JP6439217B2 - A method for producing tungsten trioxide and tungsten dioxide. - Google Patents

Description

  The present invention relates to a paint having a repellent effect on cockroaches.

  It is said that cockroaches, which are sanitary pests, harbor various pathogens on the body surface and body, and they cause illnesses, infections, and allergies due to the presence of cockroaches in the clothing, food and living environment. . Therefore, it is important to eliminate cockroaches from the environment where small children and elderly people live. As a method of eliminating cockroaches from the living environment, insecticides containing pyrethroids, insecticides using borate (bait bait) containing boric acid, trapping methods using adhesive sheets and attractants, or naturally derived JP-A-2009-73792 discloses a repelling method using essential oils and herbs and a cockroach repelling method using a photocatalyst.

  Insecticides that are one of the insecticidal methods, cockroaches with resistance to insecticidal components emerge from the speed of the generation change of cockroaches, and by the development of more powerful insecticidal components and the appearance of resistant cockroaches, Gradually, commercial insecticides are becoming ineffective. The poison bait is controlled by chain cockroaches that have returned to the nest, but it is difficult to remove dead cockroaches. In the capture method that combines the adhesive sheet and the attractant, the number of cockroaches to be captured does not increase with time even when installed in the same place for a long time, and the alarm pheromone is emitted from the captured cockroaches There is a need to periodically replace with a new capture device.

  Japanese Patent Laid-Open No. 2000-260683 discloses the use of hinokitiol, an essential oil derived from nature that takes into account the effects on the human body, describes repellent effects on cockroaches, and uses aroma oil extracted from herbs Cockroach repellents are also available on the market, but they are mainly volatile components, so they are said to be expensive considering their sustainability and cost. In addition, there are many people who dislike or do not like the smell of cockroaches because there are many different olfactory senses. A research paper published in the “National Academy of Sciences” (PNAS) also reports that cockroaches do not urinate because uric acid can be replaced with amino acids by the action of a bacterium called brattabacterium. There is an expectation that the cockroach itself can be extinguished by erasing it with a substance.

  However, even if the cockroaches temporarily disappear, the cockroaches often come back, and the strong insecticidal ingredients against the resistant cockroaches have a considerable impact on the human body, so the insecticide spray spots and There are problems such as having to consider the location, and depending on the location of the poison bait, there are problems that cause unexpected results such as accidental ingestion of dogs and cats living with infants and people. In addition, German cockroaches often grow at the outlet of vending machines due to temperature and humidity conditions. Naturally, pesticides and baits can be used for beverages such as canned coffee and plastic bottles. In addition, even if there are carcasses of cockroaches etc., there is a problem that the purchase of products has been hindered, and for the product supplier to the vending machine, there is a problem of occurrence of work such as having to ask for product removal in order to respond to customer complaints It was happening. In addition, the repellent disclosed in Japanese Patent Application Laid-Open No. 2009-73792 has a problem that the repellent effect is high, but it is a white liquid, the surface to be coated becomes white, and it is difficult to apply in places where the appearance is important. .

JP 2009-73792 A JP 2003-171619 A JP 2002-68906 A JP 2000-260683 A

Nitrogen recycling and nutritional provisioning by Blattabacterium, the cockroach endosymbiont. (PMID: 19880743 PMCID: PMC2780778) National Institute for Materials Science Material Information Station Material and Material Database

  The problem to be solved is to provide a repellent with a remarkably long-lasting repellent effect on cockroaches. Also, do not apply or paint directly on the object to which cockroach repellent action is to be applied, but simply apply and apply a repellent coating material (eg, substrate, film, three-dimensional molded body, etc.). Is to provide.

The present invention relates to a tungsten oxide dispersion represented by WO _n · (H ₂ O) _m [1.5 <n <3.0, 0.5 <m <7.0], tungsten dioxide (WO ₂ ) or three. Cockroaches are powders containing only one of the tungsten oxide compounds of tungsten oxide (WO ₃ ), or powders using a mixture of two or more, or those in which they are put in a liquid and dried. Found to have repellent effect. It has also been found that this effect has a similar effect when other elements are doped or deposited on these tungsten compounds. By using this powder or liquid depending on the application, it can be applied to various things. The main feature is that it is a cockroach repellent material made of such a material.

In particular, the tungsten compound used in the present invention includes WO ₃ -X, WO ₂ -X (X is 0 to 0.5) as tungsten oxide, and tungsten oxide compound WO _n · (H ₂ O) _m [1.5 <n <3.0, 0.5 <m <7.0] where m is the amount of crystal water contained in the compound and the amount of adsorbed water as a characteristic of fine nanoparticles. It consists of one. In particular, not only those included in the crystal structure. Furthermore, even if these tungsten compounds are doped with other elements or adhered to the surface, the same effect is obtained. Examples of the element to be doped or chemically modified include Ag, Cu, Pd, Pt, Fe, Ti, and Zr. These elements may be in the form of metal, oxide, or salt.
Further, the tungsten oxide compound powder of the present invention is not particularly limited in size, but is desirably 1000 nm or less as the powder for spraying by paint or dry method, and the average particle size is about 5 to 500 nm. . When the size is reduced, the dispersion liquid can be constituted as a highly transparent dispersion liquid. The surfactant is preferably 10% by weight or less, and desirably 0.5% by weight or less and no additive.

WO _n · (H ₂ O) _m [1.5 <n <3.0, 0.5 <m <7.0] (hereinafter referred to as tungsten suboxide hydrate) compound particle synthesis method of the present invention As a result, tungstic acid or tungsten oxide particles can be synthesized from a commercially available tungsten oxide powder of several microns by a bead mill apparatus or a sol-gel reaction using tungsten chloride. In particular, the synthesis method is not limited. As another method, a compound containing tungsten and oxygen can be synthesized by a thermal decomposition method using a tungstate such as tungstic acid, ammonium tungstate, and sodium tungstate as a tungsten raw material. Specifically, when tungstate and tungstic acid are pyrolyzed at a high concentration, at least tungstic acid or tungstate is pyrolyzed in an aqueous solution because fine particles cannot be synthesized due to grain growth during decomposition. This makes it possible to synthesize fine particles. The concentration of tungstic acid or tungstate in the aqueous solution is preferably in the range of 1 mol (M) to 0.001 mol (M). This liquid is heated to about 200 to 600 ° C. in an inert gas to cause thermal decomposition of tungstic acids. Since the tungstic acids are insoluble in water, for example, the thermal decomposability is improved by adding hydrochloric acid or nitric acid as an aid for promoting thermal decomposition. If this liquid is heated to 200 ° C. or higher in an inert gas, thermal decomposition of tungstic acids can be caused.

  In addition, as a feature of the production method of the present invention, a microreactor device is used as an apparatus for raising the temperature to 200 to 600 ° C., but tungstic acid, ammonium paratungstate and hydrochloric acid are added and dissolved in water. By using this apparatus and setting the temperature of the furnace for heating the reactor to about 200 to 600 ° C. and raising the temperature of the solution, a transparent tungsten compound could be synthesized. The reaction time at this time is about 100 to 200 hours for 0.1 kg of ammonium paratungstate. The pH of the dispersion after the reaction is between 2 and 6.

Instead of the aqueous solution, an alkali metal chloride such as Cs, Na, K, Li or the like may be dissolved at a saturated concentration, and this solution may be used to obtain a temperature of about 200 to 600 ° C.
Instead of the aqueous solution, water is vaporized, and tungstic acids are added to an inorganic ionic liquid having a melting point of about 300 to 350 ° C., so that the thermal decomposition temperature is about 300 to 600 ° C. Is synthesized. In this case, it can be synthesized in the same way by initially heating ammonium tungstate obtained by dissolving an alkali metal chloride in water and evaporating the water to raise the temperature to the thermal decomposition temperature.
When a solution in which the tungsten compound particles of the present invention are dispersed or mixed is used as a cockroach repellent, the solid content concentration is at least 0.05% by weight, preferably 0.5% by weight or more. The solution may be an aqueous solvent such as water, acetone or alcohol, or a non-aqueous solvent, and is not particularly limited to the solvent species.

A hydrated tungsten oxide according to the present invention, a powder containing only one of tungsten compounds of tungsten dioxide (WO ₂ ) or tungsten trioxide (WO ₃ ), or a powder using a mixture of two or more, or Since it is a transparent dispersion liquid with tungsten oxide as the main component, it can hide the presence or absence of application to the application target. For example, vending machine coffee makers and vending machines When applied to the product outlet, there is an advantage that can be expected to avoid insects such as cockroaches.
For example, when the size is 50 nm or less, a 1% solution can be applied as it is without adding a binder component to the organic / inorganic material surface except for a part of the plastic surface. There is an advantage that the appearance of the object is not impaired.

FIG. 1 is an energy dispersive X-ray analysis spectrum of a dry crystal of the hydrated tungsten suboxide of the present invention. (Example 1) FIG. 2 shows a crystal structure analysis spectrum of the hydrated tungsten suboxide of the present invention by X-ray diffraction. (Example 1) FIG. 3 is a crystal structure analysis spectrum by X-ray diffraction of commercially available tungsten trioxide for comparison. FIG. 4 is a crystal structure analysis spectrum of ammonium paratungstate by X-ray diffraction. FIG. 5 is an explanatory view showing an experiment method of the cockroach repellent effect using 50 German cockroaches in the test water tank 1. (Example 1 to Example 3) FIG. 6 is a graph showing the change in the number of cockroaches in each box when the experiment shown in FIG. 5 was conducted for 17 days. (Example 1 to Example 3) FIG. 7 is an explanatory diagram of an experiment in which 15 adult German cockroaches and 20 larvae were placed in the test water tank 2 and the difference in behavior between adults and larvae was observed. (Example 4) FIG. 8 is an explanatory diagram of an experiment in which 15 adult German cockroaches and 20 larvae were placed in the test water tank 3 and the presence or absence of the repellent effect of ammonium paratungstate was confirmed. (Example 4) FIG. 9 is a graph of the experimental results shown in FIG. (Example 4) FIG. 10 is a graph of the reference experiment shown in FIG. (Example 4) FIG. 11 is an explanatory view showing an experiment method of the cockroach repellent effect using 50 German cockroaches in the test water tank 4. (Example 5) FIG. 12 is a graph showing the change in the number of cockroaches in each box when the experiment shown in FIG. 11 was conducted for 17 days. (Example 5) FIG. 13 is an explanatory view showing an experiment method of the cockroach repellent effect using 50 German cockroaches in the test water tank 5. (Example 6) FIG. 14 is a graph showing the change in the number of cockroaches in each box when the experiment shown in FIG. 13 was conducted for 17 days. (Example 6) FIG. 15 is an explanatory view showing an experiment method of the cockroach repellent effect using 50 German cockroaches in the test water tank 6. (Example 7) FIG. 16 is a graph showing a change in the number of cockroaches in each box when the experiment shown in FIG. 15 was conducted for 17 days. (Example 7)

An aqueous solution prepared by mixing 1% by weight of compound particles made of only the tungsten suboxide hydrate of the present invention was applied to the inner surface of the box 3, and 1% by weight of compound particles made only of tungsten trioxide (WO ₃ ). An aqueous solution prepared by mixing is applied to the inner surface of the box 4, and an aqueous solution prepared by mixing 1% by weight of compound particles consisting only of tungsten dioxide (WO ₂ ) is applied to the inner surface of the box 5, and nothing is applied to the inner surface. Box 2 that was not applied was prepared, and Box 2 to Box 5 were sealed in water tank 1 together with 50 cockroaches to confirm the repelling effect of cockroaches. That is, in order to confine and observe cockroaches, food and drinking water are prepared for 17 days while box 2 to box 5 and around the box are prepared in a water tank 1 that is not filled with water. Was observed. The number of cockroaches is measured every morning at 9:00 am by counting the number of individuals in boxes 3 to 5 and the number of individuals in tanks other than boxes 3 to 5, and the remaining number is not applied to the box. Calculated as being inside 2.

The method for producing a hydrated tungsten suboxide of the present invention comprises mixing 20 g of ammonium paratungstate [(NH ₄ ) 10 (H ₂ W ₁₂ O ₄₂ ) · 4H ₂ O] and 2000 g of water, and adding an aqueous solution containing 10 CC of hydrochloric acid. Got ready. This liquid was reacted in a microreactor apparatus. As a microreactor configuration, an SUS (stainless steel) tube with an inner diameter of 1 mm and an outer diameter of 3 mmφ and a length of 20 m is spirally wound with a diameter of 30 cmφ in a nichrome wire heater furnace. The liquid feeding pump (JASCO PU-980) of JASCO Corporation, which can send the aqueous solution at the liquid feeding pressure, was used. The temperature at the time of reaction was set to the set temperature of the furnace as the reaction temperature. Since the SUS (stainless steel) pipe is severely corroded by hydrochloric acid, it is desirable to coat the inner surface of the SUS (stainless steel) pipe with platinum by, for example, a plating method. The internal pressure is adjusted by attaching a throttle valve at the end of the discharge side with respect to the liquid delivery port from the pump, and the internal pressure is not evaluated.

In addition, since it is dangerous if high-temperature liquid directly protrudes from the discharge side, another SUS (stainless) pipe is connected to the outlet of the SUS (stainless) pipe that has been removed from the furnace, and the connected pipe is circulated and cooled with a chiller. Therefore, a structure that can be cooled in a 90 liter bucket tub is adopted. After the cooling, a circulation type reaction apparatus was constructed in which it was collected in a 10 liter bucket made of polyvinyl chloride, and the collected liquid was reacted again with a liquid feed pump.
When a decomposition reaction is performed for 120 hours at 400 ° C. and a flow rate of 100 cc / min using this reaction apparatus, a solution containing about 0.5% of tungsten oxide crystals, which are the target substance of the present invention, is obtained. The obtained aqueous solution is almost transparent, but when it becomes amber due to oxygen deficiency during the reaction, it is desirable to react the aqueous solution with oxygen in the atmosphere for 10 hours with a stirrer.

  By the above-described method, a novel tungsten compound in which the colorless and transparent tungsten targeted by the present invention is nearly tetravalent can be synthesized. This material is smaller than 10 nm as measured with a transmission electron microscope, and the average particle size is 9 nm as a result of measurement with a particle size distribution evaluation apparatus using a laser scattering method.

(Energy dispersive X-ray analysis)
Moreover, because of the energy dispersive X-ray analysis, using the S-4800 type transmission and scanning lines elemental analysis function scanning electron microscope manufactured by Hitachi, Ltd., WO _n-nitrous oxide tungsten hydrate of the present invention Elemental analysis and quantitative analysis were performed on the powder from which moisture contained in (H ₂ O) _m was removed. Since the tungsten oxide contains about 30% by weight of water, the tungsten oxide crystal was taken out and dried, and the sample was quantitatively analyzed. FIG. 1 shows the spectrum that appeared in the quantitative analysis, and the peaks of the spectrum were only the spectrum of tungsten W and oxygen O. The results of the mass and element ratio are shown in Table 1. Here, when analysis is performed with the standardless method selected, a series of quantitative analysis can be performed from background processing, peak separation, X-ray Net intensity calculation, K value calculation, and ZAF correction. The elements detected in the analysis are only tungsten W and oxygen O. As shown in Table 1, the element ratio (At%) is W: O = 34.52: 65.48 = 1: 1. It can be seen that it is 90. In this energy dispersive X-ray analysis, hydrogen H, helium He, and lithium Li cannot be measured, but the total in the lower column of the weight ratio (Wt%) of these two elements is 100%. Tungsten oxide is presumed to be effective only in the ratio of these two elements. In addition, as shown in Table 2, hydrochloric acid may be used in the production process of the aqueous solution of tungsten oxide of the present invention, and when chlorine is quantitatively analyzed to confirm the presence or absence of elemental chlorine, It turns out that it is not contained in the tungsten oxide of invention.

Table 1 shows the results of quantitative analysis by the energy dispersive X-ray analyzer of spherical particles of the hydrated tungsten suboxide of the present invention, and the element ratio of W: O = 34.52: 65.48 = 1: 1.90. Is shown. Table 2 also shows the quantitative analysis results of the tungsten suboxide hydrate according to the present invention, and the element ratio is W: O = 35.84: 64.16 = 1: 1.79. Table 3 shows quantitative results of the tungsten oxide needle-like particles of the present invention, and shows an element ratio of W: O = 37.64: 62.36 = 1: 1.66. Here, the hydrated tungsten oxide of the present invention contains H ₂ O, and the weight loss when dried at about 400 ° C. is about 20 to 40%. Considering WO _n · (H ₂ O) _m , the weight of WO _n is 184 + 16 × n, and when the water content is y, it can be expressed by (184 + 16 × n + y) × 0.3 = y. Since y = 18 × m, m = y ÷ 18 = (184 + 16 × n) ÷ 42 can be obtained. Therefore, when n = 1.9, m = 5.10, and n = 1.79. , M = 0.06, and n = 1.66, m = 0.01. Similarly, when the water content is about 20%, when n = 1.9, m = 2.98, when n = 1.79, m = 2.93, when n = 1.66, m = 2.92. Yes, when water content is about 40%, when n = 1.9, m = 7.94, when n = 1.79, m = 7.82, and when n = 1.66, m = 7.80. .

(X-ray diffraction)
About the tungsten suboxide hydrate of this invention, the result of having performed crystal structure analysis by X-ray diffraction using the simple X-ray-diffraction apparatus MultiFlex by Rigaku Corporation is FIG. The test X-ray is Cu / 40 kV / 50 mA, the goniometer is a multi-flex & goniometer (no shutter), the sample rotation speed is 60 rpm, no filters and indented monochrome are used, diverging slits and scattering slits Both were 1 °, the counter monochromator was a fixed monochromator, the light receiving slit was 0.3 mm, the counter was a scintillation counter, and the monochrome light receiving slit was not used. The scanning mode is continuous, the scanning speed is 4.000 ° / min, the sampling width is 0.010 °, the operation axis is θ / 2θ, the scanning range is 5.000 to 65,000 °, θ The analysis was performed with an offset of 0 and an integration count of 1. As shown in FIG. 2, since 2θ (deg) has a large peak on the low angle side (20 ° or less), tungsten trioxide shown in FIG. 3 and National Institute for Materials Science Material Information Station In the X-ray diffraction data of tungsten dioxide and tungsten trioxide searched in the material database, no peak is observed on the low angle side (20 ° or less), so that it is completely different from the tungsten oxide of the present invention. Moreover, since it is different from the X-ray diffraction structure of ammonium paratungstate shown in FIG. 4, it indicates that the tungsten oxide of the present invention is a novel substance.

  Furthermore, the hydrated crystal of tungsten hydrate according to the present invention has its own binder (binder) performance. For example, in the case of a 5% by weight solution or the like, the surface of some plastics such as polycarbonate, polyethylene, styrene resin, and fluororesin is used. Except for the above, it can be applied as it is without adding a binder component to the surface of plastics including polyethylene phthalate (PET), acrylic resin, acrylic urethane, urethane, vinyl chloride, etc. and almost all inorganic materials. A 1 wt% solid dispersion of tungsten oxide particles thus prepared was applied to the inner surface of the box 2 in the water tank 1 shown in FIG. 5 to confirm the repelling effect of cockroaches.

  From the results of Box 3 in Table 4, the box 3 coated with a transparent dispersion prepared by mixing particles of hydrated tungsten oxide at 1% by weight had one animal inside from the start of the experiment to the seventh day. Not observed. On the 8th, 10th and 15th day, one individual was observed, and on the 13th, 14th and 16th days, a plurality of individuals were measured. The number of individuals was not observed. From this, it is confirmed that the tungsten oxide dispersion has a repellent effect on cockroaches, and since there is no increase or decrease in the total number of individuals, the dispersion does not contain the insecticide component of cockroaches. I understand that. The German cockroach in Box 2 with nothing applied is large in number, and adult cockroaches are small and move quickly, making it difficult to measure the number of individuals in the box. Existed. From the results in Table 4, FIG. 6 is a graph showing the number of German cockroaches with the vertical axis representing the elapsed days and the horizontal axis representing the elapsed days, and the trioxide calcined from the aqueous solution of tungsten hydrate and the tungsten oxide hydrate. It can be seen that, among tungsten dioxide baked from tungsten and the tungsten oxide hydrate, the tungsten oxide hydrate has the highest repellent effect.

  It is known that cockroaches emit various pheromones, but there is a habit of gathering in one place by collective pheromones, and in the case of danger, warning pheromones are issued and it is dangerous to friends It is speculated that the dispersion has an effect of erasing the aggregate pheromone, but the present invention does not include an antibacterial agent such as silver oxide or zinc oxide. From Example 4, the nature of tungsten oxide itself creates an environment that adults dislike, and the release of alarm pheromones is considered, but it is assumed that larvae are underdeveloped to receive alarm pheromones. It is thought that the repellent effect is reduced compared to.

  An acute oral dose toxicity test in rats with a 5% by weight aqueous solution of tungsten hydrate according to the present invention was conducted at a chemical substance evaluation and research organization (Hita Works) by a test method (OECD Guidelines for the Testing of Chemicals, No .423, Acute Oral Toxicity-Acute Toxic Class Method, December 17, 2001). As a result, “no death or moribundity occurred in all cases administered with 300 mg / kg and 2000 mg / kg, and no abnormality was observed in any of the general state observation, body weight measurement, and part examination. The hazard category of acute toxicity to rats due to the trend of administration of test substances under the test conditions is GHS “Category 5 or not”, LD50 cutoff value is “5000 mg / kg or in category (∞)” It was said that it was very safe.

  Table 5 shows that in the first test and the second test, the test substance corresponding to 300 mg / kg body weight was assigned to the individual No. 1-No. In the third test and the fourth test, administration of 2000 mg of the test substance per kg of body weight was performed for individual no. 7-No. 12 shows the measurement results of the body weight of the rat in the initial, 1st, 7th and 14th days in the oral administration test, and it can be seen that the weight of each individual increased with the passage of days. .

An aqueous solution prepared by mixing 1 wt% of tungsten trioxide (WO ₃ ) obtained by firing the tungsten suboxide hydrate crystal of the present invention described in Example 1 in an electric furnace for 1 hour at 500 ° C. Was applied to the inner surface of the box 4 in the water tank 1 of FIG. 5, and the observation experiment of the cockroach repellent effect was conducted in the same manner as in Example 1. On the 3rd day after the start of the experiment, it was confirmed that the cockroach individuals were in the box 4, and on the 4th, 7th to 9th, 15th and 16th days, Existence was confirmed. However, it can be seen from this result that the tungsten trioxide aqueous solution also has a repellent effect on cockroaches and does not contain insecticidal components against cockroaches.

An aqueous solution prepared by mixing only 1% by weight of tungsten dioxide (WO ₂ ) obtained by firing the tungsten suboxide-containing hydrate crystal of the present invention described in Example 1 in an electric furnace for 1 hour at 400 ° C. It applied to the inner surface of the box 5 in the water tank 1 in FIG. 5 and the observation experiment of the cockroach repellent effect was conducted in the same manner as in Example 1. At the time of observation, the presence of cockroaches was not confirmed only on the first day, the third day, the fifth day, the seventh day, and the 12th day, and almost all other individuals were confirmed. . In the comparison in FIG. 6, it was found that the aqueous solution of tungsten dioxide was inferior in repellent effect compared with other aqueous solutions, but since there was no decrease in the number of cockroaches, no insecticidal component against cockroaches was included. I understand.

A plate glass 7 having a length of 10 cm, a width of 15 cm, and a thickness of 3 cm coated only with an aqueous solution prepared by mixing 5% by weight of the tungsten suboxide hydrate compound particles of the present invention with a new paint bath 6 is used. FIG. 7 schematically shows the behavior of 15 adult German cockroaches and 20 larval German cockroaches. For comparison, a plate glass of the same size with nothing applied is placed in the test water tank 6, and at 9 am every morning, the coated plate glass 7, the uncoated plate glass 8 and the adult cockroach in other places Table 6 shows the results of measurement and observation of the number of larvae. Furthermore, in the new unused test water tank 9, the ammonium paratungstate [(NH ₄ ) 10 (H ₂ W ₁₂ O ₄₂ ) · 4H ₂ O], which is a raw material for the hydrated tungsten suboxide of the present invention, was originally used. In order to investigate whether or not there is a repellent effect, as shown in FIG. 8, one of the two glass sheets of the same size as the glass sheet used in FIG. 7, one sheet glass coated with ammonium paratungstate Table 7 shows the results of measurement and observation of the numbers of 15 adult German cockroaches and 20 larval German cockroaches at 9 am each morning without applying anything to 10 and the other plate glass 11.

  Of the results shown in Table 6, the number of adult and larval German cockroaches in the plate glass 7 coated with the aqueous solution of tungsten suboxide of the present invention and the plate glass 8 coated with nothing is plotted on the vertical axis and the elapsed days on the horizontal axis. FIG. 9 is a graph showing the results of Table 7. Among the results shown in Table 7, adults and larvae in the plate glass 10 coated with a 3% by weight aqueous solution of ammonium paratungstate and the plate glass 11 coated with nothing. FIG. 10 is a graph showing the number of German cockroaches in the same manner. As shown in FIG. 9, there is a difference in the repellent effect between adults and larvae, and there are about 0 to 2 adults on the plate glass 6 coated with the tungsten oxide, whereas the larvae on the first day. Except for the eyes, about 1 to 4 animals are always observed. It is speculated that some of the pheromones produced by adult cockroaches are not reacting with larvae cockroaches. Conceivable. Actually, if there are no more than a certain number of adults, they will not reproduce, so it is assumed that there will be no larvae in the space where the adults escape due to the repellent effect.

  From the results shown in FIG. 9, instead of directly applying or painting on the object to which cockroach repellent action is to be applied, it can be replaced with a repellent effect by simply placing it on the corner of the room or at the edge of the cupboard or sticking it. Even if it is a coating material (for example, a board | substrate, a film, a three-dimensional molded object etc.), a repellent effect can be exhibited.

  From the results shown in FIG. 10, many adult German cockroaches were measured on the plate glass 10 coated with ammonium paratungstate, which is a raw material of the tungsten oxide, compared to the plate glass 11 on which nothing was coated, and it was completely avoided. The effect is not seen, and the repelling effect on German cockroaches is a characteristic characteristic of tungsten oxide.

  The repelling mechanism of the tungsten oxides of the present invention against cockroaches is presumed until now, but is considered as follows. Since there is a clear repellent effect even in places where no light enters, it is not an action by a tungsten oxide photocatalyst. In addition, since the tungsten oxide itself is odorless, it is not a repellent against odors such as herbs and aromas that have a repellent effect. Therefore, it is considered promising to have a repellent effect due to body surface contact. At the Chinese Academy of Sciences Shanghai Plant Physiology and Ecology Research Institute, the engineer in charge of the repellent performance test of our other cockroach repellent, which is estimated to have a repellent mechanism similar to that of the present invention, It looks like he hates touching the membrane. " From this, it is presumed that when the hand, foot, mouth, etc. of a cockroach come into contact with the tungsten oxide coating, it is recognized that “this is not comfortable”. The comfortable space for cockroaches is a narrow space, and it is thought that the surface of the substance derived from organic matter and the place where many bacteria like cockroaches exist. However, as the tungsten oxide of the present invention is a completely inorganic oxide and there are companies advertising the high antibacterial property of the tungsten oxide photocatalyst, the tungsten oxide surface itself has the property that bacteria are difficult to live. Therefore, it is thought that cockroaches that contact this tungsten oxide coating with their hands, feet, mouth, etc. feel that they are not comfortable here and emit alarm pheromones to other cockroaches. It is presumed that other cockroaches that have received the warning will move away from the location, will not approach, and will eventually be left there.

An aqueous solution in which 10% by weight of titanium oxide TiO ₂ particles having an average particle size of 50 nm were added to an aqueous solution in which 1% by weight of the tungsten suboxide hydrate particles described in Example 1 was added was applied to the inner surface of the box 14 to obtain a commercially available trioxide. An aqueous solution in which 10% by weight of titanium oxide TiO ₂ particles having an average particle diameter of 50 nm were added to an aqueous solution in which 1% by weight of tungsten (WO ₃ ) particles were added was applied to the inner surface of the box 15 to obtain commercially available tungsten dioxide (WO ₂ ) particles. An aqueous solution obtained by adding 10% by weight of titanium oxide TiO ₂ particles having an average particle diameter of 50 nm to an aqueous solution containing 1% by weight is applied to the inner surface of the box 16, and a box 13 having nothing applied to the inner surface is prepared. The box 13 to the box 16 were sealed in a new unused water tank 12 together with 50 cockroaches, and the repellent effect of the cockroach was confirmed. That is, in order to confine and observe a cockroach, food and drinking water are prepared for 17 days in a box 14 to box 16 and around the box while the water tank 12 without water is covered and sealed. Was observed. The number of cockroaches is measured at 9 am every morning by counting the number of individuals in the boxes 14 to 16 and the number of individuals in the tank other than the boxes 13 to 16 and the remaining number is not applied. It was calculated as being inside 13. The results are shown in Table 8. From this result, it was found that there is a cockroach repellent effect.

  Based on the results in Table 8, FIG. 12 is a graph of the number of German cockroaches with the vertical axis representing the elapsed days and the horizontal axis representing the elapsed days. Improvement in the repellent effect of tungsten dioxide can be seen. Instead of the commercially available tungsten trioxide used in the box 15, the tungsten trioxide used in Example 2 may be used. Instead of the commercially available tungsten dioxide used in the box 16, the dioxide dioxide used in Example 3 may be used. Tungsten may be used.

An aqueous solution obtained by adding palladium (Pd) in an amount of 100 ppm to the tungsten compound to an aqueous solution to which 1 wt% of the tungsten suboxide hydrate described in Example 1 is added is applied to the inner surface of the box 19 and is commercially available. An aqueous solution obtained by adding silver (Ag) in an amount of 100 ppm to the tungsten compound to an aqueous solution to which 1 wt% of tungsten trioxide (WO ₃ ) was added was applied to the inner surface of the box 20 to obtain a commercially available dioxide dioxide. An aqueous solution in which copper oxide (Cu ₂ O) is added in an amount of 100 ppm with respect to the tungsten compound to an aqueous solution to which 1% by weight of tungsten (WO ₂ ) is added is applied to the inner surface of the box 21 and applied to the inner surface. Prepare a box 18 to which nothing is applied, and seal the boxes 18 to 21 together with 50 cockroaches in a new unused water tank 17 as shown in FIG. To confirm the effect. That is, in order to confine and observe a cockroach, food and drinking water are prepared for 17 days while box 18 to box 21 and a box are prepared in a water tank 17 that is not filled with water. Was observed. The number of cockroaches is measured every morning at 9 am by counting the number of individuals in the boxes 19 to 21 and the number of individuals in the water tank other than the boxes 18 to 21 and the remaining number is not applied to the box. Calculated as being inside 18. The results are shown in Table 9. From this result, it was found that there is a cockroach repellent effect.

FIG. 14 is a graph showing the number of German cockroaches on the vertical axis and the elapsed days on the horizontal axis based on the results in Table 9. Generally, palladium (Pd) having an effect of improving catalyst performance by chemical modification. ), Silver (Ag), copper oxide (Cu ₂ O), etc. are applied to improve the repellent effect, and in particular, a synergistic effect with copper oxide can be expected from the combination of tungsten dioxide and copper oxide. . Instead of the commercially available tungsten trioxide used in the box 20, the tungsten trioxide used in Example 2 may be used. Instead of the commercially available tungsten dioxide used in the box 21, the dioxide dioxide used in Example 3 may be used. Tungsten may be used.

About 1 mg per 10 cm ^{2 of} powder containing tungsten suboxide containing 30 nm hydrous powder described in Example 1 is adhered to the inner surface of the box 24, and tungsten trioxide (WO ₃ ) average particle diameter 100 nm particles described in Example 2 About 1 mg per 10 cm ² is attached to the inner surface of the box 25, and about 20 mg particles of tungsten dioxide (WO ₂ ) having an average particle diameter of 20 nm described in Example 3 are attached to the inner surface of the box 26 per 10 cm ^2. A box 23 that has nothing to wear is prepared, and the box 23 to box 26 are sealed in a new unused test water tank 22 together with 50 cockroaches, and the repellent effect of cockroaches is confirmed as shown in FIG. did. That is, in order to confine and observe a cockroach, the test water tank 22 not filled with water was covered with a lid and sealed, and food and drinking water were prepared around the boxes 23 to 26 and around the box, The observation was conducted for 17 days. The number of cockroaches is measured every morning at 9 am by counting the number of individuals in the boxes 24 to 26 and the number of individuals in the tank other than the boxes 23 to 26, and the remaining number is a box with no application. It was calculated as being inside 23. The results are shown in Table 10. From this result, it was found that there is a cockroach repellent effect.

  Based on the results shown in Table 10, the graph shows the number of German cockroaches plotted on the vertical axis and the elapsed days on the horizontal axis. FIG. 16 shows that any tungsten oxide has a repellent effect even in a dry powder state. It was done.

  Among the places where cockroaches lurk, the use of insecticides and poisonous bait is considered in the storage places such as tableware, pots, and pots that people use when eating and drinking. Cockroach repellent paint is suitable for use in such areas. First, since it does not contain an insecticidal component, there is no concern about the insecticidal component being applied to dishes, etc., and it has little effect on the human body, and is particularly suitable for use in homes where small children and the elderly live. Furthermore, in households that have pets, attention was required for accidental eating of cockroach poisons and the like, but the cockroach repellent paint of the present invention does not contain harmful ingredients, so keep pets. Even if it is applied to the shed, it can be said that the safety is high. In addition, the cockroach repellent paint of the present invention does not naturally see cockroaches, so there is little possibility that various bacteria left on the cockroach carcasses will be scattered in the air, Best of all, for those who hate cockroaches.

  Similar to tungsten trioxide and tungsten dioxide, the inventors' experiments have revealed that the tungsten suboxide hydrate includes a visible light activity (international application number: PCT / JP2016 / 003336). (Application No. 2016-547957), photocatalytic performance can be expected if there is not only sunlight but also a fluorescent lamp and LED lighting. In addition, the hydrated tungsten oxide according to the present invention can be used as an organic material or inorganic material without adding a binder. Because it is a tungsten oxide compound with a tungsten hydrate crystal that can be applied as it is to the surface of the material, it can be applied as it is to the plastic surface of the product outlet of the above vending machine, and it is transparent, so the appearance is impaired There is no advantage.

  In addition, instead of directly applying the cockroach to the object to be repelled, it is possible to provide a repellent effective coating material (for example, a substrate, a film, a three-dimensional molded body, etc.) simply by placing or sticking, It can also be placed in a corner of a cupboard or the like. Furthermore, since it is colorless and transparent, it does not impair the appearance of the cupboard even if it is applied to the inner and outer surfaces of the glass used in the cupboard, so it is possible to increase the added value of furniture, etc. is there. It can be expected to be used in a wide range of fields in hospitals, restaurants and hotels that handle foods and drinks that require a deodorizing effect due to the visible light activity, along with the cockroach avoidance effect.

1 Water tank (no water, for sealing)
2 For comparison, a box in which any tungsten oxide aqueous solution is not applied 3 A box in which only the aqueous solution of tungsten hydrate in accordance with the present invention is applied on the inner surface 4 A box in which only the tungsten trioxide aqueous solution of the new manufacturing method is applied on the inner surface 5 A box with only a new manufacturing method of tungsten dioxide applied on the inner surface 6 Water tank (no water, for sealing)
7 Sheet glass coated only with an aqueous solution of tungsten hydrate according to the present invention 8 Plate glass for comparison not coated with anything 9 Water tank (no water, for sealing)
10 Plate glass coated with 3% by weight aqueous solution of ammonium paratungstate 11 Plate glass for comparison without coating 12 Water tank (no water, for sealing)
13 For comparison, a box to which no photocatalyst aqueous solution is applied. 14 An aqueous solution obtained by adding 10% by weight of titanium oxide having an average particle diameter of 50 nm to a 1% by weight aqueous solution of the tungsten suboxide hydrate of the present invention was applied to the inner surface. Box 15 A box in which an aqueous solution obtained by adding 10% by weight of titanium oxide having an average particle size of 50 nm to a 1% by weight aqueous solution of commercially available tungsten trioxide (WO ₃ ) is coated on the inner surface. 16% by weight of commercially available tungsten dioxide (WO ₂ ) A box in which an aqueous solution in which 10% by weight of titanium oxide having an average particle diameter of 50 nm is added to the aqueous solution is applied to the inner surface. 17 Water tank (no water, for sealing)
18 For comparison, a box not coated with any photocatalyst aqueous solution 19 An aqueous solution to which 100 ppm of palladium (Pd) is added is added to the inner surface of the 1 wt% aqueous solution of tungsten suboxide of the present invention. 20 A box coated with an aqueous solution obtained by adding 100 ppm silver (Ag) to a 1% by weight aqueous solution of commercially available tungsten trioxide (WO ₃ ) 21 Commercially available tungsten dioxide (WO ₂ ) A box in which an aqueous solution to which 100 ppm of copper oxide (Cu ₂ O) is applied is added to a 1% by weight aqueous solution applied to the inner surface 22 Water tank (no water, for sealing)
23 For comparison, a box not coated with any aqueous photocatalyst solution 24 A box to which a dry powder having an average particle diameter of 30 nm of the hydrated tungsten suboxide of the present invention is attached 25 Tungsten trioxide prepared in Example 2 (WO ₃ ) A box to which dry powder with an average particle diameter of 100 nm is attached 26 A box to which dry powder with an average particle diameter of 20 nm of tungsten dioxide (WO ₂ ) prepared in Example 3 is attached

Claims (2)

WO _n · (H ₂ O) _m [1.5 <n <3.0, 0.5 <m <7.0] A method for producing a tungsten dioxide compound obtained by firing. WO _n. (H ₂ O) _m [1.5 <n <3.0, 0.5 <m <7.0] hydrated tungsten oxide hydrate crystals are fired in an electric furnace at 500 ° C. for 1 hour A method for producing a tungsten trioxide compound.