JP2019178076A - Antivirus composition, and method for adding antivirus function - Google Patents
Antivirus composition, and method for adding antivirus function Download PDFInfo
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- 239000000203 mixture Substances 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims description 7
- 230000002155 anti-virotic effect Effects 0.000 title abstract description 6
- -1 polyethylene Polymers 0.000 claims abstract description 36
- 150000003839 salts Chemical class 0.000 claims abstract description 22
- 238000000576 coating method Methods 0.000 claims abstract description 17
- 239000011248 coating agent Substances 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 13
- QGGYFTDRNKQQNT-UHFFFAOYSA-N molybdenum;oxosilver Chemical compound [Mo].[Ag]=O QGGYFTDRNKQQNT-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229920003023 plastic Polymers 0.000 claims abstract description 8
- 239000004033 plastic Substances 0.000 claims abstract description 8
- 239000012964 benzotriazole Substances 0.000 claims abstract description 5
- 230000000840 anti-viral effect Effects 0.000 claims description 46
- 229910052783 alkali metal Inorganic materials 0.000 claims description 12
- 239000004745 nonwoven fabric Substances 0.000 claims description 6
- 239000000835 fiber Substances 0.000 claims description 5
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 5
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 5
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 125000003354 benzotriazolyl group Chemical class N1N=NC2=C1C=CC=C2* 0.000 claims 1
- 238000002845 discoloration Methods 0.000 abstract description 12
- 239000004698 Polyethylene Substances 0.000 abstract description 7
- 229920000573 polyethylene Polymers 0.000 abstract description 7
- 239000004743 Polypropylene Substances 0.000 abstract description 6
- 229920001155 polypropylene Polymers 0.000 abstract description 6
- 229920000915 polyvinyl chloride Polymers 0.000 abstract description 5
- 239000004800 polyvinyl chloride Substances 0.000 abstract description 5
- 239000004566 building material Substances 0.000 abstract description 2
- 239000012756 surface treatment agent Substances 0.000 abstract description 2
- 241000700605 Viruses Species 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
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- 239000000839 emulsion Substances 0.000 description 9
- 239000003973 paint Substances 0.000 description 8
- 108090000623 proteins and genes Proteins 0.000 description 8
- 241001263478 Norovirus Species 0.000 description 6
- 229910052750 molybdenum Inorganic materials 0.000 description 6
- 239000011733 molybdenum Substances 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 5
- 241000714201 Feline calicivirus Species 0.000 description 5
- 150000001447 alkali salts Chemical class 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000004793 Polystyrene Substances 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- MHLYOTJKDAAHGI-UHFFFAOYSA-N silver molybdate Chemical compound [Ag+].[Ag+].[O-][Mo]([O-])(=O)=O MHLYOTJKDAAHGI-UHFFFAOYSA-N 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 3
- 239000002174 Styrene-butadiene Substances 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 3
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 description 3
- 239000004816 latex Substances 0.000 description 3
- 229920000126 latex Polymers 0.000 description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 239000011115 styrene butadiene Substances 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- 241000712461 unidentified influenza virus Species 0.000 description 3
- 241000991587 Enterovirus C Species 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 150000001565 benzotriazoles Chemical class 0.000 description 2
- 239000012496 blank sample Substances 0.000 description 2
- 239000012888 bovine serum Substances 0.000 description 2
- 210000000234 capsid Anatomy 0.000 description 2
- 210000003734 kidney Anatomy 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- KFJDQPJLANOOOB-UHFFFAOYSA-N 2h-benzotriazole-4-carboxylic acid Chemical compound OC(=O)C1=CC=CC2=NNN=C12 KFJDQPJLANOOOB-UHFFFAOYSA-N 0.000 description 1
- BMOKHTQIBPRXSL-UHFFFAOYSA-N 2h-benzotriazole;sodium Chemical compound [Na].C1=CC=CC2=NNN=C21 BMOKHTQIBPRXSL-UHFFFAOYSA-N 0.000 description 1
- LRUDIIUSNGCQKF-UHFFFAOYSA-N 5-methyl-1H-benzotriazole Chemical compound C1=C(C)C=CC2=NNN=C21 LRUDIIUSNGCQKF-UHFFFAOYSA-N 0.000 description 1
- 241000714198 Caliciviridae Species 0.000 description 1
- 241000282465 Canis Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 206010016952 Food poisoning Diseases 0.000 description 1
- 208000019331 Foodborne disease Diseases 0.000 description 1
- 241000712431 Influenza A virus Species 0.000 description 1
- 239000000232 Lipid Bilayer Substances 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 238000004113 cell culture Methods 0.000 description 1
- 241000902900 cellular organisms Species 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- NMHMDUCCVHOJQI-UHFFFAOYSA-N lithium molybdate Chemical compound [Li+].[Li+].[O-][Mo]([O-])(=O)=O NMHMDUCCVHOJQI-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- KHJDQHIZCZTCAE-UHFFFAOYSA-N oxosilver;silver Chemical compound [Ag].[Ag]=O KHJDQHIZCZTCAE-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 1
- 229940071536 silver acetate Drugs 0.000 description 1
- 229940100890 silver compound Drugs 0.000 description 1
- 150000003379 silver compounds Chemical class 0.000 description 1
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 description 1
- 229910000367 silver sulfate Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- RWVGQQGBQSJDQV-UHFFFAOYSA-M sodium;3-[[4-[(e)-[4-(4-ethoxyanilino)phenyl]-[4-[ethyl-[(3-sulfonatophenyl)methyl]azaniumylidene]-2-methylcyclohexa-2,5-dien-1-ylidene]methyl]-n-ethyl-3-methylanilino]methyl]benzenesulfonate Chemical compound [Na+].C1=CC(OCC)=CC=C1NC1=CC=C(C(=C2C(=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=2C(=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=C1 RWVGQQGBQSJDQV-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 241000701161 unidentified adenovirus Species 0.000 description 1
- 241001529453 unidentified herpesvirus Species 0.000 description 1
- 230000009385 viral infection Effects 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Landscapes
- Nonwoven Fabrics (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Paints Or Removers (AREA)
- Artificial Filaments (AREA)
Abstract
Description
本発明は、壁や床等の内装建材の表面を保護、美装、被覆する塗料や表面処理剤等のコーティング材、ポリ塩化ビニル、ポリエチレン、ポリプロピレン、ポリスチレン等のプラスチック、または、繊維、不織布に対して、変色の少ない抗ウイルス機能を付与することが可能な組成物に関するものであり、詳しくは、酸化モリブデン銀複塩と、ベンゾトリアゾール化合物もしくはそのアルカリ金属塩を含有する組成物に関するものである。 The present invention is applied to coating materials such as paints and surface treatment agents for protecting, beautifying and covering the surface of interior building materials such as walls and floors, plastics such as polyvinyl chloride, polyethylene, polypropylene and polystyrene, fibers, and non-woven fabrics. On the other hand, the present invention relates to a composition capable of imparting an antiviral function with little discoloration, and in particular, relates to a composition containing a molybdenum oxide silver double salt and a benzotriazole compound or an alkali metal salt thereof. .
ウイルスは遺伝子をもつものの、それ単独では生育できない、生物とは異なる非細胞性生物として分類されている。その遺伝子はカプシドと呼ばれる外殻タンパク質の中に保持され、遺伝子がDNAかまたはRNAかによって二種類に大別され、カプシドが脂質二重膜からなるエンベロープで覆われているものとそうでないものとに分類される。具体的には、遺伝子がDNAでエンベロープをもつものとしてヘルペスウイルス等が、遺伝子がDNAでエンベロープをもたないものとしてアデノウイルス等が、遺伝子がRNAでエンベロープをもつものとしてインフルエンザウイルス等が、遺伝子がRNAでエンベロープをもたないものとしてノロウイルス、ポリオウイルス等が挙げられる。 Viruses are classified as non-cellular organisms that have genes but cannot grow alone. The gene is retained in an outer protein called capsid, and is roughly divided into two types depending on whether the gene is DNA or RNA, and the capsid is covered with an envelope composed of a lipid bilayer and the other is not. are categorized. Specifically, herpes virus or the like is a gene whose DNA is enveloped, adenovirus is a gene whose DNA is not enveloped, influenza virus is a gene whose gene is RNA and has an envelope, Norovirus, poliovirus and the like can be mentioned as those having no envelope with RNA.
ノロウイルスやポリオウイルスのようなエンベロープをもたないウイルスは、一般的に薬剤に対する感受性が低く、厚生労働省の調査によればノロウイルスが原因とされる食中毒症例は近年ではもっとも高い割合を示していることから、ノロウイルスに対して効果を有する抗ウイルス組成物が望まれている。 Viruses without envelopes, such as norovirus and poliovirus, are generally less sensitive to drugs, and according to a survey by the Ministry of Health, Labor and Welfare, the number of food poisoning cases caused by norovirus has been the highest in recent years. Therefore, an antiviral composition having an effect on norovirus is desired.
銀をはじめとする無機金属系化合物が抗菌性に優れることもあり、近年ではそれを抗ウイルス組成物として適用する事例も見られる。例えば銀−アミノ酸錯体を含有する組成物が特許文献1に、2価銅化合物および銀化合物が共担持された酸化チタンを含む組成物が特許文献2に、銀、亜鉛および銅から選ばれる一種以上の塩と、モリブデンオキソ化合物のアルカリ塩とを反応させて得られる一種以上の複塩を含む組成物が特許文献3に示されている。しかし銀を含む化合物や錯体の多くは光や温度、水等の影響を受け変色しやすいことが知られている。 Inorganic metal compounds such as silver are sometimes excellent in antibacterial properties, and in recent years, examples of applying them as antiviral compositions have been seen. For example, Patent Document 1 discloses a composition containing a silver-amino acid complex, and Patent Document 2 discloses a composition containing titanium oxide in which a divalent copper compound and a silver compound are co-supported. One or more kinds selected from silver, zinc and copper Patent Document 3 discloses a composition containing one or more double salts obtained by reacting a salt of the above and an alkali salt of a molybdenum oxo compound. However, it is known that many of the compounds and complexes containing silver are easily discolored under the influence of light, temperature, water and the like.
高分子ポリマー組成物である、ウレタンやアクリル、塩化ビニル、酢酸ビニル、エチレン酢酸ビニル、スチレンブタジエンラテックス等の水系エマルションを含有する水系塗料やコーティング材、バインダーに対して、またはポリ塩化ビニル、ポリエチレン、ポリプロピレン、ポリスチレン等のプラスチックに対して、または繊維や不織布等に対して、経時的な変色が少なく、抗ウイルス性を付与することができる組成物を提供することにある。 High-molecular polymer composition, water-based paints and coating materials containing water-based emulsions such as urethane, acrylic, vinyl chloride, vinyl acetate, ethylene vinyl acetate, styrene butadiene latex, binder, or polyvinyl chloride, polyethylene, An object of the present invention is to provide a composition capable of imparting antiviral properties to a plastic such as polypropylene and polystyrene, or to a fiber, a nonwoven fabric, etc. with little discoloration over time.
本発明者は、上記課題を解決するために鋭意種々の研究を実施した結果、酸化モリブデン銀複塩と、一種以上のベンゾトリアゾール化合物またはそのアルカリ金属塩を添加することにより、高い抗ウイルス性と経時的な変色抑制を発揮することを見出し、本発明を完成させた。すなわち本発明は、
(1)(A)酸化モリブデン銀複塩と、(B)一般式(1)で示される一種以上の化合物もしくはそのアルカリ金属塩を含有する抗ウイルス用組成物に関する。
一般式(1)
(Rは水素またはメチル基またはカルボキシル基を表す。)また本発明は、
(2)(A)酸化モリブデン銀複塩1部に対して、(B)一般式(1)で示される一種以上のベンゾトリアゾール化合物もしくはそのアルカリ金属塩を0.03〜0.5部の割合で添加する前記(1)に記載の抗ウイルス用組成物に関する。また本発明は、
(3)前記(1)または(2)に記載の抗ウイルス用組成物を添加した抗ウイルス性コーティング材に関する。また本発明は、
(4)前記(1)または(2)に記載の抗ウイルス用組成物を添加した抗ウイルス性プラスチックに関する。また本発明は、
(5)前記(1)または(2)に記載の抗ウイルス用組成物を添加した抗ウイルス性繊維もしくは不織布に関する。また本発明は、
(6)前記(1)または(2)に記載の抗ウイルス用組成物を、高分子ポリマーを含有する組成物に対して添加する抗ウイルス性を付与する方法に関する。
As a result of diligent research to solve the above problems, the present inventor has achieved high antiviral properties by adding a silver molybdenum oxide double salt and one or more benzotriazole compounds or alkali metal salts thereof. The present invention was completed by finding that the color change over time was exhibited. That is, the present invention
(1) It relates to an antiviral composition containing (A) a molybdenum oxide double salt and (B) one or more compounds represented by the general formula (1) or an alkali metal salt thereof.
General formula (1)
(R represents hydrogen, a methyl group, or a carboxyl group.)
(2) A ratio of 0.03 to 0.5 part of (B) one or more benzotriazole compounds represented by the general formula (1) or an alkali metal salt thereof per 1 part of (A) silver molybdenum oxide double salt The antiviral composition according to (1), which is added in (1) above. The present invention also provides
(3) It is related with the antiviral coating material which added the antiviral composition as described in said (1) or (2). The present invention also provides
(4) The present invention relates to an antiviral plastic to which the antiviral composition according to (1) or (2) is added. The present invention also provides
(5) The present invention relates to an antiviral fiber or non-woven fabric to which the antiviral composition according to (1) or (2) is added. The present invention also provides
(6) The present invention relates to a method for imparting antiviral properties by adding the antiviral composition described in (1) or (2) above to a composition containing a polymer.
本発明の抗ウイルス機能を付与する組成物により、高分子ポリマーを含有する、ウレタンやアクリル、塩化ビニル、酢酸ビニル、エチレン酢酸ビニル、スチレンブタジエンラテックス等の水系エマルションを含有する水系塗料やコーティング材、バインダーに対して、または、ポリ塩化ビニル、ポリエチレン、ポリプロピレン、ポリスチレン等のプラスチックに対して、添加時だけでなく経時的な変色が少なく抗ウイルス機能を付与することが可能となる。 Water-based paints and coating materials containing water-based emulsions such as urethane, acrylic, vinyl chloride, vinyl acetate, ethylene vinyl acetate, and styrene-butadiene latex, which contain a high molecular weight polymer, according to the composition imparting antiviral function of the present invention, The anti-virus function can be imparted to the binder or to plastics such as polyvinyl chloride, polyethylene, polypropylene and polystyrene with little discoloration over time as well as when added.
本発明の抗ウイルス機能を付与する組成物としては、(A)酸化モリブデン銀複塩と、(B)一般式(1)
(Rは水素またはメチル基またはカルボキシル基を表す。)で示される一種以上の化合物またはそのアルカリ金属塩を含有する抗ウイルス組成物であるが、酸化モリブデン銀複塩としては、酸化銀とモリブデン酸化物を用いることができ、また銀塩と、モリブデンオキソ化合物のアルカリ塩とを反応させて得られる複塩を用いることもできる。この場合の銀塩としては、硝酸銀、酢酸銀、硫酸銀等、モリブデンオキソ化合物のアルカリ塩としては、モリブデン酸ナトリウム、モリブデン酸カリウム、モリブデン酸リチウム、モリブデン酸アンモニウム、ポリモリブデン酸ナトリウム、イソポリモリブデン酸ナトリウム等を用いることができる。反応方法は、銀塩の水溶液に、モリブデンオキソ化合物のアルカリ塩水溶液を添加するか、あるいはこの逆でも良い。本発明において得ようとする、銀塩とモリブデンオキソ化合物の複塩の粒子径は反応条件によって変えることが可能であり、粒子径の小さいものを得るにはモリブデンオキソ化合物のアルカリ塩、および銀塩の水溶液の濃度を低く、または撹拌速度を速くすれば良く、任意に粒子径をコントロールすることができる。好ましい粒子径は、抗ウイルス性能を付与する対象物の物性面への影響、または抗ウイルス性能等から10μm以下である。このようにして得られた好ましい粒子径を有する酸化モリブデン銀複塩は、反応液スラリーから水を濾別し、乾燥することにより粉末状で得られる。一般式(1)
(Rは水素またはメチル基またはカルボキシル基を表す。)で示される一種以上の化合物またはそのアルカリ金属塩としては、1,2,3−ベンゾトリアゾール、1,2,3−ベンゾトリアゾールナトリウム、1,2,3−ベンゾトリアゾールカリウム、4−メチルベンゾトリアゾール、5−メチルベンゾトリアゾール、トリルトリアゾール、カルボキシベンゾトリアゾール等を用いることができ、好ましくはトリルトリアゾールである。酸化モリブデン銀複塩と、一般式(1)で示される一種以上の化合物またはそのアルカリ金属塩を添加する本願発明の抗ウイルス機能を付与する対象物としては、高分子ポリマーを含有するものが好ましく、ポリ塩化ビニルやポリエチレン、ポリプロピレン、ポリスチレン等のプラスチック、ウレタンやアクリル、塩化ビニル、酢酸ビニル、エチレン酢酸ビニル、スチレンブタジエンラテックス等の水系エマルションを含有する水系塗料やコーティング材、バインダー類、ポリエステルや綿等の繊維、ポリプロピレンやポリエチレンテレフタレート等の不織布等を挙げることができる。酸化モリブデン銀複塩と、一般式(1)で示される一種以上の化合物はあらかじめ一剤化したものを対象物に添加することも可能であるし、それぞれ二剤を対象物に直前に添加することも可能である。酸化モリブデン銀複塩と、一般式(1)で示される一種以上の化合物またはそのアルカリ金属塩の比率については、前者1部に対して後者0.03〜0.5部の割合が好ましい。本発明に示す酸化モリブデン銀複塩の添加量は0.05〜5重量%が好ましく、より好ましくは0.1〜1重量%である。添加量が0.05重量%未満では抗ウイルス性能が乏しくなり、5重量%を超えると経済性の点で不利となる。
The composition imparting the antiviral function of the present invention includes (A) a silver molybdenum oxide double salt, and (B) a general formula (1).
(R represents hydrogen, a methyl group, or a carboxyl group.) An antiviral composition containing one or more compounds represented by the formula or an alkali metal salt thereof. In addition, a double salt obtained by reacting a silver salt with an alkali salt of a molybdenum oxo compound can also be used. Silver salts in this case include silver nitrate, silver acetate, silver sulfate, etc., and alkali salts of molybdenum oxo compounds include sodium molybdate, potassium molybdate, lithium molybdate, ammonium molybdate, sodium polymolybdate, and isopolymolybdenum. Sodium acid or the like can be used. The reaction may be performed by adding an aqueous alkali salt solution of a molybdenum oxo compound to an aqueous silver salt solution or vice versa. The particle diameter of the double salt of the silver salt and the molybdenum oxo compound to be obtained in the present invention can be changed depending on the reaction conditions. To obtain a small particle diameter, an alkali salt of a molybdenum oxo compound and a silver salt The concentration of the aqueous solution may be lowered or the stirring speed may be increased, and the particle size can be controlled arbitrarily. A preferable particle size is 10 μm or less in view of the influence on the physical properties of the object to which the antiviral performance is imparted or the antiviral performance. The molybdenum oxide silver double salt having a preferable particle size thus obtained is obtained in a powder form by filtering water from the reaction solution slurry and drying. General formula (1)
One or more compounds represented by (R represents hydrogen, a methyl group or a carboxyl group) or alkali metal salts thereof include 1,2,3-benzotriazole, 1,2,3-benzotriazole sodium, 2,3-benzotriazole potassium, 4-methylbenzotriazole, 5-methylbenzotriazole, tolyltriazole, carboxybenzotriazole, and the like can be used, and tolyltriazole is preferable. As the object for imparting an antiviral function of the present invention to which a molybdenum oxide silver double salt and one or more compounds represented by the general formula (1) or an alkali metal salt thereof are added, those containing a polymer are preferred. Water-based paints and coatings containing water-based emulsions such as plastics such as polyvinyl chloride, polyethylene, polypropylene, polystyrene, urethane, acrylic, vinyl chloride, vinyl acetate, ethylene vinyl acetate, styrene butadiene latex, binders, polyester and cotton And non-woven fabrics such as polypropylene and polyethylene terephthalate. It is also possible to add the silver oxide silver double salt and one or more compounds represented by the general formula (1) into a single object in advance, and add two agents immediately before the object. It is also possible. The ratio of the molybdenum oxide silver double salt to one or more compounds represented by the general formula (1) or an alkali metal salt thereof is preferably 0.03 to 0.5 part of the latter with respect to 1 part of the former. The addition amount of the molybdenum oxide silver double salt shown in the present invention is preferably 0.05 to 5% by weight, more preferably 0.1 to 1% by weight. When the addition amount is less than 0.05% by weight, the antiviral performance is poor, and when it exceeds 5% by weight, it is disadvantageous in terms of economy.
酸化モリブデン銀複塩と、一般式(1)で示される一種以上の化合物またはそのアルカリ金属塩を添加する場合においては、あらかじめ一剤化したものを塗料等に添加することにより抗ウイルス機能を付与することも可能であるし、酸化モリブデン銀複塩と、一般式(1)で示される一種以上の化合物またはそのアルカリ金属塩それぞれを塗料等に添加することにより抗ウイルス機能を付与することも可能である。抗ウイルス機能を付与する組成物においては、これら必須構成成分の他に、さらに必要に応じて無機物の増量剤、界面活性剤等の分散剤を用いて水や有機溶媒等に分散させたもの、これに粘度調整剤や酸化防止剤、防錆剤、金属封鎖剤等を配合することや、他の抗菌組成物等を配合することも可能である。 When adding molybdenum oxide silver double salt and one or more compounds represented by the general formula (1) or an alkali metal salt thereof, an antiviral function is imparted by adding a pre-mixed one to a paint. It is also possible to give antiviral function by adding silver molybdenum oxide double salt and one or more compounds represented by the general formula (1) or alkali metal salts thereof to paints, etc. It is. In the composition imparting antiviral function, in addition to these essential components, those further dispersed in water or an organic solvent using a dispersing agent such as an inorganic extender or a surfactant as necessary, Viscosity modifiers, antioxidants, rust inhibitors, metal sequestering agents, and the like can be blended therewith, and other antibacterial compositions and the like can be blended therein.
以下、実施例により本発明を具体的に説明するが、本発明はこれらの実施例によって限定されるものではない。
(酸化モリブデン銀複塩の調製方法)
モリブデン酸ナトリウム二水和物(関東化学(株))6.5gをイオン交換水100mlに溶解し、これに硝酸銀(関東化学(株))9.1gをイオン交換水100mlに溶解した溶液を撹拌しながら30分かけて滴下し沈殿物を得た。これを1時間の撹拌を行った後、濾過しイオン交換水で洗浄し、100℃で十分に乾燥することで黄白色の酸化モリブデン銀複塩約10gを得た。
EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited by these Examples.
(Method for preparing molybdenum oxide silver double salt)
6.5 g of sodium molybdate dihydrate (Kanto Chemical Co., Ltd.) was dissolved in 100 ml of ion-exchanged water, and a solution obtained by dissolving 9.1 g of silver nitrate (Kanto Chemical Co., Ltd.) in 100 ml of ion-exchanged water was stirred. While dropping over 30 minutes, a precipitate was obtained. After stirring for 1 hour, this was filtered, washed with ion-exchanged water, and sufficiently dried at 100 ° C. to obtain about 10 g of yellowish white molybdenum oxide double salt.
(抗ウイルス用組成物を添加したコーティング材の調製)
コーティング材として、ビニブラン(登録商標)897(日信化学工業(株)、シリコーンアクリル・フッ素アクリル系エマルション)、某社から入手したウレタンエマルション、某社から入手した水系UV塗料それぞれに対し、乳鉢で十分磨り潰した酸化モリブデン銀複塩ないし、一般式(1)に該当する化合物として表1〜4に示す濃度で添加し十分混合したものを市販のPPC用紙に60ml/m2となるように塗布し、ビニブラン897とウレタンエマルションは110℃で10分間加熱することで、水性UV塗料は250mW/cm2の光量を照射することでコーティング材塗布試験片を調製した。併せてこれらコーティング材を室内で保管して保管後のエマルションの変色を観察した。
(Preparation of coating material with antiviral composition added)
As a coating material, thoroughly polish it with a mortar for VINYBRAN (registered trademark) 897 (Nissin Chemical Industry Co., Ltd., silicone acrylic / fluorine acrylic emulsion), urethane emulsion obtained from a company, and water-based UV paint obtained from a company. A crushed molybdenum oxide double salt or a compound corresponding to the general formula (1) added at a concentration shown in Tables 1 to 4 and sufficiently mixed is applied to a commercially available PPC paper so as to be 60 ml / m 2 , Viniblanc 897 and urethane emulsion were heated at 110 ° C. for 10 minutes, and the aqueous UV paint was irradiated with a light amount of 250 mW / cm 2 to prepare a coating material application test piece. In addition, these coating materials were stored indoors and the discoloration of the emulsion after storage was observed.
(ネコカリシウイルスに対する抗ウイルス用組成物の抗ウイルス試験)
ヒトノロウイルスは、現在細胞培養や小動物での増殖方法が確立していないため、その有効性評価は同じカリシウイルス科に属するネコカリシウイルスで代替試験されることが一般的である。このため本実施例でもノロウイルスに対する抗ウイルス評価として、ネコカリシウイルスF−9株(Feline calicivirus、Strain:F−9 ATCC VR−782)を用い、このウイルスをCRFK細胞(ネコ腎臓由来細胞)で培養することによりウイルス感染価5×107PFU/mlの試験ウイルス懸濁液を得た。滅菌済シャーレに5cm×5cmに切り取った樹脂エマルション塗布試験片を置いて、この試験片の上に上述の試験ウイルス懸濁液を0.4ml接種し、4cm×4cmに切断したポリエチレン製の滅菌フィルムにより被覆した後、試験ウイルス懸濁液がフィルム全体に広がるように軽く押さえつけシャーレの蓋をかぶせた。これらのシャーレを37℃の高湿下で所定時間保管した後、シャーレから試験片を取出し滅菌済ストマッカー袋に入れ牛血清を終濃度10%添加したSCDLP培地10mlを加えてウイルスを洗い流し、プラーク測定法によりウイルス感染価を測定した。抗ウイルス活性値は、薬剤ブランク試料での感染価の対数値から、薬剤添加した試料の感染価の対数値を差し引いた数値として算出した。
(Antiviral test of antiviral composition against feline calicivirus)
Since human norovirus has not yet been established for cell culture or propagation in small animals, its effectiveness is generally evaluated by a feline calicivirus belonging to the same caliciviridae. Therefore, also in this example, as an antiviral evaluation against norovirus, feline calicivirus F-9 strain (Feline calicivirus, Strain: F-9 ATCC VR-782) was used, and this virus was cultured in CRFK cells (cat kidney-derived cells). As a result, a test virus suspension having a virus infectivity of 5 × 10 7 PFU / ml was obtained. A test piece of resin emulsion applied cut into 5 cm x 5 cm is placed on a sterilized petri dish, 0.4 ml of the above test virus suspension is inoculated on the test piece, and a sterile film made of polyethylene cut into 4 cm x 4 cm After coating, the test virus suspension was lightly pressed so as to spread over the entire film, and a petri dish lid was applied. After these petri dishes were stored for a predetermined time under high humidity at 37 ° C., the test pieces were taken out from the petri dishes, placed in a sterilized stomacher bag, 10 ml of SCDLP medium supplemented with 10% of bovine serum was added, and the virus was washed away to measure plaque. The virus infectivity titer was measured by the method. The antiviral activity value was calculated as a value obtained by subtracting the logarithmic value of the infectivity value of the drug-added sample from the logarithm value of the infectivity value of the drug blank sample.
(インフルエンザウイルスに対する抗ウイルス用組成物の抗ウイルス試験)
A型インフルエンザウイルス(H3N2、A/Hong Kong/8/68;TC adapted ATCC1679)を用い、このウイルスをMDCK細胞(イヌ腎臓由来細胞)で培養することによりウイルス感染価2×107PFU/mlの試験ウイルス懸濁液を得た。滅菌済シャーレに5cm×5cmに切り取った樹脂エマルション塗布試験片を置いて、この試験片の上に上述の試験ウイルス懸濁液を0.4ml接種し、4cm×4cmに切断したポリエチレン製の滅菌フィルムにより被覆した後、試験ウイルス懸濁液がフィルム全体に広がるように軽く押さえつけシャーレの蓋をかぶせた。これらのシャーレを34℃の高湿下で所定時間保管した後、シャーレから試験片を取出し滅菌済ストマッカー袋に入れ牛血清を終濃度10%添加したSCDLP培地10mlを加えてウイルスを洗い流し、プラーク測定法によりウイルス感染価を測定した。抗ウイルス活性値は、薬剤ブランク試料での感染価の対数値から、薬剤添加した試料の感染価の対数値を差し引いた数値として算出した。
(Antiviral test of antiviral composition against influenza virus)
Influenza A virus (H3N2, A / Hong Kong / 8/68; TC adapted ATCC1679) was used to culture this virus in MDCK cells (canine kidney-derived cells), resulting in a virus infection titer of 2 × 10 7 PFU / ml. A test virus suspension was obtained. A test piece of resin emulsion applied cut into 5 cm x 5 cm is placed on a sterilized petri dish, 0.4 ml of the above test virus suspension is inoculated on the test piece, and a sterile film made of polyethylene cut into 4 cm x 4 cm After coating, the test virus suspension was lightly pressed so as to spread over the entire film, and a petri dish lid was applied. After these petri dishes are stored for a predetermined time under high humidity at 34 ° C., test pieces are taken out of the petri dishes, put into a sterilized stomacher bag, 10 ml of SCDLP medium supplemented with 10% of bovine serum is added, and the virus is washed away to measure plaque. The virus infectivity titer was measured by the method. The antiviral activity value was calculated as a value obtained by subtracting the logarithmic value of the infectivity value of the drug-added sample from the logarithm value of the infectivity value of the drug blank sample.
コーティング材としての配合、これらコーティング材を1週間保管した後の変色の様子、ネコカリシウイルスおよびインフルエンザウイルスに対する抗ウイルス活性値を表1〜4に示す。変色については以下の基準により判定した。
◎:全く変色が認められない
○:ほとんど変色が認められない
×:明らかな変色が認められる
Tables 1 to 4 show the formulation as coating materials, the state of discoloration after storing these coating materials for 1 week, and the antiviral activity values against feline calicivirus and influenza virus. Discoloration was determined according to the following criteria.
A: No discoloration is observed. ○: Almost no discoloration is observed. X: Clear discoloration is observed.
本発明の抗ウイルス用組成物は、(A)酸化モリブデン銀複塩と、(B)ベンゾトリアゾール化合物を含有することにより、これらを添加したコーティング材、プラスチック、繊維や不織布等の変色が少なく、高い抗ウイルス性を付与することが可能となり、貯蔵安定性の向上による経済性の利点や衛生環境の改善に寄与するものである。
The antiviral composition of the present invention contains (A) a molybdenum oxide double salt and (B) a benzotriazole compound, so that there is little discoloration of coating materials, plastics, fibers, nonwoven fabrics, etc. to which these are added, High antiviral properties can be imparted, which contributes to economic advantages and improved hygienic environment due to improved storage stability.
Claims (6)
一般式(1)
(Rは水素、メチル基またはカルボキシル基を表す。) An antiviral composition comprising (A) a silver salt of molybdenum oxide and (B) one or more benzotriazole compounds represented by the general formula (1) or an alkali metal salt thereof.
General formula (1)
(R represents hydrogen, a methyl group or a carboxyl group.)
A method for imparting antiviral properties, comprising adding the antiviral composition according to claim 1 or 2 to a composition containing a polymer.
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