JP5557969B1 - Cleaning device - Google Patents

Abstract

An installation surface on which an apparatus for cleaning and sterilization and an apparatus itself are maintained hygienically.
A cleaning apparatus includes a cleaning unit, a sterilizing unit, a rinsing unit, and an installation surface on which the cleaning unit, the sterilizing unit, and the rinsing unit are installed. The installation surface 4 includes (1) a step of forming titanium nitride on the surface of the titanium material by heat treatment in an ammonia atmosphere or a nitrogen gas atmosphere having a heating temperature of 750 ° C. or higher, and (2) step (1). The titanium material with titanium nitride formed on the surface is anodized by applying a voltage of 10 V or higher in an electrolyte solution that does not have an etching action on titanium, and a titanium oxide film is formed. And (3) a titanium material having a titanium oxide film formed on the surface obtained in step (2) is selected from an atmosphere in which oxygen gas and nitrogen gas are mixed or an oxygen gas atmosphere in an air atmosphere The photocatalyst material produced in the process of performing a heat treatment at a temperature of 400 ° C. or higher under the atmosphere.
[Selection] Figure 1

Description

  The present invention relates to a container having an opening and an apparatus for cleaning agricultural products such as vegetables.

  When cultivating vegetables and fruits, since the agricultural chemicals are sprayed, the agricultural chemicals adhere to the surfaces of the vegetables and fruits even after harvesting. Therefore, it is essential to remove residual pesticides before cooking or eating raw. Various methods are used to remove this pesticide, and a method using a pesticide-removing detergent is also employed, but there is a problem that rinsing off this pesticide-removing detergent requires a large amount of water. . Therefore, in Patent Document 1, acidic water generated on the anode side by diaphragm electrolysis as an aqueous solution of sodium chloride as electrolyzed water is used as a cleaning liquid that can sufficiently remove agricultural chemicals remaining on the surface of agricultural products such as vegetables. .

  In recent years, awareness of ecology has increased, and for example, drinking water containers such as PET bottles and glass bottles are collected separately and reused to recycle limited resources. However, since the process of separating and reusing drinking water containers is laborious and the recycling of resources is not progressing at present, used drinking water is used from the viewpoint of simplification and efficiency. There has also been a movement to clean and reuse containers. As an apparatus for washing a used drinking water container as described above, for example, in Patent Document 2, a nozzle is inserted into a drinking water container, and the water is sprayed from the nozzle to cause an inner bottom surface and a side surface of the container to be used. There has been proposed an apparatus for cleaning the water. Patent Document 3 proposes an apparatus that sprays water filtered by a reverse osmosis membrane module into a drinking water container and cleans the inside of the container. However, the cleaning apparatus as described above merely rinses a used drinking water container with water, and has not been considered until the container is disinfected or the washed container is dried.

  Here, when washing PET bottles and glass bottles with a general detergent containing a surfactant, a large amount of water is required to rinse off the detergent, resulting in a mixture of a large amount of detergent. Has the problem of being discharged. Therefore, in Patent Document 4, after the oil and fat adhering to the dishes is emulsified into a microbe-decomposable fine particle state with reduced water generated on the cathode side by subjecting a sodium chloride aqueous solution to diaphragm electrolysis without using a detergent. The tableware was washed and sterilized with acidic water produced on the anode side by electrolyzing sodium chloride aqueous solution, rinsed, and then a waste liquid receiving part for collecting drainage was made, and this waste liquid part was emulsified in a fine particle state. After decomposing oils and fats with microorganisms, a cleaning technique that does not adversely affect the decomposition environment is proposed by adsorbing undecomposed oils and fats to a fine fiber cotton-like member.

JP 2010-185018 A JP-A-8-309306 Japanese Patent Laid-Open No. 2004-122000 JP 2008-272334 A

  However, as in Patent Document 1 to Patent Document 4 described above, dirt and bacteria adhering to a container having an opening, and agricultural chemicals and bacteria adhering to agricultural products such as vegetables and fruits can be obtained by diaphragm electrolysis of an aqueous sodium chloride solution. Even if the generated reduced water and acid water can be washed and sterilized, the reduced water used for washing and sterilization, the waste water of the acid water is washed, and the installation surface where the device for sterilization is installed When attached to the device itself, there is a sanitary problem. Moreover, although reduced water and acidic water are produced | generated by performing diaphragm electrolysis of sodium chloride aqueous solution, in order to raise | generate sufficient disinfection and washing | cleaning, high concentration acidic water and reduced water were produced | generated and used. If this highly concentrated acidic water or reduced water is used, there is a risk of adverse effects on the human body, such as rough skin. Furthermore, in order to produce high-concentration acidic water and reduced water, it is necessary to perform diaphragm electrolysis with a relatively high-concentration sodium chloride aqueous solution. At that time, a large amount of toxic chlorine gas may be generated on the anode side. Therefore, there is a problem that a device is required to prevent the chlorine gas, which is extremely harmful to the human body generated in large quantities, from leaking outside. Furthermore, the waste water of reduced water and acidic water used for washing and sterilization has an adverse effect on the environment, but the current situation is that these waste liquid treatments are not sufficiently performed.

  Accordingly, an object of the present invention is to provide a cleaning device that can maintain the installation surface on which a device for cleaning and sterilization, which is a problem of the above-described prior art, and the device itself are hygienically maintained. In addition, the waste liquid after washing and sterilization does not adversely affect the environment, and dirt and bacteria attached to the container, vegetables and fruits in a relatively short time using relatively low concentrations of acidic water and reduced water. It aims at providing the washing | cleaning apparatus which can remove the agrochemical and bacteria adhering to agricultural products, such as.

  As a result of diligent studies to solve the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by the following cleaning apparatus, and have reached the present invention. That is, the cleaning device according to the present invention is a device for cleaning a container having an opening, and includes a cleaning unit that supplies reducing water into the container through the opening, and an acid in the container through the opening. A disinfecting unit for supplying water; a rinsing unit for supplying a rinsing liquid into the container through the opening; and an installation surface on which the cleaning unit, the disinfecting unit, and the rinsing unit are installed. The installation surface is made of a photocatalytic material. The photocatalytic material comprises (1) a surface of a titanium metal material or a titanium alloy (alloy containing titanium as a main component) material, a heating temperature of 750 ° C. or higher, a heat treatment in an ammonia atmosphere, and a nitrogen gas atmosphere. A step of forming titanium nitride by one type of processing method selected from the group consisting of the heat treatment of (2), a metal titanium material having titanium nitride formed on the surface, obtained in step (1), or A step of anodizing the titanium alloy material by applying a voltage of 10 V or higher in an electrolyte solution having no etching action on titanium to form an oxide film of titanium; and (3) step (2). The metal titanium material or titanium alloy material having a titanium oxide film formed on the surface is selected from an atmosphere in which oxygen gas and nitrogen gas are mixed or an oxygen gas atmosphere. In an atmosphere that is, it is produced by carrying out the surface treatment method step, and heat treatment is performed at 400 ° C. or higher.

  According to the cleaning device having the above configuration, even when the reducing water, acidic water and rinsing liquid discharged from the container are dropped on the installation surface, the reducing water, acidic water and rinsing liquid droplets are installed due to the super hydrophilicity of the photocatalytic material. The installation surface can be kept clean because it hardly remains on the surface and has antibacterial action due to the photocatalytic material.

  In the cleaning apparatus having the above configuration, it is preferable that the installation surface further includes light irradiation means for irradiating near ultraviolet rays or ultraviolet rays. By irradiating the photocatalyst material with near-ultraviolet rays or ultraviolet rays excited by the photocatalyst material from a light irradiation means such as a lamp or a fluorescent lamp, OH radicals or the like which are active oxygen having high oxidizing power are generated. Since this OH radical has a sterilizing power far stronger than hydrogen peroxide, ozone, etc. widely used for disinfection and sterilization, it is possible to sterilize bacteria in the waste liquid dripping on the installation surface. Therefore, the installation surface can be more effectively maintained in a sanitary manner.

  Further, in the cleaning apparatus having the above-described configuration, the cleaning unit is provided so as to protrude above the installation surface, and includes a first nozzle that injects reducing water into the container. A second nozzle for injecting acidic water into the container; and the rinsing portion is provided to protrude above the installation surface, and the rinse liquid It is preferable to have a third nozzle that sprays into the container.

  The cleaning device according to the present invention is a device for cleaning crops, stores reduced water, has a first tank that can immerse the crops, stores acidic water, and stores the crops. The disinfection part which has the 2nd tank which can be immersed and the rinse part which has a 3rd tank which can store the rinse liquid and can immerse the said crop are provided. The inner surface of the first layer, the inner surface of the second layer, and the inner surface of the third layer are made of a photocatalytic material. The photocatalyst material is obtained by (1) a metal titanium material produced by one treatment method selected from the group consisting of a heat treatment under an ammonia atmosphere and a heat treatment under a nitrogen gas atmosphere, wherein the heating temperature is 750 ° C. or higher. Alternatively, a step of forming titanium nitride on the surface of the titanium alloy material, (2) etching the titanium metal material or titanium alloy material with titanium nitride formed on the surface obtained in step (1) with respect to titanium A step of forming an oxide film of titanium by anodizing by applying a voltage of 10 V or more in an electrolyte having no action, and (3) oxidation of titanium on the surface obtained in step (2). The metal titanium material or titanium alloy material with the coating formed is heated to 400 ° C. or higher under an atmosphere selected from an atmosphere in which oxygen gas and nitrogen gas are mixed or an oxygen gas atmosphere. Step at a temperature heat treatment is performed, it is produced by.

  According to the cleaning device having the above configuration, when the reducing water, the acidic water, and the rinsing liquid are discharged from the tank, the droplets of the reducing water, the acidic water, and the rinsing liquid are less likely to remain in the tank due to the superhydrophilicity of the photocatalytic material. In addition, since the photocatalytic material has an antibacterial action, the inside of the tank can be kept clean.

  In the cleaning apparatus having the above-described configuration, it is preferable to further include light irradiation means for irradiating the inner surfaces of the first to third layers with near ultraviolet rays or ultraviolet rays. By irradiating the photocatalyst material with near-ultraviolet rays or ultraviolet rays excited by the photocatalyst material from a light irradiation means such as a lamp or a fluorescent lamp, OH radicals or the like which are active oxygen having high oxidizing power are generated. Since this OH radical has a sterilizing power far stronger than hydrogen peroxide, ozone, etc. widely used for disinfection and sterilization, it can sterilize bacteria in the waste liquid in the tank. Therefore, the inside of the tank can be more effectively maintained in a sanitary manner.

  In the cleaning apparatus having the above-described configuration, it is preferable that the first to third layers are swingable. Further, if necessary, an ultrasonic cleaning device can be attached to effectively clean the pesticide adhering to the pesticide.

  In any of the above-described cleaning apparatuses, the heat treatment in the nitrogen gas atmosphere of the titanium metal or titanium alloy used as the material constituting the installation surface is performed in the presence of an oxygen trap agent. Is preferred.

  Further, the electrolytic solution having no etching action on titanium used in the anodic oxidation is an electrolytic solution containing at least one compound selected from the group consisting of inorganic acids, organic acids and salts thereof. preferable.

  In addition, it is preferable that at least one compound selected from the group consisting of the inorganic acid, organic acid and salts thereof is at least one compound selected from the group consisting of phosphoric acid and phosphate.

  Moreover, it is preferable that the voltage applied by the anodic oxidation of the said process (2) is 50V-300V.

  Moreover, it is preferable that the temperature of the heat processing performed in the said oxidizing atmosphere is 400 to 700 degreeC.

  The titanium oxide film formed by anodic oxidation is preferably a crystalline titanium oxide film.

  The crystalline titanium oxide film is preferably an anatase type titanium oxide film.

  Further, the reducing water waste liquid discharged from the cleaning section, the acidic water waste liquid discharged from the disinfection section and the rinse waste liquid discharged from the rinse section, and a purification processing section for purifying with a photocatalytic material, and A filtration unit that filters the reduced water waste liquid, the acidic water waste liquid, and the rinse liquid waste liquid discharged from the purification processing unit with a filter, and a light irradiation unit that irradiates the photocatalyst material of the purification processing unit with near ultraviolet rays or ultraviolet rays. And (1) one type selected from the group consisting of heat treatment in an ammonia atmosphere and heat treatment in a nitrogen gas atmosphere, wherein the heating temperature is 750 ° C. or higher. A step of forming titanium nitride on the surface of the metal titanium material or titanium alloy material by a treatment method; (2) a metal chip obtained in step (1) and having titanium nitride formed on the surface; Forming an oxide film of titanium by anodizing a titanium material or a titanium alloy material by applying a voltage of 10 V or more in an electrolyte solution having no etching action on titanium, and (3) step The metal titanium material or titanium alloy material having a titanium oxide film formed on the surface obtained in (2) was selected from an atmosphere in which oxygen gas and nitrogen gas were mixed or an oxygen gas atmosphere in an air atmosphere It is preferable to perform the purification treatment using a photocatalytic material produced by a heat treatment step at a temperature of 400 ° C. or higher in an atmosphere.

  According to this embodiment, for example, the waste liquid is poured into a waste liquid storage tank in which the photocatalytic material is installed, and the photocatalytic material is irradiated with near ultraviolet rays or ultraviolet rays that can photoexcite anatase-type titanium oxide with a lamp or a fluorescent lamp. Active oxygen such as OH radicals, which are extremely active and have strong oxidizing power, are generated. Therefore, it becomes possible to decompose and sterilize organic substances such as fats and oils, agricultural chemicals, bacteria, and the like contained in the waste liquid with the photocatalytic material. Therefore, it is possible to decompose organic substances such as fats and oils in the waste liquid and sterilize bacteria that have not been sterilized with acidic water. Unlike the conventional microbial decomposition, the waste liquid purification technology using this photocatalyst material does not have a concern that the effect is reduced even when acidic water having antibacterial properties coexists. In the microbial decomposition, the microbial layer needs to be inserted from time to time, whereas the waste liquid purification technology by the photocatalytic reaction lasts semipermanently if there is light irradiation. Moreover, in order to improve a photocatalytic reaction, you may add a trace amount ozone and hydrogen peroxide as needed. In addition, by filtering solid matter such as organic matter, agricultural chemicals, bacteria, and food residues that could not be removed with the photocatalyst material, the waste liquid can be made clean, preventing environmental pollution. it can.

  Moreover, it is preferable that the said reduced water used for washing | cleaning and the said acidic water used for disinfection are produced | generated by diaphragm electrolysis which uses sodium chloride aqueous solution whose density | concentration is 0.001%-0.5% as electrolyzed water. . When membrane electrolysis of a relatively high concentration sodium chloride aqueous solution is performed, a large amount of toxic chlorine gas may be generated on the anode side at that time. It is necessary to devise such that it does not leak. As in this embodiment, in diaphragm electrolysis using a dilute sodium chloride aqueous solution as electrolyzed water, since it is not necessary to implement a device that prevents harmful chlorine gas from leaking to the outside, simplicity, economy, It is preferable for reasons such as safety.

  Moreover, it is preferable that the said reduced water and the said acidic water after the said filtration process are reused for the production | generation of the said reduced water used for washing | cleaning and the said acidic water used for disinfection. According to this embodiment, it is possible not only to efficiently use the acidic water and the reduced water by reusing the waste liquid finally filtered through the filter and generating reduced water and acidic water by diaphragm electrolysis. By suppressing the amount of discharged liquid, it is possible to prevent the contaminated waste liquid from causing a load on the environment, so that a highly efficient circulation type cleaning apparatus can be constructed. In addition, regarding the reuse for the production of acidic water and reduced water, the chloride ion is consumed in the recovery of the rinsing liquid and the production of hypochlorous acid by electrolysis. Since the sodium chloride concentration may decrease, sodium chloride may be added in a timely manner when performing diaphragm electrolysis as necessary.

  The filter is preferably composed of at least one filter selected from a filter that removes organic matter, a filter that removes solid matter, and an ion exchange resin filter. The filtration process with a filter is intended to remove food residues, bacterial debris, and organic substances that could not be decomposed by the photocatalyst material in the waste liquid after purification treatment from the waste liquid. It is the thing of the structure which installed the filter inside. As a filter, by using a porous material such as activated carbon, a hollow fiber membrane, or a continuous porous body, dirt, oil and fat, etc. that have not been decomposed by the photocatalyst material can be filtered. Moreover, when an ionic substance is contained in the waste liquid, it can be removed by using an ion exchange resin filter. Moreover, solid matters such as food residues and dead bodies of bacteria can be removed by using a filter such as filter paper suitable for the size of the solid matter. If necessary, the present filter can be used to combine the above-described plural kinds of waste liquids, so that the waste liquid can be filtered well and discharged in a clean state. In order to improve the filterability of the filter, an aggregating agent such as polyaluminum chloride may be used in combination as necessary.

  According to the cleaning apparatus of the present invention, the installation surface on which the apparatus for cleaning and sterilization is installed and the apparatus itself can be maintained hygienically.

It is a front schematic diagram of the washing device concerning one embodiment of the present invention. It is a front schematic diagram which shows the usage method of the washing | cleaning apparatus which concerns on one Embodiment of this invention. It is the front schematic of the washing | cleaning apparatus of the modification of FIG. It is the front schematic of the washing | cleaning apparatus of the modification of FIG. It is a front schematic diagram of the washing device concerning other embodiments of the present invention. It is a graph which shows the relationship between the sodium chloride density | concentration supplied to the electrolysis apparatus, and the hypochlorous acid density | concentration in the acidic water produced | generated from the anode side.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. The cleaning apparatus 10 according to the present embodiment is for cleaning the bottle B by removing dirt, bacteria, and the like attached to the bottle B (container) having an opening, and as shown in FIG. As a cleaning unit 6 for supplying reducing water, a disinfecting unit 1 for supplying acidic water as a disinfecting liquid in the bottle B, a rinsing unit 2 for supplying a rinsing liquid into the bottle B, and a drying unit for blowing air into the bottle B 3 is provided. Moreover, the washing | cleaning apparatus 10 is provided with the installation surface 4 in which the 1st-4th nozzle 61,11,21,31 mentioned later is installed.

  The cleaning unit 6 includes a first nozzle 61 that protrudes upward from the installation surface 4 and a cleaning liquid storage tank (cleaning liquid supply source) 62 in which the reduced water is stored, and is compressed into the cleaning liquid storage tank 62 by a compressor. When the air is sent in, the reducing water in the cleaning liquid storage tank 62 is sent to the first nozzle 61. The first nozzle 61 is configured to be able to inject the reducing water from the cleaning liquid storage tank 62 into the bottle B from the tip and side surfaces, and to be able to rotate 360 ° around the axis. The first nozzle 61 may have any shape that can be inserted into the bottle B. However, the first nozzle 61 is more than the opening of the bottle B so that the reducing water injected into the bottle B can be discharged from the opening of the bottle B. The diameter is small. A first restricting tool 50 is provided on the installation surface 4, and the movement of the bottle B is prevented by the first restricting tool 50 from moving upward due to the hydraulic pressure of the reducing water ejected from the first nozzle 61. Is regulated. Although the 1st control tool 50 is not specifically limited, For example, the thing provided with the bar 501 and the upper piece 502, and the bottom piece of the bottle B contact | abutted to the upper piece 502 is mentioned. The upper piece 502 may be detachably attached to the bar 501 with a screw, or may be attached to the bar 501 so as to open a connecting portion with the bar 501 as a fulcrum. In addition, since a mouth may be directly attached to the bottle B having an opening, a nozzle may be provided so that the reducing water can be injected also to the outer peripheral surface of the opening of the bottle B.

  The temperature of the reducing water sprayed in the cleaning unit 6 is not particularly limited, and is usually 5 ° C to 30 ° C, preferably 20 ° C to 30 ° C. Further, the spray time of the reduced water varies depending on the amount of organic matter such as fats and oils adhering to the bottle B, but is 1 second to 60 seconds, preferably 1 second to 30 seconds, more preferably 3 seconds to 10 seconds. . By shortening the spraying time, it becomes possible to reduce the amount of waste water of reduced water.

  The disinfecting unit 1 includes a second nozzle 11 protruding upward from the installation surface 4 and a disinfecting liquid storage tank (disinfecting liquid supply source) 12 in which acidic water is stored, and the disinfecting liquid storage tank 12 by a compressor. The acidic water in the disinfectant liquid storage tank 12 is configured to be sent to the second nozzle 11 by sending compressed air therein. The second nozzle 11 is configured to be able to inject the acidic water from the disinfectant solution storage tank 12 into the bottle B from the tip and side surfaces, and to rotate 360 ° around the axis. In addition, since a mouth may be directly attached to the bottle B having an opening, a nozzle may be provided so that acidic water can be injected also to the outer peripheral surface of the opening of the bottle B. About the structure of the 2nd nozzle 11 and the 2nd control tool 51, since it is the same as that of the 1st nozzle 61 and the 1st control tool 61, description is abbreviate | omitted.

  The temperature of the acidic water sprayed in the disinfection unit 1 is not particularly limited, and is usually 5 ° C to 30 ° C, preferably 20 ° C to 30 ° C. Moreover, although the spray time of acidic water changes with the bacterial contamination degree adhering to the bottle B, it is 1 second-60 seconds, Preferably it is 1 second-30 seconds, More preferably, it is 3 seconds-10 seconds. By shortening the spraying time, it becomes possible to reduce the amount of waste liquid of acidic water.

  The rinsing unit 2 includes a third nozzle 21 that protrudes upward from the installation surface 4 and a rinsing liquid storage tank (rinsing liquid supply source) 22 in which the rinsing liquid is stored. The rinsing liquid in the rinsing liquid storage tank 22 is sent to the third nozzle 21 by sending the compressed air into the inside. In addition, you may make it provide a nozzle so that the rinse liquid can also be injected also with respect to the outer peripheral surface of the opening of the bottle B. About the structure of the 3rd nozzle 21 and the 3rd control tool 52, since it is the same as that of the 1st nozzle 61 and the 1st control tool 61, description is abbreviate | omitted. The rinsing liquid is not particularly limited as long as it does not remain in the bottle B, and it is preferable to use tap water in consideration of economy.

  The drying unit 3 includes a fourth nozzle 31 that protrudes upward from the installation surface 4 and an airflow generation means 32. The air flow generation means 32 is not particularly limited as long as it can generate an air flow toward the fourth nozzle 31. For example, various devices such as a compressor that generates compressed air, an air pump, and a fan are used. be able to. In order to shorten the drying time of the bottle B, the drying unit 3 is preferably provided with a heater (not shown) for heating the air sent from the airflow generation means 32 to the fourth nozzle 31. Note that the configurations of the fourth nozzle 31 and the fourth restricting tool 53 are the same as those of the first nozzle 61 and the first restricting tool 61, and thus the description thereof is omitted.

  The installation surface 4 is made of a photocatalytic material. The photocatalyst material is obtained by (1) heat treatment in an ammonia atmosphere and heat treatment in a nitrogen gas atmosphere at a heating temperature of 750 ° C. or higher on the surface of a titanium metal material or a titanium alloy (alloy containing titanium as a main component) material. After performing the step of forming titanium nitride by one type of processing method selected from the group consisting of: (2) by applying a voltage of 10 V or higher in an electrolyte solution that does not have an etching action on titanium. After performing the step of forming an oxide film of titanium by performing anodization, (3) 400 ° C. or higher in an atmosphere selected from an atmosphere in which oxygen gas and nitrogen gas are mixed or an oxygen gas atmosphere It is formed by performing the surface treatment method of performing the process of heat-processing at the temperature of this.

(1) Step of forming titanium nitride A method for producing a surface-treated metal titanium material or titanium alloy material (hereinafter, the metal titanium material and titanium alloy material may be simply referred to as “titanium material”) Forming titanium nitride on the surface of the material or titanium alloy material. In the present invention, when a titanium alloy material is used, the type thereof is not particularly limited. Examples of the titanium alloy material include Ti-6Al-4V, Ti-4.5Al-3V-2Fe-2Mo, Ti-0.5Pd, and the like. The metal titanium material is titanium itself.

  In this step, a titanium nitride layer is usually formed on the surface of the titanium material to a thickness of about 0.1 μm to 100 μm, preferably about 0.5 μm to 50 μm, more preferably about 1 μm to 10 μm. As a means for forming titanium nitride on the surface of the titanium material, heat treatment in an ammonia gas atmosphere and heat treatment in a nitrogen gas atmosphere are used. The heating temperature of the heat treatment under an ammonia gas or nitrogen gas atmosphere is preferably about 750 ° C. or higher, more preferably about 750 ° C. to 1050 ° C., and further preferably about 750 ° C. to 950 ° C. Considering simplicity, economy, and safety, a method of heating the titanium material at about 750 ° C. or higher in a nitrogen gas atmosphere is most preferable. The heat treatment in an ammonia gas or nitrogen gas atmosphere is preferably performed in the presence of an oxygen trap agent. Examples of the oxygen trap agent used in the heat treatment of the titanium material include a substance or gas having a higher affinity for oxygen than the titanium material. For example, a carbon material, metal powder, hydrogen gas, etc. are illustrated. These oxygen trap agents may be used individually by 1 type, and may be used in combination of 2 or more type.

  The carbon material is not particularly limited, and examples thereof include graphitic carbon, amorphous carbon, and carbon having an intermediate crystal structure. The carbon material may have any shape such as a flat plate shape, a foil shape, and a powder shape. It is preferable to use a flat carbon material because it is easy to handle and prevents thermal distortion during the heat treatment of the titanium material.

  The metal powder is not particularly limited. For example, titanium, titanium alloy, chromium, chromium alloy, molybdenum, molybdenum alloy, vanadium, vanadium alloy, tantalum, tantalum alloy, zirconium, zirconium, zirconium alloy, silicon, silicon alloy, aluminum, Examples thereof include metal powders such as aluminum alloys. For reasons of high oxygen affinity, it is preferable to use metal powder such as titanium, titanium alloy, chromium, chromium alloy, zirconium, zirconium alloy, aluminum, aluminum alloy. The most preferable metal powder is fine particle titanium or titanium alloy metal powder. The said metal powder may be used individually by 1 type, and may be used in combination of 2 or more type. The average particle diameter of the metal powder is preferably about 0.1 μm to 1000 μm, more preferably about 0.1 μm to 100 μm, and still more preferably about 0.1 to 10 μm.

  Conditions for using the oxygen trap agent in an ammonia gas or nitrogen gas atmosphere can be set in a timely manner according to the type and shape of the oxygen trap agent. For example, when a carbon material or metal powder is used as an oxygen trap agent, the carbon material or metal powder is brought into contact with the titanium material, the surface of the titanium material is covered with the carbon material or metal powder, and the titanium material is covered with ammonia gas or The method of heat-processing in nitrogen gas atmosphere is mentioned. In the case where hydrogen gas is used as the oxygen trap agent, there is a method in which the titanium material is heat-treated in a state where hydrogen gas is introduced in an atmosphere of ammonia gas or nitrogen gas.

  Heat treatment can be performed in an atmosphere of ammonia gas, nitrogen gas, or a mixed gas of ammonia gas and nitrogen gas. Considering simplicity, economy and safety, it is most preferable to use nitrogen gas.

  The reaction pressure of the heat treatment in an ammonia gas or nitrogen gas atmosphere is about 0.01 MPa to 100 MPa, preferably about 0.1 MPa to 10 MPa, and more preferably about 0.1 MPa to 1 MPa. Heat treatment in a nitrogen gas atmosphere is preferable.

  The heating time of the heat treatment under an ammonia gas or nitrogen gas atmosphere is preferably about 1 minute to 12 hours, more preferably about 10 minutes to 8 hours, and further preferably about 1 hour to 6 hours. It is preferable to heat-treat the titanium material for this time.

  In the method of heat-treating titanium material in an atmosphere of ammonia gas or nitrogen gas, in order to efficiently form titanium nitride on the surface of the titanium material, a rotary vacuum pump, mechanical booster pump, or oil diffusion pump is used as necessary. It is preferable that the inside of the furnace to be heat-treated is depressurized to reduce the oxygen concentration remaining in the furnace to be heat-treated (inside the nitriding furnace). Titanium nitride can be efficiently formed on the surface of the titanium material by reducing the pressure in the furnace for heat treatment to about 10 Pa or less, more preferably about 1 Pa or less, and even more preferably about 0.1 Pa or less.

  By supplying ammonia gas, nitrogen gas or a mixed gas of ammonia gas and nitrogen gas into the furnace in the decompressed furnace, the inside of the furnace is decompressed, and the titanium material is heat-treated, so that the surface of the titanium material is heated. Titanium nitride can be formed efficiently. About the heating temperature, heating time, etc. of the heat treatment using the main furnace, the same conditions as described above may be used. As the gas composition, it is most preferable to use nitrogen gas in consideration of simplicity, economy, and safety.

  In addition, by alternately repeating (several times) a decompression process for reducing the oxygen concentration remaining in the furnace to be heat-treated and a return pressure process for supplying nitrogen gas or the like into the furnace, the surface of the titanium material is made of titanium. Nitride can be formed more efficiently. Furthermore, titanium nitride can be more efficiently formed on the surface of the titanium material by performing pressure reduction treatment in the presence of an oxygen trap agent and heat treatment in a gas atmosphere such as ammonia gas or nitrogen gas.

The type of titanium nitride formed on the surface of the titanium material is not particularly limited. For example, TiN, Ti ₂ N, α-TiN _0.3 , η-Ti ₃ N _2-X , ζ-Ti ₄ N _3-X (where X represents a numerical value of 0 or more and less than 3), a mixture thereof, And amorphous titanium nitride. Among these, TiN, Ti ₂ N, and a mixture thereof, more preferably TiN, and a mixture of TiN and Ti ₂ N, particularly preferably TiN are exemplified.

  In the present invention, as a means for forming the titanium nitride, one of the above methods may be performed alone, or two or more methods may be arbitrarily combined. Among the methods for forming titanium nitride, from the viewpoints of simplicity, mass productivity, production cost, etc., heat treatment of the titanium material in a nitrogen gas atmosphere is preferable.

(2) Step of anodizing The method for producing a surface-treated metal titanium material or titanium alloy material has an etching action on titanium with a metal titanium material or titanium alloy material having titanium nitride formed on the surface. A step of forming an oxide film of titanium by performing anodic oxidation in an electrolytic solution containing at least one acid selected from the group consisting of inorganic acids and organic acids and salt compounds thereof.

  A titanium material with titanium nitride formed on the surface is anodized at an electric voltage of 10 V or more in an electrolyte solution that does not have an etching property to titanium, so that the surface of the titanium material is amorphous. An oxide film of titanium can be formed.

  The electrolytic solution having no etching action on titanium is an electrolytic solution containing at least one compound selected from the group consisting of inorganic acids, organic acids and salts thereof (hereinafter also referred to as inorganic acids). It is preferable. The electrolytic solution containing the inorganic acid or the like is preferably a dilute aqueous solution such as phosphoric acid or phosphate.

  Usually, crystalline titanium oxide such as anatase-type titanium oxide is not formed only by the step of performing the anodic oxidation of the present invention. In the next heat treatment, anatase-type titanium oxide can be formed from amorphous titanium oxide. Therefore, for the reason that an amorphous titanium oxide film is effectively formed on the surface of the titanium material, it is preferable to anodize the titanium material having titanium nitride formed on the surface.

  A highly active photocatalytic material is produced at a low cost and in a safe manner by performing an anodizing step between the above-described titanium nitride forming step and a heat treatment step described later. Can do.

  Since the step of anodizing according to the present invention does not use a strong acid such as sulfuric acid having an etching action on titanium, safety is high. The step of anodizing according to the present invention does not require etching with respect to titanium accompanying the spark discharge phenomenon, and therefore does not require a high voltage and a high current. Therefore, an expensive power supply device that applies high current and high voltage and high power associated with high current and high voltage are not required, which is economical.

  In anodic oxidation, it is preferable to use an electrolytic solution that does not have an etching action on titanium in consideration of simplicity, economy, safety, and the like. As an electrolytic solution having no etching action on titanium, at least one compound (inorganic acid, etc.) selected from the group consisting of inorganic acids (phosphoric acid, etc.), organic acids and salts thereof (phosphates, etc.) ) Is preferable.

  As an inorganic acid that does not have an etching action on titanium, phosphoric acid, carbonic acid, and the like are preferable in consideration of convenience, economy, safety, and the like. As the organic acid having no etching action on titanium, acetic acid, adipic acid, lactic acid and the like are preferable. Further, salts of these acids such as sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium hydrogen carbonate, sodium acetate, potassium adipate, sodium lactate and the like can also be used.

  In addition, it is preferable to use an electrolytic solution containing an electrolyte such as sodium sulfate, potassium sulfate, magnesium sulfate, sodium nitrate, potassium nitrate, magnesium nitrate, or calcium nitrate. As the inorganic acid, phosphoric acid and phosphate are most preferable.

  The electrolytic solution is preferably a dilute aqueous solution such as an inorganic acid. The concentration of the inorganic acid or the like in the electrolytic solution is preferably in the range of about 1% by weight for reasons such as economy. For example, in an electrolytic solution containing phosphoric acid, a concentration range of about 0.01 wt% to 10 wt% is preferable, a concentration range of about 0.1 wt% to 10 wt% is more preferable, and 1 wt% to 3 wt%. A concentration range of about% is more preferable.

  These acids may be used alone or in combination of any two or more of these acids, regardless of whether they are organic acids, inorganic acids, or salts thereof. As an example of the preferable aspect of the electrolyte solution containing 2 or more types of acids and salts, the aqueous solution containing a phosphate and phosphoric acid is mentioned. The mixing ratio of the acid in the electrolytic solution varies depending on the type of acid and acid salt used, anodization conditions, and the like, but is generally 0.01% to 10% by weight, preferably 0, in terms of the total amount of the acid. A ratio of 1 wt% to 10 wt%, more preferably 1 wt% to 3 wt% can be mentioned.

  In the step of anodizing according to the present invention, an electrolytic solution containing an inorganic acid or the like that does not have an etching action on titanium is used. Compared with the anodic oxidation accompanied by the spark discharge phenomenon disclosed in 2011-200406, a high current is not required. In addition, since the step of anodizing according to the present invention can suppress an increase in the temperature of the electrolytic bath used for anodizing, compared with anodizing associated with the spark discharge phenomenon, the cost for cooling the electrolytic solution can be suppressed. It is possible. Therefore, as compared with the anodizing process accompanied by the spark discharge phenomenon, the process of anodizing according to the present invention can process a material over a large area, which is advantageous in terms of economy, safety, mass productivity, and the like.

  A titanium material in which titanium nitride is formed is immersed in a dilute electrolytic solution containing an inorganic acid or the like that does not have an etching action on titanium on the surface obtained in the step of forming titanium nitride. Next, anodization is preferably performed by applying a voltage of about 10V to 300V. It is more preferable to perform anodization at a voltage of about 50V to 300V, and it is even more preferable to perform anodization at a voltage of about 50V to 200V.

  The treatment temperature for anodization is preferably about 0 ° C. to 80 ° C. for reasons such as simplicity, economy and safety. It is more preferable to perform anodization at a temperature of about 10 ° C to 50 ° C, and it is more preferable to perform anodization at a temperature of about 20 ° C to 30 ° C.

  The treatment time for anodization is preferably about 1 second to 1 hour. It is more preferable to perform anodization in a time of about 10 seconds to 30 minutes, and it is further preferable to perform anodization in a time of about 5 minutes to 20 minutes. Anodizing treatment that does not generate spark discharge is a preferred anodizing treatment because the treatment time is short and the cost is high.

(3) Step of performing heat treatment The method for producing a surface-treated metal titanium material or titanium alloy material is obtained by combining a metal titanium material or titanium alloy material having a titanium oxide film formed on the surface thereof with oxygen gas in an air atmosphere. A step of performing a heat treatment at a temperature of 400 ° C. or higher in an atmosphere selected from an atmosphere in which nitrogen gas is mixed or an oxygen gas atmosphere.

  By simply heat-treating a metal titanium material or the like, rutile type titanium oxide having poor photocatalytic activity is formed, but anatase type titanium oxide having high photocatalytic activity is not formed. In the present invention, a titanium material (titanium material after anodizing treatment) on which a titanium oxide film (amorphous titanium oxide film) is formed is heated in an oxidizing atmosphere (such as atmospheric oxidation treatment). Since anatase-type titanium oxide film useful for a highly active photocatalyst can be formed in crystalline titanium oxide, the titanium material after the heat treatment is excellent in photocatalytic activity.

  The oxidizing atmosphere for performing the heat treatment may be selected from an atmospheric oxidizing atmosphere, an atmosphere having an arbitrary oxygen gas concentration in which oxygen gas and nitrogen gas are mixed, an oxygen gas atmosphere, and the like. Heat treatment in an atmospheric oxidation atmosphere is preferable for reasons such as safety and safety.

  The temperature of the heat treatment in an oxidizing atmosphere is preferably about 400 ° C. or higher because it efficiently changes from amorphous titanium oxide to anatase titanium oxide. The temperature of the heat treatment in an oxidizing atmosphere is preferably about 800 ° C. or lower for the purpose of preventing phase transition from anatase-type titanium oxide to rutile-type titanium oxide. This is because rutile type titanium oxide has poor photocatalytic properties as compared with anatase type titanium oxide. The temperature of heat treatment in an oxidizing atmosphere is particularly preferably about 400 to 700 ° C.

  The reaction pressure for performing the heat treatment is about 0.01 MPa to 10 MPa, preferably about 0.01 MPa to 5 MPa, and more preferably about 0.1 MPa to 1 MPa. The heating time for performing the heat treatment is preferably about 1 minute to 12 hours, more preferably about 10 minutes to 8 hours, and further preferably about 1 hour to 6 hours.

  By configuring the installation surface 4 with such a photocatalyst material, it is possible to provide the installation surface 4 with a photocatalyst function that exhibits super-hydrophilicity. Therefore, the reduced water, acidic water, and rinse discharged from the bottle B Liquid droplets are unlikely to remain on the installation surface 4, and the installation surface 4 can be kept clean. Moreover, since the antibacterial action by the photocatalytic material is present, the installation surface 4 can be kept clean.

  Moreover, it is preferable to irradiate the photocatalyst material of the installation surface 4 with light using light irradiation means 14 such as a lamp or a fluorescent lamp that irradiates near ultraviolet rays or ultraviolet rays. When the photocatalyst material is irradiated with light, OH radicals or the like which are active oxygen having high oxidizing power are generated. Since this OH radical has a sterilizing power far stronger than hydrogen peroxide and ozone widely used for disinfection and sterilization, bacteria attached to the bottle B can be sterilized. It can be kept hygienic. The shape and the installation position of the light irradiation means 14 are not particularly limited as long as the installation surface 4 can be irradiated with light, but near ultraviolet rays or ultraviolet rays are emitted in order to improve the reactivity of the photocatalyst. The lamp, the fluorescent lamp, and the like are preferably provided at a position close to the installation surface 4.

  In addition, in the above-mentioned Japanese Patent Application Laid-Open No. 2011-200406, in order to produce a photocatalytic material, after forming titanium nitride on the surface of metal titanium, electrolysis containing an acid having an etching property with respect to metal titanium. There has been proposed a technique for forming anatase-type titanium oxide on the surface of titanium metal by performing anodization by applying a voltage higher than the spark discharge generation voltage in the liquid. However, in this technique, it is necessary to use a dangerous strong acid such as sulfuric acid in order to etch metal titanium having extremely high corrosion resistance. In addition, in anodizing at a voltage higher than the spark discharge generation voltage, an expensive power source capable of outputting high voltage and high current is required. In addition, a cooling device for suppressing the heat generation of the electrolytic solution due to the occurrence of spark discharge is required, and there is a problem that the cost is high for producing the photocatalyst. The method for producing a photocatalytic material in the present invention has an effect that the above-described problems can be solved.

  The above-described reduced water and acidic water can be generated, for example, by the following method. That is, reducing water is generated on the cathode side simultaneously with an aqueous solution of sodium chloride in an electrolytic cell provided with an anode plate and a cathode plate through an ion permeable membrane that transmits anions or cations. On the side, acid water having sterilization and disinfection is generated. The aqueous sodium chloride solution in this electrolytic cell has a dilute concentration of 0.001 to 0.5%, preferably 0.01 to 0.5%, more preferably 0.01 to 0.2%. An aqueous sodium chloride solution can be used. As a result, dilute reduced water and acidic water are generated that have little environmental impact and do not affect the human body. The reduced water has a pH of 10.25 to 12.00 and an ORP (redox potential) of about −121 mV to −858 mV, and the acidic water has a pH of 2.10 to 3.50 and an ORP (redox potential). ) Is about +746 mV to +1171 mV. In the present embodiment, the above-described diluted reduced water and acidic water are generated in the electrolyzed water production apparatus 9 and supplied to the cleaning liquid storage tank (cleaning liquid supply source) 62 and the disinfecting liquid storage tank (disinfecting liquid supply source) 12, respectively. Is done.

  Next, a method of using the cleaning apparatus 10 as described above will be described with reference to FIGS.

  First, as shown in FIG. 2, the opening of the empty bottle B is directed downward, the first nozzle 61 of the cleaning unit 6 is inserted into the bottle B from this opening, and the bottle B comes off from the first nozzle 61. The upper piece member 502 of the first restricting tool 50 is disposed above the bottle B so as not to be present (FIG. 2A). In this state, compressed air is supplied to the cleaning liquid storage tank 62 by a compressor, and the reducing water in the cleaning liquid storage tank 62 is injected into the bottle B from the tip and side surfaces of the first nozzle 50. At this time, the 1st nozzle 61 rotates 360 degrees around an axis | shaft so that reduced water may spread evenly in the bottle B. After reducing water is injected into the bottle B for a predetermined time, the supply of compressed air into the cleaning liquid storage tank 62 is stopped, and the injection of reducing water from the first nozzle 61 is stopped.

  Next, the bottle B is removed from the first restricting tool 50 and the first nozzle 61 and moved to the disinfection unit 1 (FIG. 2B). And the 2nd nozzle 11 of the disinfection part 1 is inserted in the bottle B, and the upper piece material 512 of the 2nd control tool 51 is arrange | positioned above the bottle B so that it may not remove | deviate from the 2nd nozzle 11 (FIG. 2 (b)). In this state, compressed air is supplied into the disinfecting liquid storage tank 12 by a compressor, and acidic water in the disinfecting liquid storage tank 12 is injected into the bottle B from the tip and side surfaces of the second nozzle 11. At this time, the second nozzle 11 rotates 360 ° around the axis so that the acidic water is evenly distributed in the bottle B. After the acidic water is sprayed into the bottle B for a predetermined time, the supply of compressed air into the disinfecting liquid storage tank 12 is stopped, and the disinfecting liquid injection from the second nozzle 11 is stopped.

  Next, the bottle B is removed from the second restricting tool 51 and the second nozzle 11 and moved to the rinsing section 2 (FIG. 2C). Then, the third nozzle 21 is inserted into the bottle B and the third restrictor 52 is set, and the compressed air is supplied into the rinse liquid storage tank 22 by a compressor, thereby rinsing the rinse liquid storage tank 22. The liquid is sprayed into the bottle B from the tip and side surfaces of the third nozzle 21. At this time, the third nozzle 21 rotates 360 ° around the axis so that the rinsing liquid is evenly distributed in the bottle B. The temperature of the rinsing liquid is not particularly limited, and is usually 5 to 80 ° C., preferably 20 to 30 ° C., although it depends on the material of the bottle B. The higher the temperature of the rinsing liquid, the shorter the drying time for the next step. After the rinsing liquid is injected into the bottle B for about 1 second to 60 seconds, the supply of the compressed air into the rinsing liquid storage tank 22 is stopped, and the injection of the rinsing liquid from the third nozzle 21 is stopped. Let

  Next, the bottle B is removed from the third restrictor 52 and the third nozzle 21 and moved to the drying unit 3, and the fourth nozzle 31 is inserted into the bottle B and the fourth restrictor 53 is set. (FIG. 2D). Then, the airflow generation means 32 is operated to inject air from the airflow generation means 32 into the bottle B from the tip and side surfaces of the fourth nozzle 31. At this time, if necessary, the air sent from the airflow generating means 32 to the fourth nozzle 31 may be heated by a heater, and the heating temperature at this time depends on the material of the bottle B to be washed, but 30 It can be set to -100 degreeC. The fourth nozzle 31 rotates 360 ° around the axis so that the inside of the bottle B is uniformly dried. Depending on the material of the bottle B to be cleaned, if the air flow generating means 32 is stopped after jetting air into the bottle B for about 1 second to 60 seconds, the cleaning of the bottle B is completed, and the bottle B is Can be used.

  As described above, the cleaning device 10 according to the present embodiment includes the cleaning unit 6 for cleaning and disinfecting the bottle B and the disinfecting unit 1 in addition to the rinsing unit 2, and the drying unit 3 for drying the bottle B. In addition to rinsing the bottle B, the bottle B can be cleaned and disinfected, and the rinsed bottle B can be dried. In addition, since the cleaning unit 6, the sterilizing unit 1, the rinsing unit 2, and the drying unit 3 are each provided with a nozzle, it is possible to simultaneously perform cleaning, disinfection, rinsing, and drying of a plurality of bottles B, The bottle B can be washed efficiently and speedily. In the present embodiment, washing with reducing water, sterilization with acidic water, rinsing and drying are performed through different nozzles, but a plurality of bottles B are washed together. It is also possible to change the design to sterilize, rinse and dry.

  Furthermore, dilute reduced water and acidic water are produced by diaphragm electrolysis of a dilute sodium chloride aqueous solution, and dirt and bacteria attached to the bottle B are washed using the dilute reduced water and acidic water. Therefore, it can prevent adversely affecting the human body.

  Furthermore, since the installation surface 4 on which the cleaning unit 6, the sterilizing unit 1 and the rinsing unit 2 are installed is composed of a photocatalytic material produced by a predetermined production method, reduced water and acidic water discharged from the bottle B Even when the rinsing liquid is dropped on the installation surface 4, the reduced water, acidic water and rinsing liquid droplets are unlikely to remain on the installation surface 4 due to the superhydrophilicity of the photocatalytic material, and there is an antibacterial action by the photocatalytic material. The installation surface 4 can be kept clean. In addition, when the installation surface 4 is irradiated with near ultraviolet rays or ultraviolet rays, the photocatalytic material is excited to generate OH radicals or the like that are active oxygen having high oxidizing power. Since this OH radical has a sterilizing power far stronger than hydrogen peroxide, ozone, etc. widely used for disinfection and sterilization, it is possible to sterilize bacteria in the waste liquid dripping on the installation surface 4. Therefore, the installation surface 4 can be more effectively maintained in a sanitary manner.

  As mentioned above, although one Embodiment of this invention was described, this invention is not limited to the said embodiment, A various change is possible unless it deviates from the meaning of this invention. For example, in the above embodiment, the cleaning liquid storage tank 62 and the disinfecting liquid storage tank 12 are used as the cleaning liquid supply source and the disinfecting liquid supply source, but the reducing water and the acidic water are supplied to the first and second nozzles 61 and 11. For example, the electrolyzed water production apparatus may be directly connected to the first and second nozzles 61 and 11. Similarly, instead of the rinsing liquid storage tank 22, the rinsing liquid supply source may be, for example, a water supply connected to the third nozzle 21.

  Moreover, in the said embodiment, although the washing | cleaning part 6, the disinfection part 1, and the rinse part 2 were each equipped with the nozzles 61, 11, and 21, it is not limited to this, For example, as shown in FIG. The disinfecting liquid supply source and the rinsing liquid supply source are connected to the single nozzle 15, and the reducing water, the acidic water or the rinsing liquid is selectively supplied to the nozzle 15 by the switching valve 16 and the like, and the single nozzle 15 is injected. You may comprise so that it may perform. According to this embodiment, the apparatus 10 can be reduced in size. In this embodiment, the cleaning unit 6, the disinfecting unit 1, and the rinsing unit 2 are integrated.

  Moreover, in the said embodiment, although reducing water, acidic water, and the rinse liquid were supplied or ventilated in the bottle B via the nozzle, reducing water, acidic water, or a rinse liquid was supplied in the container, If the air can be blown, the nozzle need not be used.

  Moreover, in the said embodiment, although the washing | cleaning apparatus 10 was equipped with the washing | cleaning part 6, the disinfection part 1, the rinse part 2, and the drying part 3, one washing | cleaning part, disinfection part, a rinse part, and a drying part are provided. It can also be provided.

  In addition, as shown in FIG. 4, a purification treatment unit 7 that collects waste liquid such as reduced water used for cleaning and acidic water used for disinfection and performs purification treatment with a photocatalytic material, and a photocatalytic material after purification treatment. It may be configured to further include a filtering unit 8 that filters what could not be removed. In FIG. 4, the basic configuration is the same as the configuration of the embodiment in FIGS. 1 and 2, and the detailed description is omitted here by assigning the same reference numerals to the corresponding configurations.

  In FIG. 4, a cleaning unit 6 that supplies reducing water as a cleaning liquid into the bottle B, a disinfection unit 1 that supplies acidic water as a disinfecting liquid into the bottle B, and a rinsing unit 2 that supplies a rinsing liquid into the bottle B. , A drying unit 3 that blows air into the bottle B, and a purification processing unit that recovers waste liquid such as reduced water used for cleaning and acidic water used for disinfection and performs purification using the photocatalyst material produced by the above production method. 7 and a filtration unit 8 for filtering what could not be removed by the photocatalyst material after the purification treatment.

  The purification treatment unit 7 collects the reducing water waste liquid, acidic water waste liquid and rinse liquid (all collectively referred to as waste liquid) used for the cleaning, disinfection and rinsing described above, and performs the purification treatment, and can store the waste liquid. In this configuration, a photocatalyst material is installed inside a waste liquid storage tank. As the photocatalyst material used for the waste liquid purification treatment, a material formed by the same method as the photocatalyst material constituting the installation surface 4 is used.

  By pouring waste liquid into a waste liquid storage tank in which such a photocatalyst material is installed and irradiating the photocatalyst material with near-ultraviolet light or ultraviolet light capable of photoexciting anatase-type titanium oxide by a light irradiation means 14 such as a lamp or a fluorescent lamp. In addition, active oxygen such as OH radicals having extremely high activity and strong oxidizing power is generated, and it is possible to decompose hardly decomposable organic substances in the waste liquid. Therefore, it is possible to decompose organic substances such as fats and oils in the waste liquid and sterilize bacteria that have not been sterilized with acidic water. In addition, in order to improve a photocatalytic reaction, you may add a trace amount ozone and hydrogen peroxide as needed.

  The filtration unit 8 is for removing food residues, bacteria debris, and organic substances that could not be decomposed by the photocatalyst material from the waste liquid after the purification treatment. It has a configuration with a filter installed inside. As a filter, by using a porous material such as activated carbon, a hollow fiber membrane, or a continuous porous body, it is possible to filter dirt, oil and fat, etc. of the bottle B that has not been decomposed by the photocatalytic material. Moreover, when an ionic substance is contained in the waste liquid, it can be removed by using an ion exchange resin filter. Moreover, solid matters such as food residues and dead bodies of bacteria can be removed by using a filter such as filter paper suitable for the size of the solid matter. If necessary, the filter can be used in combination with a plurality of types described above, so that the waste liquid can be filtered well and discharged in a clean state. In order to improve the filterability of the filter, an aggregating agent such as polyaluminum chloride may be used in combination as necessary.

  The waste liquid cleaned by the purification treatment unit 7 and the filtration unit 8 may be discharged, but may be introduced into the electrolyzed water production apparatus 9 and reused to generate acidic water and reduced water. . Thus, by circulating the acidic water and the reduced water, the acidic water and the reduced water can be used efficiently. Moreover, regarding the reuse for production | generation of acidic water and reduced water, when introducing into the electrolyzed water manufacturing apparatus 9 as needed, you may add sodium chloride timely.

  Moreover, in the said embodiment, although the case where the bottle B (container) which has an opening was wash | cleaned was demonstrated to the example, as shown in FIG. 5, crops A, such as a vegetable and a fruit, can also be wash | cleaned. In the case of cleaning the crop A, the pesticide can be effectively removed in addition to the dirt adhering to the crop A.

  Reduced water and acidic water used for washing the crop A are 0.001% to 0.5%, preferably 0.01% to 0.5%, more preferably 0.1% to 0.2%. It is produced by electrolyzing a dilute aqueous sodium chloride solution by a diaphragm electrolysis method. The agricultural chemical A adhering to the crop A is removed by putting the crop A in, for example, a tub and immersing it in the tank 63 storing the reduced water generated in this way, and swinging the tank 63. Can do. At this time, when the crop A is subjected to ultrasonic cleaning, the removal efficiency of the pesticide is improved.

  Next, bacteria attached to the crop A can be sterilized by similarly putting the crop A in a basket or the like and immersing it in the tank 13 in which the acidic water is stored. . Next, the crop A is similarly put in a tub or the like and immersed in a tank 23 in which tap water or the like is stored as a rinsing solution, and rinsed with reducing water and acidic water.

  The inner surfaces of the tanks 63, 13, and 23 have a heating temperature on the surface of a metal titanium material or a titanium alloy (alloy containing titanium as a main component) material, like the installation surface 4 of the embodiment of FIGS. 1 and 2. After carrying out the step of forming titanium nitride by one kind of treatment method selected from the group consisting of heat treatment in an ammonia atmosphere at 750 ° C. or higher and heat treatment in a nitrogen gas atmosphere, On the other hand, after anodization was performed by applying a voltage of 10 V or higher in an electrolyte solution having no etching action, and a titanium oxide film was formed, (3) oxygen gas and nitrogen in an atmospheric atmosphere A photocatalyst material formed by performing a surface treatment method of performing a heat treatment step at a temperature of 400 ° C. or higher in an atmosphere selected from an atmosphere mixed with gas or an oxygen gas atmosphere It is composed of. Thereby, the droplets of reduced water, acidic water, and rinsing liquid discharged from the tanks 63, 13, and 23 are less likely to remain in the tanks 63, 13, and 23 due to the superhydrophilicity of the photocatalytic material. The inside can be kept clean. Moreover, it has high oxidizing power by irradiating the photocatalyst material on the inner surfaces of the tanks 63, 13, and 23 using a light irradiation means (not shown) such as a lamp or a fluorescent lamp that irradiates near ultraviolet rays or ultraviolet rays. Active radicals such as OH radicals are generated. Since this OH radical has a sterilizing power far stronger than hydrogen peroxide, ozone, etc. widely used for disinfection and sterilization, it is possible to sterilize bacteria adhering to the tanks 63, 13, and 23. Therefore, the inside of the apparatus can be maintained in a sanitary manner.

  In addition, the waste liquid discharged in this way (reduced water waste liquid and acidic water waste liquid and further rinse liquid waste liquid) is stored in the waste liquid storage tank (purification processing unit 7) in which the photocatalytic material is installed, as in the above-described embodiment. To be introduced. At this time, the photocatalyst material is irradiated with near-ultraviolet rays or ultraviolet rays capable of photoexciting anatase-type titanium oxide from a light irradiation means (not shown), so that active oxygen such as OH radical having extremely high activity and strong oxidizing power can be obtained. Occurs, the agricultural chemicals that are hardly decomposable organic substances in the waste liquid are decomposed, and the bacteria that have not been sterilized with acidic water are sterilized. In addition, the photocatalyst material produced by the same method as the above-described embodiment is used. Further, in order to improve the photocatalytic reaction, a trace amount of ozone or hydrogen peroxide may be added.

  Then, by introducing the organic matter and bacteria debris that could not be decomposed by the photocatalyst material in the waste liquid into the filtration unit 8 and filtering through the filter, the waste liquid can be discharged in a clean state, and environmental pollution can be prevented. Can be prevented. In addition, if the waste liquid in the purified state is not discharged, but is circulated through the electrolyzed water production apparatus 9 and used for the production of reduced water and acidic water, the water is not discharged. A circulation type cleaning device that is not newly added can be realized. Thereby, it is possible not only to use the acidic water and the reduced water efficiently, but also to prevent the contaminated waste liquid from giving a load to the environment by suppressing the amount of drainage.

  The cleaning device according to the present invention is not limited to cleaning of containers having openings, cleaning of agricultural products such as vegetables and fruits, but to anything that can be cleaned by nozzles or by immersion. Can also be applied.

  Hereinafter, the present invention will be described with reference to examples. The present invention is not limited to these examples.

Example 1
Titanium nitride was formed on the surface of the degreased metal titanium plate using a nitriding furnace (NVF-600-PC, manufactured by Central Nippon Reactor Industry). First, a metal titanium plate was sandwiched between flat carbon materials installed in a nitriding furnace. Next, in order to remove oxygen, the nitriding furnace was depressurized to 1 Pa or less, and 99.99% or more of high-purity nitrogen gas was introduced into the nitriding furnace to restore the pressure to 0.1 MPa (atmospheric pressure). By reducing the pressure of the nitriding furnace to 1 Pa or less, oxygen in the air can be removed and titanium having high oxygen affinity can be prevented from being oxidized. Next, the temperature of the nitriding furnace was raised to 950 ° C. over 2 hours. Next, heat treatment was performed for 1 hour in the 950 ° C. nitriding furnace to form titanium nitride on the surface of the metal titanium plate.

  A metal titanium plate having titanium nitride formed on the surface was immersed in a 1% by weight phosphoric acid aqueous solution (electrolytic solution). Next, using a function generator HB-105 (made by Hokuto Denko) and a direct current stabilized power supply PU300-5 (made by TEXIO), the carbon material was connected to the anode with a titanium metal plate with titanium nitride formed on the surface. The voltage between the cathode and the cathode was increased at 100 mV / second, and while maintaining 200 V for 10 minutes, the metal titanium plate having titanium nitride formed on the surface was anodized to form an oxide film of titanium.

  The metal titanium plate having a titanium oxide film formed on the surface was subjected to heat treatment (atmospheric oxidation) at 500 ° C. for 1 hour in the air (in an oxidizing atmosphere).

  By the above treatment, a metal titanium plate (titanium material) having an anatase-type titanium oxide film formed on the surface could be produced. Example 1 is a surface-treated titanium material prepared by a manufacturing method including (1) a step of forming titanium nitride, (2) a step of anodizing, and (3) a step of heat treatment.

  In the comparative example, the material was produced by carrying out the same anodic oxidation and atmospheric oxidation as in Example 1 except that a metal titanium plate having no titanium nitride formed on the surface was used. The comparative example is a surface-treated titanium material prepared by a manufacturing method including (2) a process for anodizing and (3) a process for heat treatment.

Using a black light (manufactured by Toshiba Lighting & Technology Corp.) that irradiates the surface-treated metal titanium plate with near-ultraviolet light photoexcited by anatase-type titanium oxide, the light intensity is adjusted to ² mW / cm ² from the top, Light was irradiated. This sample was taken out every hour, 1 drop of distilled water was dropped on this sample, and the contact angle between this sample and distilled water was measured with a contact angle meter CA-X type (manufactured by Kyowa Interface Science).

  The results are shown in Table 1. It can be seen that the titanium material manufactured by performing anodization and heat treatment after forming titanium nitride on the titanium material has a small contact angle with water and exhibits superhydrophilicity of 10 ° or less. On the other hand, the titanium material produced by simply anodizing and heating without forming titanium nitride on the titanium material clearly has a larger contact angle than the examples and does not show super hydrophilicity. It was.

Example 2
Electrolysis of sodium chloride solution diluted with distilled water using ALTRON-MINI AL-700A (voltage 100V, current 0.6A, electrolysis time 10 minutes) manufactured by Altec as an electrolyzed water preparation device which is a diaphragm electrolyzer An antibacterial test using acid water obtained from the side was carried out. Hypochlorous acid produced in acidic water is colored using a commercially available pack test reagent (manufactured by Kyoritsu Riken) by the DPD method (diethyl-p-phenyldiamine method) specified in the water test method. Using an ultraviolet-visible spectrophotometer UV mini 1240 (manufactured by Shimadzu Corporation), the absorbance was determined from 550 nm.

  FIG. 6 shows the results of determining the hypochlorous acid concentration in the acidic water generated from the anode side of the electrolyzer using an aqueous solution with varying sodium chloride concentration. A correlation was obtained between the sodium chloride concentration and the hypochlorous acid concentration, and it was found that the hypochlorous acid concentration can be changed by changing the sodium chloride concentration.

  After opening, it is stored in a refrigerator for a long period of time, and is a commercially available beverage that has been bred with bacteria. The refreshing tea (registered trademark) manufactured by Coca-Cola Japan is used. It adjusted so that it might become 1 volume% respectively with the acidic water to contain, and a tap water and distilled water as a comparison, and the antibacterial test was done from the number of bacteria which remain | survived in the adjusted solution. The number of bacteria was measured by the general method for measuring the number of bacteria specified in the water test method. Specifically, it is produced by smearing 0.1 ml of a solution containing 1% by volume of refreshing beauty tea with the above-mentioned various solutions on a standard agar medium (Nissui) and culturing at 37 ° C. for about 24 hours. The number of bacteria was determined from the number of colonies. Table 2 shows the results of examining the antibacterial properties by preparing acidic water of various hypochlorous acid concentrations by diluting acidic water prepared from diaphragm electrolysis of 0.015% sodium chloride aqueous solution in a timely manner. . It was found that when the concentration of hypochlorous acid in acidic water was 0.6 ppm or more, remarkable antibacterial properties were exhibited, and when there was about 1 ppm of hypochlorous acid, no bacteria remained. It was also found that about 1 ppm of hypochlorous acid is present in tap water, but it does not exhibit antibacterial properties at all.

  Paying attention to the fact that antibacterial properties differ between tap water and acidic water even when hypochlorous acid is contained at the same concentration, a phosphate buffer solution (manufactured by Horiba) is added to acidic water as needed. Table 3 shows the results of the same general bacterial count test using a pH-controlled solution. It shows strong antibacterial properties in weak acidity (pH 3.4) obtained by diaphragm electrolysis of dilute sodium chloride aqueous solution of 0.01%, but if it is made neutral by adjusting pH, it is the same as tap water It showed no antibacterial properties. From the results of this test, acid water obtained by diaphragm electrolysis of dilute sodium chloride aqueous solution has strong antibacterial properties even though it has hypochlorous acid concentration that does not cause any harm to the human body at the same level as tap water. I understood.

Example 3
A container cleaning test was conducted using reduced water produced on the cathode side by diaphragm electrolysis of a dilute sodium chloride aqueous solution. Evaluation was made using oleic acid contained in a large amount in edible oil as a contaminant. The oleic acid concentration was determined by measuring oleic acid derivatized with a methyl esterification kit (manufactured by Nacalai Tesque) for 3 hours using a gas chromatograph GC-2014 (manufactured by Shimadzu Corporation). As a test method, a beaker was used as a container having an opening. In a beaker to which oleic acid was attached, reduced water produced on the cathode side by diaphragm electrolysis of a dilute sodium chloride aqueous solution was sprayed at a spray rate of 1800 ml / min for 3 seconds. After spraying, a solution obtained by dissolving oleic acid adhering to a beaker with hexane (manufactured by Wako Pure Chemical Industries, Ltd.) as a methyl ester was analyzed with a gas chromatograph to determine the remaining amount of oleic acid. Table 4 shows the results of evaluating the detergency of the container from the initial adhesion amount and the remaining amount of oleic acid. The concentration of sodium chloride used for diaphragm electrolysis is increased. The higher the pH of the acidic water on the anode side and the higher the pH, the higher the washing rate of oleic acid. About 90% removal rate has been achieved in reduced water obtained by diaphragm electrolysis of a 0.01% sodium chloride aqueous solution having a hypochlorous acid concentration comparable to tap water. In addition, since spraying for only 3 seconds ensured high washability with reduced water produced by diaphragm electrolysis of dilute sodium chloride aqueous solution, the amount of solution used for washing can be limited, and finally The amount of discharged waste liquid is also reduced, and the efficiency of treatment with a photocatalytic material and filtration with a filter is improved when the waste liquid is reused.

Example 4
A pesticide removal test using reduced water produced on the cathode side by diaphragm electrolysis of dilute sodium chloride aqueous solution was carried out. A Sumithion emulsion (manufactured by Sumitomo Chemical Co., Ltd., main component: fenitrothion C ₉ H ₁₂ NO ₅ PS) was used as a contaminant. 0.05 ml of a solution obtained by diluting the Sumithion emulsion 10 times with distilled water was attached to a 76 mm × 26 mm slide glass and dried at room temperature for 1 day to attach the pesticide to the slide glass. A slide glass with this pesticide attached immersed in 200 ml of reducing water for 30 seconds is again immersed in 50 ml of distilled water and used for 15 minutes at 43 KHz using an ultrasonic cleaner ASU CLEANER ASU-3D (manufactured by ASONE). Sonication was performed, and the pesticide adhering to the slide glass was completely dissolved in the solution. A solution in which the pesticide adhering to the slide glass before and after washing with reduced water was completely dissolved was prepared and analyzed. The pesticide removal rate was determined from the amount of pesticide attached to the slide glass before and after washing with reduced water.

  The analysis of the pesticide Sumithion emulsion is based on the JISK0102 46.3.1 potassium peroxodisulfate decomposition method, changing the phosphorus in fenitrothion to phosphoric acid. The phosphoric acid concentration was developed by JISK0102 46.1.1 molybdenum blue absorbance method, and the absorbance at 880 nm was measured using UV-visible spectrophotometer UV mini 1240 (manufactured by Shimadzu Corporation), and the amount of adhering pesticide was determined.

  Tables 5 and 6 show measurement results of the pesticide removal rate using reduced water generated on the cathode side by membrane electrolysis from a dilute sodium chloride aqueous solution. Specifically, as the reduced water in Tables 5 and 6, reduced water prepared from the cathode side by diaphragm electrolysis of 0.13% and 0.20% sodium chloride aqueous solution was used. The reducing water produced simultaneously at the acidic water side hypochlorous acid concentration produced at the same time on the anode side during the production of the reduced water was 20 ppm and 40 ppm, respectively. It was found that the pesticide removal rate was improved by increasing the concentration of reduced water. Compared with the container cleaning method described above, reduced water cannot be effectively removed unless high-concentration water is used, but the above-mentioned container cleaning method sprays and cleans, whereas pesticide cleaning is reduced water. Since it is only necessary to supply a part of the waste liquid for cleaning by immersing it in a tank in which the waste liquid is stored, the amount of waste liquid is limited and the efficiency of treatment with a photocatalyst and filtration with a filter are reduced. improves.

DESCRIPTION OF SYMBOLS 10 Cleaning apparatus 1 Disinfection part 11 2nd nozzle 12 Disinfection liquid storage tank (disinfection liquid supply source)
13 Second tank 2 Rinsing section 21 Third nozzle 22 Rinsing liquid storage tank (rinsing liquid supply source)
23 3rd tank 3 Drying part 31 4th nozzle 32 Airflow generation means 4 Installation surface 6 Cleaning part 61 1st nozzle 62 Cleaning liquid storage tank (cleaning liquid supply source)
63 First tank

Claims (17)

An apparatus for cleaning a container having an opening,
A cleaning unit for supplying reducing water into the container through the opening;
A disinfection unit for supplying acidic water into the container through the opening;
A rinsing section for supplying a rinsing liquid into the container through the opening;
An installation surface on which the cleaning unit, the disinfecting unit and the rinsing unit are installed,
The installation surface is made of a photocatalytic material,
The photocatalytic material is
(1) The heating temperature is 750 ° C. or higher, and the metal titanium material or the titanium alloy material is subjected to one treatment method selected from the group consisting of a heat treatment in an ammonia atmosphere and a heat treatment in a nitrogen gas atmosphere. Forming titanium nitride on the surface;
(2) Applying a voltage of 10 V or more to the titanium titanium material or titanium alloy material having titanium nitride formed on the surface, obtained in step (1), in an electrolyte solution having no etching action on titanium. And a step of forming an oxide film of titanium by anodizing, and (3) a metal titanium material or titanium alloy material having a titanium oxide film formed on the surface, obtained in step (2). A cleaning apparatus manufactured in a process of performing heat treatment at a temperature of 400 ° C. or higher in an atmosphere selected from an atmosphere in which oxygen gas and nitrogen gas are mixed or an oxygen gas atmosphere.   The cleaning apparatus according to claim 1, further comprising light irradiation means for irradiating the installation surface with near ultraviolet rays or ultraviolet rays. The cleaning unit includes a first nozzle that is provided so as to protrude above the installation surface and that injects reducing water into the container,
The disinfection unit is provided to protrude above the installation surface, and has a second nozzle that injects acidic water into the container.
The cleaning apparatus according to claim 1, wherein the rinsing portion includes a third nozzle that is provided so as to protrude above the installation surface and that jets a rinsing liquid into the container. A device for cleaning crops,
A cleaning unit that stores reduced water and has a first tank capable of immersing the crops;
A disinfecting part having a second tank for storing acidic water and capable of immersing the crops;
A rinsing section for storing a rinsing liquid and having a third tank in which the crop can be immersed, and
The inner surface of the first tank, the inner surface of the second tank , and the inner surface of the third tank are made of a photocatalytic material,
The photocatalytic material is
(1) The heating temperature is 750 ° C. or higher, and the metal titanium material or the titanium alloy material is subjected to one treatment method selected from the group consisting of a heat treatment in an ammonia atmosphere and a heat treatment in a nitrogen gas atmosphere. Forming titanium nitride on the surface;
(2) Applying a voltage of 10 V or more to the titanium titanium material or titanium alloy material having titanium nitride formed on the surface, obtained in step (1), in an electrolyte solution having no etching action on titanium. And a step of forming an oxide film of titanium by anodizing, and (3) a metal titanium material or titanium alloy material having a titanium oxide film formed on the surface, obtained in step (2). A cleaning apparatus manufactured in a process of performing heat treatment at a temperature of 400 ° C. or higher in an atmosphere selected from an atmosphere in which oxygen gas and nitrogen gas are mixed or an oxygen gas atmosphere. The cleaning apparatus according to claim 4, further comprising light irradiation means for irradiating the inner surfaces of the first to third tanks with near ultraviolet rays or ultraviolet rays. The cleaning apparatus according to claim 4 or 5, wherein the first to third tanks are swingable. Heat treatment under the nitrogen gas atmosphere, the cleaning apparatus according to claim 1 carried out in the presence of oxygen trapping agent.   The electrolytic solution having no etching action on titanium used in the anodization is an electrolytic solution containing at least one compound selected from the group consisting of inorganic acids, organic acids and salts thereof. The cleaning apparatus according to any one of 7.   9. The at least one compound selected from the group consisting of the inorganic acid, organic acid and salts thereof is at least one compound selected from the group consisting of phosphoric acid and phosphate. Cleaning device. The cleaning apparatus according to any one of claims 1 to 9, wherein a voltage applied in the anodic oxidation in the step (2) is 50 to 300V. The temperature of the heat processing performed in the atmosphere of the said process (3) is 400 to 700 degreeC, The washing | cleaning apparatus in any one of Claims 1-10.   The cleaning apparatus according to claim 1, wherein the titanium oxide film formed by the anodic oxidation is a crystalline titanium oxide film.   The cleaning apparatus according to claim 12, wherein the crystalline titanium oxide film is an anatase type titanium oxide film. A purification processing unit that collects the reduced water waste liquid discharged from the cleaning unit, the acidic water waste liquid discharged from the disinfection unit, and the rinse liquid waste liquid discharged from the rinse unit, and performs purification treatment with a photocatalytic material;
A filtration unit that filters the reduced water waste liquid, the acidic water waste liquid, and the rinse liquid waste liquid discharged from the purification treatment unit with a filter;
A light irradiation means for irradiating the photocatalyst material of the purification treatment unit with near ultraviolet rays or ultraviolet rays, and further comprising:
In the purification processing unit,
(1) The heating temperature is 750 ° C. or higher, and the metal titanium material or the titanium alloy material is subjected to one treatment method selected from the group consisting of a heat treatment in an ammonia atmosphere and a heat treatment in a nitrogen gas atmosphere. Forming titanium nitride on the surface;
(2) Applying a voltage of 10 V or more to the titanium titanium material or titanium alloy material having titanium nitride formed on the surface, obtained in step (1), in an electrolyte solution having no etching action on titanium. And a step of forming an oxide film of titanium by anodizing, and (3) a metal titanium material or titanium alloy material having a titanium oxide film formed on the surface, obtained in step (2). Purifying treatment with a photocatalyst material produced in a step of performing heat treatment at a temperature of 400 ° C. or higher in an atmosphere, an atmosphere selected from an atmosphere in which oxygen gas and nitrogen gas are mixed, or an oxygen gas atmosphere The cleaning apparatus according to claim 1, wherein the cleaning apparatus is performed.   The reduced water used for cleaning and the acidic water used for disinfection are generated by diaphragm electrolysis using a sodium chloride aqueous solution having a concentration of 0.001% to 0.5% as electrolyzed water. The cleaning apparatus according to any one of the above. The cleaning according to claim 15, wherein the reduced water and the acidic water after being cleaned in the filtration unit are reused for the production of the reduced water used for cleaning and the acidic water used for disinfection. apparatus.   The cleaning device according to any one of claims 14 to 16, wherein the filter includes at least one type of filter selected from a filter that removes organic matter, a filter that removes solid matter, and an ion exchange resin filter.

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