll is used, if the sheet on which the base sheet and the surface sheet are superposed is heated so that the surface sheet side is in contact with the heating roll, the binder will ooze on the surface of the surface sheet. There is no risk of taking out and adhering to the heating roll.

すなわち、前述のごとく、バインダー入りの湿紙を加熱ロールで乾燥させる際には、表面に滲み出したバインダーによって紙が加熱ロールに貼り付くのを防止するために剥離剤が使用されていた。剥離剤は、通常、予め抄紙原料に内添するか、加熱ロールに塗布して使用されるが、紙表面を被覆するため、光触媒が剥離剤によって覆われて光触媒活性が著しく低下するという問題が生じていた。   That is, as described above, when a wet paper containing a binder is dried with a heating roll, a release agent has been used to prevent the paper from sticking to the heating roll due to the binder that has oozed out on the surface. The release agent is usually added to the papermaking raw material in advance or applied to a heating roll. However, since the paper surface is coated, the photocatalyst is covered with the release agent and the photocatalytic activity is significantly reduced. It was happening.

ところが、本発明に係る製造方法によれば、バインダーの滲み出しによる紙の加熱ロールへの貼り付きを防止できるだけでなく、剥離剤が不要となり、光触媒活性を良好に維持することができる。なお、この場合、加熱ロールへの紙の貼り付きを確実に防止するために、光触媒活性に影響を及ぼさない程度の微量の剥離剤を使用することもできる。   However, according to the production method according to the present invention, not only can the sticking of the paper to the heating roll due to the bleeding of the binder be prevented, but a release agent is not required, and the photocatalytic activity can be maintained well. In this case, a small amount of release agent that does not affect the photocatalytic activity can also be used in order to reliably prevent the paper from sticking to the heating roll.

上記方法によって得られる光触媒紙状体は、基材シート及び表面用シートとを用いた表面層/基材層の2層構造に限らず、例えば、繊維と、バインダーとを混合して湿式抄造してなる基材シートの両側に、光触媒担持体と、繊維とを混合して湿式抄造してなるノーバインダーの表面用シートを重ねた表面層/基材層/表面層の3層構造とし、これを乾燥手段により乾燥させることも可能である。   The photocatalytic paper-like body obtained by the above method is not limited to a two-layer structure of a surface layer / base material layer using a base material sheet and a surface sheet, and, for example, wet papermaking by mixing fibers and a binder. A three-layer structure of surface layer / base material layer / surface layer in which a photocatalyst carrier and fibers are wet-made to form a non-binder surface sheet on both sides of the base material sheet, Can be dried by a drying means.

この場合、紙状体の両面に表面用シートが配されているため、両面ともにバインダーの滲み出しを防止することができる。したがって、乾燥手段としては、単筒式加熱ロールのみならず、多筒式加熱ロールを使用した場合でも加熱ロールへのバインダーの付着を効果的に防止することが可能となる。   In this case, since the surface sheets are arranged on both sides of the paper-like body, it is possible to prevent the binder from oozing out on both sides. Therefore, as a drying means, it is possible to effectively prevent the binder from adhering to the heating roll even when a multi-cylinder heating roll is used as well as a single cylinder heating roll.

また、基材シート及び表面用シートの2層構造において、基材シートの他面側(表面用シートを積層していない側)に他のシートを積層することも可能である。この場合、他のシートとして、ポリオレフィンフィルムを例示することができる。   Further, in the two-layer structure of the base sheet and the surface sheet, it is possible to stack another sheet on the other surface side (side where the surface sheet is not stacked). In this case, a polyolefin film can be illustrated as another sheet.

本発明において表面用シートがノーバインダーであるとは、バインダーをまったく含まない場合はもちろんのこと、光触媒活性を低下させず、剥離剤を使用しなくてもすむ程度の微量のバインダーを含有するものをも含む意である。   In the present invention, the surface sheet is a no-binder, not to mention that it contains no binder at all, but contains a trace amount of binder that does not decrease the photocatalytic activity and does not require the use of a release agent. Is also included.

本発明で得られた光触媒紙状体は、基材シートと表面用シートとが積層された積層構造を備えている。すなわち、本発明に係る光触媒紙状体は、繊維とバインダーとを含有する基材層と、基材層の少なくとも一方の面に形成された、光触媒担持体と繊維とを含有する表面層とを備えており、バインダーの存在量が、前記基材層よりも表面層の方が少ないことが特徴とされる。   The photocatalytic paper-like body obtained in the present invention has a laminated structure in which a base sheet and a surface sheet are laminated. That is, the photocatalytic paper-like body according to the present invention comprises a base material layer containing fibers and a binder, and a surface layer containing a photocatalyst carrier and fibers formed on at least one surface of the base material layer. And the amount of the binder present in the surface layer is smaller than that in the substrate layer.

すなわち、多層抄きによって形成された基材層及び表面層を加熱乾燥すると、基材層に存在するバインダーが溶融して表面層へとしみ出すようになる。本発明では、このバインダーが表面層の表面から滲み出さないように、基材層から表面層に向ってバインダーの存在量が減少するように基材層のバインダー量及び乾燥条件を調節しており、これにより加熱ロールへのバインダーの付着が防止できる。   That is, when the base material layer and the surface layer formed by multilayer papermaking are heated and dried, the binder existing in the base material layer melts and exudes to the surface layer. In the present invention, the binder amount and drying conditions of the base material layer are adjusted so that the amount of the binder is reduced from the base material layer toward the surface layer so that the binder does not ooze out from the surface of the surface layer. Thus, adhesion of the binder to the heating roll can be prevented.

各層におけるバインダーの存在量を簡単に比較する方法としては、熱板上に光触媒紙状体を所定時間置き、熱板側に表面層を向けた場合と、紙基材層を向けた場合とで、熱板上に付着するバインダーの量を比較すればよい。   A simple method for comparing the amount of binder present in each layer is when the photocatalyst paper is placed on the hot plate for a predetermined time, with the surface layer facing the hot plate, and with the paper substrate layer facing. What is necessary is just to compare the quantity of the binder adhering on a hot platen.

本発明における繊維は、抄紙原料として使用できるものであればよく、天然繊維や合成繊維などの有機繊維のほかにガラス繊維のような無機繊維を併用することも可能である。光触媒担持体に使用される光触媒としては、酸化チタン、酸化亜鉛、酸化セリウム、金属酸化物光触媒、無機光触媒または有機光触媒およびこれらの複合物が挙げられる。   The fiber in the present invention may be any fiber as long as it can be used as a papermaking raw material. In addition to organic fibers such as natural fibers and synthetic fibers, inorganic fibers such as glass fibers can be used in combination. Examples of the photocatalyst used for the photocatalyst carrier include titanium oxide, zinc oxide, cerium oxide, metal oxide photocatalyst, inorganic photocatalyst, organic photocatalyst, and composites thereof.

光触媒の担体としては耐久性の観点から無機物質が好ましく、また、繊維と混抄できて脱落しにくい点から繊維状物質が好ましい。このような繊維状の担体としては、セラミック繊維、ガラス繊維、鉱滓繊維等が挙げられるが、安全性、強度等に優れたセラミック繊維が好適に使用される。   The photocatalyst carrier is preferably an inorganic substance from the viewpoint of durability, and is preferably a fibrous substance from the viewpoint that it can be mixed with fibers and hardly fall off. Examples of such fibrous carriers include ceramic fibers, glass fibers, ore fibers, and ceramic fibers excellent in safety, strength, and the like are preferably used.

また、バインダーとしては、ポリビニルアルコール(PVA)のほかに、ビニロン、ポリエチレン、ポリエステル、ポリプロピレン、エチレン−酢酸ビニル共重合体(EVA)やその他熱融着性複合繊維等を使用することができる。   As the binder, in addition to polyvinyl alcohol (PVA), vinylon, polyethylene, polyester, polypropylene, ethylene-vinyl acetate copolymer (EVA), other heat-fusible composite fibers, and the like can be used.

本発明では、繊維と、バインダーとを混合して湿式抄造してなる基材シートと、光触媒担持体と、繊維とを混合して湿式抄造してなるノーバインダーの表面用シートとを重ねて乾燥手段により乾燥させたため、バインダーによって紙力強度が向上するとともに、光触媒がバインダーに覆われることなく、良好な光触媒活性を維持することが可能となる。   In the present invention, a base sheet made by wet papermaking by mixing fibers and a binder, a photocatalyst carrier, and a non-binder surface sheet made by wet paper making by mixing fibers are dried and dried. Since it is dried by the means, the paper strength is improved by the binder, and the photocatalyst is not covered with the binder, and good photocatalytic activity can be maintained.

また、湿紙を加熱ロールで乾燥する際にも、加熱ロール上にバインダーが付着するおそれがなく、また剥離剤を使用する必要がないため、光触媒の活性を良好に維持することができる。   Moreover, when drying a wet paper with a heating roll, there is no fear that a binder adheres to the heating roll, and it is not necessary to use a release agent, so that the activity of the photocatalyst can be maintained well.

以下、図面に基づいて本発明の実施形態について説明する。図1は、本発明に係る光触媒紙状体の製造方法を実施する多層抄き機を示す概略図である。この多層抄き機は、ハーバー抄紙機の短網と同じ構造の傾斜短網パート1と、一般の順流式円網である円網パート2と、乾燥手段としての単筒式加熱ロール3とを備え、傾斜短網パート1で抄き上げた湿紙の下面に円網パート2で抄き上げた湿紙を重ね、重ね合わせた状態で単筒式加熱ロール3に接触させて乾燥する構成とされている。   Hereinafter, embodiments of the present invention will be described with reference to the drawings. FIG. 1 is a schematic view showing a multilayer paper machine for carrying out the method for producing a photocatalytic paper according to the present invention. This multi-layer machine has an inclined short net part 1 having the same structure as the short net of the harbor paper machine, a circular net part 2 which is a general forward flow type net, and a single cylinder heating roll 3 as a drying means. A wet paper web made by the circular mesh part 2 is stacked on the lower surface of the wet paper web made by the inclined short mesh part 1 and is brought into contact with the single-tube heating roll 3 in a superposed state and dried. Has been.

すなわち、傾斜短網パート1で表面用シート4が抄造され、円網パート2で基材シート5が抄造されて、これらシートが重ね合わせされた状態で搬送ベルト6によって単筒式加熱ロール3を有するヤンキードライパート7に搬送される。   That is, the surface sheet 4 is made by the inclined short part 1, the base sheet 5 is made by the circular part 2, and the single cylinder heating roll 3 is moved by the transport belt 6 in a state where these sheets are overlapped. It is conveyed to the Yankee dry part 7 which has.

図2は、単筒式加熱ロール3を示す概略図であり、図3はその拡大図である。搬送ベルト6によって単筒式加熱ロール3まで搬送された湿紙は、表面用シート4側が単筒式加熱ロール3に接触するようにして加熱乾燥され、これによって、2層構造の光触媒紙状体8が得られる。   FIG. 2 is a schematic view showing the single-tube heating roll 3, and FIG. 3 is an enlarged view thereof. The wet paper web conveyed to the single cylinder heating roll 3 by the conveyance belt 6 is dried by heating so that the surface sheet 4 side is in contact with the single cylinder heating roll 3, whereby a photocatalytic paper-like body having a two-layer structure. 8 is obtained.

基材シート5と表面シート4との比は基材シート/表面シート=10/90〜40/60(重量比)の範囲にするのが好ましい。上記範囲よりも基材層の割合が増えると場合によっては紙状体が加熱ロールからスムーズに剥離できなくなるおそれが生じ、また、上記範囲よりも基材層の割合が低くなると、紙力強度の改善効果が低くなる。   The ratio of the base sheet 5 to the top sheet 4 is preferably in the range of base sheet / top sheet = 10/90 to 40/60 (weight ratio). When the ratio of the base material layer is increased from the above range, the paper body may not be smoothly peeled off from the heating roll in some cases, and when the ratio of the base material layer is lower than the above range, Improvement effect is reduced.

表面層/基材層/表面層の3層構造の光触媒紙状体を製造するには、上記構成にさらに傾斜短網パートを組合わせればよい。なお、この場合の乾燥手段としては、単筒式加熱ロールの他に多筒式加熱ロールを使用することも可能である。   In order to produce a photocatalytic paper-like body having a three-layer structure of surface layer / base material layer / surface layer, an inclined short net part may be further combined with the above configuration. In addition, as a drying means in this case, it is also possible to use a multi-cylinder heating roll in addition to the single-cylinder heating roll.

以下、実施例を挙げて更に説明するが、本発明はこれらに限定されるものではない。なお、「%」の表示は「重量%」を意味し、「部」は「重量部」を意味するものである。
本実施例においては、本発明に係る光触媒紙状体として、具体的に障子紙及び耐水性向上紙を作製してその性能を評価した。
Hereinafter, although an example is given and explained further, the present invention is not limited to these. Note that “%” means “% by weight”, and “parts” means “parts by weight”.
In this example, as a photocatalytic paper-like body according to the present invention, a shoji paper and a water-resistant paper were produced specifically, and their performance was evaluated.

[実施例1(障子紙の作製)]
先ず、上記多層抄き機の傾斜短網パート1の抄槽に、セラミック繊維の0.12%水懸濁液10部に、カチオン性凝集剤であるポリジアリルジメチルアンモニウムクロリドの0.012%水溶液1部を添加して600rpmで撹拌し、3分後に酸化チタン(石原産業社製、ST−01)の0.15%水懸濁液10部を加え、その3分後にアニオン性凝集剤(栗田工業社製、HH−351)の0.012%水溶液1部を加えて、セラミック繊維に酸化チタンを担持させた光触媒担持体の水懸濁液を調製した。
[Example 1 (Production of shoji paper)]
First, in the papermaking tank of the slanted short mesh part 1 of the multilayer paper machine, 10 parts of a 0.12% aqueous suspension of ceramic fibers and 0.012% aqueous solution of polydiallyldimethylammonium chloride as a cationic flocculant. 1 part was added and stirred at 600 rpm. After 3 minutes, 10 parts of a 0.15% aqueous suspension of titanium oxide (manufactured by Ishihara Sangyo Co., Ltd., ST-01) was added. After 3 minutes, an anionic flocculant (Kurita) An aqueous suspension of a photocatalyst carrier in which titanium oxide was supported on ceramic fibers was added by adding 1 part of a 0.012% aqueous solution of HH-351) manufactured by Kogyo Co., Ltd.

次に、光触媒担持体の懸濁液が収容された上記抄槽に、リファイナーやビーターなどにより叩解したパルプと、パルパーなどにより分散させたレーヨンとを加え、原料の比率がパルプ/レーヨン/光触媒担持体(重量比)=55/35/10となるように調製した懸濁液を使用して混抄し、表面用シート4を得た。   Next, pulp beaten with a refiner or beater and rayon dispersed with a pulper or the like are added to the paper making tank containing the suspension of the photocatalyst carrier, and the ratio of raw materials is pulp / rayon / photocatalyst carrier. Using the suspension prepared so that the body (weight ratio) = 55/35/10, it was mixed and the surface sheet 4 was obtained.

円網パート2の抄槽にはリファイナーやビーターなどにより叩解したパルプと、パルパーなどにより分散させた繊維状のバインダー(PVA)とを加えて水に懸濁させ、原料の比率がパルプ/PVA(重量比)=95/5となるように調製した懸濁液を使用して混抄し基材シート5を得た。   In the papermaking tank of part 2 of the net, a pulp beaten by a refiner or a beater and a fibrous binder (PVA) dispersed by a pulper are added and suspended in water, and the ratio of raw materials is pulp / PVA ( The base sheet 5 was obtained by mixing using a suspension prepared so that the weight ratio was 95/5.

以上のようにして得られた表面用シート4及び基材シート5を重ね合せて表面側シート4側が加熱ロール3(ロール表面温度:105℃)に接触するようにして加熱乾燥し、障子紙を作製した。得られた障子紙の坪量は、約60g/m2で、表面用シートと基材シートの重量比は80/20であった。 The surface sheet 4 and the base sheet 5 obtained as described above are overlaid and heat-dried so that the surface side sheet 4 side is in contact with the heating roll 3 (roll surface temperature: 105 ° C.), Produced. The basis weight of the obtained shoji paper was about 60 g / m 2 , and the weight ratio of the surface sheet and the base sheet was 80/20.

[実施例2(耐水性向上紙の作製)]
光触媒担持体の調製は実施例1と同様にして、傾斜短網パート1の抄槽にパルプとポリエチレンテレフタレート(PET)とを加えて水に懸濁させ、原料の比率がパルプ/PET/光触媒担持体(重量比)=75/15/10となるように調製した懸濁液を使用して混抄し、表面用シート4を得た。
[Example 2 (Preparation of improved water resistance paper)]
The photocatalyst carrier was prepared in the same manner as in Example 1, and pulp and polyethylene terephthalate (PET) were added to the paper tank of the inclined short part 1 and suspended in water. The ratio of raw materials was pulp / PET / photocatalyst carrier. The suspension (prepared so that the body (weight ratio) = 75/15/10 was used and mixed to obtain the surface sheet 4.

次に、円網パート2の抄槽に原料の比率がパルプ/繊維状PVA(乾燥重量比)=95/5となるように調製した懸濁液を使用して混抄し基材シート5を得た。   Next, using a suspension prepared so that the ratio of raw materials becomes pulp / fibrous PVA (dry weight ratio) = 95/5 in the papermaking tank of the circular mesh part 2, the base material sheet 5 is obtained by mixing. It was.

以上のようにして得られた表面用シート4及び基材シート5を重ね合せて表面用シート側が加熱ロール3(ロール表面温度:105℃)に接触するようにして加熱乾燥した。得られた耐水性向上紙の坪量は、約50g/m2で、表面用シート/基材シート(重量比)=80/20であった。 The surface sheet 4 and the base sheet 5 obtained as described above were superposed and heat-dried so that the surface sheet side was in contact with the heating roll 3 (roll surface temperature: 105 ° C.). The basis weight of the obtained water resistant improved paper was about 50 g / m 2 and the surface sheet / base sheet (weight ratio) was 80/20.

[比較例]
実施例1で使用したのと同じ原料を使用し、多層抄き機の傾斜短網パート1の抄槽に原料の比率がパルプ/レーヨン/PVA/光触媒担持体(重量比)=52.5/32.5/5/10となるような懸濁液を調製して抄紙した。その後、抄紙した湿紙を単筒式加熱ロール(ロール表面温度:105℃)で乾燥させたところ、紙から滲み出たPVAにより、紙が加熱ロールに接着して剥離不能となった。
[Comparative example]
The same raw material as used in Example 1 was used, and the ratio of the raw material in the sloping short mesh part 1 of the multilayer paper machine was pulp / rayon / PVA / photocatalyst carrier (weight ratio) = 52.5 / A suspension was prepared to make 32.5 / 5/10 and paper was made. Thereafter, the wet paper thus made was dried with a single-cylinder heating roll (roll surface temperature: 105 ° C.). As a result, PVA exuded from the paper adhered the paper to the heating roll and became impossible to peel.

そこで、加熱ロール3に剥離剤としてシリコーン系剥離剤(日華化学社製サントール311)を塗布することにより加熱ロール3から紙を剥離して坪量約60g/m2の障子紙を得た。これを比較例1とした。 Therefore, by applying a silicone release agent (Santor 311 manufactured by Nikka Chemical Co., Ltd.) as a release agent to the heating roll 3, the paper was peeled from the heating roll 3 to obtain a shoji paper having a basis weight of about 60 g / m 2 . This was designated as Comparative Example 1.

次に、実施例1で使用したのと同じ原料を使用し、多層抄き機の傾斜短網パート1の抄槽に原料の比率がパルプ/レーヨン/光触媒担持体(重量比)=55/35/10となるような懸濁液を調製して抄紙した。その後、抄紙した湿紙を単筒式加熱ロール3(ロール表面温度:105℃、剥離剤不使用)で乾燥させて坪量約60g/m2の障子紙を得た。これを比較例2とした。 Next, the same raw material as used in Example 1 was used, and the ratio of the raw material to the paper making tank of the inclined short net part 1 of the multilayer paper machine was pulp / rayon / photocatalyst carrier (weight ratio) = 55/35. A suspension was prepared to make / 10 paper. Thereafter, the wet paper thus made was dried with a single cylinder heating roll 3 (roll surface temperature: 105 ° C., no release agent used) to obtain a shoji paper having a basis weight of about 60 g / m 2 . This was designated as Comparative Example 2.

[評価試験]
上記4種類の試料(実施例1、2及び比較例1、2)を用いて以下の試験を行なった。
(1)ホルムアルデヒド吸着分解試験
石英製のカバーを有する体積200ccのステンレス反応容器に、25mm×25mmの大きさの実施例および比較例の紙状物を設置した後、反応容器に25ppmになるようにホルムアルデヒドをマイクロシリンジで注入した。紫外線照射下(波長365nm、0.3mW/cm2)において、所定時間毎に反応容器内のホルムアルデヒド濃度を測定した。ホルムアルデヒドの定量には、ガスクロマトグラフを使用した。試験結果を表1に示す。
[Evaluation test]
The following tests were performed using the above four types of samples (Examples 1 and 2 and Comparative Examples 1 and 2).
(1) Formaldehyde adsorption decomposition test After placing the paper-like materials of Examples and Comparative Examples having a size of 25 mm × 25 mm in a 200 cc stainless steel reaction vessel having a quartz cover, the reaction vessel was adjusted to 25 ppm. Formaldehyde was injected with a microsyringe. Under ultraviolet irradiation (wavelength 365 nm, 0.3 mW / cm 2), the formaldehyde concentration in the reaction vessel was measured every predetermined time. A gas chromatograph was used for quantitative determination of formaldehyde. The test results are shown in Table 1.

(2)紙力強度試験
紙力強度試験はJIS P 8113に準拠して、乾燥引張強度を測定した。試験結果を表1に示す。
(2) Paper strength test The paper strength test measured dry tensile strength according to JIS P8113. The test results are shown in Table 1.

Figure 2006214044
Figure 2006214044

[評価結果]
比較例1の結果より、従来の1層構造の光触媒紙状体は、バインダーを配合することで加熱ロールに紙状体が貼り付いて剥離不可になるため、剥離剤を使用せざるを得ないのに対して、本発明に係る実施例1及び実施例2においては、2層構造で基材層にのみバインダーを配合したため、加熱ロールへの貼り付きはまったく見られず、剥離剤を使用する必要がない。
[Evaluation results]
From the result of Comparative Example 1, the conventional photocatalytic paper-like body having a single-layer structure cannot be peeled off due to the paper-like body sticking to the heating roll by blending a binder, and thus a release agent must be used. On the other hand, in Example 1 and Example 2 according to the present invention, since the binder was blended only in the base material layer in a two-layer structure, no sticking to the heating roll was observed and a release agent was used. There is no need.

また、表1によれば、光触媒のホルムアルデヒド分解除去効果は、実施例1及び2ともに良好であり、バインダーを使用していない比較例2と同等レベルであることが確認された。これに対して、バインダー及び剥離剤を使用した比較例1ではホルムアルデヒドはほとんど分解されておらず、光触媒活性がほとんど発揮されていないことが判明した。   Moreover, according to Table 1, the formaldehyde decomposition | disassembly removal effect of a photocatalyst was favorable in both Example 1 and 2, and it was confirmed that it is a level equivalent to the comparative example 2 which does not use the binder. On the other hand, in Comparative Example 1 using a binder and a release agent, it was found that formaldehyde was hardly decomposed and the photocatalytic activity was hardly exhibited.

紙力強度については、2層構造で基材層にのみバインダーを含有させた実施例1の紙力強度は、1層構造でバインダーを使用した比較例1とほとんど同等レベルであり、バインダーを使用していない比較例2よりも大幅に紙力強度が向上していることが判る。また、繊維として強度の高いPETを配合した実施例2は、実施例1や比較例1よりもさらに紙力強度が向上していることが確認された。   Regarding the paper strength, the paper strength of Example 1 in which a binder is contained only in the base material layer in a two-layer structure is almost the same level as in Comparative Example 1 in which a binder is used in a one-layer structure, and a binder is used. It can be seen that the strength of the paper strength is significantly improved as compared with Comparative Example 2 which is not performed. Moreover, it was confirmed that Example 2 which mix | blended PET with high intensity | strength as a fiber has improved the paper strength intensity | strength further than Example 1 or Comparative Example 1. FIG.

以上の結果より、本発明に係る光触媒紙状体の製造方法により得られた光触媒紙状体は、優れた紙力強度及び光触媒活性を兼ね備えていることが確認された。   From the above results, it was confirmed that the photocatalytic paper-like body obtained by the method for producing a photocatalytic paper-like body according to the present invention has excellent paper strength and photocatalytic activity.

本発明に係る光触媒紙状体の製造方法を実施する多層抄き機の概略図Schematic of a multi-layer paper machine for carrying out the method for producing a photocatalytic paper according to the present invention 多層抄き機における単筒式加熱ロールを示す図Diagram showing a single-cylinder heating roll in a multilayer paper machine 図2の拡大図Enlarged view of FIG.

符号の説明Explanation of symbols

1 傾斜短網パート
2 円網パート
3 単筒式加熱ロール
4 表面用シート
5 基材シート
6 搬送ベルト
7 ヤンキードライパート
8 光触媒紙状体
DESCRIPTION OF SYMBOLS 1 Inclined short mesh part 2 Circular mesh part 3 Single cylinder heating roll 4 Surface sheet 5 Base material sheet 6 Conveying belt 7 Yankee dry part 8 Photocatalyst paper

Claims (8)

繊維と、バインダーとを混合して湿式抄造してなる基材シートと、光触媒担持体と、繊維とを混合して湿式抄造してなるノーバインダーの表面用シートとを重ねて乾燥手段により乾燥させることを特徴とする光触媒紙状体の製造方法。 A base sheet made by wet papermaking by mixing fibers and a binder, a photocatalyst carrier, and a non-binder surface sheet made by wet paper making by mixing fibers are stacked and dried by a drying means. A method for producing a photocatalytic paper-like material. 前記乾燥手段として単筒式加熱ロールを使用し、前記基材シートと表面用シートとを重ね合せたシートを、表面用シート側が前記加熱ロールと接触するようにして加熱することを特徴とする請求項1記載の光触媒紙状体の製造方法。 A single-cylinder heating roll is used as the drying means, and the sheet obtained by superimposing the base sheet and the surface sheet is heated so that the surface sheet side is in contact with the heating roll. Item 2. A method for producing a photocatalytic paper-like material according to Item 1. 繊維と、バインダーとを混合して湿式抄造してなる基材シートの両側に、光触媒担持体と、繊維とを混合して湿式抄造してなるノーバインダーの表面用シートを重ねて乾燥手段により乾燥させることを特徴とする光触媒紙状体の製造方法。 A photocatalyst carrier and a non-binder surface sheet formed by mixing a fiber and wet paper are stacked on both sides of a base sheet formed by mixing a fiber and a binder and wet-papered, and then dried by a drying means. A method for producing a photocatalytic paper-like body characterized by comprising: 前記加熱手段として多筒式加熱ロールを使用することを特徴とする請求項3記載の光触媒紙状体の製造方法。 The method for producing a photocatalytic paper-like body according to claim 3, wherein a multi-cylinder heating roll is used as the heating means. 前記光触媒担持体は、光触媒を無機繊維に担持させたものである請求項1〜4のいずれかに記載の光触媒紙状体の製造方法。 The method for producing a photocatalyst paper-like body according to any one of claims 1 to 4, wherein the photocatalyst support is a photocatalyst supported on an inorganic fiber. 繊維とバインダーとを含有する基材層と、該基材層の少なくとも一方の面に形成された、光触媒担持体と繊維とを含有する表面層とを備え、前記バインダーの存在量が、前記基材層よりも表面層の方が少ないことを特徴とする光触媒紙状体。 A substrate layer containing fibers and a binder, and a surface layer containing a photocatalyst carrier and fibers formed on at least one surface of the substrate layer, and the amount of the binder is A photocatalytic paper-like body characterized in that there are fewer surface layers than material layers. 前記基材層及び表面層が多層抄きによって形成され、前記表面層に存在するバインダーは、前記基材層及び表面層を加熱乾燥するときに、前記基材層に存在するバインダーが溶融して表面層にしみ出したものである請求項6記載の光触媒紙状体。 The base material layer and the surface layer are formed by multilayer papermaking, and the binder existing in the surface layer is melted when the base material layer and the surface layer are heated and dried. 7. The photocatalytic paper-like body according to claim 6, which oozes into the surface layer. 前記光触媒担持体は、光触媒を無機繊維に担持させたものである請求項6又は7記載の光触媒紙状体。
The photocatalyst paper-like body according to claim 6 or 7, wherein the photocatalyst carrier is obtained by carrying a photocatalyst on an inorganic fiber.
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JPH04306139A (en) * 1991-03-15 1992-10-28 Daiwa:Kk Electricity removing mat and manufactutre thereof
JP2000027095A (en) * 1998-07-03 2000-01-25 Hour Seishi Kk Photocatalyst titanium oxide-containing paper
JP2000325785A (en) * 1999-03-12 2000-11-28 Kawatetsu Mining Co Ltd Method for bonding photocatalytic substance to carrier and photocatalytic substance bonded carrier
JP2002266297A (en) * 2001-03-05 2002-09-18 Yamaichi Washi Kogyo Kk Shoji paper and method of producing the same
JP2003024796A (en) * 2001-07-13 2003-01-28 Yamaichi Washi Kogyo Kk Sheet-shaped member having photocatalytic function
JP2003073964A (en) * 2001-06-08 2003-03-12 Japan Vilene Co Ltd Method for producing inorganic structure and the resultant inorganic structure
JP2003236391A (en) * 2002-02-08 2003-08-26 Takuya Kitaoka Photocatalytic paper material and method for producing the same

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04306139A (en) * 1991-03-15 1992-10-28 Daiwa:Kk Electricity removing mat and manufactutre thereof
JP2000027095A (en) * 1998-07-03 2000-01-25 Hour Seishi Kk Photocatalyst titanium oxide-containing paper
JP2000325785A (en) * 1999-03-12 2000-11-28 Kawatetsu Mining Co Ltd Method for bonding photocatalytic substance to carrier and photocatalytic substance bonded carrier
JP2002266297A (en) * 2001-03-05 2002-09-18 Yamaichi Washi Kogyo Kk Shoji paper and method of producing the same
JP2003073964A (en) * 2001-06-08 2003-03-12 Japan Vilene Co Ltd Method for producing inorganic structure and the resultant inorganic structure
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