Virus inactivator
Abstract
It is a virus inactivation agent which can demonstrate an inactivating action accompanied by structural destruction of denaturation, decomposition, etc. to a virus, A virus inactivation agent which contains 1 value copper compounds, such as copper I oxide, the first copper of sulfuration, copper iodide, or a cuprous chloride, as an active ingredient, and virus inactivation material which contains the virus inactivation agent in the substrate surface and/or an inside.

Term
No projected expiry on record.
- Priority and filed
- Published
- Today
14 claims: 4 independent, 10 dependent
- 1一価銅化合物を有効成分として含むウイルス不活化剤。
- 2一価銅化合物が酸化第一銅、硫化第一銅、ヨウ化第一銅、及び塩化第一銅からなる群から選ばれる1種又は2種以上の化合物である請求項1に記載のウイルス不活化剤。
- 3微粒子形態の一価銅化合物を含む請求項1に記載のウイルス不活化剤。
- 41種又は2種以上の一価銅化合物とともに1種又は2種以上の光触媒物質を含む請求項1に記載のウイルス不活化剤。
- 5光触媒物質が可視光応答性光触媒物質である請求項4に記載のウイルス不活化剤。
- 6一価銅化合物及び光触媒物質を含む組成物の形態である請求項4又は5に記載のウイルス不活化剤。
- 7一価銅化合物及び二価銅化合物を含む混合物を表面に担持した光触媒物質を含む請求項4に記載のウイルス不活化剤。
- 8請求項1~7のいずれか1項に記載のウイルス不活化剤を基材表面及び/又は内部に含むウイルス不活化材料。
- 9ウイルス不活化剤をバインダーを用いて基材表面に固定化した請求項8に記載のウイルス不活化材料。
- 10樹脂中にウイルス不活化剤を分散させた分散物を硬化させることにより得ることができる請求項8に記載のウイルス不活化材料。
- 11請求項1~7のいずれか1項に記載のウイルス不活化剤を含むコーティング剤。
- 12請求項7に記載のウイルス不活化剤の製造方法であって、二価銅化合物と酸化チタン粒子とを含む懸濁液に還元剤を添加する工程を含む方法。
- 13還元剤がアルデヒド結合を含む物質である請求項12に記載の方法。
- 14一価銅化合物及び二価銅化合物を含む混合物を表面に担持した光触媒物質。
Independent claims14
48 paragraphs, as filed
Virus inactivation agent
The present invention relates to a virus inactivation agent which demonstrates inactivating actions, such as denaturation and decomposition, to viruses, such as an influenza virus.
The former, a silver ion (Ag)<sup>+</sup>Zinc ion (Zn)<sup>2+</sup>And a 2 value copper ion (Cu)<sup>2+</sup>etc. -- a metal ion controlling multiplication of a microorganism or acting in sterilization to a microorganism is knownMuch antimicrobial materials which made substances, such as zeolite and silica gel, support these metal ions, antimicrobial materials combined with titanium oxide which has a photocatalyst operation, etc. are developed.
About antimicrobial [of a 2 value copper ion], or an antiviral action, A structural change of a cell membraneAnd a functional destructive operation (Progress*in*Medicinal*Chemistry, *31, *pp. 351-370, *1994) and a 変成 operation on nucleic acid (CRC*Critical*Rev. *Environ. *Cont., *18, *pp. 295-315) * 1989 is solved, With a virusTo a receiving operation of a 2 value copper ionFor Sangripanti and others [therefore, ] (Appl. *Environ. *Microbiol., *58, *pp. 3157-3162, *1992;*Appl. *environ. *microbiol., *59, *pp. 4374-4376, *1993; with a report to depend*AIDS*Res. *Hum. *Retrovir., *12, *pp. 333-336, *1996;*Antimicrob. *Agent*Chemother., *41, *pp. 812-817, *1997). They are a thin film, or CuO and titanium oxide (TiO) of copper oxide (II) (CuO) about a glass surface.<sub>2</sub>It has been reported that material covered with an included thin film has a phage inactivating action in a bacteriophage T4 experiment system (virus inactivation model) (Appl. *Microbiol. *Biotechnol., *79, *pp. 127-133, *2008).
A 1 value copper compound to bacteria, such as a methicillin-resistant staphylococcus aureus (MRSA), coliform bacillus, and 緑膿菌, on the other hand although there is almost no report conventionally about an antimicrobial operation of a 1 value copper compound (Cu)<sub>2</sub>An antibacterial action (MBC) of O) is inferior compared with a 2 value copper compound (CuO) or metal copper (Cu), A thing weak farther than silver (Ag) has been reported (*pp. 587- International*Journal*of*Antimicrobial*Agents, *33, 590, *2009, especially Table*1 of p. 589). It is although a bacteriostatic action to a bacillus bacillus, Staphylococcus aureus, 緑膿菌, etc. (Media Interface Connector) has a crystal form difference although there is also a report about a difference in an antibacterial action by crystal many forms of copper I oxide (Chem. *Commun. and *pp. 1076-1078, *2009), It has not been reported that especially an antibacterial action has a 1 value copper compound stronger than a 2 value copper compound..
About an antiviral action of a 1 value copper compound, a nanoparticle to average-particle-diameter abbreviation 500*nm which has an antiviral action in 特 table No. 526828 [2009 to] gazette is indicated, and the nanoparticle is Cu in a paragraph number [0020] of the gazette.<sub>2</sub>There is explanation that O may also be included. However, in the above-mentioned publication, it is Cu.<sub>2</sub>An antiviral action of the O itself is not indicated concretely and the person skilled in the art cannot understand whether a 1 value copper compound has an inactivating action to a virus based on an indication of the above-mentioned publication.
<p><patcit num="1"><text>特 table No. 526828 [2009 to] gazette</text></patcit></p>
<p><nplcit num="1"><text>Progress*in*Medicinal*Chemistry, *31, *pp. 351-370, *1994</text></nplcit><nplcit num="2"><text>CRC*Critical*Rev. *Environ. *Cont., *18, *pp. 295-315, *1989</text></nplcit><nplcit num="3"><text>Appl. *Environ. *Microbiol., *58, *pp. 3157-3162, *1992</text></nplcit><nplcit num="4"><text>Appl. *environ. *microbiol., *59, *pp. 4374-4376, *1993</text></nplcit><nplcit num="5"><text>AIDS*Res. *Hum. *Retrovir., *12, *pp. 333-336, *1996</text></nplcit><nplcit num="6"><text>Antimicrob. *Agent*Chemother., *41, *pp. 812-817, *1997</text></nplcit><nplcit num="7"><text>Appl. *Microbiol. *Biotechnol., *79, *pp. 127-133, *2008</text></nplcit><nplcit num="8"><text>International*Journal*of*Antimicrobial*Agents, *33, *pp. 587-590, *2009</text></nplcit><nplcit num="9"><text>Chem. *Commun., *pp. 1076-1078, *2009</text></nplcit></p>
<p num="0008">There is a subject of the present invention in providing a virus inactivation agent which can demonstrate an inactivating action accompanied by structural destruction of denaturation, decomposition, etc. to a virus.</p>
<p num="0009">As a result of inquiring wholeheartedly that the above-mentioned subject should be solved, these artificers compare with 2 value copper compounds, such as the second copper (CuO) of oxidization, and the second copper (CuS) of sulfuration, and are copper I oxides (Cu).<sub>2</sub>O), the first copper of sulfuration (Cu)<sub>2</sub>It found out that 1 value copper compounds, such as S), copper iodide (CuI), and cuprous chloride * (CuCl), had a far strong inactivating action to a virus. It also found that a remarkable virus inactivation operation is attained also in a constituent which combined a photocatalyst substance and 1 value copper compounds, such as titanium oxide and metal support titanium oxide. The present invention is completed based on the above-mentioned knowledge.</p><p num="0010">That is, a virus inactivation agent which contains a 1 value copper compound as an active ingredient is provided by the present invention. The above-mentioned virus inactivation agent which are one sort or two sorts or more of compounds in which a 1 value copper compound is chosen from a group which consists of copper I oxide, the first copper of sulfuration, copper iodide, and a cuprous chloride according to the desirable mode of the present invention; the above-mentioned virus inactivation agent containing copper I oxide of particulate morphology is provided.</p><p num="0011">According to another desirable mode, the above-mentioned virus inactivation agent whose above-mentioned virus inactivation agent; and photocatalyst substance which contain one sort or two sorts or more of photocatalyst substances with one sort or two sorts or more of 1 value copper compounds are a visible light response photocatalyst substance is provided.</p><p num="0012">According to the desirable mode, the above-mentioned virus inactivation agent which is the photocatalyst substance which supported on the surface a mixture in which above-mentioned virus inactivation agent; and the photocatalyst substance which are the forms of a constituent containing a 1 value copper compound and a photocatalyst substance contain a 1 value copper compound and a 2 value copper compound is provided.</p><p num="0013">By the present invention, virus inactivation material which contains the above-mentioned virus inactivation agent in the substrate surface and/or an inside is provided. According to a desirable mode of this inventionThe above-mentioned virus inactivation agentAn included coating agent; virus inactivation material which fixed the above-mentioned virus inactivation agent on the substrate surface; virus inactivation material which fixed the above-mentioned virus inactivation agent on the substrate surface using a binder; a distributed thing which distributed the above-mentioned virus inactivation agent in resin is stiffened. Virus inactivation material which can be obtained; the above-mentioned virus inactivation material whose resin is a natural resin or a synthetic resin is provided.</p><p num="0014">From another viewpoint, use of a 1 value copper compound for manufacture of a method; of being the method of carrying out inactivation of the virus, and including a process which contacts a virus to a 1 value copper compound by the present invention, and the above-mentioned virus inactivation agent is provided.</p><p num="0015">It is a manufacturing method of a virus inactivation agent containing a photocatalyst substance which supported on the surface a mixture containing a 1 value copper compound and a 2 value copper compound, and a method of including a process of adding a reducing agent in suspension containing a 2 value copper compound and titanium oxide particles is provided. From another viewpoint, a photocatalyst substance which supported on the surface a mixture containing a 1 value copper compound and a 2 value copper compound is provided by the present invention.</p>
<p num="0016">There is the feature that the virus inactivation agent provided by the present invention can demonstrate an inactivating action accompanied by structural destruction of denaturation, decomposition, etc. to various viruses, such as an influenza virus, and it can demonstrate an inactivating action also in a dark place besides a bright place. An inactivating action can be demonstrated under existence of a dry state and water or coexistence of an organic matter etc. For example, it can reach far and wide by blending into a coat formed of a paint, a floor polish, etc., inactivation of the virus can be carried out efficiently, and inactivation of the virus can also be locally carried out by blending with resin casts, such as a plastic article. Since a virus inactivation operation can be demonstrated under nonexistence of visible light or purple outdoor daylight by applying in a filter inside an air wash opportunity, a warehouse, or a refrigerator etc., it is useful.</p>
<figref num="1">It is a key map of a test method (Example 1 and Example 2) of phage inactivation ability.</figref><figref num="2">It is a figure showing an effect of a virus inactivation agent of the present invention. WL shows a test result [in / in Dark / a dark place] under white light irradiation among a figure.</figref><figref num="3">It is a figure showing an effect of a virus inactivation agent of the present invention to T4 phage.</figref><figref num="4">It is a figure showing an effect of a virus inactivation agent of the present invention to an influenza virus. WL shows a test result [in / in Dark / a dark place] under white light irradiation among a figure.</figref><figref num="5">It is a figure showing an effect of a virus inactivation agent of the present invention fixed in a glass substrate using a binder.</figref><figref num="6">It is a figure showing an effect of a virus inactivation agent of a form of a constituent containing copper I oxide and a photocatalyst substance.</figref><figref num="7">Cu used in Example 1<sub>2</sub>It is a scanning electron microscope image of O powder.</figref><figref num="8">It is a figure showing how to evaluate a virus inactivation operation in a dry state.</figref><figref num="9">It is a figure showing an effect of a virus inactivation agent of the present invention in a dry state.</figref><figref num="10">It is a figure showing an effect of a virus inactivation agent of the present invention to a sample which made gelatin live together as an organic matter.</figref><figref num="11">When you make it repeatedly exposed to a virus in underwater, a virus inactivation agent of the present invention is a figure showing demonstrating a continuous inactivating action. The inside of a figure and the upper left are Cu (s).<sub>2</sub>O milt balloon and the lower right are Cu (s).<sub>2</sub>A result of O powder is shown.</figref><figref num="12">It is a figure showing an X diffraction (XRD) pattern and XPS (X ray photoelectron spectrum) of particles which were obtained in Example 9.</figref><figref num="13">It is a figure showing a visible-purple outside absorption spectrum of complex particles obtained in Example 9.</figref><figref num="14">It is a figure showing a result of having analyzed composition with an image and an energy dispersion form X-rays spectroscope (EDX) which observed complex particles obtained in Example 9 with a transmission electron microscope.</figref><figref num="15">It is a figure showing a result of having checked 2-propanol (IPA) disintegration under visible light irradiation about complex particles obtained in Example 9.</figref><figref num="16">It is a figure showing a result of having evaluated a virus inactivation operation about complex particles obtained in Example 9. Complex particles (0.25%*CuxO/TiO)<sub>2</sub>+8 times the amount of glucose NaOH</figref>
Although a term of a virus as used herein means a DNA virus or a RNA virus, a bacteriophage infected with bacteria is also included. Although a candidate for application in particular of a virus inactivation agent of the present invention is not limitedFor example, an influenza virus, a hepatitis virus, a meningitis virus, A human immunodeficiency virus (HIV), an adult-T-cell-leukemia virus, an Ebola-hemorrhagic-fever virus, A yellow fever virus, a rabies virus, a cytomegalovirus, severe acute respiratory syndrome (SARS) (a virus, a chickenpox virus, a German measles virus, a poliomyelitis virus, a measles virus, a mumps virus, etc. can be mentioned.) Viruses infected aerially, such as a SARS virus and an influenza virus, can be mentioned as a desirable object. But it is not necessarily limited to these specific modes.
As an active ingredient of a virus inactivation agent of the present invention, one sort or two sorts or more of 1 value copper compounds can be used. Especially a kind of 1 value copper compound is copper I oxide (Cu), for example, although not limited.<sub>2</sub>O), the first copper of sulfuration (Cu)<sub>2</sub>S) or copper iodide (CuI), a cuprous chloride (CuCl), etc. can be mentioned.
Although arbitrary sizes and a 1 value copper compound of arbitrary crystal forms can also be used as it is as a virus inactivation agent of the present invention, It is preferred to use a 1 value copper compound etc. of a form of a particulate granular material prepared by a 1 value copper compound, a mechanical grinding process, etc. of a crystal state prepared by particulate morphology according to a proper chemical process. When using a 1 value copper compound by particulate morphology, particle diameter in particular of particulates is not limited, but particulates whose average particle diameter is about 1*nm-1, 000micrometer can be used, for example. A minimum of average particle diameter is 1 micrometer or more especially preferably 500*nm or more still more preferably preferably a 100*nm grade or more than it more preferably a 200*nm grade, or more. Although a maximum in particular of average particle diameter is not limited, it is the range of 800 micrometers or less, more preferably 500 micrometers or less preferably. For example, copper I oxide (Cu)<sub>2</sub>When using O), different crystallized type particulates on condition of versatility can be prepared, but (Chem. *Commun. and *pp. 1076-1078, *2009) copper I oxide of arbitrary particle diameter and a crystal form can be used.
As a 1 value copper compound, it is not limited to a letter substance of a crystal, and a substance of arbitrary forms, such as a micro crystallite-like substance whose mixture of arbitrary rates of an amorphous-like substance, a crystal, and an amorphous-like substance or periodicity is not perfect, can be used. A 1 value copper compound may contain a little 2 value copper compounds, unless a virus inactivation operation is checked. For example, it is also possible to use particulates etc. which contain 1 value copper and 2 value copper at a proper rate as a 1 value copper compound. Therefore, a term of "1 Value copper compound" used in this specification must not be restrictively interpreted in any meanings, and it must interpret in a broad sense most.
A virus inactivation agent of this specification can be used also in a dark place besides under light existence under infrared light existence, visible light existence, and purple outdoor daylight existence etc. A "dark place" as used herein means the state where light does not exist substantially, Visible light etc. whose wavelength is more specifically a 400 - 800*nm gradeLight of a purple outdoor daylight line (UV-A of UV-B of UV-C of wavelength 10 - 280*nm, wavelength 280 - 315*nm and wavelength 315 - 400*nm) originating in a germicidal lamp, sunrays, etc. or an infrared light line (wavelength 800* - 400, 000*nm grade) means the state where it does not exist substantially.
As a virus inactivation agent of the present invention, a virus inactivation agent containing one sort or two sorts or more of 1 value copper compounds, one sort, or two sorts or more of photocatalyst substances can also be used, for example. A photocatalyst substance as used herein means a substance which has a photoinduced degradation operation and/or an optical induction hydrophilicity-ized operation which act [photocatalyst], namely, disassemble an organic matter. Especially as a photocatalyst substance, a substance excellent in a photoinduced degradation operation can be used conveniently. As a photocatalyst substance, a purple outdoor daylight response type photocatalyst substance, a visible light 応光触媒 substance, etc. can be used. Thus, demonstrating photoinduced degradation activity under purple outdoor daylight existence and visible light existence by using a virus inactivation agent which combined a 1 value copper compound and a photocatalyst substance, a virus inactivation operation can also be demonstrated and also sufficient virus inactivation operation can be attained also in a dark place.
Although a ratio in particular of a 1 value copper compound and a photocatalyst substance is not limited to when using a virus inactivation agent containing a 1 value copper compound and a photocatalyst substance as a virus inactivation agent, a 1 value copper compound can be used in 0.1% - about 95% of range, for example to mass of a photocatalyst substance. Usually, a 1 value copper compound and a photocatalyst substance may be mixed so that predetermined may become comparatively, and a constituent may be prepared.
Hereinafter, although an usable photocatalyst substance is concretely explained in combination with a 1 value copper compound in a virus inactivation agent of the present invention, in the present invention, an usable photocatalyst substance is not limited to the following concrete substance.
Among photocatalyst substances, a purple outdoor daylight response type photocatalyst substance is a substance which has a photocatalyst operation under existence of light containing purple outdoor daylight below 400*nm, and can use a titanium oxide photocatalyst typically. A photoinduced degradation operation in a titanium oxide photocatalyst is an operation to which generation, an electron hole which has carried out surface diffusion, a molecule by which an electron is sticking to the surface, and an oxidation-reduction reaction are performed by purple outdoor daylight excitation of 3.0 eV or more.
Titanium oxide which various titanium oxide photocatalysts which have a photoinduced degradation operation are known, for example, has arbitrary crystal structures, such as a アナターゼ type, a rutile type, and a brookite type, can be used. These titanium oxide can be prepared by publicly known methods, such as the gaseous phase oxidizing method, a sol gel process, or a hydrothermal method. One sort or two sorts of metal chosen, for example from platinum group metals, such as platinum, palladium, rhodium, and ルテニウム, can also be made to contain as a photocatalyst catalyst with titanium oxide. Although the amount in particular of photocatalyst catalyst used is not limited, a photocatalyst catalyst can be made into about 1 to 20% of the weight of a rate to the total quantity of titanium oxide and a photocatalyst catalyst, for example.
These days, As the visible light response photocatalyst which demonstrates photocatalyst activity under visible light, such as indoor lightNitrogenDoped titanium oxide catalyst (Science, *293, *pp. 269-271, *2001;*J. *Phys. *Chem. *B, *107, *pp. 5483-5486, *2003;*Thin*Solid*Films, *510, *pp. 21-25, *2006) is proposed. As the visible light response photocatalyst of a structure different from it, It is a nano cluster of a copper compound and/or an iron compound to titanium oxide. Titanium oxide and tungstic oxide which were made to support are also proposed. (J. *Am. *Chem. *Soc., *129, *pp. 9596-9597, *2007;*Chem. *Phys. *Lett., *457, *pp. 202-205, *2008;J. *Phys. *Chem. *C., *113, *pp. 10761-) 10766, *2009;*J. *Am. *Chem. *Soc., *132, *pp. 6898-6899, *2010;*J. *Am. *Chem. *Soc., *132, *pp. 15259-15267, *2010*. Under visible light irradiation, for example, light containing light of 400 - 530*nm, these visible light response type photocatalysts have photocatalyst activity. Although these visible light 応光触媒 substances can be mixed with a 1 value copper compound and it can also be used with a form of a constituent, a visible light response catalyst substance is not limited to the above-mentioned specific catalyst.
More specifically as a visible light response type photocatalyst substance, it is, For example, a substance of a form of a constituent including combination of at least one sort of photocatalysts chosen from a group which consists of the (A) copper compound and/or an iron compound, (B) tungstic oxide, titanium oxide, and titanium oxide that controlled a conducting zone by doping is preferred.
As a copper compound and an iron compound which are used as the above-mentioned (A) ingredient, copper 2 value salt and the Tetsuzo value salt to a photocatalyst of the (B) ingredient which can perform electron transfer smoothly as a reduction catalyst of oxygen are preferred. As copper 2 value salt or Tetsuzo value salt, hydrogen halide salt (hydrogen fluoride salt, hydrogen chloride salt, hydrogen bromide salt, hydrogen iodide salt), acetate, sulfate, a nitrate, etc. can be mentioned, for example. (A) It is preferred to be able to use as an ingredient one sort or two sorts or more of arbitrary compounds chosen from a group which consists of a copper compound and an iron compound, and to make the surface of a photocatalyst of the (B) ingredient support the (A) ingredient.
(B) It is indicated by JP, 2008-149312, A that combination of tungstic oxide which is an ingredient, and a copper compound as a catalyst active catalyst which is the (A) ingredient is useful as a visible light response type photocatalyst, It is indicated by a report photocatalyst, *28, *pp. 4, and *2009 that tungstic oxide which supported a copper ion and ferric iron is useful as a visible light response type photocatalyst. As the method of combining a copper compound and tungstic oxide, For example, a method of carrying out 1-5 mass % grade mixture of the CuO powder to tungstic oxide powder, Polar solvent solution which contains copper 2 value salt (a copper chloride, copper acetate, copper sulfate, a cupric nitrate, etc.) in tungstic oxide powder can be added, and it can mix, and can use a method of calcinating at temperature of about 500-600 ℃ after a drying process, and making the tungstic oxide surface supporting a copper ion etc. The amount of support of a copper ion can be suitably chosen in consideration of quality of a visible light response type photocatalyst, etc., and is not limited in particular.
In order to prepare a visible light response type photocatalyst using titanium oxide, it is preferred to consider it as copper ornamentation titanium oxide or iron ornamentation titanium oxide, combining the (A) ingredient. Although a crystal form in particular of titanium oxide used as materials is not limited, titanium oxide which has a crystal structure of a アナターゼ type, a rutile type, or a brookite type, for example can be used.
As the copper ion kind which exists in the surface of copper ornamentation titanium oxide, For example, a copper ion kind originating in copper chloride (II), copper acetate (II), copper sulfate (II), cupric nitrate (II), copper fluoride (II), copper iodide (II), copper bromide (II), etc. can be used, and a copper ion kind originating in copper chloride (II) can be used preferably. A copper ion kind is generated by physicochemical changes of decomposing or oxidizing copper compounds, such as copper chloride (II), on titanium oxide, such as a chemical reaction and precipitation.
Although the amount of ornamentation in particular by a copper ion kind is not limited, from a viewpoint of improvement in performance of a photocatalyst, they are more than 0.05 mass %, preferably more than 0.1 mass % in metal copper (Cu) conversion to titanium oxide, and are below 0.3 mass % from a viewpoint of condensation control of a copper ion kind, and degradation prevention of a photocatalyst, for example.
Copper ornamentation titanium oxide can be manufactured according to a process of hydrolyzing a titanium compound which generates titanium oxide, for example in reaction solution, and a process of mixing solution which contains a copper ion kind in solution after hydrolysis, and performing surface ornamentation of titanium oxide.
In a hydrolysis process, titanium chloride solution can be hydrolyzed, for example, titanium oxide slurry can be obtained, and arbitrary crystal forms can be manufactured by changing conditions of solution at the time of hydrolysis. For example, titanium oxide particles whose brookite content is seven to 60 mass %, and a brookite crystal whose crystal child size is a 9 - 24*nm grade can be obtained. For example, a process which added a process of performing hydrolysis and maturing in 60-101 ℃, and considering dropping speed of titanium tetrachloride solution as a part for 0.6*g - 2.1*g/, or doing 5-20 mass % dropping of chloride, or combined these arbitrarily can be added.
The surface ornamentation process can embellish a copper ion kind on the surface of titanium oxide efficiently by carrying out the range of 80-95 ℃, preferably, for example in 90-95 ℃. A method by which ornamentation of a copper ion kind is indicated, for example to a report photocatalyst, *28, *pp. 4, and *2009, After mixing a method of washing and collecting after specifically mixing photocatalyst particles and a copper chloride under heating in a medium or photocatalyst particles, and a copper chloride under heating in a medium, it can carry out by a method of evaporating to dryness and collecting, etc.
A アナターゼ type, a rutile type, or brookite type any may be sufficient as a crystal form of titanium oxide in iron ornamentation titanium oxide, and they may be these arbitrary mixtures. It is preferred to use titanium oxide with high crystallinity in the case of iron ornamentation titanium oxide, and it is preferred that there is little content of amorphous titanium oxide or titanium hydroxide.
Titanium oxide in which a conducting zone was controlled by doping, It is the titanium oxide which doped a metal ion which can expect an effect of shifting conducting-zone lower end potential of titanium oxide to the positive potential side, or a metal ion which can expect an effect which forms isolated semi- grade in the positive potential side of conducting-zone lower end potential of titanium oxide. As a metal ion which can expect the above-mentioned effect, tungsten (VI), gallium (III), cerium (IV), germanium (IV), or barium (V) can be mentioned, and it may use combining these two or more sorts, for example. As desirable titanium oxide in which a conducting zone was controlled by doping, tungsten dope titanium oxide and tungsten gallium can mention dope titanium oxide etc., for example. A visible light response type catalyst which made a mixture which combined these dope titanium oxide with a copper compound and an iron compound of the (A) ingredient, and the surface of dope titanium oxide support copper 2 value salt and/or Tetsuzo value salt is preferred.
Although a form in particular of titanium oxide doped is not limited, for example, particulate-like titanium oxide, filmy titanium oxide, etc. can be used, it is preferred to use titanium oxide of particulates with large specific surface area. A crystal structure in particular of titanium oxide is not limited, but can use a rutile type, a アナターゼ type, brookite type crystals, or those arbitrary mixtures. When titanium oxide includes a rutile type crystal as the main ingredients, it is preferred that it is the content more than 50 mass %, and it is still more preferred that it is the content more than 65 mass %. The same may be said of a case where a アナターゼ type or brookite type crystal is included as the main ingredients.
As for a molar ratio (W:Ti molar ratio) of tungsten and titanium, when performing a dope by tungsten, it is preferred that it is the range of 0.01:1 to 0.1:1, It is more preferred that it is the range of 0.01:1 to 0.05:1, and it is still more preferred that it is the range of 0.02:1 to 0.04:1. When a 共 dope of tungsten and gallium is performed, It is ideal that a molar ratio (W:Ga molar ratio) of tungsten and gallium is [1:2] near, It is preferred that it is in the range of at least 1:1.5 to 1:2.5, it is more preferred that it is the range of 1:1.7 to 1:2.3, and it is still more preferred that it is the range of 1:1.8 to 1:2.2. Quantity of copper 2 value salt supported by the surface of dope titanium oxide or Tetsuzo value salt is a 0.0001 - 1 mass % grade to the photocatalyst substance whole quantity, and it is more preferred that it is 0.01 to 0.3 mass %.
A visible light response type photocatalyst which made the surface of dope titanium oxide support copper 2 value salt and/or Tetsuzo value salt, For example, tungsten dope titanium oxide or tungsten gallium can be manufactured according to a metal salt support process of making a doping process of obtaining dope titanium oxide and copper 2 value salt, and/or Tetsuzo value salt supporting.
The method; (3) gaseous-phase method for manufacturing dope titanium oxide, when a doping process mixes solution which contains tetravalent titanium salt in a dopant solution heated by method; (2) prescribed temperature which manufactures dope titanium oxide with (1) sol-gel method, for example, Gas containing volatile titanium compound steam and volatile tungsten compound steam, Or tungsten 6 value salt or tungsten 6 value salt, and gallium acid-ized salt are supported on the surface of a method; and titanium oxide powder which manufactures dope titanium oxide by mixing gas which contains volatile gallium compound steam further with gas containing oxidizing gas, It can carry out by a method of manufacturing dope titanium oxide, by calcinating at temperature of about 800-1, 000 ℃.
A process of supporting copper 2 value salt and/or Tetsuzo value salt on the surface of dope titanium oxide can be performed by a method of making copper 2 value salt and/or Tetsuzo value salt supporting as thinly as possible so that copper 2 value salt and/or Tetsuzo value salt can maintain a high dispersion state by the shape of a particulate in the dope titanium oxide surface. Preferably, this process can contact solution of dope titanium oxide, copper 2 value salt, and/or Tetsuzo value salt, can be heated at temperature of about 85-100 ℃, preferably about 90-98 ℃, and can be performed by a method of filtration, centrifugal separation, etc. recovering a solid after that, and performing sufficient flush.
As a virus inactivation agent of the present invention, a virus inactivation agent of a form of a constituent containing a 1 value copper compound and a photocatalyst substance may be used. In order to make a high antiviral effect and photocatalyst activity make compatible, a virus inactivation agent which made the surface of a photocatalyst substance support a mixture containing a 1 value copper compound and a 2 value copper compound can also be used. a desirable mode of a virus inactivation agent which made the surface of a photocatalyst substance support a mixture containing a 1 value copper compound and a 2 value copper compound -- as a photocatalyst substance -- titanium oxide -- still more preferably particles of titanium oxide can be used. Although particle diameter in particular of titanium oxide particles is not limited, they are 5*nm - a 1, 000*nm grade, for example. A nano cluster of a mixture containing copper oxide of 1 value and copper oxide of 2 values can be made to be able to form in the surface of particles of a photocatalyst substance, preferably a photocatalyst substance, and it can be made to support with a desirable mode. Although a 1 value copper compound or a 2 value copper compound contained in the mixture may be crystal form voice, it may be amorphous [-like] and may be in a state where a crystal and アモルファス live together. It is preferred that both a 1 value copper compound and a 2 value copper compound are supported by the surface of a photocatalyst substance as an amorphous-like substance.
As a method of making a nano cluster containing a mixture of copper oxide of 1 value, and copper oxide of 2 values forming in the surface of titanium oxide particles, a method including a process of adding a reducing agent can be mentioned to suspension containing a 2 value copper compound and titanium oxide particles, for example. Although suspension containing a 2 value copper compound and titanium oxide particles can preferably be prepared and a method including a process of adjusting pH to nine or more and adding a reducing agent, and a method of maintaining temperature of the suspension at 60 ℃ or more in a described method can be listed under a basic condition, It is not necessarily limited to these specific methods.
As a reducing agent, they are an alkaline metal, alkaline-earth metals, and aluminum, for example, Amalgam of zinc, and an alkaline metal and zinc, a hydrogenation thing of boron or aluminum, At least one sort of substances chosen from a group which consists of metal salt of a low oxidation state, hydrogen sulfide, a sulfide, thiosulfate salt, oxalic acid, formic acid, ascorbic acid, a substance that has aldehyde binding, an alcoholic compound containing phenol, etc. can be used. Preferably, a substance which has aldehyde binding can be used as a reducing agent. As a substance which has aldehyde binding, although sugars, more preferably glucose can be used, it is not limited to these, for example. Sugars are desirable reducing agents from it being cheap, and there being no toxicity and being able to remove easily by general-purpose operation of washing etc. after a reduction reaction. When reacting by adjusting to base suspension containing a 2 value copper compound and titanium oxide particles, regulation of pH can generally be performed using alkali metal hydroxide, such as metal hydroxide, for example, sodium hydroxide etc., but it is not limited to when performing a reaction under basic conditions.
Although a concrete example of the above-mentioned manufacturing method is shown, the present invention is not limited to this. (For example, a 2 value copper compound, for example, CuCl)<sub>2</sub>titanium oxide particles are suspended to の水溶液 -- warming -- the bottom of more than, for example, 60 ℃, preferably about 90 ℃ -- several hours, preferably after agitating for about 1 hour and preparing suspension -- this suspension -- sodium hydroxide (NaOH/Cu)<sup>2+</sup>= 0-8, and sugars (for example, glucose etc. : an aldehyde compound/Cu)<sup>2+</sup>= adding 4 -- pH nine or more conditions -- further -- warming -- drying, the bottom, preferably after ろ取 (ing) and washing still more preferably several hours, preferably a solid produced by agitating for about 1 hour at about 90 ℃ 60 ℃ or more -- copper oxide (Cu)<sub>X</sub>O) A nano cluster can prepare titanium oxide particles supported by the surface. Particulates obtained by this reaction are R-CHO+2CU.<sup>2+</sup>+4OH<sup>-</sup>->R-COOH+Cu<sub>2</sub>O+2H<sub>2</sub>Cu which arises by the reaction denoted by O<sub>2</sub>Cu which makes O the main ingredients<sub>X</sub>A nano cluster of O (mixture of copper oxide of 1 value and 2 values) is TiO.<sub>2</sub>It is the complex particles supported on the surface of particles, and can use it conveniently in the present invention as complex particles which unite and have a photoinduced degradation operation and a virus inactivation operation.
Although the type of usage in particular of a virus inactivation agent of the present invention is not limitedFor example, a proper container can be filled up with solid-like forms, such as fine powder and granulation, and it can be used as it is, or can be used for the surface and/or an inside of arbitrary substrates according to a form containing a virus inactivation agent, and, generally the latter mode is preferred. "Virus inactivation material" as used herein means material which contains the above-mentioned virus inactivation agent the surface and/or inside a substrate. Although a compound substrate which consists of a substrate and two or more sorts of members which consist of general single members, such as metal, ceramics, and glass, for example as a substrate can be mentioned, it is not limited to these. Material which contains the above-mentioned virus inactivation agent in a coating agent which can exfoliate by a proper means like a floor polish is also included by virus inactivation material of the present invention. Complex particles which made the surface of titanium oxide particles support a nano cluster containing a mixture of copper oxide of 1 value and copper oxide of 2 values can be fixed on a film, and a nano cluster containing a mixture of copper oxide of 1 value and copper oxide of 2 values can also be exposed on the surface of a continuation film. Or a virus inactivation agent etc. of the shape of a film which carried out sputtering of the thin film of a nano cluster containing a mixture of copper oxide of 1 value and copper oxide of 2 values can also be used for the surface of filmy titanium oxide which スッパッタ― (ed) on glass.
generally material which fixed a virus inactivation agent on the substrate surface using fixed means, such as a binder, as a virus inactivation material which fixed a virus inactivation agent on the substrate surface is mentioned -- things can be carried out. Although any of an organic system binder or an inorganic system binder may be used as a binder, when using a constituent containing a 1 value copper compound and a photocatalyst substance as a virus inactivation agent, in order to avoid disassembly of a binder by a photocatalyst substance, it is preferred to use an inorganic system binder. Since it is not limited, for example, a photocatalyst substance is fixed on the substrate surface, especially the kind of binder can use arbitrary binders, such as a polymers binder which can form a thin film, by a polymerization or solvent volatilization besides inorganic system binders usually used, such as a silica system.
Material which can be obtained by stiffening a distributed thing which distributed the above-mentioned virus inactivation agent in resin as a virus inactivation material which contains a virus inactivation agent inside a substrate can be mentioned. As resin, any of a natural resin or a synthetic resin may be used. Although an acrylic resin, phenol resin, polyurethane resin, acrylonitrile / styrene copolymerization resin, acrylonitrile / butadiene / styrene copolymerization (ABS) resin, polyester resin, an epoxy resin, etc. can be mentioned, It is not limited to these specific resin.
Forms of application in particular of a virus inactivation agent of the present invention are not limited, but can be used also in a dark place besides under existence of arbitrary light. Under existence of water and dry states (for example, state of low humidity in winter etc., etc.), a state of high humidity, or coexistence (for example, underwater, inside of sea water, etc.) of an organic matter, a virus inactivation agent of the present invention has high virus inactivation ability, and can carry out inactivation of the virus continuously. For example, it is applicable to arbitrary subjects, such as buildings, such as others and a hospital which are a wall, a floor, a ceiling, etc., and a factory, a machine tool, an inside of measuring devices and electric appliances, and parts (insides, such as inside of a refrigerator and a washing machine, and a dish washer, a filter of an air wash machine, etc.). Although application to hospital plants (a waiting room, an operating room, etc.) which serve as a dark place, for example at the time of an inside of machinery, a storage room of a refrigerator, night, or non-use is mentioned as a suitable example as an example of a dark place, it is not limited to these. It is although a product which incorporated a light source for coating and carrying out the ultraviolet exposure of the titanium oxide to a ceramics filter of an air wash machine as one of the measures against influenza, for example is proposed, By applying a virus inactivation agent of the present invention to a filter, a source of ultraviolet light can become unnecessary, cost can be reduced, and safety can be improved.
<p>Hereinafter, although an example explains the present invention still more concretely, the range of the present invention is not limited to the following example. Example 1 Although virus inactivation ability was evaluated also in an influenza virus, it mainly checked by the following methods by the model experiment using a bacteriophage. How to use inactivation ability to a bacteriophage as a model of virus inactivation ability, For example, it is indicated to Appl. *Microbiol. *Biotechnol., *79, *pp. 127-133, and *2008, and it is known that a reliable result will be obtained.</p><p>It covered with filter paper in a 深型 petri dish, and added a little sterile water. The glass stands about 5*mm are placed on filter paper, and it is Cu on it.<sub>2</sub>A glass board which applied specimens, such as O, was placed. Besides it purifies beforehand and 50micro of Qbeta phage (NBRC20012) suspension whose concentration is also clear was dropped L times, and an OHP film was put in order to contact a material list side and phage. This petri dish was covered with a glass board. Only the number of the number of times of a measurement schedule of the number of phage prepared same set for measurement, and it settled it on a dark place of room temperature. It is a 15W white fluorescent light (Panasonic incorporated company, full white fluorescent light) as a light source. Using what attached an ultraviolet-rays cut filter (an incorporated company king factory, KU-1000100) to FL15N, a set for measurement was settled on a position where illumination will be 800 luxs (illuminometer: measure in TOPCON*IM-5), respectively. Phage density measurement of each sample was performed after progress for a predetermined period. A key map of a measuring method was shown in Drawing 1.</p><p>Measurement of phage concentration was performed by the following methods. A sample was immersed in recovering liquid (SM*Buffer) of 10*mL, and it was made to shake for 10 minutes with a shaker. Culture solution (OD) of coliform bacillus (NBRC13965) which diluted this phage recovering liquid suitably and cultivated it independently<sub>600</sub>>1.0, *1x10<sup>8</sup>* It mixes with CFU/mL, and after agitating, it settled for 10 minutes into a 37 ℃ homoiothermal warehouse, and infected phage with coliform bacillus. This liquid was sprinkled in an agar medium, and after cultivating at 37 ℃ for 15 hours, the number of plaques of phage was measured visually. It asked for phage concentration by multiplying the obtained number of plaques by dilution magnification of phage recovering liquid.</p><p>Cu<sub>2</sub>O powder was granule-ized by a mortar and ethanol slurry of 0.1 mass % was prepared. Cu<sub>2</sub>Particle diameter of O was 1-4 micrometers under a scanning electron microscope (SEM) (Drawing 7). In slurry manufacture, it irradiated with an ultrasonic wave for 20 minutes with an ultrasonic washing machine, and distributed powder. These dispersion liquid were dropped at the whole so that it might not fall on a glass board of 2.5*cmx2.5*cmx1*mm* (thickness), this glass board was put into a constant temperature drier set as 120 ℃, and it dried for 3 hours. Cu on an obtained glass board<sub>2</sub>O is 0.15*mg/6.25*cm.<sup>2</sup>* (=0.24*g/m<sup>2</sup>It was. Although a sample of CuO as well as the above was produced, in order that the amount of support may make a rate of a copper ion the same, they are 0.17*mg/6.25*cm.<sup>2</sup>* (=0.27*g/m<sup>2</sup>It carries out and they are 0.2*mg/6.25*cm also about CuS.<sup>2</sup>* (=0.32*g/m<sup>2</sup>It carried out. Similarly, it is Cu.<sub>2</sub>S is *0.17*mg/6.25*cm.<sup>2</sup>* (=0.27*g/m<sup>2</sup>Carrying out, CuI (s) are *0.4*mg/6.25*cm.<sup>2</sup>* (=0.64*g/m<sup>2</sup>It carried out. Cu<sub>2</sub>S had tens of micrometers particle diameter by condensation after granule-izing.</p><p>A result is shown in Drawing 2. Cu which consists of a 1 value copper compound<sub>2</sub>When phage suspension is contacted to O for 30 minutes, phage concentration is 1/10 of initial concentration.<sup>6</sup>although the until fall was carried out, CuO which consists of a 2 value copper compound hardly showed the inactivation effect in 30 minutes (left figure of Drawing 2). Cu<sub>2</sub>The phage inactivation effect of O was accepted also in any of the bottom of light irradiation (WL:*white*light), and a dark place (Dark). Also in CuS which consists of a 2 value copper compound, the inactivation effect was hardly accepted like CuO (right figure of Drawing 2). Cu which consists of a 1 value copper compound on the other hand<sub>2</sub>It is Cu also about S and CuI.<sub>2</sub>The high phage inactivation effect was accepted like O, and it was checked that a 1 value copper compound demonstrates a prominent effect to phage inactivation (right figure of Drawing 2). When phage inactivation ability was similarly investigated using a cuprous chloride (CuCl), having the almost same phage inactivation ability as copper I oxide was checked.</p><p>Example 2 When a virus inactivation operation on T4 phage (NBRC*20004) was investigated like Example 1, it is Cu under irradiation of white fluorescence.<sub>2</sub>Concentration of T4 phage is 1/10 by making O contact for 60 minutes.<sup>6</sup>the until fall was carried out (Drawing 3).</p><p>Example 3 A/PR / 8/34 (H1N1) were used as an influenza virus, virus liquid was inoculated and infected with the 12th day age growth chicken egg, and it cultivated for two days at 35.5 ℃. After making it settle at 4 ℃ overnight, 奨尿液 were collected and a concentrate was obtained by precision filtration (egg origin mixed living thing removal) and ultrafiltration (impurities removal, virus concentration). This concentrate was refined with a sucrose density gradient sedimentation velocity method (5-50% sucrose Linear*Gradient, 141, 000xg, 3 hours) by super-centrifugality, and high purity virus liquid was obtained. In order to stabilize a virus on the occasion of test implementation, bovine serum albumin (BSA) was added as a stabilizer.</p><p>A virus inactivation operation on an influenza virus was checked by a method shown in Drawing 1 like Example 1. Manufacture of a support sample was performed like Example 1. Evaluation covered with filter paper in a 深 type petri dish, and added a little sterile water. About 5-mm glass stands are set on filter paper, and it is Cu on it.<sub>2</sub>A glass board (2.5-cm square) which applied materials, such as O, was placed. 50micro of influenza virus liquid refined besides was dropped L times, and an OHP film was put in order to contact a material list side and a virus. This petri dish was covered with a glass board, and light irradiation was performed. Only the number of the number of times of a measurement schedule of the number of phage prepared same set for measurement, a 20W white fluorescent light (Toshiba Lighting & Technology; FL20 S-W) was used as a dark place of room temperature, or a light source, and a set for measurement was settled on a position where illumination will be 1, 000 luxs (illuminometer: measure in TOPCON*IM-5). For a predetermined period, viral infectivity of a sample after dark place neglect and light irradiation was measured.</p><p>After carrying out light irradiation, it was immersed in recovering liquid (PBS+1%BSA) of 5mL, and with a shaker, for 10 minutes, a glass board which inoculated a virus was made to shake at 100 rpm, and were collected. It is a collected influenza virus by 10 time stage dilution 10<sup>-8</sup>To 個/ml, you dilute, and make it infected with a MDCK cell (dog kidney origin established cell line) cultured, respectively, and they are 37 ℃ and CO.<sub>2</sub>It cultivated for five days at 5% of concentration. It is computing quantity which observed existence of a cytopathic effect (CPE) of a cell after cultivation, and was infected with a cultured cell 50% by the Reed-Muench method, and is the viral infectivity (TCID) per ml.<sub>50</sub>/ml was calculated.</p><p>A result is shown in Drawing 4. When an influenza virus was contacted to CuO which comprises a copper ion of 2 values on condition of Dark, after 30min, it is changeless to infection value and the inactivation effect was not shown. When CuO was made to contact on condition of under irradiation of a 1000 luxs white fluorescent light similarly, after 30min, reduction of infection value was seldom seen and was not able to check the virus inactivation effect. Cu which consists an influenza virus of a copper compound of 1 value on condition of Dark on the other hand<sub>2</sub>When O is made to contact, infection value is falling in proportion to time, and after 30min, it is 1/10.<sup>3</sup>* up to -- it was falling. It is the conditions under irradiation of a 1000 luxs white fluorescent light similarly, and is Cu.<sub>2</sub>When O was made to contact, after 30min, it is 1/10 below a detection limit.<sup>4</sup>* up to -- it was falling. Therefore, it compares with CuO and is Cu.<sub>2</sub>In O, reducing infection value dramatically on conditions which irradiated with white fluorescence, and carrying out inactivation of the influenza virus was checked.</p><p>Example 4 Cu<sub>2</sub>O powder is granule-ized by a mortar and it is Cu of 0.1 mass %.<sub>2</sub>Hydrolysis liquid of TEOS (ethyl silicate 28, made in a col coat) was added, and ethanol slurry was prepared so that O and solid content concentration might be 0.1%. It irradiated with an ultrasonic wave for 20 minutes, and made an ultrasonic washing machine distribute in that case. These dispersion liquid were dropped at the whole so that it might not fall on a glass board of 2.5*cmx2.5*cmx1*mm* (thickness) like Example 1, this glass board was put into a constant temperature drier set as 120 ℃, and it dried for 3 hours. Cu on an obtained glass board<sub>2</sub>O is 0.15*mg/6.25*cm.<sup>2</sup>* (=0.24*g/m<sup>2</sup>It was. Also when phage suspension was contacted for 30 minutes like Example 1, phage concentration decreased notably and a binder was used, it has checked that the same phage inactivation activity as a case of Example 1 was obtained (Drawing 5).</p><p>Example 5 Cu (II) /TiO<sub>2</sub>Cu<sub>2</sub>O powder was granule-ized by a mortar and ethanol slurry of 0.9 mass % was prepared. It irradiated with an ultrasonic wave for 20 minutes, and made an ultrasonic washing machine distribute in that case. These dispersion liquid were dropped at the whole so that it might not fall on a glass board of 2.5*cmx2.5*cmx1*mm* (thickness) like Example 1, this glass board was put into a constant temperature drier set as 120 ℃, and it dried for 3 hours. Cu (II) /TiO on an obtained glass board<sub>2</sub>は 2.5*mg/6.25*cm<sup>2</sup>* (=4*g/m<sup>2</sup>Cu<sub>2</sub>O is 0.15*mg/6.25*cm.<sup>2</sup>* (=0.24*g/m<sup>2</sup>It was. If phage solution is contacted for 30 minutes like Example 1, phage concentration will decrease notably, and it is Cu.<sub>2</sub>It has checked that the same phage inactivation activity as a case of Example 1 was obtained also in a form of a constituent containing O and a photocatalyst substance (Drawing 6).</p><p>Example 6 Since evaluation of a virus inactivation operation in Example 1 etc. has adopted an evaluation system which covered with filter paper in which water was included, humidity at the time of evaluation is about 80% or more. Generally, at high humidity, activity of a virus is low, and it is known that activity will become high at low humidity. Then, it was checked whether a virus inactivation agent of the present invention could maintain high activity on low humidity conditions. A key map of a valuation method is shown in Drawing 8. Cu<sub>2</sub>It is the amount of support of O 1/3 (0.08g/ (m)) of Example 1<sup>2</sup>When it evaluates by carrying out and making humidity conditions 40% or 13% and dries, it is 1/10.<sup>3</sup>It is [in / although phage concentration falls to twice, at 40% of humidity, can carry out inactivation to below a detection limit by light irradiation of only 1 hour after that, and / the bottom of a dark place condition of 13% of humidity] Cu for 4 hours.<sub>2</sub>Inactivation was able to be carried out to below a detection limit only by making O contact (Drawing 9). This result is a general life space in winter etc., and is Cu.<sub>2</sub>It is shown that O can demonstrate sufficient virus inactivation effect.</p><p>Example 7 It was examined whether since a virus which exists in a general life space coexists with various organic matters, such as dust, it could demonstrate inactivating action with a virus inactivation agent of the present invention sufficient under coexistence of an organic matter. Phage suspension containing 0.1% of gelatin was produced, and it evaluated like a method of Example 1. Cu<sub>2</sub>It is 0.24g/m about the amount of support of O.<sup>2</sup>When it carried out, it was checked that a prompt virus inactivation operation is demonstrated to a sample containing 0.1% of gelatin. On the other hand, to a sample which does not contain gelatin, it is Cu.<sub>2</sub>When the amount of support of O is reduced to 1/10, comparable virus inactivation is attained, and it was suggested that existence of an organic matter may influence virus inactivation ability.</p><p>Example 8 Phage liquid 25mL and Cu which were suspended on an arrogant petri dish at 1 / 500NB culture medium as shown in Drawing 11<sub>2</sub>A milt balloon which coated O (left-hand side:3g*Cu of the inside of a figure, and a lower left photograph)<sub>2</sub>O / 25mL (1 / 500NB culture medium), or Cu<sub>2</sub>Powder of O (right-hand side:4 mg*Cu of the inside of a figure, and a lower left photograph)<sub>2</sub>O / 25mL (1 / 500NB culture medium) was put in, and it irradiated with a white fluorescent light (WL) from a top. The same experiment system was placed also under a dark place. When it sampled about 24h afterward and having been asked for phage concentration, phage concentration was falling [the bottom of WL and a dark place] below to a detection limit. When phage was again added after a sampling, and it sampled about 24h afterward similarly and having been asked for phage concentration, it was below a detection limit. When this operation was repeated 5 times, even if the inactivation effect was accepted 5 times and it was repeatedly exposed to a virus in underwater, it was checked that a virus inactivation operation continues (Drawing 11, Cu).<sub>2</sub>O milt balloon: The upper left, Cu<sub>2</sub>O powder: Lower right.</p><p>Example 9 CuCl<sub>2</sub>It is TiO to solution (10 ml, 0.1 - 2*Wt%).<sub>2</sub>It was suspended, (1.0g) was agitated at 90 ℃ for 1 hour, and suspension was prepared. Sodium hydroxide is NaOH/Cu to the number of Mol of a copper ion to obtained suspension.<sup>2+</sup>= adding so that it may be set to 0-8 -- furthermore -- as a reducing substance -- glucose -- mol of a copper ion -- as opposed to a number -- glucose/Cu<sup>2+</sup>= It agitated at 90 ℃ for 1 hour so that it might be set to 4. It dries, after ろ取 (ing) and washing a solid, and it is Cu.<sub>X</sub>O-TiO<sub>2</sub>を得た. Cu obtained by this reaction<sub>X</sub>O-TiO<sub>2</sub>は, R-CHO+2Cu<sup>2+</sup>+4OH<sup>-</sup>->R-COOH+Cu<sub>2</sub>O+2H<sub>2</sub>Cu which arises by the reaction denoted by O<sub>2</sub>Cu which uses O as an ingredient<sub>X</sub>A nano cluster containing O (mixture of copper oxide of 1 value and 2 values) is TiO.<sub>2</sub>They are the complex particles supported on the surface of particles. An X diffraction (XRD) pattern and XPS (X ray photoelectron spectrum) of particles which were obtained are shown in Drawing 12. The outside of purple of complex particles and a visible absorption spectrum are shown in Drawing 13. It is Cu as quantity of NaOH is increased.<sub>2</sub>It was checked that absorption of O origin increases. A copper compound currently supported by the surface of the above-mentioned particles became clear [that it is a mixture of 2 value copper oxide and 1 value copper oxide] from this result.</p><p>A result of having observed complex particles with a transmission electron microscope (TEM) is shown in Drawing 14. It became clear from this result that particulates of the shape of a nano cluster whose particle diameter is about 5 nm are formed in the titanium oxide surface, and are supported. When nano cluster particles of the above were analyzed with an energy dispersion form X-rays spectroscope (EDX), copper was detected only from a position of nano cluster-like particles. It became clear from these results that nano cluster-like particulates are particulates which consist of copper compounds.</p><p>2-propanol (IPA) disintegration in visible light was checked about obtained particles. It is 5.5 cm about 300 mg of powder samples to Bessel made from pyrex glass of 500mL.<sup>2</sup>After putting into a の petri dish, settling and replacing air in Bessel with pure air, 6micromol is supplied and light irradiation of the 2-propanol is carried out in a dark place after about 12-hour neglect and by a キセノン light source (400 to 530 nm), and it is CO.<sub>2</sub>Under [a fixed quantity / in gas chromatography / の発生量]. An obtained result is shown in Drawing 15. Complex particles prepared using glucose are Cu (II) /TiO.<sub>2</sub>It was alike, and it compared and high activity was shown. Quantity of sodium hydroxide used when preparing complex particles did not have big influence active.</p><p>A sample was prepared like Example 1 using obtained particles, and evaluation of a virus inactivation operation was presented. Complex particles prepared by 4 times as much glucose as a copper quantity and 8 times as many sodium hydroxide carried out inactivation of the virus to below a detection limit also in any under a dark place and white light irradiation, and demonstrated a remarkable virus inactivation operation (Drawing 16). It is clear from the above result that complex particulates' obtained it can use as a material which can demonstrate remarkable virus inactivation activity with outstanding photoinduced degradation activity.</p>
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| JPH11349423A | Cites | Japan | Y | International search |
| See also references of EP 2671451A4 | Non-patent | – | – | International search |
| PROGRESS IN MEDICINAL CHEMISTRY, vol. 31, 1994, pages 351 - 370 | Non-patent | – | – | Applicant |
| CRC CRITICAL REV. ENVIRON. CONT., vol. 18, 1989, pages 295 - 315 | Non-patent | – | – | Applicant |
| SANGRIPANTI ET AL., APPL. ENVIRON. MICROBIOL., vol. 58, 1992, pages 3157 - 3162 | Non-patent | – | – | Applicant |
| APPL. ENVIRON. MICROBIOL., vol. 59, 1993, pages 4374 - 4376 | Non-patent | – | – | Applicant |
| AIDS RES. HUM. RETROVIR., vol. 12, 1996, pages 333 - 336 | Non-patent | – | – | Applicant |
| ANTIMICROB. AGENT CHEMOTHER., vol. 41, 1997, pages 812 - 817 | Non-patent | – | – | Applicant |
| APPL. MICROBIOL. BIOTECHNOL., vol. 79, 2008, pages 127 - 133 | Non-patent | – | – | Applicant |
| INTERNATIONAL JOURNAL OF ANTIMICROBIALAGENTS, vol. 33, 2009, pages 587 - 590 | Non-patent | – | – | Applicant |
| CHEM. COMMUN., 2009, pages 1076 - 1078 | Non-patent | – | – | Applicant |
| APPL. ENVIRON. MICROBIOL., vol. 58, 1992, pages 3157 - 3162 | Non-patent | – | – | Applicant |
| INTERNATIONAL JOURNAL OF ANTIMICROBIAL AGENTS, vol. 33, 2009, pages 587 - 590 | Non-patent | – | – | Applicant |
| SCIENCE, vol. 293, 2001, pages 269 - 271 | Non-patent | – | – | Applicant |
| J. PHYS. CHEM. B, vol. 107, 2003, pages 5483 - 5486 | Non-patent | – | – | Applicant |
| THIN SOLID FILMS, vol. 510, 2006, pages 21 - 25 | Non-patent | – | – | Applicant |
| J. AM. CHEM. SOC., vol. 129, 2007, pages 9596 - 9597 | Non-patent | – | – | Applicant |
| CHEM. PHYS. LETT., vol. 457, 2008, pages 202 - 205 | Non-patent | – | – | Applicant |
| J. PHYS. CHEM. C., vol. 113, 2009, pages 10761 - 10766 | Non-patent | – | – | Applicant |
| J. AM. CHEM. SOC., vol. 132, 2010, pages 6898 - 6899 | Non-patent | – | – | Applicant |
| J. AM. CHEM. SOC., vol. 132, 2010, pages 15259 - 15267 | Non-patent | – | – | Applicant |
| "Proceedings of Photo Functionalized Materials Society", PHOTOCATALYSIS, vol. 28, 2009, pages 4 | Non-patent | – | – | Applicant |
14 members in 7 offices
Members14
| Document | Office | Kind | |
|---|---|---|---|
| WO2011078203A1This record | World Intellectual Property Organization (WIPO) | A1 | |
| JP2011153163A | Japan | A | |
| TW201138637A | Taiwan Province of China | A | |
| CN103338641A | China | A | |
| KR20130114686A | Republic of Korea | A | |
| EP2671451A1 | European Patent Office (EPO) | A1 | |
| US2013344124A1 | United States of America | A1 | |
| EP2671451A4 | European Patent Office (EPO) | A4 | |
| JP5570006B2 | Japan | B2 | |
| CN103338641B | China | B | |
| TWI533806B | Taiwan Province of China | B | |
| KR101657517B1 | Republic of Korea | B1 | |
| US9572347B2 | United States of America | B2 | |
| EP2671451B1 | European Patent Office (EPO) | B1 |
7 legal events, as 3 offices reported them to INPADOC
Over the term
Point at a mark for the eventEvents
| Event | Code | Office | |
|---|---|---|---|
| Wipo information: entry into national phaseWWE | WWE | WO | |
| Entry into the national phaseENP | ENP | KR | |
| Wipo information: entry into national phaseWWE | WWE | WO | |
| Ep: pct application non-entry in european phase122 | 122 | WO | |
| Non-entry into the national phaseNENP | NENP | DE | |
| Ep: the epo has been informed by wipo that ep was designated in this application121 | 121 | WO | |
| Withdrawal of priority claims after completion of the technical preparations for international publicationWITHDRAWN AFTER TECHNICAL PREPARATION FINISHEDWPC | WPC | WO |
Numbers
- Publication
- 2011/078203
- Application
- 73087
Titles4
- English
- Virus inactivation agent
- French
- INACTIVATEUR DE VIRUS
- Unlabeled
- ウイルス不活化剤
- Japanese
- Virus inactivation agent
Classification
- CPC, 3
- A01N59/20
- A01N59/16
- A01N25/26
- IPC, 3
- A01N59 20
- A01N59 16
- A01P1 00
Designated states141
- Regional, 78
- Botswana
- Ghana
- Gambia
- Kenya
- Liberia
- Lesotho
- Malawi
- Mozambique
- Namibia
- Sudan
- Sierra Leone
- Eswatini
- United Republic of Tanzania
- Uganda
- Zambia
- Zimbabwe
- Armenia
- Azerbaijan
- Belarus
- Kyrgyzstan
- Kazakhstan
- Republic of Moldova
- Russian Federation
- Tajikistan
and 54 moreShow fewer
- Turkmenistan
- Albania
- Austria
- Belgium
- Bulgaria
- Switzerland
- Cyprus
- Czechia
- Germany
- Denmark
- Estonia
- Spain
- Finland
- France
- United Kingdom
- Greece
- Croatia
- Hungary
- Ireland
- Iceland
- Italy
- Lithuania
- Luxembourg
- Latvia
- Monaco
- North Macedonia
- Malta
- Netherlands (Kingdom of the)
- Norway
- Poland
- Portugal
- Romania
- Serbia
- Sweden
- Slovenia
- Slovakia
- San Marino
- Türkiye
- Burkina Faso
- Benin
- Central African Republic
- Congo
- Côte d’Ivoire
- Cameroon
- Gabon
- Guinea
- Equatorial Guinea
- Guinea-Bissau
- Mali
- Mauritania
- Niger
- Senegal
- Chad
- Togo
- National, 63
- United Arab Emirates
- Antigua and Barbuda
- Angola
- Australia
- Bosnia and Herzegovina
- Barbados
- Bahrain
- Brazil
- Belize
- Canada
- Chile
- China
- Colombia
- Costa Rica
- Cuba
- Dominica
- Dominican Republic
- Algeria
- Ecuador
- Egypt
- Grenada
- Georgia
- Guatemala
- Honduras
and 39 moreShow fewer
- Indonesia
- Israel
- India
- Japan
- Comoros
- Saint Kitts and Nevis
- Democratic People’s Republic of Korea
- Republic of Korea
- Lao People’s Democratic Republic
- Saint Lucia
- Sri Lanka
- Libya
- Morocco
- Montenegro
- Madagascar
- Mongolia
- Mexico
- Malaysia
- Nigeria
- Nicaragua
- New Zealand
- Oman
- Peru
- Papua New Guinea
- Philippines
- Seychelles
- Singapore
- Sao Tome and Principe
- El Salvador
- Syrian Arab Republic
- Thailand
- Tunisia
- Trinidad and Tobago
- Ukraine
- United States of America
- Uzbekistan
- Saint Vincent and the Grenadines
- Viet Nam
- South Africa