JP4489235B2 - Filter with photocatalytic activity - Google Patents
Filter with photocatalytic activity Download PDFInfo
- Publication number
- JP4489235B2 JP4489235B2 JP2000077196A JP2000077196A JP4489235B2 JP 4489235 B2 JP4489235 B2 JP 4489235B2 JP 2000077196 A JP2000077196 A JP 2000077196A JP 2000077196 A JP2000077196 A JP 2000077196A JP 4489235 B2 JP4489235 B2 JP 4489235B2
- Authority
- JP
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- Prior art keywords
- fiber
- antibacterial
- filter
- fibers
- acrylonitrile
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- 230000001699 photocatalysis Effects 0.000 title claims description 29
- 239000000835 fiber Substances 0.000 claims description 232
- 230000000844 anti-bacterial effect Effects 0.000 claims description 115
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 77
- 239000011230 binding agent Substances 0.000 claims description 45
- 229920000728 polyester Polymers 0.000 claims description 24
- 150000002736 metal compounds Chemical class 0.000 claims description 20
- 238000001914 filtration Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 7
- 125000000129 anionic group Chemical group 0.000 claims description 3
- 125000000524 functional group Chemical group 0.000 claims description 3
- 229940100890 silver compound Drugs 0.000 claims description 3
- 150000003379 silver compounds Chemical group 0.000 claims description 3
- 239000004745 nonwoven fabric Substances 0.000 description 45
- 238000000034 method Methods 0.000 description 31
- 238000004519 manufacturing process Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 9
- 238000012545 processing Methods 0.000 description 8
- 241000894006 Bacteria Species 0.000 description 7
- 230000001965 increasing effect Effects 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 5
- 230000000845 anti-microbial effect Effects 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 229910052709 silver Inorganic materials 0.000 description 5
- 239000004332 silver Substances 0.000 description 5
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 230000001580 bacterial effect Effects 0.000 description 4
- 229910001431 copper ion Inorganic materials 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- -1 Silver ions Chemical class 0.000 description 3
- 238000007731 hot pressing Methods 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000000542 sulfonic acid group Chemical group 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229920002972 Acrylic fiber Polymers 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 229920006231 aramid fiber Polymers 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000005304 joining Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- XEEYSDHEOQHCDA-UHFFFAOYSA-N 2-methylprop-2-ene-1-sulfonic acid Chemical compound CC(=C)CS(O)(=O)=O XEEYSDHEOQHCDA-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- INLLPKCGLOXCIV-UHFFFAOYSA-N bromoethene Chemical compound BrC=C INLLPKCGLOXCIV-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000003501 hydroponics Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 description 1
- 229940039790 sodium oxalate Drugs 0.000 description 1
- SZHIIIPPJJXYRY-UHFFFAOYSA-M sodium;2-methylprop-2-ene-1-sulfonate Chemical compound [Na+].CC(=C)CS([O-])(=O)=O SZHIIIPPJJXYRY-UHFFFAOYSA-M 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Disinfection, Sterilisation Or Deodorisation Of Air (AREA)
- Filtering Materials (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
- Nonwoven Fabrics (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、空気や水等に含まれる異物を除去して清澄に濾過すると共に、優れた抗菌性のあるフィルターに関し、とくに、光が照射される環境において抗菌性が著しく向上する、いわゆる光触媒活性を有するフィルターに関する。
【０００２】
【従来の技術】
空気を濾過するフィルターとして、空気清浄機用、室内用エアコン用、空調機用、自動車の車内空気用等の用途に使用される。また、水を濾過するフィルターは、飲料水用、食品工業用、農業用、水耕栽培用、ＲＯ、ＮＦ、ＵＦ、ＭＦ用等の多種多様な用途に使用される。
【０００３】
これ等の用途に使用されるフィルターは、空気や水に含まれる異物を除去して綺麗に濾過する。フィルターに濾過された異物は、細菌が発生しやすい環境となることがある。また、フィルターは、特殊な用途のものを除いて、空気や水に含まれる異物を除去する空隙に設計されるので、細菌を除去できない。
【０００４】
抗菌性のあるフィルターは、通過する空気や水を清澄に濾過できると共に、細菌をも除去できる特長がある。抗菌性のあるフィルターは、抗菌性の繊維を使用して実現できる。合成樹脂の抗菌性を実現する方法として、銀イオン又は銅イオンが知られている。これら金属イオンの特性を利用して、繊維に抗菌性を付与する方法は知られている。例えば、アクリル系繊維に銀イオンを付与する方法が、特開昭５２−９２０００号公報と特開平３−１９９４１８号公報に記載される。この公報は、スルホン酸基、カルポン酸基、水酸基等のイオン交換性基を有するアクリル繊維に、イオン交換性基の一部もしくは全部に、錯イオンまたは銅イオンを結合して金属銀、銅または該金属の化合物として残存させる抗菌性アクリロニトリル系繊維が記載される。
【０００５】
この公報に記載される繊維でフィルターを製作して、ある程度の抗菌性を実現できる。ただ、抗菌性に対する要求に充分応えられるものは実現できず、抗菌性を高めるに、抗菌性アクリロニトリル系繊維に含有させる、銀または銅イオンの量を増加しなければならない問題があった。
【０００６】
【発明が解決しようとする課題】
本発明は、この欠点を解決することを目的に開発されたもので、本発明の大切な目的は、繊維に含有させる抗菌活性金属化合物の量を増やすことなく、光照射により抗菌性を高めることのできる光触媒活性を有するフィルターを提供することにある。
【０００７】
【課題を解決するための手段】
本発明の光触媒活性を有するフィルターは、繊維を立体的に集合して、繊維の間に空気または水等の液体が通過できる濾過空隙を設けている。フィルターは繊維として、抗菌活性金属化合物を含有するアクリロニトリル系繊維を、ｐＨｌ〜６の範囲内で熱処理をしてなることで光触媒活性を有する状態としてなる抗菌性アクリロニトリル系繊維を使用する。
【０００８】
抗菌性アクリロニトリル系繊維は、抗菌活性金属化合物を、好ましくは銀系化合物とし、さらに、アクリロニトリル系繊維としてアニオン性官能基を有するものとする。
【０００９】
さらに、抗菌性アクリロニトリル系繊維は、アクリロニトリル系繊維を、たとえば、１００〜１６０℃の湿熱又は乾熱で熱処理してなるもので、この抗菌性アクリロニトリル系繊維の含有量は、好ましくは１０重量％以上としている。
【００１０】
フィルターは、抗菌性アクリロニトリル系繊維にバインダー繊維を添加し、このバインダー繊維として、未延伸ポリエステル繊維を使用し、さらに、バインダー繊維の含有率を２０〜９０重量％とする。このフィルターは、バインダー繊維でもって、繊維の交点を連結できる。
【００１１】
【発明の実施の形態】
以下、本発明の実施例を説明する。ただし、以下に示す実施例は、本発明の技術思想を具体化するためのフィルターを例示するものであって、本発明はフィルターを下記のものに特定しない。
【００１２】
フィルターは、繊維を湿式あるいは乾式で立体的に集合して繊維の交点を結合した不織布である。繊維の交点を結合した不織布は、強靭で繊維が分離し難い特長がある。ただ、本発明のフィルターは、必ずしも繊維の交点を結合する必要はない。それは、フィルターが、強度の要求されない状態で使用できる用途もあるからである。
【００１３】
繊維の交点を結合する不織布は、未硬化で液状のバインダーを繊維に塗布してこれを硬化させる方法と、主体繊維とバインダー繊維を混合して両繊維を立体的に集合して不織布とした後、バインダー繊維を溶融する方法とがある。
【００１４】
液状のバインダーで繊維の交点を結合する方法は、不織布に液状のバインダーを噴霧して塗布し、あるいは、不織布を液状のバインダーに浸漬した後、余分のバインダーを絞りとってバインダーを硬化させる。バインダー繊維を使用する方法は、バインダー繊維を熱風で溶融し、あるいは、不織布を熱圧してバインダー繊維を溶融して主体繊維の交点を結合する。
【００１５】
不織布は、乾式、湿式等の各種製法で製造される。バインダー繊維を混合して製造される不織布は、主体繊維とバインダー繊維とを混合し、両繊維を立体的に集合して製造される。この不織布は、バインダー繊維の添加量を、０〜９０重量％、好ましくは１０〜８０重量％、さらに好ましくは１５〜８０重量％とする。不織布は、バインダー繊維を添加しないで製造することもできる。ただ、バインダー繊維を添加して製作した不織布を加熱してバインダー繊維で溶着したフィルターは、強度を向上できる。バインダー繊維が主体繊維の交点を溶着するからである。
【００１６】
不織布は、光触媒活性を有する抗菌性アクリロニトリル系繊維を含んでいる。抗菌性アクリロニトリル系繊維の混合量は、たとえば、１０〜１００重量％とするが、一般的には１０〜９０重量％、好ましくは２０〜７０重量％、さらに好ましくは３０〜６０重量％、最適には４０〜６０重量％とする。
【００１７】
不織布に含まれる抗菌性アクリロニトリル系繊維は、混合量が少なすぎると抗菌性能が低下する。ただ、抗菌性アクリロニトリル系繊維の添加量を多くすると、原料コストが高くなる。また、バインダー繊維で繊維の交点を結合するフィルターは、抗菌性アクリロニトリル系繊維の添加量を多くすると、バインダー繊維の添加量が少なくなって強度が低下する。不織布に含まれる抗菌性アクリロニトリル系繊維の混合量は、用途に要求される抗菌性能とコストと強度とを考慮して、用途に最適な前述の範囲とする。
【００１８】
不織布は、抗菌性アクリロニトリル系繊維に加えて、主体繊維またはバインダー繊維として、ポリエステル繊維、ポリオレフィン繊維、ナイロン繊維、アラミド繊維、ポリフェニレンサルファイド繊維等の合成繊維を、単独であるいは複数を混合して添加することもできる。ポリエステル繊維、ポリオレフィン繊維、ナイロン繊維、アラミド繊維、ポリフェニレンサルファイド繊維等の熱可塑性繊維は、バインダー繊維として使用することができる。これ等のバインダー繊維を含む不織布は、熱圧加工して繊維を交点で結合して強靭にできる。
【００１９】
フィルターは、抗菌性アクリロニトリル系繊維に、ポリエステル繊維を添加したものが、機械的強度、耐薬品性、熱加工適性、コスト等の総合的な見地から最適である。抗菌性アクリロニトリル系繊維に添加するポリエステル繊維は、低融点ポリエステル繊維あるいは未延伸ポリエステル繊維をバインダー繊維として使用できる。
【００２０】
不織布を構成する繊維は、長さをたとえば、１〜２５ｍｍ、好ましくは、３〜１５ｍｍとするものが適している。
【００２１】
不織布は、好ましくは、湿式法で製造される。それは湿式法が、全体的に均一な不織布を製造できるからである。ただし、乾式その他の方法で製造した不織布もフィルターとして使用できるのはいうまでもない。
【００２２】
フィルターは、不織布を構成する繊維の間に多くの濾過空隙を有する。濾過空隙は、空気や水を透過させて、これを清澄に濾過する。したがって、濾過空隙の大きさは、フィルターの用途に最適に設定される。濾過空隙の小さいフィルターは、より小さい異物を除去できるが、空気や水の通過抵抗が大きくなる。したがって、濾過空隙は除去する異物の大きさと、通過抵抗とを考慮して最適値に設定される。
【００２３】
フィルターは、太さをたとえば０．１〜２０デニール、好ましくは０．３〜６デニールとする繊維を、６０重量％以上含む不織布で構成する。
【００２４】
フィルターは、面積当たりの重量を同じとして、太い繊維を使用すると、面積当りの繊維本数が減少して、濾過空隙が大きくなる。反対に細い繊維を使用すると濾過空隙が小さくなる。
【００２５】
フィルターの均一性を得るためには、不織布を構成する繊維は、太さを０．１〜２０デニールとするものを６０重量％以上含む。不織布の繊維を、０．１デニールよりも細かくすると、濾過空隙が小さくなって通過抵抗が大きくなる。反対に不織布を構成する繊維が２０デニールよりも太くなると、フィルターとして異物を濾過して除去する性能が低下する。
【００２６】
繊維を立体的に集合している不織布を熱圧加工してフィルターとする方法は、熱圧加工の条件を調整して、目的とする濾過空隙とする。熱可塑性繊維をバインダー繊維として添加している不織布は、熱加工して、繊維の交点を結合してシート状に結合される。不織布は、熱圧加工するときの圧力と温度と時間を変更して、用途に最適な濾過空隙のフィルターとする。フィルターは、不織布を熱圧加工する圧力と温度を高くして、押圧時間を長くすると、繊維が密に集合されて、濾過空隙が小さくなって通過抵抗が大きくなり強度は向上する。反対に、熱圧加工する圧力と温度を低くして押圧時間を短くすると、繊維の集合が粗になって、濾過空隙が大きく通過抵抗が小さくなって強度が低下する。
【００２７】
フィルターに使用される光触媒活性を有する抗菌性アクリロニトリル系繊維は、アクリロニトリル系重合体から形成された繊維であって、抗菌活性金属化合物を含有するものである限り特に制約はない。アクリロニトリル系重合体は、好ましくは６０重量％以上、更に好ましくは８０％重量以上のアクリロニトリルと公知のモノマーとの共重合体を用いることができる。
【００２８】
共重合に用いられるコモノマーとしては、他の重合性不飽和ビニル化合物など、アクリロニトリルと共重合するものであれば特に制限はなく、例えば、酢酸ビニル等のビニルエステル類、塩化ビニル、臭化ビニル、塩化ビニリデン等のハロゲン化ビニル又はビニリデン類、アクリル酸メチル、メタアクリル酸メチル等の（メタ）アクリル酸低級アルキルエステル類（以下、（メタ）アクリルの記載はアクリルとメタアクリルの両方を表現するものとする）、アクリルアミド、スチレン、メタアリルスルホン酸ソーダ、２−アクリルアミドー２−メチルプロパンスルホン酸、パラスチレンスルホン酸ソーダ、ビニルスルホン酸ソーダ等のスルホン酸基含有単量体、（メタ）アクリル酸、マレイン酸等のカルポン酸基含有単量体等を使用することができるが、抗菌活性金属化合物を効率的に含有させるため、スルホン酸基あるいはカルポン酸基含有単量体等のアニオン性官能基含有単量体を０．１〜２０重量％含有することが望ましい。
【００２９】
抗菌活性金属化合物としては、抗菌活性を有する金属化合物である限り特に制約はないが、光触媒活性を有効に付与するために銀系化合物であることが好ましい。ここで、本発明において繊維に含有せしめるべき抗菌活性金属化合物の量は、特に限定はないが、より好ましくは、繊維に対して金属イオンとして１〜２００ｍ・ｍｏｌ／ｋｇ含有させるのが良い。即ち金属化合物の含有量は要求される抗菌性のレベルにより異なるのであり、係る範囲の下限に満たない場合は生活環境での見るべき光触媒活性やこれに伴う充分な抗菌性能が得られにくく、上限を越える場合は、繊維が乾燥等の熱処理工程で著しく着色する問題が生じ易い。さらに係る範囲内で生活用途或いは工業用途への充分な光触媒活性に伴う抗菌性能が恒久的に得られることから、上述した範囲を越えてまで含有せしめることは、不必要にコストが高くなり工業的に有利でない。
【００３０】
かかる抗菌活性金属化合物をアクリロニトリル系繊維に含有せしめる方法としては特に制約はない。例えば、特開平３−１９９４１８号公報に開示されている方法、すなわちアクリロニトリル系繊維を製造するに際し、乾燥、熱緩和工程前のゲル構造繊維を抗菌活性金属塩水溶液で連続的に処理し、繊維に抗菌活性金属化合物を含有させる方法。特開昭５２−９２０００号公報や特開平７−２４３１６９号公報に開示されている方法、すなわち通常の方法によりアクリロニトリル系繊維を製造した後、後加工により抗菌活性金属化合物を含有させる方法をあげることができる。
【００３１】
抗菌性アクリロニトリル系繊維は、かくして得られた抗菌活性金属化合物を含有するアクリロニトリル系繊維に、ｐＨｌ〜６好ましくはｐＨ２〜４の範囲内で熱処理を施すことが必要である。かかる熱処理の方法としては特に限定されるものではないが、１００〜１６０℃の湿熱又は乾熱で処理する方法が好ましく、例えば、抗菌活性金属化合物を含有するアクリロニトリル系繊維をｐＨｌ〜６の酸性水溶液に浸漬し水切りした繊維を、オートクレープ中でスチームにより湿熱処理する方法、あるいは水切りした繊維をそのまま熱風乾燥機にて乾熱処理する方法などが挙げられる。なお処理時間は処理温度により設定される。
【００３２】
ここで熱処理時のｐＨが１未満の場合には、繊維物性が著しく阻害されるため、又ｐＨが６を超える場合には、光触媒活性が付与されないため本発明が達成されない。また、熱処理温度が１００℃未満の場合は、処理時間が長くなり工業的に有利な方法ではなく、又１６０℃を超えるとアクリロニトリル系繊維の物性を阻害するため好ましくない。
【００３３】
フィルターの繊維に使用する抗菌性アクリロニトリル系繊維は、具体的には以下の方法で製造される。ただ、以下の方法は、抗菌性アクリロニトリル系繊維の製造方法を例示するものであって、抗菌性アクリロニトリル系繊維を以下の方法で製造したものに特定しない。なお、以下の製造方法において、部及び百分率は特に断りのない限り重量基準で示す。さらに、以下の製造方法において記述する金属イオン含有量および抗菌性能は下記の方法で測定したものである。
（１）金属イオン含有量
０．１ｇｒの繊維を、９５％の濃硫酸と６２％の濃硝酸溶液で湿式分解した溶液を日本ジャーレルアッシュ（株）製原子吸光分析装置ＡＡ８５５型を用いて原子吸光度を測定して求めた。
【００３４】
（２）抗菌性
本発明のフィルターは、繊維に抗菌性アクリロニトリル系繊維を使用することを特徴とする。抗菌性アクリロニトリル系繊維の抗菌性能は、フィルターの抗菌性能を決定する。したがって、最初に繊維の抗菌性能を測定する。抗菌性能は、黄色ブドウ球菌の菌数が１．５〜３．０×１０６個／ｍｌとなるように菌懸濁液を調整し、試験菌液とした。三角フラスコに、繊維０．２ｇ、試験菌液２０ｍｌを加え、３０℃で３０分振盪した後、生菌数を測定し、残存生菌率（ＬｏｇＳ（％））を求めた。ここで、残存生菌率とは加えた試験菌液の菌数をＡ、３０分振盪後の菌数をＢとして次式で算出する。
残存生菌率（ＬｏｇＳ（％））＝Ｌｏｇ［（Ｂ／Ａ）×１００］
残存生菌率が２の場合は、Ｂ＝Ａとなって全く抗菌性がないことを示し、残存生菌率が−２はＢ／Ａが１／１００００となって強い抗菌性（９９．９９％の菌が死滅）があることを示している。
【００３５】
なお、抗菌性アクリロニトリル系繊維の光触媒活性を調べるため、上述の３０℃での振盪は、光照射下（タングステンランプ１００Ｖ、１００Ｗ）及び暗室下で行い、暗室下の残一存生菌率から光照射下の残存生菌率を減じた値を残存生菌率差とした。該残存生菌率差の値は、光触媒活性能を表すパラメーターであり、この値が大きいほど光触媒活性能力が高いといえる。
【００３６】
抗菌活性金属を含有するアクリロニトリル系繊維の製造例１
常法に従って重合して得られたアクリロニトリル９１．１％、アクリル酸メチルエステル８．６％、メタアリルスルホン酸ソーダ０．３％からなるアクリロニトリル系重合体を、濃度４５％のロダンソーダ水溶液に溶解し、重合体濃度が１２％である紡糸原液を作成した。該原液を１０％、−３℃のロダンソーダ水溶液中に公知である口金を用いて押し出し、水洗、延伸、熱処理を行い、アクリロニトリル系繊維（繊維Ａ）を作成した。次いで、抗菌活性金属である銀を該繊維に導入するため、２０ｍ・ｍｏｌ／１に調整した硝酸銀水溶液１０００ｍｌを１％の硝酸水溶液でｐＨ３に調整した溶液中に繊維Ａを１００ｇ投入して、９８℃で１０分間処理を行い、水洗、乾燥した後、１０ｍ・ｍｏｌ／１に調整したシュウ酸ナトリウム水溶液１０００ｍｌに投入して、９８℃で１０分間処理を行い、水洗、乾爆を行い、抗菌活性金属を含有するアクリロニトリル系繊維（繊維Ｂ）を作成した。
【００３７】
抗菌活性金属を含有するアクリロニトリル系繊維の製造例２
ＡＮ９５％、酢酸ビニル５％からなるアクリロニトリル系重合体を用い、硝酸銀水溶液での処理時間を３０分とした以外は、抗菌活性金属を含有するアクリロニトリル系繊維の製造例１と同様にして、抗菌活性金属を含有するアクリロニトリル系繊維（繊維Ｃ）を作成した。
【００３８】
上述の如くして得られた抗菌活性金属を含有するアクリロニトリル系繊維（繊維Ｂ、Ｃ）を、硝酸でｐＨを調整した水溶液に浸漬した後、水切りして、オートクレープ（熱処理温度が１００℃を超える場合）もしくは熱風乾燥機（熱処理温度が１００℃以下の場合）に入れ、表１に示したｐＨ、温度で熱処理し、抗菌性アクリロニトリル系繊維Ｎｏ１〜５、比較繊維３の繊維の６種類の繊維を作成した。比較繊維１、２は、夫々抗菌活性金属を含有するアクリロニトリル系繊維の製造例１のアクリロニトリル系繊維（繊維Ａ、Ｂ）であって熱処理されないアクリロニトリル系繊維である。
【００３９】
【表１】
かくして得られた抗菌性アクリロニトリル系繊維例Ｎｏ１〜５及び比較繊維１〜３の繊維について、金属含有量並びに光照射下及び暗室下で残存生菌率で表される抗菌性能及び残存生菌率差で表される光触媒活性能を測定、算出した結果を表２に示す。
【００４１】
【表２】
表２から、抗菌性アクリロニトリル系繊維Ｎｏ１〜５は、残存生菌率差の値が１．２以上と光照射下での残存生菌率が暗室下での残存生菌率に較べ優れており、光触媒活性の有ること、すなわち光を当てることにより抗菌性能が向上すること、また光照射時の残存生菌率も−２以下であり、優れた抗菌性能を有していることがわかる。特に抗菌性アクリロニトリル系繊維１及び２は残存生菌率差が１．８以上と極めて優れた光触媒活性能を持ち、残存生菌率も−２．４以下と極めて優れた抗菌性能を有している。
【００４３】
これに対し、抗菌活性金属を含まない比較繊維１は、全く抗菌性能、光触媒活性能を示さず、抗菌活性金属を含んだ比較繊維２及びｐＨ７で熱処理した比較繊維３は、ある程度の抗菌性能は有するものの、光触媒活性能は認められなかった。
【００４４】
【実施例】
［実施例１］
抗菌性アクリロニトリル系繊維を使用したフィルターは、以下の方法で製造する。
（１）不織布の製造工程
湿式で不織布を製造する。不織布を構成する繊維として、５０重量％の抗菌性アクリロニトリル系繊維と、５０重量％のポリエステル繊維を用いる。抗菌性アクリロニトリル系繊維は、表１のＮｏ１に示す繊維であって平均長さは５ｍｍとするものである。ポリエステル繊維は、１０重量％の主体繊維と、４０重量％のバインダー繊維を混合する。バインダー繊維には、ポリエステル未延伸繊維を使用する。さらに、主体繊維は、１．５デニールと３デニールの繊維を同じ重量に混合したものである。バインダー繊維の太さは１デニールである。ポリエステル繊維の加重平均密度は１．３９ｇ／ｃｍ３、抗菌性アクリロニトリル系繊維の加重平均密度は１．１５ｇ／ｃｍ３である。
【００４５】
湿式法による不織布の製造においては、製紙機械としてすでに湿式の不織布製造装置に使用されている長網抄紙機、傾斜金網等を利用する。繊維の分散が良いこと、配向性の調整が容易であること等の点からすると、傾斜金網を使用する装置が最適である。以上の装置と繊維を使用して、単位面積に対する重量を７６．１ｇ／ｍ２とする不織布を製造する。
【００４６】
（２） 不織布繊維の交点を結合する工程
抄紙機で製造した不織布に、バインダーを塗布して繊維の交点を結合する。バインダーには、未硬化で液状のもの、たとえばウレタン系の接着剤を使用する。バインダーは、スプレーノズルから霧状に噴霧して、不織布に塗布する。バインダーは不織布の両面から塗布する。不織布は、液状のバインダーに浸漬し、ローラーで余分なバインダーを絞りとって乾燥することもできる。
【００４７】
この実施例で製造したフィルターは、表３に示すように、極めて優れた抗菌性能を実現した。表３は、前述の表２と同じ条件で測定した。
【００４８】
【表３】
［実施例２］
不織布を構成する繊維を、１０重量％の抗菌性アクリロニトリル系繊維と、９０重量％のポリエステル繊維を用い、ポリエステル繊維には、５０重量％の主体繊維と、４０重量％のバインダー繊維を使用する以外、実施例１と同様にして、フィルターを製造した。抗菌性アクリロニトリル系繊維は、表１のＮｏ２に示す繊維であり、ポリエステル繊維は、実施例１に使用した繊維と同じものを使用した。この実施例で製造したフィルターは表３に示すように優れた抗菌性能を実現した。
【００５０】
［実施例３］
不織布を構成する繊維を、６０重量％の抗菌性アクリロニトリル系繊維と、４０重量％のポリエステル繊維を用い、全てのポリエステル繊維をバインダー繊維とする以外、実施例１と同様にして、表１に示す物性のフィルターを製造した。抗菌性アクリロニトリル系繊維は、表１のＮｏ３に示す繊維であり、ポリエステル繊維には実施例１に使用した繊維と同じものを使用した。この実施例で試作したフィルターは、表３に示すように、実施例１のフィルターを卓越する極めて優れた抗菌性能を実現した。
【００５１】
［実施例４］
不織布を構成する繊維を、８０重量％の抗菌性アクリロニトリル系繊維と、２０重量％のポリエステル繊維を用い、全てのポリエステル繊維をバインダー繊維とする以外、実施例１と同様にして、表１に示す物性のフィルターを製造した。抗菌性アクリロニトリル系繊維は、表１のＮｏ４に示す繊維であり、ポリエステル繊維には実施例１に使用した繊維と同じものを使用した。この実施例で試作したフィルターも、表３に示すように、実施例１のフィルターを卓越する極めて優れた抗菌性能を実現した。
【００５２】
［実施例５］
不織布を構成する繊維を、７０重量％の抗菌性アクリロニトリル系繊維と、３０重量％のポリエステル繊維を用い、全てのポリエステル繊維をバインダー繊維とする以外、実施例１と同様にして、表１に示す物性のフィルターを製造した。抗菌性アクリロニトリル系繊維は、表１のＮｏ５に示す繊維であり、ポリエステル繊維には実施例１に使用した繊維と同じものを使用した。この実施例で試作したフィルターも、表３に示すように、実施例１のフィルターを卓越する極めて優れた抗菌性能を実現した。
【００５３】
［比較例１］
実施例１の抗菌性アクリロニトリル系繊維に代わって、比較繊維１を使用する以外、実施例１と同様にして、フィルターを製造した。このフィルターは、表３に示すように、本発明のフィルターに比較して抗菌性能が著しく低下した。
【００５４】
［比較例２］
実施例１の抗菌性アクリロニトリル系繊維に代わって、比較繊維２を使用する以外、実施例１と同様にして、フィルターを製造した。このフィルターは、表３に示すように、抗菌性を示さなかった。
【００５５】
［比較例３］
実施例１の抗菌性アクリロニトリル系繊維に代わって、比較繊維３を使用する以外、実施例１と同様にして、フィルターを製造した。このフィルターは、表３に示すように、ほとんど抗菌性を示さなかった。
【００５６】
【発明の効果】
本発明のフィルターは、光照射により抗菌性を高めることのできる光触媒活性を有し、光が照射される用途に使用されて、極めて優れた抗菌性能を実現する特長がある。それは、本発明のフィルターが、光触媒活性のある抗菌性アクリロニトリル系繊維を繊維として使用し、さらに、この抗菌性アクリロニトリル系繊維には、抗菌活性金属化合物を含有するアクリロニトリル系繊維を、ｐＨｌ〜６の範囲内で熱処理を施すことにより、抗菌活性金属化合物の量を増やすことなく、光照射により抗菌性を高めることの出来る繊維を使用しているからである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a filter having excellent antibacterial properties while removing foreign substances contained in air, water, etc., and more particularly, a so-called photocatalytic activity that significantly improves antibacterial properties in an environment where light is irradiated. Relates to a filter having
[0002]
[Prior art]
As a filter for filtering air, it is used for applications such as air purifiers, indoor air conditioners, air conditioners, and car interior air. Moreover, the filter which filters water is used for various uses, such as for drinking water, food industry, agriculture, hydroponics, RO, NF, UF, and MF.
[0003]
The filter used for these applications removes foreign matters contained in air and water and filters them cleanly. The foreign matter filtered by the filter may be in an environment where bacteria are likely to be generated. In addition, except for special applications, the filter is designed as a void that removes foreign substances contained in air and water, and therefore bacteria cannot be removed.
[0004]
An antibacterial filter has the feature that it can filter out air and water passing through it and can also remove bacteria. Antibacterial filters can be realized using antibacterial fibers. Silver ions or copper ions are known as methods for realizing the antibacterial properties of synthetic resins. A method for imparting antibacterial properties to fibers using the characteristics of these metal ions is known. For example, methods for imparting silver ions to acrylic fibers are described in JP-A-52-92000 and JP-A-3-199418. This publication describes metallic silver, copper or copper ions by binding complex ions or copper ions to some or all of the ion exchange groups to acrylic fibers having ion exchange groups such as sulfonic acid groups, carboxylic acid groups, and hydroxyl groups. Antibacterial acrylonitrile fibers that remain as the metal compounds are described.
[0005]
A certain degree of antibacterial properties can be realized by manufacturing a filter with the fibers described in this publication. However, it has not been possible to realize a product that can sufficiently satisfy the antibacterial requirements, and in order to increase the antibacterial properties, there is a problem that the amount of silver or copper ions to be contained in the antibacterial acrylonitrile fiber must be increased.
[0006]
[Problems to be solved by the invention]
The present invention was developed for the purpose of solving this drawback, and an important object of the present invention is to increase the antibacterial property by light irradiation without increasing the amount of the antibacterial active metal compound contained in the fiber. It is an object of the present invention to provide a filter having a photocatalytic activity that can be applied.
[0007]
[Means for Solving the Problems]
In the filter having photocatalytic activity of the present invention, fibers are three-dimensionally aggregated, and a filtration gap through which a liquid such as air or water can pass is provided between the fibers. Filter as fibers, the acrylonitrile-based fiber containing the antimicrobial active metal compound, using the antimicrobial acrylonitrile fiber comprising a state having a photocatalytic activity by formed by a heat treatment in the range of PHl～6.
[0008]
In the antibacterial acrylonitrile fiber, the antibacterial active metal compound is preferably a silver compound, and further has an anionic functional group as the acrylonitrile fiber.
[0009]
Further, the antibacterial acrylonitrile fiber is obtained by heat-treating acrylonitrile fiber with, for example, 100 to 160 ° C. wet heat or dry heat, and the content of the antibacterial acrylonitrile fiber is preferably 10% by weight or more. It is said.
[0010]
In the filter, binder fiber is added to antibacterial acrylonitrile fiber, unstretched polyester fiber is used as the binder fiber, and the binder fiber content is 20 to 90% by weight. This filter can connect the intersections of the fibers with binder fibers.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
Examples of the present invention will be described below. However, the example shown below illustrates the filter for embodying the technical idea of the present invention, and the present invention does not specify the filter as described below.
[0012]
The filter is a non-woven fabric in which fibers are gathered in a three-dimensional manner, wet or dry, and the intersections of the fibers are combined. Nonwoven fabrics that join the intersections of fibers are strong and difficult to separate fibers. However, the filter of the present invention does not necessarily have to join the intersections of fibers. This is because the filter can be used in a state where strength is not required.
[0013]
The nonwoven fabric that joins the intersections of fibers is a method in which an uncured and liquid binder is applied to the fiber and cured, and after mixing the main fiber and the binder fiber, the fibers are three-dimensionally assembled into a nonwoven fabric. And a method of melting the binder fiber.
[0014]
In the method of bonding the intersections of fibers with a liquid binder, the liquid binder is sprayed and applied to the nonwoven fabric, or after the nonwoven fabric is immersed in the liquid binder, the excess binder is squeezed to cure the binder. In the method of using the binder fiber, the binder fiber is melted with hot air, or the nonwoven fabric is hot-pressed to melt the binder fiber and bond the intersections of the main fibers.
[0015]
Nonwoven fabrics are produced by various production methods such as dry and wet. The nonwoven fabric produced by mixing the binder fibers is produced by mixing the main fibers and the binder fibers and gathering both the fibers three-dimensionally. In this nonwoven fabric, the amount of binder fiber added is 0 to 90% by weight, preferably 10 to 80% by weight, and more preferably 15 to 80% by weight. A nonwoven fabric can also be manufactured without adding a binder fiber. However, a filter in which a nonwoven fabric produced by adding binder fibers is heated and welded with binder fibers can improve strength. This is because the binder fiber welds the intersection of the main fibers.
[0016]
The nonwoven fabric contains an antibacterial acrylonitrile fiber having photocatalytic activity. The mixing amount of the antibacterial acrylonitrile fiber is, for example, 10 to 100% by weight, but generally 10 to 90% by weight, preferably 20 to 70% by weight, more preferably 30 to 60% by weight, optimally. Is 40-60% by weight.
[0017]
If the amount of the antibacterial acrylonitrile fiber contained in the nonwoven fabric is too small, the antibacterial performance deteriorates. However, if the amount of the antibacterial acrylonitrile fiber added is increased, the raw material cost increases. Moreover, the filter which couple | bonds the intersection of a fiber with a binder fiber will reduce an intensity | strength and the amount of binder fiber addition will decrease, if the addition amount of an antibacterial acrylonitrile type fiber is increased. The mixing amount of the antibacterial acrylonitrile fiber contained in the non-woven fabric is set to the above-mentioned range optimum for the application in consideration of the antibacterial performance, cost and strength required for the application.
[0018]
In addition to antibacterial acrylonitrile fiber, non-woven fabric is added as a main fiber or binder fiber, and synthetic fibers such as polyester fiber, polyolefin fiber, nylon fiber, aramid fiber and polyphenylene sulfide fiber are added singly or in combination. You can also. Thermoplastic fibers such as polyester fibers, polyolefin fibers, nylon fibers, aramid fibers, and polyphenylene sulfide fibers can be used as binder fibers. Nonwoven fabrics containing these binder fibers can be made tough by hot pressing and bonding the fibers at intersections.
[0019]
A filter obtained by adding a polyester fiber to an antibacterial acrylonitrile fiber is optimal from the comprehensive viewpoint of mechanical strength, chemical resistance, suitability for heat processing, cost, and the like. The polyester fiber added to the antibacterial acrylonitrile fiber can be a low-melting polyester fiber or an unstretched polyester fiber as a binder fiber.
[0020]
The fibers constituting the nonwoven fabric have a length of, for example, 1 to 25 mm, preferably 3 to 15 mm.
[0021]
The nonwoven fabric is preferably produced by a wet method. This is because the wet method can produce a uniform nonwoven fabric as a whole. However, it goes without saying that a nonwoven fabric produced by a dry method or other methods can also be used as a filter.
[0022]
A filter has many filtration space | gap between the fibers which comprise a nonwoven fabric. The filter gaps allow air and water to pass through and filter them clearly. Therefore, the size of the filtration gap is optimally set for the use of the filter. A filter with a small filtering gap can remove smaller foreign matters, but increases the passage resistance of air and water. Therefore, the filtration gap is set to an optimum value in consideration of the size of the foreign matter to be removed and the passage resistance.
[0023]
The filter is composed of a nonwoven fabric containing 60% by weight or more of fibers having a thickness of, for example, 0.1 to 20 denier, preferably 0.3 to 6 denier.
[0024]
If the filter has the same weight per area and thick fibers are used, the number of fibers per area decreases and the filtration gap increases. On the other hand, when fine fibers are used, the filtration gap becomes small.
[0025]
In order to obtain the uniformity of the filter, the fibers constituting the nonwoven fabric contain 60% by weight or more of a fiber having a thickness of 0.1 to 20 denier. If the nonwoven fabric fibers are made finer than 0.1 denier, the filtration gap becomes smaller and the passage resistance becomes larger. On the other hand, when the fibers constituting the nonwoven fabric are thicker than 20 denier, the performance of filtering and removing foreign matters as a filter is lowered.
[0026]
The method of forming a filter by subjecting a nonwoven fabric in which fibers are three-dimensionally to hot pressure processing to obtain a target filtration void by adjusting the conditions of hot pressure processing. The nonwoven fabric to which the thermoplastic fiber is added as the binder fiber is heat-processed, and is joined in a sheet form by joining the intersections of the fibers. The non-woven fabric is made into a filter with a filtration gap that is optimal for the application by changing the pressure, temperature, and time during hot pressing. When the pressure and temperature at which the non-woven fabric is hot-pressed is increased and the pressing time is increased, the filter gathers fibers densely, the filtration gap becomes smaller, the passage resistance increases, and the strength improves. On the other hand, when the pressure and temperature for hot pressing are lowered and the pressing time is shortened, the aggregate of fibers becomes rough, the filtration gap is large, the passage resistance is reduced, and the strength is lowered.
[0027]
The antibacterial acrylonitrile fiber having photocatalytic activity used for the filter is a fiber formed from an acrylonitrile polymer, and is not particularly limited as long as it contains an antibacterial active metal compound. As the acrylonitrile-based polymer, a copolymer of acrylonitrile and a known monomer, preferably 60% by weight or more, more preferably 80% by weight or more can be used.
[0028]
The comonomer used for copolymerization is not particularly limited as long as it is copolymerizable with acrylonitrile, such as other polymerizable unsaturated vinyl compounds. For example, vinyl esters such as vinyl acetate, vinyl chloride, vinyl bromide, Vinyl halides such as vinylidene chloride or vinylidenes, (meth) acrylic acid lower alkyl esters such as methyl acrylate and methyl methacrylate (hereinafter, (meth) acrylic represents both acrylic and methacrylic) ), Sulfonic acid group-containing monomers such as acrylamide, styrene, methallyl sulfonic acid soda, 2-acrylamido-2-methylpropane sulfonic acid, parastyrene sulfonic acid soda, vinyl sulfonic acid soda, (meth) acrylic acid , Using carboxylic acid group-containing monomers such as maleic acid Possible, in order to contain antimicrobial active metal compound efficiently, it is desirable to include an anionic functional group-containing monomers such as sulfonic acid group or Karupon acid group-containing monomer and 0.1 to 20 wt%.
[0029]
The antibacterial active metal compound is not particularly limited as long as it is a metal compound having antibacterial activity, but is preferably a silver compound in order to effectively impart photocatalytic activity. Here, the amount of the antibacterial active metal compound to be contained in the fiber in the present invention is not particularly limited, but more preferably 1 to 200 m · mol / kg is contained as a metal ion with respect to the fiber. In other words, the content of the metal compound varies depending on the level of antibacterial properties required, and if it is less than the lower limit of such a range, it is difficult to obtain the photocatalytic activity to be seen in the living environment and the sufficient antibacterial performance associated therewith. If it exceeds 1, the problem that the fiber is remarkably colored in a heat treatment step such as drying tends to occur. Furthermore, since antibacterial performance with sufficient photocatalytic activity for daily use or industrial use can be permanently obtained within such a range, it is unnecessarily expensive and industrial to contain beyond the above range. Is not advantageous to.
[0030]
There is no restriction | limiting in particular as a method of making this antimicrobial active metal compound contain an acrylonitrile fiber. For example, in the method disclosed in JP-A-3-199418, that is, when producing acrylonitrile fiber, the gel structure fiber before drying and heat relaxation process is continuously treated with an antibacterial active metal salt aqueous solution, A method of containing an antibacterial active metal compound. A method disclosed in JP-A-52-92000 and JP-A-7-243169, that is, a method of producing an acrylonitrile fiber by a normal method and then incorporating an antibacterial active metal compound by post-processing. Can do.
[0031]
Antibacterial acrylonitrile fiber is thus the resultant acrylonitrile-based textiles containing an antimicrobial active metal compound, PHl～6 preferably must be subjected to heat treatment in the range of pH 2 to 4. Although it does not specifically limit as the method of this heat processing, The method of processing with 100-160 degreeC wet heat or dry heat is preferable, for example, the acidic aqueous solution of pH 1-6 containing the acrylonitrile type | system | group fiber containing an antibacterial active metal compound is preferable. Examples thereof include a method in which the fibers soaked in water and drained are subjected to a wet heat treatment with steam in an autoclave, or a method in which the water-drained fibers are directly subjected to a dry heat treatment in a hot air dryer. The processing time is set according to the processing temperature.
[0032]
Here, when the pH during the heat treatment is less than 1, the fiber physical properties are remarkably inhibited, and when the pH exceeds 6, the photocatalytic activity is not imparted, so that the present invention is not achieved. Further, when the heat treatment temperature is less than 100 ° C., the treatment time becomes long and this is not an industrially advantageous method. When the heat treatment temperature exceeds 160 ° C., the physical properties of the acrylonitrile fiber are hindered.
[0033]
The antibacterial acrylonitrile fiber used for the filter fiber is specifically produced by the following method. However, the following method exemplifies the production method of the antibacterial acrylonitrile fiber, and does not specify that the antibacterial acrylonitrile fiber is produced by the following method. In the following production methods, parts and percentages are shown on a weight basis unless otherwise specified. Furthermore, the metal ion content and antibacterial performance described in the following production methods were measured by the following methods.
(1) Metal ion content A solution obtained by wet-degrading a 0.1 gr fiber with 95% concentrated sulfuric acid and 62% concentrated nitric acid solution using an atomic absorption spectrometer AA855 manufactured by Nippon Jarrell Ash Co., Ltd. Absorbance was measured and determined.
[0034]
(2) Antibacterial property The filter of the present invention is characterized by using an antibacterial acrylonitrile fiber for the fiber. The antibacterial performance of the antibacterial acrylonitrile fiber determines the antibacterial performance of the filter. Therefore, the antibacterial performance of the fiber is first measured. For antibacterial performance, the bacterial suspension was adjusted so that the number of Staphylococcus aureus was 1.5 to 3.0 × 10 6 cells / ml, and used as a test bacterial solution. To the Erlenmeyer flask, 0.2 g of fiber and 20 ml of the test bacterial solution were added and shaken at 30 ° C. for 30 minutes, and then the viable cell count was measured to determine the residual viable cell rate (LogS (%)). Here, the residual viable cell rate is calculated by the following formula, where A is the number of bacteria in the added test bacterial solution, and B is the number of bacteria after shaking for 30 minutes.
Residual viable cell rate (LogS (%)) = Log [(B / A) × 100]
When the residual viable cell rate is 2, B = A, indicating that there is no antibacterial activity, and when the residual viable cell rate is -2, B / A is 1/10000 and strong antibacterial activity (99.99). % Of the bacteria are dead).
[0035]
In addition, in order to investigate the photocatalytic activity of the antibacterial acrylonitrile fiber, the above-mentioned shaking at 30 ° C. is performed under light irradiation (tungsten lamp 100V, 100W) and under a dark room. The value obtained by subtracting the residual viable cell rate under irradiation was defined as the residual viable cell rate difference. The value of the residual viable cell rate difference is a parameter representing the photocatalytic activity ability, and it can be said that the larger this value, the higher the photocatalytic activity ability.
[0036]
Production Example 1 of Acrylonitrile Fiber Containing Antibacterial Active Metal
An acrylonitrile-based polymer comprising 91.1% acrylonitrile, 8.6% acrylic acid methyl ester, and 0.3% sodium methallyl sulfonate obtained by polymerization according to a conventional method is dissolved in a 45% concentration aqueous rhodium soda solution. A spinning stock solution having a polymer concentration of 12% was prepared. The stock solution was extruded into a 10%, -3 ° C aqueous rhodium soda solution using a known die, washed with water, stretched, and heat-treated to prepare acrylonitrile fiber (fiber A). Next, in order to introduce silver, which is an antibacterial active metal, into the fiber, 100 g of fiber A was introduced into a solution in which 1000 ml of a silver nitrate aqueous solution adjusted to 20 m · mol / 1 was adjusted to pH 3 with a 1% nitric acid aqueous solution. Treated at 10 ° C. for 10 minutes, washed with water and dried, then poured into 1000 ml of sodium oxalate aqueous solution adjusted to 10 m · mol / 1, treated at 98 ° C. for 10 minutes, washed with water and dry-explosion, antibacterial activity An acrylonitrile-based fiber (fiber B) containing a metal was prepared.
[0037]
Production example 2 of acrylonitrile fiber containing antibacterial active metal
An antibacterial activity was obtained in the same manner as in Production Example 1 of an acrylonitrile fiber containing an antibacterial active metal, except that an acrylonitrile polymer composed of 95% AN and 5% vinyl acetate was used and the treatment time in an aqueous silver nitrate solution was 30 minutes. An acrylonitrile-based fiber (fiber C) containing metal was prepared.
[0038]
The acrylonitrile fiber (fibers B and C) containing the antibacterial active metal obtained as described above is immersed in an aqueous solution adjusted to pH with nitric acid, drained, and autoclaved (heat treatment temperature is 100 ° C.). In the case where the heat treatment temperature is 100 ° C. or less, heat treatment is performed at the pH and temperature shown in Table 1, and the antibacterial acrylonitrile fiber Nos. 1 to 5 and the fiber of the comparative fiber 3 have six types. Fiber was created. Comparative fibers 1 and 2 are acrylonitrile fibers (fibers A and B) of Production Example 1 of acrylonitrile fibers each containing an antibacterial active metal and are not subjected to heat treatment.
[0039]
[Table 1]
For the fibers of the antibacterial acrylonitrile fiber examples No. 1 to 5 and the comparative fibers 1 to 3 thus obtained, the metal content and the antibacterial performance represented by the residual viable cell rate under light irradiation and dark room, and the residual viable cell rate difference Table 2 shows the results of measurement and calculation of the photocatalytic activity represented by
[0041]
[Table 2]
From Table 2, the antibacterial acrylonitrile fiber Nos. 1 to 5 have a residual viable cell rate difference value of 1.2 or more, and the remaining viable cell rate under light irradiation is superior to the remaining viable cell rate in the dark room. It can be seen that it has photocatalytic activity, that is, the antibacterial performance is improved by exposure to light, and the residual viable cell rate at the time of light irradiation is -2 or less, and has excellent antibacterial performance. In particular, the antibacterial acrylonitrile fibers 1 and 2 have an extremely excellent photocatalytic activity with a difference in residual viable bacteria rate of 1.8 or more, and have an excellent antibacterial performance with a residual viable cell rate of -2.4 or less. Yes.
[0043]
On the other hand, the comparative fiber 1 containing no antibacterial active metal does not exhibit any antibacterial performance or photocatalytic activity, and the comparative fiber 2 containing the antibacterial active metal and the comparative fiber 3 heat-treated at pH 7 have some antibacterial performance. However, the photocatalytic activity was not recognized.
[0044]
【Example】
[Example 1]
A filter using antibacterial acrylonitrile fiber is produced by the following method.
(1) Nonwoven fabric manufacturing process Nonwoven fabric is manufactured by a wet process. As fibers constituting the nonwoven fabric, 50% by weight of antibacterial acrylonitrile fiber and 50% by weight of polyester fiber are used. The antibacterial acrylonitrile fiber is a fiber shown in No. 1 in Table 1 and has an average length of 5 mm. The polyester fiber is mixed with 10% by weight of the main fiber and 40% by weight of the binder fiber. A polyester unstretched fiber is used for the binder fiber. Further, the main fiber is a mixture of 1.5 denier and 3 denier fibers in the same weight. The thickness of the binder fiber is 1 denier. The weighted average density of the polyester fiber is 1.39 g / cm 3 , and the weighted average density of the antibacterial acrylonitrile fiber is 1.15 g / cm 3 .
[0045]
In the production of a nonwoven fabric by a wet method, a long paper machine, a slanted wire mesh, or the like already used in a wet nonwoven fabric production apparatus is used as a papermaking machine. From the viewpoints of good fiber dispersion and easy adjustment of orientation, an apparatus using an inclined wire mesh is optimal. The nonwoven fabric which manufactures the weight with respect to a unit area to 76.1 g / m < 2 > using the above apparatus and fiber is manufactured.
[0046]
(2) The process of joining the intersection of a nonwoven fabric fiber A binder is apply | coated to the nonwoven fabric manufactured with the paper machine, and the intersection of a fiber is couple | bonded. As the binder, an uncured and liquid material, for example, a urethane-based adhesive is used. The binder is sprayed in a mist form from a spray nozzle and applied to the nonwoven fabric. The binder is applied from both sides of the nonwoven fabric. The nonwoven fabric can be dipped in a liquid binder, and the excess binder can be squeezed out with a roller and dried.
[0047]
As shown in Table 3, the filter produced in this example realized extremely excellent antibacterial performance. Table 3 was measured under the same conditions as in Table 2 above.
[0048]
[Table 3]
[Example 2]
Non-woven fabric is composed of 10% by weight of antibacterial acrylonitrile fiber and 90% by weight of polyester fiber, except that 50% by weight of the main fiber and 40% by weight of binder fiber are used as the polyester fiber. A filter was produced in the same manner as in Example 1. The antibacterial acrylonitrile fiber is a fiber shown in No. 2 of Table 1, and the same fiber as that used in Example 1 was used as the polyester fiber. The filter produced in this example realized excellent antibacterial performance as shown in Table 3.
[0050]
[Example 3]
Table 1 shows the fibers constituting the nonwoven fabric in the same manner as in Example 1, except that 60% by weight of antibacterial acrylonitrile fiber and 40% by weight of polyester fiber are used, and all the polyester fibers are binder fibers. A filter with physical properties was manufactured. The antibacterial acrylonitrile fiber is a fiber shown in No. 3 of Table 1, and the same fiber as that used in Example 1 was used as the polyester fiber. As shown in Table 3, the filter prototyped in this example realized extremely excellent antibacterial performance superior to the filter of Example 1.
[0051]
[Example 4]
Table 1 shows the fibers constituting the nonwoven fabric in the same manner as in Example 1 except that 80% by weight of antibacterial acrylonitrile fiber and 20% by weight of polyester fiber are used, and all the polyester fibers are used as binder fibers. A filter with physical properties was manufactured. The antibacterial acrylonitrile fiber is a fiber shown in No. 4 of Table 1, and the same fiber as that used in Example 1 was used as the polyester fiber. As shown in Table 3, the filter prototyped in this example also realized extremely excellent antibacterial performance superior to the filter of Example 1.
[0052]
[Example 5]
Table 1 shows the fibers constituting the nonwoven fabric in the same manner as in Example 1 except that 70% by weight of antibacterial acrylonitrile-based fibers and 30% by weight of polyester fibers are used and all polyester fibers are binder fibers. A filter with physical properties was manufactured. The antibacterial acrylonitrile fiber is a fiber shown in No. 5 of Table 1, and the same fiber as that used in Example 1 was used as the polyester fiber. As shown in Table 3, the filter prototyped in this example also realized extremely excellent antibacterial performance superior to the filter of Example 1.
[0053]
[Comparative Example 1]
A filter was produced in the same manner as in Example 1 except that the comparative fiber 1 was used in place of the antibacterial acrylonitrile fiber of Example 1. As shown in Table 3, the antibacterial performance of this filter was significantly reduced as compared with the filter of the present invention.
[0054]
[Comparative Example 2]
A filter was produced in the same manner as in Example 1 except that the comparative fiber 2 was used in place of the antibacterial acrylonitrile fiber of Example 1. This filter did not show antibacterial properties as shown in Table 3.
[0055]
[Comparative Example 3]
A filter was produced in the same manner as in Example 1 except that the comparative fiber 3 was used in place of the antibacterial acrylonitrile fiber of Example 1. As shown in Table 3, this filter showed almost no antibacterial property.
[0056]
【The invention's effect】
The filter of the present invention has a photocatalytic activity capable of enhancing antibacterial properties by light irradiation, and has an advantage of realizing extremely excellent antibacterial performance when used in applications where light is irradiated. That is, the filter of the present invention uses an antibacterial acrylonitrile fiber having photocatalytic activity as a fiber, and further, an acrylonitrile fiber containing an antibacterial active metal compound is added to the antibacterial acrylonitrile fiber having a pH of 1 to 6. It is because the fiber which can improve an antibacterial property by light irradiation is used, without increasing the quantity of an antibacterial active metal compound by performing heat processing within the range.
Claims (7)
繊維が、抗菌活性金属化合物を含有するアクリロニトリル系繊維を、ｐＨｌ〜６の範囲内で熱処理をしてなることで光触媒活性を有する状態としてなる抗菌性アクリロニトリル系繊維を含むことを特徴とする光触媒活性を有するフィルター。In a filter in which fibers are three-dimensionally gathered and a filtration gap through which a liquid such as air or water can pass between the fibers is provided.
Fibers, the acrylonitrile fibers containing antibacterial active metal compound, the photocatalytic activity which comprises an antibacterial acrylonitrile fiber comprising a state having a photocatalytic activity by formed by a heat treatment in the range of pHl~6 Having a filter.
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| JP2000077196A JP4489235B2 (en) | 2000-03-17 | 2000-03-17 | Filter with photocatalytic activity |
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| JP2000077196A JP4489235B2 (en) | 2000-03-17 | 2000-03-17 | Filter with photocatalytic activity |
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|---|---|---|---|---|
| JP2007237065A (en) * | 2006-03-08 | 2007-09-20 | Miyoshi Oil & Fat Co Ltd | Antimicrobial agent having photocatalytic activity and antimicrobial treatment method |
| JP6171670B2 (en) * | 2013-07-24 | 2017-08-02 | コニカミノルタ株式会社 | Operation screen display device and display control program |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5292000A (en) * | 1976-01-29 | 1977-08-02 | Toray Industries | Antiibacterial fiber |
| JPH0913221A (en) * | 1995-06-26 | 1997-01-14 | Japan Exlan Co Ltd | High-strength acrylic fiber having antibacterial and antifungal properties and its production |
| JPH11342310A (en) * | 1998-03-31 | 1999-12-14 | Mitsubishi Paper Mills Ltd | Functional electret filter and its production and air purifier |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09227319A (en) * | 1995-12-21 | 1997-09-02 | Ishihara Sangyo Kaisha Ltd | Antimicrobial powder and production thereof |
| JPH10127742A (en) * | 1996-10-25 | 1998-05-19 | Shoji Hirayama | Method and apparatus for purifying gas |
| JP3558807B2 (en) * | 1997-01-21 | 2004-08-25 | 三菱製紙株式会社 | Adsorption decomposition sheet |
| JPH10309417A (en) * | 1997-05-01 | 1998-11-24 | Besutekusu Kk | Manufacture of filter material |
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- 2000-03-17 JP JP2000077196A patent/JP4489235B2/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5292000A (en) * | 1976-01-29 | 1977-08-02 | Toray Industries | Antiibacterial fiber |
| JPH0913221A (en) * | 1995-06-26 | 1997-01-14 | Japan Exlan Co Ltd | High-strength acrylic fiber having antibacterial and antifungal properties and its production |
| JPH11342310A (en) * | 1998-03-31 | 1999-12-14 | Mitsubishi Paper Mills Ltd | Functional electret filter and its production and air purifier |
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| JP2001259012A (en) | 2001-09-25 |
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