JP3948671B2 - Inorganic film forming method and apparatus - Google Patents

Description

  TECHNICAL FIELD The present invention relates to a method and apparatus for forming an inorganic film for surfaces of iron, aluminum, synthetic resin, glass, rubber and the like used for automobiles, railway vehicles, ships, airplanes, home appliances, and the like, and painted surfaces thereof.

  Conventionally, the surfaces of devices used outdoors such as automobiles, railway vehicles, ships, and airplanes are liable to adhere to dust, dust, insects, etc., and have to be constantly cleaned. Although the surface of these devices is usually coated and protected with a surface coating such as wax or polymer processing, it has been pointed out that these materials are organic products and become environmental pollution sources.

  In addition, these protective coatings are easily affected by weathering due to ultraviolet rays, etc., and have weaknesses such as fading and gloss deterioration of the coating and deterioration in appearance and function, and further, the protective coating itself is soft and easily damaged. Appearance protection was not enough. For this reason, it is necessary to frequently repeat the wax and polymer processing, and there is a problem that material costs and man-hours are required.

In order to cope with such a problem, a method of forming a silica borate film by an electrodeposition action by an electric charge generated by tourmaline has been proposed. (See Patent Document 1)
However, the protective coating obtained by this method has not been sufficient in terms of coating durability.
Japanese Patent Laid-Open No. 2000-192086: “Claims” paragraphs (0009) and (0010)

  The present invention has been made in order to solve the above-mentioned problems, realizes an inorganic coating having excellent durability and low cost, eliminates the need for conventional wax and polymer processing, and suppresses contamination and protects the environment. Provided are an inorganic film forming method and apparatus capable of contributing. Furthermore, the present invention provides an inorganic film forming method and apparatus having a purification function capable of removing contaminants by oxidative decomposition.

The above problem is that in the first aspect of the invention, one or more ores selected from quartz porphyry, tourmaline, and barley stone that can elute at least silicon and aluminum in contact with water are mixed. The ceramic particles having a coating containing these ore ores as coating components and raw water are brought into contact with the raw water, and the eluted components charged with the raw water are eluted together with the excitation current to form charged water. The problem is solved by an inorganic film forming method characterized by forming an inorganic film mainly composed of an oxide of the elution component on the surface by spraying or immersing the work in the charged water on the work surface. be able to.

And wherein in the invention, after the pre-Symbol charge water to generate an induction current is passed through the electromagnetic field inside is preferably embodied in a form as subjected to the film formation. And this 1st invention can be embodied in the form which uses the ceramic particle | grains which contain titanium as an elution component in addition to the said silicon and aluminum.

  Moreover, said problem can be solved also by the inorganic film forming apparatus which is the following 2nd invention. That is, an inorganic film forming apparatus for carrying out the inorganic film forming method of the first invention, comprising a raw water supply port, and inside thereof, quartz porphyry that can elute at least silicon and aluminum in contact with water, Loading ceramic particles containing at least one or more kinds of ores selected from tourmaline and barleystone in the surface portion so that the raw water fed from the raw water supply port can pass while contacting the ceramic particles A charged water generation tank having a charged water outlet for taking out the generated charged water, a charged water inlet for feeding the charged water and a magnetically treated water outlet for taking out the magnetically treated water, and forming an electromagnetic field inside. And a film forming tank provided with means for bringing magnetically treated water into contact with the surface of a workpiece disposed in the tank, and a magnetic field treating tank in which an S water pole and an N pole are arranged, and a water passage for charged water is provided therebetween. An inorganic film forming apparatus characterized by being al structure, can be solved.

  According to the present invention, in addition to silicon and aluminum, ceramic particles containing at least one or more kinds of ores selected from quartz porphyry, tourmaline and barleystone capable of eluting titanium at least on the surface portion are loaded. It is embodied in the form.

The inorganic film forming method and apparatus of the present invention are configured as described above and are based on the following characteristic principle.
That is, (1) the inorganic coating of the present invention is a SiO ₂ —Al ₂ O ₃ -based ore (stone) coating in the first embodiment and a SiO ₂ —Al ₂ O ₃ —TiO ₂ -based in the second embodiment. (2) It has the characteristics of ultra-thin type plating at the nanometer level, and (3) is an electrochemical reaction plating performed by a specific means.

Thus, in the case of the SiO ₂ —Al ₂ O ₃ -based coating (first embodiment), the obtained inorganic coating realizes low cost and excellent durability, eliminates the need for conventional wax and polymer processing, and suppresses contamination. There is an excellent effect that it can contribute to environmental conservation. Furthermore, in the case of the SiO ₂ —Al ₂ O ₃ —TiO ₂ based coating (second embodiment), the contaminants can be decomposed and removed, which is particularly suitable for suppressing organic contamination. . Therefore, the present invention has an extremely large practical value as an inorganic film forming method and apparatus for solving the conventional problems.

Next, an embodiment relating to an inorganic film forming method and an apparatus thereof according to the present invention will be described with reference to FIGS.
(First embodiment)
The first embodiment of the inorganic film forming method of the present invention will be described together with the inorganic film forming apparatus. The apparatus of the present invention is a charged water generating tank 1, a magnetic field processing tank 2, and a film forming tank as illustrated in FIG. 3 at least.

  This charged water generation tank 1 is provided with a raw water supply port 11 for introducing raw water a such as tap water and well water, and a charged water outlet 12 for taking out treated water b, and is in contact with the water at least. The ceramic particle loading unit 13 is loaded with innumerable ceramic particles 14 containing at least silicon and aluminum as elution components so as to elute silicon and aluminum.

The ceramic particles 14 are preferably substantially spherical particles having a particle diameter of 3 to 10 mm made of a SiO ₂ —Al ₂ O ₃ based ceramic. However, in order to increase the generation efficiency of charged water described later, at least silicon and aluminum are included. More preferably, ceramic particles containing 50% or more of one or more ores selected from quartz porphyry, tourmaline, and barleystone, or at least one of the above-described one or more containing silicon and aluminum Ceramic particles having a coating containing 50% or more of two or more kinds of ores as coating components are more preferable.

  These ceramic particles are loaded in the ceramic particle loading unit 13 so that the raw water a fed from the raw water supply port 11 can pass while contacting the ceramic particles 14. For example, since the ceramic particles 14 are flowed and stirred by the water flow of the raw water a, and the ceramic particles 14 and the raw water a are preferably in sufficient contact, the ceramic particles 14 are preferably loaded in a flowable manner.

  In the charged water generation tank 1, when the raw water a comes into contact with the ceramic particles 14, the water is instantaneously discharged into the water, and at least the elution components of silicon and aluminum are charged from the ceramic particles 14 together with the excitation current. Charged water b which is activated by elution is obtained. This excitation current is obtained semipermanently from the ceramic particles 14 and is the main starting force for forming the inorganic coating of the present invention.

  Next, the magnetic field treatment tank 2 includes a charged water inlet 21 through which the charged water b obtained in the charged water generation tank 1 is fed, and a magnetic field treated water outlet 22 through which the magnetic field treated water c is taken out. The S pole 23a and the N pole 23b to be formed are arranged, and a passage water passage 24 for the charged water b is provided between them.

  In the magnetic field treatment tank 2, the charged water b having a charge passes through the electromagnetic field formed by the S pole 23a and the N pole 23b, so that a predetermined induced current is generated according to Faraday's law. Water b is taken out as more activated magnetic field treated water c. For the purpose of this magnetic field treatment, the intensity of the electromagnetic field is preferably set to 0.10 to 0.80 mG, more preferably 0.30 to 0.80 mG.

  In the inorganic film forming method of the present invention, a certain amount of inorganic film can be obtained without performing this magnetic field treatment. However, when the magnetic field treatment is performed, particularly in terms of stability of film formation, durability of the formed film, and the like. Favorable results are obtained. Therefore, in the present invention, it is more preferable to perform this magnetic field treatment.

  Next, the film formation tank 3 in the present invention includes a magnetic field treatment water inlet 31 for feeding the magnetic field treatment water c obtained in the magnetic field treatment tank 2 and a treatment waste water outlet 32 for taking out the treatment waste water d. As a means for bringing the magnetic field treated water c into contact with the surface of the workpiece 33 arranged, in the example of FIG. 1, a nozzle 34 that ejects the pressurized magnetic field treated water c to the surface of the workpiece 33 is provided.

In the coating film forming tank 3, when the magnetic field treated water c comes into contact with the surface of the work 33, at least the elution components of silicon and aluminum in the magnetic field treated water c are subjected to an electrochemical reaction in accordance with the cathode reduction deposition. An inorganic coating is formed on the surface. As a result of photoelectron analysis (ESCA), this inorganic coating is a SiO ₂ —Al ₂ O ₃ based glassy coating composed mainly of oxides of elution components of silicon and aluminum, and bonded to the respective oxides. It has been found.

  For such film formation, a method of immersing the work 33 in the magnetic field treated water c is of course possible, but the entire surface of the work 33 is pressurized using an injection nozzle as illustrated in FIG. It is preferable to spray the magnetic field treated water c. The reason is that when an impact is applied by spraying from the nozzle 34, an impact current is generated and the efficiency of film formation is improved.

  In the present invention, the sum of the excitation current, the induction current, and the impact current described above is preferably maintained at 0.05 to 0.07 mA. The reason is that an inorganic coating having excellent durability as described later is reliably formed.

In addition, the relationship between the spray pressure and the thickness of the coating obtained in the present invention is as illustrated in FIG. 2, and the film thickness is stable in the range of 10 to 60 nm in the pressure range of 10 to 500 N / cm ^2. I found that it was obtained. (The circles in the figure indicate the results of changing the conditions. The same applies hereinafter.)

  Moreover, the relationship between the processing time of the film formation tank 3 of the present invention and the thickness of the obtained film is as illustrated in FIG. 3, and a film having a thickness of 10 to 100 nm can be obtained even for about 1 second instantaneously. In order to obtain a stable film of 10 to 60 nm, 10 seconds or more is preferable, and 60 seconds or more is not economical and unnecessary. In addition, when the charged water is used for the film formation, the temperature of the treatment liquid in the film formation tank 3 of the present invention is preferably maintained at 30 to 50 ° C. This is because the electrochemical reaction is promoted at a temperature in this range, and the coating film is formed in the above-mentioned short time.

  It should be noted that a variety of members such as iron, aluminum, synthetic resin, glass, and rubber used as components of automobiles, railway vehicles, ships, airplanes, home appliances, and the like can be targeted for processing of the present invention. The surface properties of these workpieces can be applied without any problem on either the exposed material surface or the painted surface such as resin paint, but the coated surface is preferable from the viewpoint of protecting the surface of the member. is there.

Next, several advantages of the inorganic coating obtained by the present invention will be described with reference to FIGS.
First, FIG. 4 shows a specular reflectance that serves as an indicator of rough surface, fading or gloss deterioration of the coating surface, and the once-treated surface f, the twice-treated surface g, the five-time treated surface h, and the wax-treated surface of the present invention. e (hereinafter, the same applies to FIGS. 5 and 6) are graphs comparing each other, and it can be seen that the protective effect of the coating of the present invention on the coating surface of the base is also great.

  FIG. 5 shows a comparison between the treated surface of the present invention and the wax-treated surface in the same manner as in FIG. 4 with respect to the coefficient of friction (dynamic friction), which is an index of the difficulty of adhering dust and dirt to the painted surface and the ease of cleaning. This graph also shows that the adhesion of dust and the like by the coating of the present invention and the ease of cleaning are remarkably excellent.

  Further, FIG. 6 shows the result of comparing the surface hardness, which is also an index of durability of the paint surface, with respect to the pencil hardness, and the same treatment surface as described above. It is understood that the durability is excellent.

  As described above, the inorganic coating obtained by the first embodiment of the present invention exhibits superior performance compared to wax and polymer processing similar thereto, and as described above, the inorganic coating forming method of the present invention. In addition, since the apparatus requires almost no consumables and requires only a small amount of driving power, the operating cost of the apparatus is very low and the maintenance is easy, so that its economic efficiency is particularly excellent.

(Second Embodiment)
Next, a second embodiment of the inorganic film forming method of the present invention will be described with reference to FIGS. 7 and 8. As illustrated in FIG. 1, a charged water generation tank 1, a magnetic field treatment tank 2, and a film formation tank. 3 is the same as the first embodiment in that a forming apparatus is used. The difference is that the ceramic particle loading part 13 of the charged water generation tank 1 has innumerable ceramic particles containing silicon, aluminum, and titanium as elution components so as to elute at least silicon, aluminum, and titanium in contact with water. 14 is at the point of loading.

The ceramic particles 14 of the second embodiment are made of SiO ₂ —Al ₂ O ₃ —TiO ₂ ceramic, and include one kind selected from quartz porphyry, tourmaline, and barley stone, including silicon, aluminum, and titanium. Ceramic particles containing 50% or more of two or more kinds of ores are more preferable, or ceramic particles having a coating containing 50% or more of the one or more ores as coating components are more preferable. And as for the said ore, what contains 0.20 to 3.0% of titanium in conversion to a titanium oxide can be utilized preferably.

  Also in the second embodiment, the loaded state of the ceramic particles in the charged water generation tank 1 and the behavior of the raw water a and the ceramic particles 14 are the same as in the previous case, and at least the elution components of silicon, aluminum, and titanium are extracted from the ceramic particles 14. Thus, the charged water b that is eluted and activated in a charged state is obtained.

Next, the charged water b is taken out as more activated magnetic field treated water c by the magnetic field treatment tank 2 having the same configuration and function as described above. The preferable magnetic field strength is the same.
Further, in the inorganic film forming method of the second embodiment, although a certain amount of inorganic film can be obtained without performing this magnetic field treatment, it is preferable to perform the magnetic field treatment as in the previous case.

  Next, a coating film is formed in the coating film forming tank 3, and the equipment configuration, operation, and the like here are the same as those in the first embodiment. In the second embodiment, the elution components of silicon, aluminum, and titanium in the magnetically treated water c form an inorganic coating on the surface of the work 33 by an electrochemical reaction according to cathode reduction deposition.

In addition, as shown in FIG. 7, this inorganic coating has SiO ₂ -Al ₂ in which oxides of elution components of silicon, aluminum, and titanium are the main components and bonded to each other as a result of photoelectron analysis (ESCA). It has been found that the O ₃ —TiO ₂ -based glassy film is formed as a NM level film layer having a maximum depth of about 80 nm. In FIG. 7, ◯ indicates the number of photoelectrons / second based on Si, and Δ indicates Ti. (For reference, the case of the first embodiment is indicated by ●.)

  Furthermore, also in the second embodiment, it is preferable to spray the pressurized magnetic field treated water c on the entire surface of the work 33 by using a spray nozzle as illustrated in FIG. Moreover, it is preferable also from the point of the oxidative decomposition function mentioned later to hold | maintain the sum total of an excitation current, an induced current, and an impact current at 0.05-0.07 mA.

  Also in the second embodiment, as in the first embodiment, a wide variety of products such as iron, aluminum, synthetic resin, glass, rubber, etc. used as components of automobiles, railway vehicles, ships, aircraft, home appliances, etc. A member may be a processing target. And the function of the film illustrated in FIGS. 4, 5, and 6 is exhibited similarly, and as shown in FIG. 8, the film of the second embodiment (circle mark in the figure) is organic as exemplified by ink. It has a special feature in that it has a purification function to decompose and remove pollutants during outdoor exposure.

  The graph of FIG. 8 shows a state in which the coating film of the present invention is formed on a white glass plate, the ink liquor is applied as a contaminant on the white glass plate, is exposed to the outdoors, and fades. The transparency (completely transparent = 100, opaque) = 0 indicates the case of the second embodiment of the present invention, Δ indicates the first embodiment, □ indicates a case where a titanium oxide photocatalyst is applied, and X indicates an untreated case. ing. According to this, it turned out that the membrane | film | coat of 2nd Embodiment has a decomposition characteristic comparable to a titanium oxide photocatalyst.

The typical block diagram of the main apparatuses for demonstrating this invention. The graph which shows the relationship between the injection pressure of this invention, and a film thickness. The graph which shows the relationship between the processing time of this invention, and a film thickness. The graph which shows the reflectance of the process surface of this invention. The graph which shows the friction coefficient of the process surface of this invention. The graph which shows the surface hardness of the process surface of this invention. The graph which shows the photoelectron analysis (ESCA) result of the processing surface of this invention. The graph which shows the pollution decomposability | degradability of 2nd Embodiment.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Charge water production tank, 11 Raw water supply port, 12 Charge water extraction port, 13 Ceramic particle loading part, 14 Ceramic particle, 2 Magnetic field treatment tank, 21 Charge water supply port, 22 Magnetic field treatment water extraction port, 23a S pole, 23b N pole, 24 passage water channel, 3 film formation tank, 31 magnetic field treated water inlet, 32 treated drain outlet, 33 work, 34 nozzle, a raw water, b charged water, c magnetically treated water, d treated waste water.

Claims (9)

Ceramic particles containing a mixture of one or more ores selected from quartz porphyry, tourmaline, and barley stone that can elute at least silicon and aluminum in contact with water, or these ores as coating components The ceramic particles having a coating are brought into contact with the raw water, and the elution component charged with the raw water is eluted together with the excitation current to form the charged water, and the charged water is sprayed on the work surface or the work is immersed in the charged water. And forming an inorganic coating mainly composed of the oxide of the elution component on the surface thereof. The inorganic film forming method according to claim 1, wherein the charged water is passed through an electromagnetic field to generate an induced current, and then used for forming the film. When the charged water is used for forming the film, the charged water is 10 to 500 N / cm. ² The inorganic coating film forming method according to claim 2, wherein the impact current is generated by applying an impact by spraying from a nozzle while adjusting the pressure of the ink. The inorganic film forming method according to any one of claims 1 to 3, wherein a liquid temperature is maintained at 10 to 50 ° C when the charged water is used for forming the film. The method for forming an inorganic coating film according to any one of claims 1 to 4, wherein the time for contacting the charged water with the workpiece is 1 to 60 seconds, and the thickness of the inorganic coating film to be formed is 10 to 100 nm. The inorganic film forming method according to any one of claims 1 to 5, wherein ceramic particles containing titanium as an eluting component in addition to silicon and aluminum are used. An inorganic coating film forming apparatus for performing the inorganic coating film forming method according to claim 1, comprising a raw water supply port, and a quartz spot capable of eluting at least silicon and aluminum in contact with water. Loaded with ceramic particles containing at least one or more kinds of ores selected from rock, tourmaline, and barley stone in the surface portion so that the raw water fed from the raw water supply port can pass while contacting the ceramic particles In addition, a charged water generating tank provided with a charged water outlet for taking out the generated charged water, a charged water inlet for feeding the charged water, and a magnetically treated water outlet for taking out the magnetically treated water are provided. A film forming tank provided with a means for bringing magnetically treated water into contact with the surface of a workpiece disposed in the tank, and a magnetic field treating tank in which a water passage for charged water is provided therebetween Inorganic coating forming apparatus characterized by being al configuration. The inorganic film formation apparatus of Claim 7 provided with the nozzle which injects a magnetic field process water on the workpiece | work surface arrange | positioned in the said film formation tank. In addition to the silicon and aluminum, ceramic particles containing at least one or more kinds of ores selected from quartz porphyry, tourmaline, and barley stone capable of eluting titanium are loaded at least in a surface portion. The inorganic film forming apparatus according to 7 or 8.

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