JPWO2007058287A1 - Substance reforming method and reforming apparatus - Google Patents

Abstract

Provided are a method and apparatus for modifying the substance itself, the substance surface, or a deposit on the substance surface in a state where a solution of nitrous oxide (N2O) is in contact with the substance, and an article obtained by the method and apparatus. By irradiating the solution S with ultraviolet light in a state where the solution S of nitrous oxide is in contact with the substance X, the substance X itself or the surface of the substance X, or the substance to be modified on the surface of the substance X is modified. A reforming method, a reforming apparatus for a substance that modifies the substance X using the reforming method, the reforming method, or the substance X modified by the reforming apparatus.

Description

The present invention relates to a method for modifying a substance, in particular, a method for modifying a substance itself or a substance surface or a substance surface adhering substance by irradiating ultraviolet light in a state in which the N ₂ O solution is in contact with the substance, and this The substance obtained by the method.

  Conventionally, the characteristics and properties of a substance are governed by the characteristics of the constituent material, and the characteristics and properties of the substance surface are no exception, but the substance itself or the characteristics of the substance surface or the substance surface deposits, etc. are modified. In addition, desired characteristics are given.

  For example, as a technique for hydrophilizing the surface of a resin substrate, a technique is known in which etching is performed using a strong oxidizing agent such as chromic acid or permanganic acid when plating a resin substrate used for a printed wiring board or the like. (See Patent Document 1). In addition, as a technique for modifying the material surface, a technique using corona discharge, plasma, or ozone is also known.

  Moreover, in the technology for sterilizing the surface of a substance, for example, the substance to which microorganisms are attached is stored in a heatable device such as an autoclave or a retort cooker, and the substance to which the microorganisms are attached is raised to a temperature at which it can be sterilized. Then, the surface of the substance is modified by killing the microorganisms (see, for example, Patent Document 2). In addition, by immersing the substance with microorganisms in the medicine bath or spraying the drug on the substance with microorganisms, the microorganisms are brought into contact with the substance with microorganisms to kill the microorganisms. (For example, refer to Patent Document 3).

  In addition, as a technique for cleaning the surface of a substance, for example, a method is known in which an organic substance that is a main cause of dirt is cleaned and removed using a detergent or the like (see Patent Document 4).

  In addition, as a technology for decolorizing substances, conventionally, various organic solvents such as acetone and alcohols, oxidants such as hydrogen peroxide, ozone, and chlorine-based oxidizers have been used as decolorizers. Decoloring agents are used. It is known that decolorization is performed by an oxidation reaction. For example, among the above-mentioned decolorizing agents, oxidizing agents such as hydrogen peroxide, ozone, and chlorine-based oxidizing agents are decolorized by oxidation. Hydrogen oxide is used for bleaching paper and pulp (see Patent Document 5). By using such an oxidizing agent, the material surface is modified, in this case, decolorized.

  In the manufacture of industrial products by oxidation of organic compounds, for example, the surface of a substance is modified by mixing an oxidant and an organic compound and performing an oxidation reaction in combination with a catalyst or heat. Then industrial products are manufactured.

  One of the important substances in the industrial products is carboxylic acid. Carboxylic acids are widely used in various industrial fields including the chemical industry as plasticizers, lubricants, electric heating media, dielectric media, fibers, copolymers, paints, surfactants, fungicides, insecticides, adhesives, etc. It is an organic compound known as an important intermediate in the synthesis of the useful chemicals used, diesters, polyesters and polyamides.

  For example, adipic acid is one of carboxylic acids. Adipic acid is a substance used as a raw material for nylon. In the production of adipic acid, a nitric acid oxidation method in which a large amount of nitric acid is used to oxidize raw material cyclohexanone or cyclohexanol is industrially implemented (see, for example, Patent Document 6).

  Further, in the production of terephthalic acid, which is a raw material for polyester, an air oxidation method for oxidizing raw material para-xylene using oxygen in the air is industrially implemented (see, for example, Patent Document 7).

  Furthermore, in the production of ε-caprolactone, which is widely used as a raw material for polymer polyols for polyurethane synthesis, such as polyester polyols for polyurethane synthesis, which are industrial products other than carboxylic acids, cyclohexanone is passed over arsonic acids and diphenylarsines as catalysts. Production method of oxidizing with hydrogen oxide (for example, see Patent Document 8 and Patent Document 9), glycidyl methacrylate, which is an important industrial raw material having a wide range of uses such as powder coating materials, adhesives, curing agents, modifiers, etc. In production, a production method by oxidation of allyl methacrylate (for example, see Patent Document 10) has been proposed.

  Furthermore, a depolymerization method by oxidation has also been proposed for lowering the molecular weight of polysaccharides such as chitin, chitosan and its derivatives having antifungal and antibacterial properties, and heparin and cellulose having anticoagulant activity ( For example, see Patent Document 11).

JP 2003-283123 A JP 2003-319767 A JP 2004-43411 A Japanese Patent Application Laid-Open No. 11-243085 JP-A-9-87985 Japanese Patent Laid-Open No. 2002-30027 JP 2004-175797 A JP-A-4-279579 JP-A-4-288071 Japanese Patent Publication No. 4-5028 JP 2002-128802 A

  However, the conventional technology for hydrophilizing the surface of a material has a problem that it is difficult to handle. In the above-described technology using an oxidant, the reactivity of the oxidant is strong and the oxidation reaction continues to occur when the oxidant and the substrate are in contact with each other. There is a problem that it must be treated and the environment must be considered. The technologies using corona discharge, plasma, and ozone also have problems that it is difficult to control the degree of reforming, and that ozone treatment must be taken into consideration for the environment.

  Further, in the technology for sterilizing a substance, in the above conventional sterilization method by heating, the substance itself to which microorganisms are attached is also heated, so that the substance that is deformed or denatured by heating has the original function of the substance. In some cases, it could not be sterilized.

  Furthermore, in the above-described conventional sterilization method using a drug, even after the substance is in a desired sterilized state, the drug adhering to the substance retains its medicinal properties, and thus may adversely affect the substance. A substance that is denatured by contact with an excessive drug may not be able to sterilize because it cannot perform its original function.

  In addition, in the technology for washing substances, it is difficult to remove the oil film adhering to the glass cup with water or wiping with a cloth. It may be difficult to remove organic matter simply by wiping with a cloth. In such a case, it is possible to wash with a detergent, but there are problems such as taking time and labor to remove organic substances to a high degree and requiring a large amount of water to remove the detergent. . In addition, residual detergent or waste liquid treatment may be a problem.

  Moreover, in the technology for decolorizing substances, for example, hydrogen peroxide used as an oxidizing agent is relatively stable, so that waste liquid treatment after decolorization is necessary, and ozone is relatively unstable. In addition, it is a problem that long-term storage is virtually impossible.

  In addition, in the production of industrial products by oxidation of organic compounds, the above-described method of synthesizing adipic acid using nitric acid uses a strong acid as an oxidant, and thus costs for countermeasures against corrosion of the equipment are increased. However, there is a problem that costs are required to reduce the manufacturing risk.

  Furthermore, in the above-described terephthalic acid synthesis method, cobalt, manganese and bromine compounds are used as catalysts. However, in order to reduce costs for measures against corrosion of equipment caused by bromine and to reduce the environmental load caused by bromine. There was a problem that it was expensive.

  Furthermore, in the above-described synthesis method of ε-caprolactone, the reaction crude liquid usually obtained contains cyclohexanone, hydrogen peroxide and by-products as raw materials in addition to ε-caprolactone, which requires much labor for separation and purification. There was a problem that it was expensive.

  Also in the synthesis method of glycidyl methacrylate, there is a problem that much labor and cost are required to remove methanol and water, which are commonly used reaction solvents, by distillation.

  Furthermore, with regard to reducing the molecular weight of polysaccharides, acid hydrolysis with concentrated hydrochloric acid or the like, and methods for reducing the molecular weight with enzymes are generally used, but even monosaccharides are hydrolyzed and have a desired degree of polymerization. There were a problem that polysaccharides could not be produced efficiently and a problem that required a long time of several hours to about 1 day or more to lower the molecular weight. In recent years, low-molecular-weight shortening by oxidation treatment under high pressure has been proposed, but an expensive high-pressure vessel with high corrosion resistance is required, and there is a problem that costs increase.

  As a result of earnest research, the present inventors have solved this problem by applying an oxidation technique using a nitrous oxide solution to the modification of the substance itself, the substance surface, or the deposit on the substance surface. I got the technology.

The present invention relates to a method and apparatus for modifying a substance, and substances obtained by these methods and apparatuses, and in particular, irradiation with ultraviolet light in a state where a nitrous oxide (N ₂ O) solution is in contact with the substance. It is an object of the present invention to provide a method for modifying a substance itself, a substance surface, a substance surface deposit or the like, and a substance obtained by these methods.

  Another object of the present invention is to provide a hydrophilization method and apparatus that are easy to handle, easily control the degree of hydrophilization, and have a low environmental load, and a hydrophilized substance obtained by these methods and apparatuses. It is said.

  In addition, the present invention provides a method and apparatus for sterilizing a substance capable of managing the sterilization time as strictly as possible without causing thermal deformation or thermal denaturation even when the substance to which microorganisms adhere is sterilized. And it aims at providing the sterilized substance obtained by these methods and apparatuses.

The present invention also relates to a method and apparatus for cleaning a substance, and substances obtained by these methods and apparatuses, in particular, oxidizing an organic substance attached to the substance using a nitrous oxide (N ₂ O) solution. It is an object of the present invention to provide a method and an apparatus for cleaning by the above and a substance obtained by the method and apparatus.

The present invention also relates to a method and apparatus for decolorizing a substance and substances obtained by these methods and apparatuses, and in particular, irradiates ultraviolet light of a specific wavelength in a state where a solution of nitrous oxide (N ₂ O) is in contact. It is an object of the present invention to provide a method and apparatus for decolorizing a substance, and a substance obtained by these method and apparatus.

In addition, the present invention relates to a method and apparatus for producing a substance and substances obtained by these methods and apparatuses, and in particular, a substance having functionality is produced by an oxidation reaction using a nitrous oxide (N ₂ O) solution. It is an object of the present invention to provide a method, a device, and a functional substance obtained by these method and device.

In order to achieve the above object, the present invention provides a modification of a substance that modifies the substance by irradiating the solution with ultraviolet light in a state where the solution containing nitrous oxide (N ₂ O) is in contact with the substance. Is in the quality method.

  Furthermore, the modification is characterized by hydrophilization.

  Further, the modification is sterilization.

  Further, the modification is cleaning performed by decomposing and removing organic substances by oxidation.

  Further, the modification is decolorization.

  The decolorization time of the substance is controlled by the irradiation time of the ultraviolet light.

  Further, the decoloring region of the substance is controlled by the ultraviolet light irradiation region.

  Furthermore, the modification is made to be a substance having a function different from that of the original substance.

  The original substance is an alcohol or a ketone.

  Further, the original substance is an organic compound having at least one unsaturated bond.

  Further, the original substance is a polysaccharide.

  Further, the substance having a function different from that of the original substance is carboxylic acid.

  Further, the modification with the function different from that of the original substance is obtained in the microreactor.

  Further, in the modification to the substance having a function different from that of the original substance, the irradiation with ultraviolet light is performed from a solution containing the nitrous oxide and a substance having a function different from that of the original substance. It is characterized in that it is carried out after separating a substance having a function different from that of the original substance.

  In addition, the irradiation time of the ultraviolet light is controlled in order to obtain a substance having a function different from that of the original substance.

  The present invention is characterized in that the solution contains a thickener.

  The present invention is characterized by using a krypton-iodine (KrI) excimer lamp as an ultraviolet light source.

  The present invention is a substance obtained by the method for modifying a substance described above.

The present invention provides a solution contact means for bringing a solution containing nitrous oxide (N ₂ O) into contact with a substance, and the solution is irradiated with ultraviolet light in a state where the solution and the substance are brought into contact with each other. A substance reforming apparatus comprising a light source and configured to hydrophilize the substance by irradiation with the ultraviolet light.

The present invention provides a solution contact means for bringing a solution containing nitrous oxide (N ₂ O) into contact with a substance, and the solution is irradiated with ultraviolet light in a state where the solution and the substance are brought into contact with each other. A substance reforming apparatus comprising a light source and configured to sterilize the substance by irradiation with the ultraviolet light.

The present invention includes a solution contact means for bringing a solution containing nitrous oxide (N ₂ O) into contact with an organic substance attached to a substance, and the solution and the organic substance in contact with the solution while the solution and the organic substance are in contact with each other. A substance reforming apparatus comprising a light source for irradiating light and configured to wash the substance by irradiation with the ultraviolet light.

The present invention provides a solution contact means for bringing a solution containing nitrous oxide (N ₂ O) into contact with a substance, and the solution is irradiated with ultraviolet light in a state where the solution and the substance are brought into contact with each other. A substance reforming apparatus comprising a light source and configured to decolorize the substance by irradiation with the ultraviolet light.

The present invention provides a solution contact means for bringing a solution containing nitrous oxide (N ₂ O) into contact with a substance, and the solution is irradiated with ultraviolet light in a state where the solution and the substance are brought into contact with each other. A substance reforming apparatus comprising a light source and configured to produce a functional substance different from the substance by irradiation with the ultraviolet light.

According to the present invention, since the substance is hydrophilized by irradiating the solution with ultraviolet light in a state where a solution containing nitrous oxide (N ₂ O) is in contact with the substance, the substance is hydrophilized. In addition, it is possible to provide a method for hydrophilizing a substance that has a low environmental load, is easy to handle, and can efficiently hydrophilize the surface of the substance.

  According to the present invention, since there is a substance hydrophilizing apparatus that uses the method for hydrophilizing a substance to make the surface of the substance hydrophilic, the load on the environment is small and the handling is easy. It is possible to provide a device for hydrophilizing a substance that can be efficiently converted.

  According to the present invention, since there is a hydrophilic substance obtained by hydrophilizing the substance using a method for hydrophilizing the substance or a hydrophilizing apparatus for the substance, it is possible to provide a highly hydrophilic substance. it can.

According to the present invention, since the substance is sterilized by irradiating the solution with ultraviolet light in contact with a solution containing nitrous oxide (N ₂ O), the burden on the environment is small and the handling is easy. In addition, there can be provided a method for sterilizing microorganisms that can reliably sterilize microorganisms.

According to the present invention, solution contact means for bringing a solution containing nitrous oxide (N ₂ O) into contact with a substance, and ultraviolet light is applied to the solution in a state where the solution and the substance are brought into contact with each other by the solution contact means. The present invention provides a microorganism sterilization apparatus that has a light source for irradiating and sterilizes the substance by irradiation with the ultraviolet light, so that the load on the environment is small, the handling is easy, and the microorganism can be sterilized reliably. be able to.

  ADVANTAGE OF THE INVENTION According to this invention, the substance by which the microorganisms were sterilized reliably by the method or apparatus with a small load with respect to an environment and easy to handle can be provided.

According to the present invention, in a state in which a solution containing nitrous oxide (N ₂ O) is in contact with an organic substance attached to the substance, the organic substance is oxidized by irradiating the solution with ultraviolet light to oxidize the organic substance. Provided is a method for cleaning a substance, which is washed by decomposing and removing the substance, has a low environmental load, is easy to handle, and can be highly washed by oxidizing and decomposing organic substances. Can do.

According to the present invention, since there is a method for decolorizing a substance by decolorizing the substance by irradiating the solution with ultraviolet light in a state where the solution containing nitrous oxide (N ₂ O) is in contact with the substance, It is possible to provide a method for decolorizing a substance that is light in load, easy to handle, can efficiently decompose colored substances such as dyes, and can decolorize a substance with high efficiency.

  According to the present invention, since there is a substance decolorizing apparatus for decolorizing a substance using such a method for decolorizing a substance, the load on the environment is small, the handling is easy, and the decomposition of colored substances such as dyes is efficiently performed. It is possible to provide a substance decolorizing apparatus that can perform decolorization of a substance with high efficiency.

  According to the present invention, since there is a decolorized material obtained by performing decolorization by a decoloring method of such a material or a decoloring apparatus for such a material, a colored substance such as a dye is decomposed with high efficiency and decolorized with high efficiency. A substance can be provided.

According to the present invention, a functional substance different from the predetermined substance is produced by irradiating the solution with ultraviolet light in a state where the solution containing nitrous oxide (N ₂ O) is in contact with the predetermined substance. A method for producing a substance capable of producing a functional substance quickly can be provided.

  According to the present invention, since the predetermined substance is alcohol or ketone, it is possible to provide a method for producing a substance that can quickly produce an oxide of alcohol or ketone.

  According to the present invention, since the predetermined substance is an organic compound having at least one unsaturated bond, it is possible to provide a method for producing a substance capable of generating an oxide in which an unsaturated bond site is oxidized. .

  According to the present invention, since the predetermined substance is a polysaccharide, a method for producing a substance capable of reducing the molecular weight by oxidative degradation of the polysaccharide can be provided.

  According to the present invention, since the functional substance is a carboxylic acid, it is possible to provide a method for producing a substance that can quickly produce a carboxylic acid that can be used in various fields.

  According to the present invention, since the state is obtained in the microreactor, it is possible to provide a method for producing a substance that can produce a functional substance more quickly.

  According to the present invention, the ultraviolet irradiation is performed by a separation unit that separates a substance different from the predetermined substance from a solution containing the nitrous oxide, the predetermined substance, and a substance different from the predetermined substance. Therefore, it is possible to provide a method for manufacturing a substance that can selectively oxidize a predetermined substance and manufacture a substance having a function different from that of the predetermined substance.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing apparatus of the substance which can manufacture a functional substance rapidly can be provided.

  According to the present invention, a functional substance can be obtained quickly.

  According to the present invention, the nitrous oxide-containing solution that comes into contact with the object also contains a thickener and has the property of easily staying at the contact position when brought into contact with the object. It is possible to oxidize by bringing the solution into contact with only the desired part.

  Further, since the nitrous oxide-containing solution supplied by the solution supply means of the object oxidation apparatus according to the present invention contains a thickener, the solution brought into contact with the object tends to stay at the contact position. Therefore, it is possible to oxidize by bringing the solution into contact with only the portion to be oxidized.

It is a schematic diagram of the experimental apparatus for clarifying the characteristic of a nitrous oxide solution. It is a graph which shows the experimental result by the experimental apparatus shown in FIG. It is a graph which shows the experimental result by the comparative example using the solution different from a nitrous oxide solution in the experimental apparatus shown in FIG. It is a graph which shows the experimental result by the comparative example which did not irradiate with ultraviolet light in the experimental apparatus shown in FIG. It is a graph which shows the experimental result performed by switching the irradiation state of an ultraviolet light in the experimental apparatus shown in FIG. It is a graph which shows the experimental result performed by changing the wavelength and irradiation time of an ultraviolet light in the experimental apparatus shown in FIG. It is a schematic diagram of the other experimental apparatus for clarifying the characteristic of a nitrous oxide solution. It is a graph which shows the experimental result performed while changing the gas dissolved in the experimental apparatus shown in FIG. It is a schematic diagram of the other experimental apparatus for clarifying the characteristic of a nitrous oxide solution. It is the schematic of the hydrophilization apparatus to which this invention is applied. It is a graph which shows the UV absorption spectrum of a nitrous oxide solution. It is a graph which shows the UV absorption spectrum of an oxygen molecule. It is the schematic of the hydrophilization apparatus for hydrophilizing the substance with a comparatively complicated surface shape to which this invention is applied. It is the schematic of the hydrophilization apparatus for hydrophilizing the substance which has space inside to which this invention is applied. It is the schematic of the hydrophilization apparatus for applying the present invention and hydrophilizing while moving a substance. It is the schematic of the hydrophilization apparatus applicable to the hydrophilization of the substance which is difficult to move to which the present invention is applied. It is the schematic of the hydrophilization apparatus which can replace | exchange the nitrous oxide solution which immersed the substance to which this invention is applied, and can perform local modification | reformation of a substance. It is the schematic of the hydrophilization apparatus with a high freedom degree of selection of the hydrophilization position to which this invention is applied. It is the schematic of the hydrophilization apparatus which apply | coats a nitrous oxide solution to a substance by spraying to which this invention is applied. This is a substance manufacturing apparatus for manufacturing a substance having a function different from that of the original substance to which the present invention is applied. It is explanatory drawing which showed the microreactor. This is a substance manufacturing apparatus for manufacturing a substance having a function different from that of the original substance to which the present invention is applied. This is a substance manufacturing apparatus for manufacturing a substance having a function different from that of the original substance to which the present invention is applied. This is a substance manufacturing apparatus for manufacturing a substance having a function different from that of the original substance to which the present invention is applied. It is a schematic perspective view which shows the principal part of the oxidation apparatus in which the brush is used as a solution supply means. It is a schematic perspective view which shows the principal part of the oxidation apparatus in which the printing unit of an offset printing system is used as a solution supply means. It is a schematic perspective view which shows the principal part of the oxidation apparatus in which the printing unit of a relief printing system is used as a solution supply means. It is a schematic perspective view which shows the principal part of the oxidation apparatus in which the printing unit of an intaglio printing system is used as a solution supply means. It is a schematic perspective view which shows the principal part of the oxidation apparatus in which the printing unit of a stencil printing system is used as a solution supply means. It is a chart which contrasts the transmittance | permeability (% T) of the ultraviolet light (wavelength 191nm-240nm) with water and air, and each organic solvent. It is the schematic of the oxidation apparatus which can exchange the nitrous oxide solution which immersed the to-be-processed object, and can perform local oxidation of a to-be-processed object.

Explanation of symbols

DESCRIPTION OF SYMBOLS 30 Hydrophilization apparatus, sterilization apparatus, washing | cleaning apparatus, decoloring apparatus, oxidation apparatus 31 Solution contact means 40 Hydrophilization apparatus, sterilization apparatus, washing | cleaning apparatus, decoloring apparatus, oxidation apparatus 41 Solution contact means 50 Hydrophilization apparatus, sterilization apparatus, washing | cleaning apparatus , Decolorizing device 51 Solution contacting means 60 Hydrophilizing device, sterilizing device, cleaning device, decolorizing device, oxidizing device 61, 62 Solution contacting means 70 Hydrophilizing device, sterilizing device, cleaning device, decoloring device, oxidizing device 71 Solution contacting means 80 Hydrophilizing device, sterilizing device, cleaning device, decolorizing device 81,83 Solution contact means 90 Hydrophilizing device, sterilizing device, cleaning device, decoloring device, oxidation device 91 Solution contacting means 100 Hydrophilizing device, sterilizing device, cleaning device, decolorizing Equipment 103 Solution contact means 110 Production equipment L Light source, krypton-iodine (KrI) excimer lamp S Solution containing nitrous oxide X Substance

In the method for modifying a substance according to the present invention, the substance itself, the substance surface or the substance surface is irradiated by irradiating the solution with ultraviolet light in a state where the solution containing nitrous oxide (N ₂ O) is in contact with the substance. Reform deposits, etc.

  Here, the modification means hydrophilization, sterilization, washing, decolorization, and production of a substance having a function different from that of the original substance.

Moreover, the solution containing nitrous oxide (N ₂ O) refers to a solution in which nitrous oxide gas is dissolved.

  In the method for modifying the substance itself or the substance surface or deposits on the substance surface according to the present invention, since an oxidation reaction occurs only when irradiated with ultraviolet light, there is no need to take countermeasures against corrosion in the reformer and it is safe. . Further, since nitrous oxide is stable and harmless, a waste liquid treatment for decomposing nitrous oxide is unnecessary, and nitrous oxide itself is inexpensive, so that running costs are reduced. Since the oxidizing power of atomic oxygen generated by irradiation with ultraviolet light is extremely large, the reforming is performed strongly. Atomic oxygen is generated not only on the surface of the material to be modified, but also in the ultraviolet light irradiation range. For example, unlike oxidation using a titanium dioxide catalyst, rate limiting is unlikely to occur, and rapid reforming treatment is performed. Is done. Since the reforming reaction is performed in the liquid phase, generation of ozone due to irradiation with ultraviolet light is suppressed. As described above, the environmental load is small, the handling is easy, and good reforming is performed at low cost.

  The adhesion of the modified material surface is improved, and problems such as uneven ink application and repelling are improved in printing for various purposes performed on the resin substrate surface, for example. Adhesiveness of the modified material surface is improved, and for example, labeling or the like can be easily and satisfactorily performed.

  As the ultraviolet light source, a krypton-iodine (KrI) excimer lamp is used.

  Therefore, the reforming reaction is carried out only when desired by turning on and off the KrI excimer lamp with good rise and fall. The ultraviolet light irradiated by the KrI excimer lamp is easily absorbed by nitrous oxide and not easily absorbed by oxygen, so it has excellent nitrous oxide resolution, high efficiency of oxidation reaction, low generation of ozone, high The reforming is performed with efficiency. In addition, a device for preventing ozone is not essential, and the load on the environment is small and handling is easy. For these reasons, the structure is relatively simple, the degree of freedom in design is high, and it contributes to the provision of a compact and low-cost reformer.

  The substance reforming apparatus according to the present invention reforms a substance using such a reforming method. Therefore, since an oxidation reaction occurs only when irradiated with ultraviolet light, it is not necessary to take countermeasures against corrosion and it is safe. Further, since nitrous oxide is stable and harmless, a waste liquid treatment for decomposing nitrous oxide is unnecessary, and nitrous oxide itself is inexpensive, so that running costs are reduced. Since the oxidizing power of atomic oxygen generated by irradiation with ultraviolet light is extremely large, the reforming is performed strongly. Atomic oxygen is generated not only on the surface of the material to be modified, but also in the ultraviolet light irradiation range. For example, unlike oxidation using a titanium dioxide catalyst, rate limiting is unlikely to occur, and rapid reforming treatment is performed. Is done. Since the oxidation reaction is performed in the liquid phase, generation of ozone due to irradiation with ultraviolet light is suppressed. As described above, the environmental load is small, the handling is easy, and good reforming is performed at low cost.

  The substance according to the present invention can be obtained by reforming the substance using the substance reforming method or the substance reforming apparatus.

  Therefore, a safe and highly efficient modified substance can be provided at low cost.

These advantages obtained by the present invention will be more clearly understood from the following circumstances.
Conventionally, in various fields such as the manufacture of industrial products by oxidation of organic compounds and the manufacture of silicon wafers, techniques using oxidation reactions in liquid phase or gas phase using various substances have been proposed. However, while each of these technologies has advantages, it is also known to have problems.
This will be described below.

  In the manufacture of industrial products by oxidation of an organic compound, a method is carried out in which an oxygen-containing substance called an oxidant and an organic compound are mixed and an oxidation reaction is performed using a catalyst, heat, or the like.

  For example, in the production of adipic acid, which is a raw material for nylon, a nitric acid oxidation method for oxidizing a raw material cyclohexanone or cyclohexanol using a large amount of nitric acid is industrially implemented. This method uses nitric acid, which is a strong acid, as an oxidant, so it costs money to take measures against corrosion of the equipment and costs to reduce manufacturing risk. There is.

  Also, in the production of terephthalic acid, which is a raw material for polyester, an air oxidation method for oxidizing raw material para-xylene using oxygen in the air is industrially implemented. Cobalt, manganese and bromine compounds are used as catalysts in this method. However, it is expensive to take measures against bromine corrosion, and it is expensive to reduce the environmental impact of bromine. There is a problem.

  As a method of oxidizing a substance such as a silicon wafer, there is a method of bringing a substrate into contact with water in which an oxidizing substance such as hydrogen peroxide water or ozone water is dissolved.

  Hydrogen peroxide water is used for bleaching paper and pulp, cleaning semiconductors, sterilizing and disinfecting, etc., using its oxidizing power. Ozone water is also used to sterilize water and sewage, sterilize food and tableware, and recently cleans semiconductors by using its oxidizing power.

  Since the hydrogen peroxide solution is relatively stable, the hydrogen peroxide remains in the waste liquid after being used for various purposes for a relatively long time. Therefore, hydrogen peroxide wastewater needs to be decomposed in order to reduce the environmental burden, and when a large amount of hydrogen peroxide water is industrially used, the cost required for the decomposition treatment increases. is there.

  On the other hand, since ozone water is relatively unstable, it naturally decomposes in a relatively short time. However, even if the concentration is low, there is a problem in that it is harmful to the human body and the load applied to the material of the piping equipment or the like is large.

  In addition, since ozone water is relatively unstable, long-term storage with its oxidizing power maintained is virtually impossible. In other words, there is an inconvenience that it is impossible to take out and use only a necessary amount from a large amount of stored ozone water when necessary.

  Furthermore, a certain amount of apparatus startup time is required until the ozone water is stably supplied after the operation of the ozone water production apparatus in the stopped state is started. If you want to use ozone water intermittently, if the device startup time is longer than the non-use time when ozone water is not used, the ozone water production device is also used during the non-use time of ozone water. Therefore, it is inevitable that the wasteful raw material cost and the unnecessary running cost will be generated.

  As another method for oxidizing the substance, there is a method using a photocatalyst. A photocatalyst is a substance that exhibits a catalytic action when irradiated with light, and a typical example thereof is titanium dioxide having an anatase type crystal structure. Titanium dioxide exhibits an oxidizing action when irradiated with light having a wavelength shorter than about 380 nm.

  When the target substance to be oxidized is present in the gas phase, titanium dioxide is also present in the gas phase, and the target substance is oxidized by irradiating it with light. When the target substance to be oxidized is present in water, the target substance is oxidized by causing titanium dioxide to exist in water and irradiating it with light.

  Titanium dioxide is used for deodorizing and decomposing malodorous components such as ammonia and formaldehyde, and sterilizing and purifying drinking water and wastewater by utilizing the oxidizing power as a photocatalyst. In order to facilitate the handling of titanium dioxide, titanium oxide is often used in the form of a thin film immobilized on a suitable substrate surface. Only exhibits an oxidizing action. Therefore, there is a problem in that the oxidation rate is relatively slow because diffusion / adsorption on the surface of titanium dioxide in the gas phase and in water of the substance itself intended for oxidation becomes rate limiting.

  When titanium dioxide is used in water, hydroxy radicals having oxidizing power are generated by oxidizing water molecules adsorbed on the surface of titanium dioxide. Since this hydroxy radical has a very short lifetime and can only exist in the immediate vicinity of titanium dioxide, it is effectively oxidized in water at a distance from titanium dioxide, resulting from the diffusion of hydroxy radicals. It is not allowed.

  Therefore, unlike hydrogen peroxide water and ozone water, even if a solid substance that does not show solubility in water, such as a semiconductor substrate, is immersed in water in which titanium dioxide exists, light is not emitted. There is a problem that the surface of the solid material cannot be oxidized regardless of the presence or absence of irradiation. Even if fine powdered titanium dioxide is dispersed in water and an attempt is made to increase the oxidation rate, there is a problem that it is not easy to separate and recover the titanium dioxide after the oxidation treatment.

As described above, this conventional technique has problems in terms of environmental load and difficulty in handling.
In this regard, there are reports that should be noted about an oxidation method using nitrous oxide (N ₂ O).

  For example, the following document, Naotoshi Yamanouchi, Mitsuo Takeda, “Nitrous oxide”, high pressure gas, Vol. 13 No. 3 (1976) p105-111, nitrous oxide is a stable gas at normal temperature and pressure, and does not decompose by visible light.

For this nitrous oxide, for example, the following document “Photochemical reaction in the gas phase”, edited by the Chemical Society of Japan, Chemical Review, Inorganic Photochemical Society Press Center No. 39, (1983) p14-38
As described in, nitrous oxide decomposes into nitrogen molecules (N ₂ ) and atomic oxygen (O) when irradiated with light having a wavelength shorter than 240 nm. Therefore, nitrous oxide has excellent properties with respect to the problems described above.

With respect to nitrous oxide having such characteristics, for example, the following document, K.I. Uno, A .; Namiki, S .; Zaima, T .; Nakamura, N .; Ohtake, “XPS Study of the Oxidation Process of Si (111) via Photochemical Decomposition of N ₂ O by an UV Excimer Laser”, Surface Science, 193 (1988), p321-335.
As described in Japanese Patent Application Laid-Open No. 4-36456, a technique for oxidizing the surface of a Si wafer using generated atomic oxygen, as described in Japanese Patent Publication No. 4-36456. Various researches have been conducted on techniques for oxidizing a target substance, such as a technique for forming a natural oxide on the surface of a semiconductor substrate using silicon.

  However, even when nitrous oxide is used, when oxidation is performed in a gas phase, there is a problem that handling of the gas is difficult. Moreover, in order to suppress generation | occurrence | production of ozone, since sealing apparatuses, such as a processing chamber, are needed and the temperature in a processing chamber must be heated up as needed, the cost of the oxidation by nitrous oxide will become high. There is a problem.

  In this regard, as a result of intensive studies, the present inventors have applied light to nitrous oxide dissolved in the liquid as described in [Japanese Patent Application No. 2005-146361] filed earlier. I came to have a way to solve this conventional problem at once. That is, a method of oxidizing a substance using a nitrous oxide solution, wherein the solution is brought into contact with the substance, and the substance is oxidized by irradiating the solution with light having a wavelength of at least 240 nm or less. A method and apparatus for oxidizing a substance using a sub-oxygen solution.

Under such circumstances, the expansion of the application field of the oxidation technology utilizing the characteristics of the nitrous oxide solution has been awaited.
Under such circumstances, the present inventors have made the present invention having the various advantages described above.

  Therefore, the oxidation reaction performed by irradiating the nitrous oxide solution with ultraviolet rays has the following characteristics.

  Such characteristics cause dissociation of nitrous oxide by irradiating ultraviolet light of 240 nm or less in the solution, and oxidize the substance by atomic oxygen (O) generated thereby.

  It oxidizes a substance only when irradiated with ultraviolet light, and is stable unless irradiated with ultraviolet light. Therefore, if the light irradiation time is controlled, the oxidation time is controlled, and an oxidation reaction can be caused only for a desired time.

  If the light irradiation region is controlled, the oxidation region is controlled, and an oxidation reaction can be caused only in a desired region.

  Strong oxidizing power and strong oxidation reaction.

Hereinafter, these characteristics will be described in more detail based on experimental results.
In addition to the above-described characteristics, nitrous oxide and this solution simultaneously satisfy the excellent characteristics that are not seen in conventional oxidizing substances and are considered to be contradictory. In other words, nitrous oxide is highly safe, for example, the aqueous solution is harmless, and because it is highly safe, it does not require a decomposition treatment and is easy to handle. No measures are required, nitrous oxide itself is inexpensive, and there is no need for decomposition treatment or corrosion measures, so running costs can be reduced. No ozone is generated in the solution. Various excellent properties such as no problem.

<Oxidative decomposition of methylene blue>
A standard method used in evaluating the oxidizing power of a photocatalyst is oxidative decomposition of water-soluble methylene blue. Using this, the oxidizing power of the nitrous oxide solution is evaluated using a mixed aqueous solution of methylene blue and nitrous oxide.

  Methylene blue exhibits a blue color in the form of an aqueous solution, and when oxidized, the blue color disappears and becomes colorless. In the evaluation of the oxidizing power of a photocatalyst, the change in absorbance at 665 nm of a methylene blue (10 ppm) aqueous solution is generally measured. Further, in order for the absorbance at 665 nm of a methylene blue (10 ppm) aqueous solution to decrease to about 10% of the initial value, it usually takes a time of several tens of minutes to several hundred minutes for a photocatalyst.

  FIG. 1 is a schematic diagram of an experimental apparatus in which methylene blue was oxidatively decomposed. The experimental apparatus 11 includes a container 12 whose upper surface is open, and a high-pressure mercury lamp 13 as a light source disposed immediately above the container 12. The container 12 is processed with Teflon (registered trademark). The high-pressure mercury lamp 13 generates light including a wavelength of at least 240 nm or less, and the output is 1200 W. The high-pressure mercury lamp 13 is arranged close to the container 12 so that the light irradiates the entire surface of the container 12. The container 12 is filled with a methylene blue aqueous solution 14 in which methylene blue (10 ppm) and nitrous oxide are dissolved.

  FIG. 2 is a graph showing the results of an oxidative decomposition experiment of methylene blue by the experimental apparatus 11, in which about 1000 ppm of nitrous oxide is dissolved. In the graph, the horizontal axis represents the light irradiation time (minutes), and the vertical axis represents the 665 nm absorbance of the methylene blue aqueous solution. Here, the light transmittance (T) is expressed by Equation 1 where Ii is the intensity of light incident on the substance and Io is the intensity of light emitted therefrom. And the light absorbency at that time is represented by Numerical formula 2.

  From the graph of FIG. 2, it was confirmed that about 50% of methylene blue was decomposed after 1 minute of irradiation time, and about 90% of methylene blue was decomposed after 3 minutes of irradiation time.

  FIG. 3 shows a result of an oxidative decomposition experiment of methylene blue using an aqueous solution in which methylene blue (10 ppm) and helium (He) (content of about 16 ppm) are dissolved in the experimental apparatus 11. Min) and the 665 nm absorbance of the methylene blue aqueous solution.

Helium (He) is a well-known inert gas and has been found not to absorb light at 665 nm. This time, in comparison with nitrous oxide-dissolved water, helium is forcibly submerged in water to expel air components (N ₂ , O ₂ , CO _2, etc.) dissolved in the water used. (He) was dissolved.

  As is clear from the graph shown in FIG. 3, unlike the result shown in FIG. 2 in the case of using water in which nitrous oxide was dissolved, almost no decomposition was observed in the irradiation time of 1 minute. It was confirmed that methylene blue was not decomposed much even after the irradiation time of 3 minutes. That is, it was confirmed from the comparison between FIG. 2 and FIG. 3 that methylene blue can be oxidatively decomposed by irradiating light to nitrous oxide.

  FIG. 4 is a graph showing the relationship between the time during which the methylene blue aqueous solution 14 is simply left without turning on the high pressure mercury lamp 13 and the 665 nm absorbance of the methylene blue aqueous solution in the experimental apparatus 11. Methylene blue and nitrous oxide were dissolved in the aqueous solution 14, but it was confirmed that the absorbance at 665 nm did not change even when left for 60 minutes in a state where light having a wavelength of 240 nm or less was not irradiated. That is, it was confirmed from a comparison between FIG. 2 and FIG. 4 that methylene blue is not oxidatively decomposed unless light is irradiated to nitrous oxide.

  FIG. 5 shows a state in which irradiation of the ultraviolet light to the aqueous solution 14 is stopped when 0.5 minute has elapsed after the irradiation of the ultraviolet light to the aqueous solution 14 by the high-pressure mercury lamp 13 in the experimental apparatus 11. It is a graph which shows the change of 665 nm light absorbency of the methylene blue aqueous solution at the time of returning to the state which irradiated the ultraviolet light to the aqueous solution 14 again when one minute passed since that time.

  From the graph shown in FIG. 5, the irradiation with ultraviolet light starts and the methylene blue in the aqueous solution is decomposed. However, the decomposition of methylene blue is also stopped for 1 minute after the irradiation with ultraviolet light is stopped. After that, it was confirmed that the decomposition of methylene blue started as soon as it returned to the state irradiated with ultraviolet light. From this, it was confirmed that the oxidation time of the substance can be controlled by selecting the irradiation time of ultraviolet light.

  All the above experiments were conducted at room temperature around 24 ° C. From this result, it was confirmed that the oxidation time of the substance can be controlled by selecting the irradiation time of ultraviolet light. Note that the lifetime of atomic oxygen is extremely short, and the generation of atomic oxygen stops at the same time as the irradiation of ultraviolet light is stopped. Therefore, stopping the irradiation of ultraviolet light substantially stops the oxidation. I mean.

  In the experiment, the high-pressure mercury lamp 13 was used as a light source for dissociating nitrous oxide. However, a light source other than the high-pressure mercury lamp may be used as long as it generates light having a wavelength of 240 nm or less. Is possible. Although 1200 W was used as the lamp output, the oxidative decomposition is possible even if the output is performed at other power. In general, when the same lamp is used, the rate of oxidative decomposition is affected by the output. In other words, when the lamp output is small, the oxidative decomposition rate decreases, and conversely, when the lamp output is large, the oxidative decomposition rate increases. The lamp output may be appropriately selected according to the desired oxidative decomposition rate.

FIG. 6 shows an absorption spectrum of an aqueous nitrous oxide solution (nitrogen oxide content of about 1000 ppm) when irradiated with ultraviolet light using the experimental apparatus 11. There is no methylene blue in the container 12. The horizontal axis indicates the wavelength band of the measurement range 200 to 340 nm, and the vertical axis indicates the absorbance. Curves C1 to C3 indicate the absorbance of nitrous oxide (N ₂ O), where C3 is irradiated for 3 minutes, C2 is irradiated for 1 minute, and C1 is not irradiated. As is apparent from the graph, the light having a wavelength of 240 nm or more has zero absorbance and no light is absorbed. In other words, it can be seen that nitrous oxide is not dissociated by light energy irradiation.

  Table 1 shows the change in the concentration of nitrous oxide determined from the absorbance at a wavelength of 205 nm shown in FIG. In addition, the density | concentration with zero irradiation time is made into a saturated density | concentration (value at the water temperature of 25 degreeC), and the relative value of each light absorbency is computed by multiplication. It can be seen that the concentration of nitrous oxide is considerably reduced by irradiation for 3 minutes.

In addition, from the experimental results shown in FIG. 6, substantially no ozone (O ₃ ) by-product was detected. That is, the maximum wavelength (λmax) of ozone is 260 nm, but the absorbance at that is below the detection limit.

<Oxidation of silicon wafer>
Next, experimental results of silicon wafer oxidation will be described. FIG. 7 is a schematic view of an oxidizer that oxidizes a silicon wafer. Compared with the experimental apparatus 11, the oxidation apparatus 15 includes a low-pressure mercury lamp 16 instead of the high-pressure mercury lamp 13 as a light source, and a plurality of protrusions 17 having the same height on the bottom surface of the container 12. Are different, but are the same in other respects.

The low-pressure mercury lamp 16 generates light including a wavelength of 240 nm or less, centering on an ultraviolet wavelength of 185 nm, like the high-pressure mercury lamp 13, but its output is 110 W.
What is filled in the container 12 is not the aqueous solution 14 in which methylene blue and nitrous oxide are mixed, but the aqueous solution 18 that does not contain methylene blue and contains about 0.1% (1068 ppm) of nitrous oxide.

The container 12 supports the back surface of the silicon wafer W, which is a substance to be oxidized, by the protrusion 17.
The aqueous solution 18 is filled in the container 12 to such an extent that the entire silicon wafer W is sufficiently immersed after the silicon wafer W is placed in the container 12.
In this example, the silicon wafer W to be oxidized was obtained by removing the oxide existing on the surface in advance with an aqueous hydrogen fluoride solution.

  FIG. 8 is a graph showing the behavior of the oxide film on the silicon wafer W when an aqueous solution in which various gases are dissolved in the oxidizer 15 is used. The horizontal axis represents the ultraviolet irradiation time (minutes), and the vertical axis represents the oxide film thickness (Å). Note that an ozone-less high-pressure mercury lamp is used as the light source instead of the low-pressure mercury lamp 16.

In the graph, G1 represents N ₂ O, G2 represents O ₂ , G3 represents air, and G4 represents a solution in which an inert gas (He, N ₂ , Ar) is dissolved. As is clear from this graph, it can be seen that N ₂ O dissolved water has a significantly higher oxidation rate than other dissolved water. Thus, the oxidizing power is very strong. By the way, N ₂ O grew by 6 照射, irradiation time of 1 minute, 3 Ｏ O ₂ , ₂空 気 air, and other He, N ₂ , Ar were 1-2 成長.

  The decrease in the oxidation rate curve with the irradiation time is considered to be caused by the decrease in the concentration of oxidizing active species present in water. Therefore, it is considered that a decrease in the oxidation rate can be suppressed by injecting unused nitrous oxide into the container 12 so that the concentration of the oxidation active species in water does not decrease.

  Next, an experimental result of silicon wafer oxidation when an area that is irradiated with light and an area that is not irradiated with light are provided using an aqueous solution containing nitrous oxide, hydrogen peroxide solution, and ozone water. FIG. 9 is a schematic diagram of an oxidizer that oxidizes a silicon wafer. Compared with the oxidizer 15, the oxidizer 19 includes an ozone-less high-pressure mercury lamp 20 as a light source instead of the low-pressure mercury lamp 16, and a light shielding plate that shields light irradiation on a prescribed region of the silicon wafer W. 21 is different, but the configuration is the same in other respects.

The ozone-less high-pressure mercury lamp 20 generates light including a wavelength of 240 nm or less.
As the aqueous solution 22 filled in the container 12, an aqueous solution containing about 0.1% nitrous oxide, 31% hydrogen peroxide water, or 4 ppm ozone water was used.

The light shielding plate 21 is disposed above the aqueous solution 22 so as to cover a part of the silicon wafer W. The silicon wafer W is obtained by removing in advance an oxide present on the surface with a hydrogen fluoride aqueous solution.
Whichever type of solution is used, the oxidation treatment is performed at room temperature for 1 minute.

The experimental results were as follows.
The thickness of the oxide film of the silicon wafer W immersed in about 0.1% N ₂ O dissolved water was 4.5 mm in the area irradiated with light, whereas it was detected in the area not irradiated with light. Below the lower limit (0.1%), oxidation did not proceed at all. The thickness of the oxide film with 31% hydrogen peroxide solution is 3.7 mm in the region irradiated with light and 2.7 mm in the region not irradiated with light, and the thickness of the oxide film with 4 ppm ozone water is The area irradiated with light was 1.9 mm, and the area not irradiated with light was 3.2 mm.

That is, when converted to the ratio of the oxide film thickness of the region irradiated with light to the oxide film thickness of the region not irradiated with light, about 0.1% N ₂ O dissolved water is 45 times or more, and 31% hydrogen peroxide solution. 1.4 times and 4 ppm ozone water became 0.6 times, and in ozone water, the oxide film thickness decreased in the region irradiated with light.

Therefore, compared with hydrogen peroxide water and ozone water, N ₂ O dissolved water has a very large difference in oxidizing power between the region irradiated with light and the region not irradiated with light, which controls the light irradiation region. Thus, it was confirmed that it is possible to oxidize only the silicon in the region irradiated with light without oxidizing the region not irradiated with light.

  This is because the lifetime of atomic oxygen is very short, about nanoseconds, and the diffusion transfer distance in the solution of atomic oxygen is extremely small. Therefore, the atomic oxygen dissociated by light irradiation moves and is irradiated with light. This is considered to be because the probability of causing an oxidation reaction in a region where there is not is extremely low.

  In this embodiment, as shown in FIG. 9, the light shielding plate 21 is disposed above the aqueous solution 18, but it is sufficient that the light irradiating the aqueous solution 18 in contact with the silicon wafer W can be shielded. The light shielding plate 21 may be disposed in the aqueous solution 18, and the light shielding plate 21 may be disposed in contact with the silicon wafer W.

  Since the oxidation of the silicon wafer W does not directly give light energy to the silicon wafer W but to nitrous oxide in the aqueous solution 18 in contact with the silicon wafer W, the light is not necessarily supplied to the silicon wafer. It is not necessary to reach the W surface. For example, the aqueous solution 18 in contact with the silicon wafer W is irradiated with light from the lateral direction so that the surface of the silicon wafer W is not directly irradiated with light. Alternatively, the silicon wafer W may be oxidized by dissociating nitrous oxide. In this case, the light shielding plate 21 can be disposed on the side of the silicon wafer W to shield light. In any case, even if light eventually reaches the surface of the silicon wafer W, unless a chemical reaction that suppresses oxidation occurs on the surface of the silicon wafer W itself, There is no problem.

  In the oxidizers 15 and 19 shown in FIGS. 7 and 9, the distances between the low pressure mercury lamp 16 and the ozoneless high pressure mercury lamp 20 as the light source and the container 12 and the silicon wafer W are not particularly defined. However, in general, when the same light source is used, the smaller the distance from the light source to the nitrous oxide present in the immediate vicinity of the oxidation target substance, the more the light illuminance increases, the more nitrous oxide dissociates. It is efficient and increases the oxidation rate of the oxidation target substance. Conversely, the greater the distance from the light source to the nitrous oxide in the immediate vicinity of the oxidation target substance, the lower the light illuminance, the lower the efficiency of dissociation of nitrous oxide, and the oxidation of the oxidation target substance. The speed is reduced. From this point of view, it is possible to change the distance according to the desired oxidation rate for the silicon wafer W.

  Next, an oxidation experiment of a silicon wafer when using a dielectric barrier discharge lamp using xenon as a light source, that is, a xenon excimer lamp will be described. The used xenon excimer lamp emits light having a wavelength of 172 nm. If this lamp is used in the atmosphere, ozone is greatly generated, that is, light is absorbed by the atmosphere. For this reason, in order to eliminate attenuation of light by the atmosphere, light was irradiated while purging with nitrogen gas.

  As experimental conditions, the internal volume of the chamber: 8 liters, the flow rate of nitrogen: 12 liters / minute, the water temperature: 23 degrees, the amount of water: 50 ml, the distance between the xenon excimer lamp and the container: 3 mm, 1 minute during a purge of about 5 minutes Light irradiation was performed. There are three types of aqueous solutions used in the experiment: helium aqueous solution (helium content about 16 ppm), nitrous oxide aqueous solution (nitrous oxide content about 1000 ppm), and oxygen aqueous solution (oxygen content about 40 ppm).

  The thickness of the silicon wafer W immersed in the helium aqueous solution was 0.4 mm, the thickness of the oxide film was 0.3 mm in the nitrous oxide aqueous solution, and 0.5 mm in the oxygen aqueous solution. As a result, it was confirmed that oxidation hardly progressed in any aqueous solution. Furthermore, regarding the nitrous oxide aqueous solution, the thickness of the oxide film did not change even when the irradiation time was extended by 3 minutes.

  In addition, a water droplet (0.2 ml) was placed on the silicon wafer, and light irradiation was performed in a state of being in contact with a xenon excimer lamp. Here, light irradiation was performed while purging with nitrogen gas in the same manner as described above. As a result, in the nitrous oxide aqueous solution, the oxide film thickness was 0.6 mm and in the oxygen aqueous solution was 0.4 mm, and it was confirmed that the oxidation hardly proceeded.

  From these experimental results, most of the light having a wavelength of 172 nm emitted from the xenon excimer lamp is absorbed by water, so that nitrous oxide is hardly decomposed and an oxide film grows almost on the surface of the silicon wafer. It is estimated that there was not. Since the absorbance of water has a maximum wavelength of 167 nm, the light applied to the aqueous solution must be longer than the wavelength at which the absorbance of water is sufficiently low. At the same time, the absorption of light by nitrous oxide must be shorter than 240 nm. From the above, the wavelength of the light irradiated to the aqueous nitrous oxide solution is preferably 173 nm or more and 240 nm or less.

The characteristics of the oxidation reaction performed by irradiating the nitrous oxide solution with ultraviolet rays are as described above.
On the other hand, as already mentioned, the expansion of the application field of the oxidation technology utilizing the characteristics of the nitrous oxide solution has been awaited. Under such circumstances, the present inventors have come to obtain a technique for using such an oxidation reaction as a modification action for the substance itself, the substance surface, or a deposit on the substance surface.

  Hereinafter, the hydrophilization of the substance according to the first embodiment of the present invention will be described with reference to the drawings. FIG. 10 shows a substance hydrophilizing apparatus for hydrophilizing a substance using the substance hydrophilizing method to which the present invention is applied.

  The hydrophilizing device 30 has a tray-like container 31 for storing the nitrous oxide solution S, and a KrI excimer lamp L as a light source that is disposed above the container 31 and irradiates ultraviolet rays toward the inside of the container 31. is doing.

  A symbol X indicates an object to be processed as a substance that is a hydrophilic object.

  The object to be processed X in this example is a sheet such as a semiconductor substrate such as a silicon wafer, a substrate such as a printed wiring board, a plastic such as polycarbonate, a resin or the like, which has a relatively simple shape such as a flat plate shape.

The container 31 is open at the top, and has a plurality of protrusions 31a having the same height for placing the workpiece X on the bottom thereof. The container 31 functions as a solution contact means for bringing the solution S into contact with the workpiece X in such a manner that the workpiece X is immersed in the solution S.
The solution S is an aqueous solution using water as a nitrous oxide solvent, and nitrous oxide is dissolved in the solution S at a concentration of about 1000 ppm.

  The KrI excimer lamp L was developed by the present inventors based on the characteristics of the UV absorption spectrum (cited from Brit. J. Anaesth., 44, 310 (1972)) of the nitrous oxide aqueous solution shown in FIG. The device 30 is employed. In FIG. 11, the horizontal axis represents wavelength and the vertical axis represents absorbance. The UV absorption spectrum in the figure represents the absorption spectrum of water that has reached equilibrium with 100% nitrous oxide, and water that has been equilibrated with helium is used as a reference cell.

  As can be seen from FIG. 11, the UV absorption spectrum of the aqueous nitrous oxide solution shows a peak exceeding 0.7 in the vicinity of 190 nm.

  The emission wavelength of the low-pressure mercury lamp 16 shown in FIG. 7 is centered on 185 nm, and the absorbance at the wavelength of 185 nm is about 0, which is much lower than 0.7, which is the peak of the UV absorption spectrum of the aqueous nitrous oxide solution. .05, so the efficiency is very low.

  On the other hand, as a light source that emits light at a wavelength centered around 190 nm where the UV absorption spectrum of a nitrous oxide aqueous solution shows a peak, an electrolytically coupled high-frequency discharge lamp using argon-fluorine is a so-called fluorinated excimer lamp. . The fluorinated excimer lamp emits light at a wavelength centered at 193 nm.

  In general, excimer lamps have characteristics suitable for the reforming reaction according to the present invention, such as good rise and fall.

  However, in the fluorinated excimer lamp, the quartz tube is easily deteriorated by fluorine enclosed therein. That is, the excimer lamp has a problem that the compatibility between fluorine and the quartz tube is poor and the life is short. As is clear from FIG. 11, the UV absorption spectrum of the aqueous nitrous oxide solution is steep in the vicinity of the peak. Therefore, even at a wavelength of 193 nm, the absorbance is greatly reduced compared to the peak value even though it is close to 190 nm. .

  Therefore, the present inventors have developed a KrI excimer that emits light at an ultraviolet wavelength of 191 nm, which is very close to the wavelength of 190 nm, which is very close to the wavelength of 190 nm, which is the highest absorbance by the aqueous nitrous oxide solution, for example, within a range of ± 1 nm. The lamp L was developed and adopted in the hydrophilization device 30.

  The absorbance of the nitrous oxide solution may vary slightly depending on the solvent, and the wavelength at which the absorbance is highest may be slightly shifted. In the aqueous solution in this example, based on the absorbance peak shape, the range almost the same as the wavelength with the highest absorbance was set to ± 1 nm, but this range varies depending on the type of solution, in other words, the type of solvent. In some cases, the same range as the highest wavelength may be different.

  The KrI excimer lamp L is manufactured by a method in which solid iodine is vaporized and a predetermined amount is measured and sealed in a quartz tube.

  Since the absorbance of the nitrous oxide aqueous solution having an emission wavelength of 191 nm of the KrI excimer lamp L is about 0.65, which is close to the absorbance at the peak of the UV absorption spectrum of the nitrous oxide aqueous solution, the efficiency is good. Therefore, considering the generation of oxygen atoms due to the photodissociation of nitrous oxide, for example, the KrI excimer lamp L is less than the low pressure mercury lamp 16 because the absorbance at the emission wavelength of 185 nm of the low pressure mercury lamp 16 is about 0.05. It is possible to generate oxygen atoms with an efficiency exceeding 10 times, and the generation efficiency of oxygen atoms is extremely high compared to conventional light sources.

  The KrI excimer lamp has the general characteristics of an excimer lamp suitable for the reforming reaction according to the present invention, such that the rise and fall are good, and the quartz tube is not easily deteriorated by the enclosed iodine. And the quartz tube have good compatibility, so there is an advantage that the life is long.

  In addition, the ultraviolet light with a wavelength of 191 nm emitted by the KrI excimer lamp L has substantially the same energy as the ultraviolet light with a wavelength of 185 nm emitted by the low-pressure mercury lamp, which is sufficiently large to decompose nitrous oxide and perform an oxidation reaction. .

  Furthermore, it has been found that the KrI excimer lamp L has an excellent characteristic that less ozone is generated due to light emission.

  FIG. 12 shows the UV absorption spectrum of oxygen (cited from J. Chem. Phys., 21, 1206 (1953)). In such a spectrum, in the region from the wavelength of about 175 nm to the wavelength of about 200 nm, a very fine periodic variation of the absorption coefficient is observed. Such a region is called the Schumann Runge band.

  The wavelength of 191 nm emitted by the KrI excimer lamp L is included in the Schumann Runge band, corresponds to a so-called valley portion between the 5-0 band and the 4-0 band, and has a small absorption coefficient. As described above, the wavelength of 191 nm emitted by the KrI excimer lamp L is in a range substantially the same as the wavelength at which the absorbance is minimal in the Schumann-Runge band where the absorbance due to oxygen molecules changes periodically. Therefore, there is little absorption by oxygen molecules, and there is little dissociation of oxygen molecules and subsequent generation of ozone.

  Although the range that can be said to be almost the same as the wavelength at which the absorbance is minimized is different based on the periodic variation shape of the absorbance, the shape between the 5-0 band and the 4-0 band is different by the KrI excimer lamp L. It can be said that the emitted wavelength of 191 nm is substantially in the same range.

  Since the generation of ozone, which is an environmental load, is small, the KrI excimer lamp L is easy to handle.

  In this respect, for example, the wavelength 185 nm of the ultraviolet light emitted by the low-pressure mercury lamp is located on the 8-0 band in the Schumann-Lunge band and has a large absorption coefficient. Therefore, if air exists between the low-pressure mercury lamp and the nitrous oxide solution, the energy of ultraviolet light is easily absorbed by oxygen molecules, and a large amount of ozone is generated. The efficiency of the reaction is low, resulting in a complicated structure, a design problem, an increase in size, and an increase in price of an apparatus equipped with the reaction.

In contrast, the KrI excimer lamp L has the following advantages.
That is, even if the atmosphere exists between the KrI excimer lamp L and the nitrous oxide solution, the energy of the ultraviolet light emitted from the KrI excimer lamp L is not easily absorbed by the oxygen molecules, so that the ultraviolet light is not absorbed by the nitrous oxide solution. Nitrous oxide can be decomposed with high efficiency. Further, since the influence of the atmosphere is small, the degree of freedom of the arrangement position of the KrI excimer lamp L is high. Devices such as a sealing device such as a processing chamber for measures against ozone can be omitted or simplified.

Therefore, the efficiency of the hydrophilization reaction of the hydrophilizing device 30 is high, the structure is simple, the degree of freedom in design is high, and the size and cost can be reduced.
This is because the wavelength of 191 nm emitted by the KrI excimer lamp L is almost in the same range as the wavelength at which the absorbance of the solution S is highest, and the wavelength at which the absorbance of the oxygen molecules in the Schumann-Lunge band is minimized. The synergistic effect due to the simultaneous fulfillment of the two conditions of being in the same range is particularly remarkable.
Even if the light source is not the KrI excimer lamp L, the light source has sufficient applicability to the present invention when only one of the two conditions is satisfied.

  In the hydrophilization apparatus 30 having such a configuration, after the object to be processed X is placed on the protrusion 31a and placed in the container 31, the solution S is a portion where the object to be processed X should be hydrophilized. Here, the entire upper surface in the state shown in FIG. 10 is filled in the container 31 so as to be sufficiently immersed. The KrI excimer lamp L is caused to emit light, and the entire solution S located on the upper surface of the workpiece X is irradiated with ultraviolet rays.

  Nitrous oxide dissolved in the solution S in the ultraviolet irradiation region is dissociated to generate atomic oxygen (O). This atomic oxygen strongly oxidizes the workpiece X, and the hydrophilicity of the workpiece X Is done. By oxidizing the surface of the substrate or sheet, which is the object to be processed X, a polar functional group, specifically, a hydroxyl group, a carboxyl group, a carbonyl group, or the like is introduced into the surface. In addition, the molecular chains of the polymer constituting the substrate and the sheet partially break, recombine, etc., forming fine irregularities on the molecular level, resulting in a rough surface, Hydrophilization is performed.

  As a result, for example, labeling on a sheet or the like can be easily and satisfactorily performed, and when a resin substrate used for a printed wiring board or the like is made hydrophilic, plating is performed well, resulting in high quality. A printed wiring board is provided. It becomes possible to perform printing on the surface of the workpiece X that has been made hydrophilic. The surface of the object to be treated X that has been made hydrophilic has an anti-fogging / anti-fouling function, and the feeling of use under use conditions that require such a function is improved. Moreover, even if it gets dirty, it is easily removed by washing with water.

  The hydrophilicity, in other words, the ease of wetting of an object can be expressed by the contact angle. The contact angle is determined by placing a droplet of a solution (solution S in this example) on the surface of a solid (object X in this example) and measuring the angle between the end of the droplet and the solid surface. Measured by The easier it gets wet, i.e. the higher the hydrophilicity, i.e. the lower the hydrophobicity, the smaller the droplet, the smaller the contact angle, and the less wet, i.e. the lower the hydrophilicity, i.e. The higher it is, the closer the droplet is to a sphere and the larger the contact angle.

  When the desired hydrophilization is performed, the hydrophilization is terminated, and the hydrophilized workpiece X is obtained. After the hydrophilization, the solution S adhering to the workpiece X is removed as necessary by drying or blowing air. Since nitrous oxide is safe, it is not always necessary to treat nitrous oxide dissolved in the solution S after hydrophilization.

  The ultraviolet light emitted by the KrI excimer lamp L is highly straight, but the part to be hydrophilized is relatively simple, such as when the workpiece X is plate-shaped and only the upper surface is to be hydrophilized as shown in FIG. In the case of a simple shape, it is easy to irradiate with ultraviolet light, and desired hydrophilicity can be achieved.

  However, when the part to be hydrophilized is relatively complicated, such as when the shape of the object to be processed X is complicated, such ultraviolet light is used except for a special case where the object to be processed X is a substance that transmits ultraviolet light. Due to the high linearity of light, it may be difficult to irradiate the desired part with light, and hydrophilicity may not be sufficiently achieved. Even in the case where the workpiece X has a simple shape such as a plate shape as in the example shown in FIG. 10, it is difficult to make the whole hydrophilic.

  Also in the example shown in FIG. 10, when the workpiece X is a substance that transmits ultraviolet light from the KrI excimer lamp L, for example, it is a lens such as an optical device or a spectacle lens, or the bottom of the container 31 is mirror-finished. When the configuration is such that the ultraviolet light is sufficiently guided to the entire workpiece X by reflection from the mirror surface, the entire workpiece X can be made hydrophilic.

  However, in general, it is difficult to make the entire surface of the workpiece X having a three-dimensional shape hydrophilic with the configuration shown in FIG. 10 without changing the state of the workpiece X. This is remarkable, for example, when the workpiece X is a substance having irregularities on the surface.

  FIG. 13 shows a hydrophilizing apparatus in view of such circumstances. In addition, about the structure similar to the structure shown in FIG. 10, the code | symbol same as the code | symbol attached | subjected to the structure shown in FIG. 10 is attached | subjected, and description is abbreviate | omitted suitably. The same applies to each configuration example described below.

  The hydrophilizing device 40 includes a container 41 that stores the nitrous oxide solution S therein, and a KrI excimer lamp L that is provided integrally with the container 41 and that irradiates the inside of the container 41 with ultraviolet rays.

The container 41 has a main body 43 having an opening 42 on the upper side and a lid 44 that closes the opening 42 and has a spherical shape. The inner surface of the main body 43 and the lid 44 is mirror-finished. The container 41 functions as a solution contact means for bringing the solution S into contact with the workpiece X in such a manner that the workpiece X is immersed in the solution S.
A plurality of KrI excimer lamps L are arranged on the side and bottom so as to be exposed inside the main body 43.
The workpiece X has a relatively complicated shape with irregularities on the surface. The object to be processed X may be any object as long as it has such a shape and the surface needs to be hydrophilized. However, in this example, the casing of an electric product made of plastic such as polycarbonate, resin, etc. It is.

  In the hydrophilizing device 40 having such a configuration, after the workpiece X is put into the main body 43 from the opening 42, the solution S is poured from the opening 42 to fill the main body 43, thereby the workpiece X Immerse the whole of. After the solution S is poured from the opening 42 to fill the main body 43, the workpiece X may be put into the main body 43 from the opening 42. The opening 42 is closed with a lid 44 in a state where the entire workpiece X is immersed.

  When the KrI excimer lamp L is caused to emit light, a plurality of KrI excimer lamps L disposed on the side and the bottom irradiate ultraviolet light from the side and below, and ultraviolet light is provided on the inner surfaces of the main body 43 and the lid 44. The entire surface of the solution S positioned on the surface of the workpiece X is irradiated with ultraviolet rays by being reflected by the mirror surface.

  Nitrous oxide dissolved in the solution S in the ultraviolet irradiation region is dissociated to generate atomic oxygen (O). This atomic oxygen strongly oxidizes the workpiece X, and the hydrophilicity of the workpiece X Is done. Oxidizing the surface of the above-mentioned housing, which is the workpiece X, introduces the above-mentioned polar functional groups into the surface, and forms the above-mentioned fine irregularities at the molecular level, resulting in a rough surface. It becomes a state and hydrophilicity is performed.

  Thereby, for example, a label or the like can be easily and satisfactorily attached to the housing. It becomes possible to perform printing on the surface of the workpiece X that has been made hydrophilic. The surface of the object to be treated X that has been made hydrophilic has an anti-fogging / anti-fouling function, and the feeling of use under use conditions that require such a function is improved. Moreover, even if it gets dirty, it is easily removed by washing with water.

  When the desired hydrophilization is performed, the hydrophilization is terminated, and the hydrophilized workpiece X is obtained. After the hydrophilization, the solution S adhering to the workpiece X is removed as necessary by drying or blowing air.

  By such hydrophilization, a desired hydrophilization of the workpiece X having a relatively complicated shape with irregularities on the surface is performed. Since nitrous oxide is safe, it is not always necessary to treat nitrous oxide dissolved in the solution S after hydrophilization.

  When it is necessary to hold the workpiece X in the main body 43, a holding member in which the shape, position, and material that transmits the ultraviolet light are appropriately selected is provided in the main body 43. By doing so, the holding can be performed. Such a holding member can be omitted when the specific gravity of the workpiece X is almost equal to the specific gravity of the solution S and is floated in the solution S. Therefore, a regulator for adjusting the specific gravity can be dissolved in the solution S.

  According to the hydrophilization device 40, the surface of the workpiece X having a relatively complicated shape with irregularities on the surface can be hydrophilized, but the workpiece X is like a cylinder, a bottle, a cup, When it is necessary to form a space with an interior and to make this portion hydrophilic, the inner surface constituting the space is shown in FIG. 13 except in a special case where the workpiece X is a substance that transmits ultraviolet light. It is difficult to make it hydrophilic with the configuration shown in FIG.

  FIG. 14 shows a hydrophilizing apparatus in view of such circumstances.

  The hydrophilizing device 50 includes a container 51 that stores the nitrous oxide solution S therein, a KrI excimer lamp L that is provided integrally with the container 51 and that irradiates the inside of the container 51 with ultraviolet light, and is disposed inside the container 51. KrI excimer lamp L.

The container 51 has a main body 53 having an opening 52 on the upper side and a lid 54 that closes the opening 52, has a spherical shape, and the inner surfaces of the main body 53 and the lid 54 are mirror-finished. The container 51 functions as a solution contact means for bringing the solution S into contact with the workpiece X in such a manner that the workpiece X is immersed in the solution S.
A plurality of KrI excimer lamps L that are integral with the container 51 are arranged on the side and bottom in a manner that they are exposed inside the main body 53.
The workpiece X has a bin shape. The object to be processed X may be any shape as long as it has a space inside and it is necessary to hydrophilize this part and the outer surface. In this example, plastic such as polycarbonate, resin, etc. In particular, it is a bottle made of fluororesin or a Western-style toilet.

  In the hydrophilizing apparatus 50 having such a configuration, after the workpiece X is put into the main body 53 from the opening 52, the solution S is poured from the opening 52 to fill the main body 53, thereby the workpiece X And the KrI excimer lamp L is inserted into the workpiece X. After the solution S is poured from the opening 52 to fill the inside of the main body 53, the workpiece X is put into the main body 53 from the opening 52 and the whole is immersed, and a KrI excimer lamp L is inserted into the processing object X. Also good. After the workpiece X is put into the main body 53 through the opening 52, a KrI excimer lamp L is inserted into the workpiece X, and the solution S is poured from the opening 52 to fill the main body 53, so that the workpiece X is filled. It may be immersed.

The opening 52 is closed with a lid 54 in a state where the entire workpiece X is immersed.
If the KrI excimer lamp L to be inserted into the workpiece X is integrated with the lid 54 and the opening 52 is closed with the lid 54, the KrI excimer lamp L may be inserted into the workpiece X.

  When the KrI excimer lamp L is caused to emit light, a plurality of KrI excimer lamps L disposed on the side and bottom of the main body 53 are irradiated with ultraviolet light from the side and below, and are disposed inside the workpiece X. The KrI excimer lamp L emits ultraviolet light from the inside, and the ultraviolet light is reflected by the mirror surfaces provided on the inner surfaces of the main body 53 and the lid 54, so that the ultraviolet light is positioned on the outer surface and the inner surface of the workpiece X. The entire solution S is irradiated.

  Nitrous oxide dissolved in the solution S in the ultraviolet irradiation region is dissociated to generate atomic oxygen (O). This atomic oxygen strongly oxidizes the workpiece X, and the hydrophilicity of the workpiece X Is done. Oxidizing the surface of the above-mentioned housing, which is the workpiece X, introduces the above-mentioned polar functional groups into the surface, and forms the above-mentioned fine irregularities at the molecular level, resulting in a rough surface. It becomes a state and hydrophilicity is performed.

  Thereby, for example, a label or the like can be easily and satisfactorily attached to the toilet bowl. It becomes possible to perform printing on the surface of the workpiece X that has been made hydrophilic. The surface of the object to be treated X that has been made hydrophilic has an anti-fogging / anti-fouling function, and the feeling of use under use conditions that require such a function is improved. Moreover, even if it gets dirty, it is easily removed by washing with water.

  When the desired hydrophilization is performed, the hydrophilization is terminated, and the hydrophilized workpiece X is obtained. After the hydrophilization, the solution S adhering to the workpiece X is removed as necessary by drying or blowing air.

By such hydrophilization, desired hydrophilization of the inner and outer surfaces of the workpiece X having a space inside and an opening in the space is performed.
Even if the internal space is narrow, high hydrophilicity can be achieved if the KrI excimer lamp L can be inserted and irradiated with ultraviolet rays.
Further, for example, even a hollow object such as a hole pipette in which the KrI excimer lamp L cannot be inserted can highly hydrophilize the inside if ultraviolet light is transmitted.
Since nitrous oxide is safe, it is not always necessary to treat nitrous oxide dissolved in the solution S after hydrophilization.

  In addition, when it is necessary to hold the workpiece X in the main body 53, a holding member in which the shape, position, and material that transmits the ultraviolet light are appropriately selected is provided in the main body 53. By doing so, the holding can be performed. Such a holding member can be omitted when the specific gravity of the workpiece X is almost equal to the specific gravity of the solution S and is floated in the solution S. Therefore, a regulator for adjusting the specific gravity can be dissolved in the solution S.

  According to the hydrophilization devices 40 and 50, the object to be processed X that can be stored in the containers 41 and 51 and immersed in the solution S in the containers 41 and 51 and can be irradiated with ultraviolet light in this state is subjected to hydrophilization. Can do. However, if the object to be treated X is a relatively large object, or if it is an object that needs to be expanded to increase the surface area to be rendered hydrophilic by irradiating it with ultraviolet rays, such as a fabric, In order to achieve this, it is necessary to make the containers 41 and 51 very large, leading to an increase in the size of the hydrophilizing devices 40 and 50.

FIG. 15 shows a hydrophilizing apparatus in view of such circumstances.
The hydrophilizing device 60 is mainly intended for a sheet-like workpiece X, and includes a tray-like container 61 for storing a nitrous oxide solution S and a plurality of rollers around which the workpiece X is wound. 62, a blade 63 for removing a part of the solution S supplied to the surface of the workpiece X pulled up from the container 61 as needed, and a downstream side of the blade 63 in the feed direction of the workpiece. It has an installed KrI excimer lamp L for irradiating ultraviolet rays, and a winding mechanism (not shown) as moving means for moving the workpiece X.

  The container 61, the roller 62, and the winding mechanism function as solution supply means for bringing the solution S into contact with the object to be processed X in a mode in which the object X is immersed in the solution S. Further, the blade 63 is movable between an illustrated operating position and a non-operating position (not illustrated). When the blade 63 is moved to the operating position, the blade 63 scrapes off part of the solution S supplied to the surface of the workpiece X as necessary. Thereby, the thickness of the supplied solution S on the surface of the workpiece X becomes uniform, and the solution supply amount is equalized. The KrI excimer lamps L extend in parallel with a predetermined interval in the vertical direction so as to face each other, and irradiate ultraviolet light in the direction facing each other. The plurality of rollers 62 are rotatable, and support the workpiece X so that the workpiece X passes between the KrI excimer lamps L.

The winding mechanism has a core rod around which the workpiece X is wound and a motor as a drive source for rotationally driving the core rod, and moves the inside of the container 61 by winding up the workpiece X. is there.
The object to be processed X may be any sheet, such as a plastic sheet or fabric, as long as it is a sheet and can be wound by a winding mechanism. In this example, a film such as a plastic such as polycarbonate or a resin film is used. It is.

  In the hydrophilizing device 60 having such a configuration, the solution S is placed between the KrI excimer lamps L after the workpiece X is wound around the roller 62 and can be wound by the winding mechanism. The container 61 is filled to such an extent that the positioned workpiece X is immersed. Then, the workpiece X is fed by the winding mechanism. Then, after being immersed in the solution S, a part of the solution S supplied to the wound workpiece X is scraped off by the blade 63 as necessary, and the supply amount of the solution S is equalized. Thereafter, the workpiece X sent between the KrI excimer lamps L is made hydrophilic by being irradiated with ultraviolet rays from the lamps.

  Nitrous oxide dissolved in the solution S in the ultraviolet irradiation region is dissociated to generate atomic oxygen (O). This atomic oxygen strongly oxidizes the workpiece X, and the hydrophilicity of the workpiece X Is done. When the surface of the above-mentioned film as the object to be processed X is oxidized, the above-mentioned polar functional group is introduced into the surface, and the above-mentioned molecular level fine irregularities are formed, and the surface is rough. It becomes a state and hydrophilization is performed.

  Thereby, for example, a label or the like can be easily and satisfactorily attached to the film. It becomes possible to perform printing on the surface of the workpiece X that has been made hydrophilic. The surface of the object to be treated X that has been made hydrophilic has an anti-fogging / anti-fouling function, and the feeling of use under use conditions that require such a function is improved. Moreover, even if it gets dirty, it is easily removed by washing with water.

  The winding speed of the object to be processed X by the winding mechanism is adjusted so that the hydrophilicity is sufficiently performed while the object to be processed X moves between the KrI excimer lamps L. When the winding of the workpiece X by the winding mechanism is completed, the hydrophilization is finished, and the hydrophilic workpiece X is obtained. After the hydrophilization, the solution S adhering to the workpiece X is removed as necessary by drying or blowing air. When drying is performed, this may be performed while winding.

  By such hydrophilization, a desired hydrophilization of the surface of the workpiece X is performed. Since nitrous oxide is safe, it is not always necessary to treat nitrous oxide dissolved in the solution S after hydrophilization.

  The moving means for moving the object to be processed X may be a configuration provided with a transport member such as a belt for moving the object to be processed X in a mode in which the object to be processed X is placed or fixed, instead of the winding mechanism described above. If it is such a structure, the to-be-processed object X is not restricted to a sheet-like thing, A comparatively big thing can be made into the to-be-processed object X, and this can be hydrophilized. According to this configuration, a plurality of workpieces X can be continuously hydrophilized while being conveyed by the conveying member. In order to make the entire workpiece X hydrophilic while being transported by such a transporting member, the placement position and shape of the transporting member, the use of a material that transmits ultraviolet rays, the placement position and number of KrI excimer lamps L are appropriately selected. it can.

In such a hydrophilizing device 60, when the object to be processed X is a relatively large object, or when it is an object that needs to be expanded to increase the surface area to be hydrophilized by irradiation with ultraviolet rays, The size of the container 61 is not greatly affected by the workpiece X, and the increase in size is suppressed.
Moreover, it is easy to carry and can be immersed in the solution S inside the container 61, and the workpiece X that can be irradiated with ultraviolet light in this state can be hydrophilized.
However, when the workpiece X is not easily transportable, such as a desk, floor, or wall, it may be difficult or impossible to make it hydrophilic.

FIG. 16 shows a hydrophilizing apparatus in view of such circumstances.
The hydrophilizing device 70 is intended for an object not shown, and has a rectangular container 71 for storing the nitrous oxide solution S, and is disposed inside the container 71 toward the outside of the container 71. While supplying the solution S to the KrI excimer lamp L that irradiates ultraviolet rays, the liquid supply pipe 72 that supplies the solution S into the container 71, the waste liquid pipe 73 that discharges the solution S inside the container 71, and the liquid supply pipe 72 Solution control means for discharging the solution S from the waste liquid pipe 73 and controlling the solution S in the container 71 is provided.

  The material to be treated is mainly difficult to transport, such as the top surface of the desk, the floor, and the wall. In this example, the material to be treated such as mold, dirt, etc. is difficult to adhere by making it hydrophilic. For example, a wall surface such as a wall used in a bathroom is used. Examples of such a material include a fluororesin, but other appropriate plastics such as polycarbonate, resins, and the like can also be used.

The container 71 includes a container body 74 that is open on one surface, a glass 75 that is disposed in the container body 74 in parallel with the opened surface so as to partition the space in the container body 74, and the container body 74. And a rubber 76 as an elastic member disposed corresponding to the edge of the opened surface.
The container main body 74 is formed with holes (not shown) through which the solution S is communicated with each of the liquid supply pipe 72 and the waste liquid pipe 73. These holes are located outside the space of the container body 74 closed by the glass 75.
The inner surface of the container body 74 is mirror-finished.

  A plurality of KrI excimer lamps L are disposed in the space of the container body 74 closed by the glass 75. The KrI excimer lamp L irradiates ultraviolet light toward the glass side. Since the KrI excimer lamp L is located inside the space closed by the glass 75, it is not wetted by the solution S.

  The rubber 76 functions as a buffer member for elastically contacting the object to be treated and not scratching when the container 71 is placed on the object to be treated to make the object to be treated hydrophilic. It functions as a sealing member for sealing so that ultraviolet light irradiated by the KrI excimer lamp L does not leak to the outside.

The solution control means is connected to the liquid supply pipe 72 and is sufficient to store the solution S stored in an amount sufficient to hydrophilize the object to be processed and the solution S discharged through the waste liquid pipe 73. A waste liquid storage unit having a capacity and a waste liquid pipe 73 are connected to each other, and a negative pressure is generated in the waste liquid pipe 73, a sealed space to be described later, and a liquid supply pipe 72, so that the solution S in the solution storage part is supplied. A suction pump for guiding the solution S in the container 71 through the pipe 72 to the waste liquid storage section through the liquid supply pipe 72 is provided.
The container 71 and the solution control means function as solution contact means for bringing the solution S into contact with the object to be processed.

  In the hydrophilizing device 70 having such a configuration, the container 71 is brought into close contact with the portion where the object to be processed is to be hydrophilicized by using the elasticity of the rubber 76, and the object to be processed, the container main body 74, and the glass 75. After forming the sealed space, the suction pump is operated to fill the sealed space with the solution S. In this state, the KrI excimer lamp L is caused to emit light, and ultraviolet light is irradiated to the solution S located on the site where the treatment object should be hydrophilized.

  Nitrous oxide dissolved in the solution S in the ultraviolet irradiation region is dissociated to generate atomic oxygen (O). This atomic oxygen strongly oxidizes the object to be processed, and the object to be processed becomes hydrophilic. Done. Oxidizing the surface of the above-mentioned housing, which is the workpiece X, introduces the above-mentioned polar functional groups into the surface, and forms the above-mentioned fine irregularities at the molecular level, resulting in a rough surface. It becomes a state and hydrophilicity is performed.

Thereby, for example, a label or the like can be easily and satisfactorily attached to the wall. It becomes possible to perform printing on the surface of the workpiece X that has been made hydrophilic. The surface of the object to be treated X that has been made hydrophilic has an anti-fogging / anti-fouling function, and the feeling of use under use conditions that require such a function is improved. Moreover, even if it gets dirty, it is easily removed by washing with water.
Since nitrous oxide is consumed in the process of hydrophilization, the suction pump may be appropriately driven to replace the solution S in the sealed space.

  A concentration detecting means for detecting the concentration of nitrous oxide in the solution S in the sealed space, and a suction pump when the nitrous oxide concentration detected by the concentration detecting means falls below a predetermined concentration suitable for hydrophilization Control means for driving can be provided in the solution control means, and feedback control can be performed to keep the concentration of nitrous oxide in the solution S in the sealed space within a range suitable for hydrophilization.

  When the desired hydrophilization is performed, the hydrophilization is finished, and a hydrophilized workpiece is obtained. After the hydrophilization, the suction pump is driven after the supply pipe 72 is removed from the solution storage unit or the container 71 to prevent the solution S from being supplied from the solution storage unit to the container 71. The solution S inside is discharged to the waste liquid storage unit, and the container 71 is detached from the object to be processed. If necessary, the solution S adhering to the object to be processed is removed by drying or blowing air.

  With this hydrophilic treatment, in this example, the surface of the wall is subjected to a hydrophilic treatment such that mold or dirt such as dirt is less likely to adhere. In addition, depending on the other object to be processed, desired hydrophilicity of the surface of the object to be processed, which is mainly difficult to transport, such as the upper surface of the desk, the floor, or the wall, is performed. Since nitrous oxide is safe, it is not always necessary to treat nitrous oxide dissolved in the solution S discharged to the waste liquid storage unit.

  When the close contact state between the container 71 and the object to be processed is maintained, and the leakage of the solution S does not become a problem, the hydrophilization may be performed while moving the hydrophilizing device 70, particularly the container 71. Since the time for discharging the solution S before the container 71 is moved becomes unnecessary and the hydrophilicity can be continuously obtained, the hydrophilicity can be efficiently performed.

When the container 71 and the object to be processed are in close contact with each other, the ultraviolet light is prevented from leaking from the sealed space, and the influence of the ultraviolet light on the outside can be avoided.
In the examples shown in FIGS. 13 and 14, since the inside of the containers 41 and 51 is sealed, the influence due to leakage of ultraviolet light to the outside is avoided.

  In consideration of the fact that nitrous oxide is consumed during the hydrophilization process as in the hydrophilization apparatus 70, the configuration in which the solution S is replaceable is extremely excellent in exhibiting high hydrophilization performance. Moreover, even if the concentration of nitrous oxide in the solution S is lowered, it is possible to ensure sufficient hydrophilic performance. Also in the configuration examples shown in FIGS. 10, 13 to 15, the solution S can be configured to be exchangeable in the process of hydrophilization.

  For example, FIG. 17 shows a hydrophilization device configured such that the solution S can be exchanged during the hydrophilization process. The hydrophilizing device 80 corresponds to the hydrophilizing device 30 shown in FIG.

  The hydrophilizing device 80 includes a tray-like container 81 that stores the solution S, a KrI excimer lamp L that is disposed above the container 81 and irradiates ultraviolet rays toward the inside of the container 81, and an object to be processed inside the container 81. A holding member 82 for holding X, a solution control means 83 for supplying the solution S to the container 81 and discharging the solution S from the container 81 to control the solution S in the container 81, and the KrI excimer lamp L are detachable. And a mask 89 as shielding means that are integrally disposed in the manner described above.

The solution control means 83 is connected to a liquid supply pipe 84 for supplying the solution S into the container 81, a waste liquid pipe 85 for discharging the solution S inside the container 81, and an upper end of the liquid supply pipe 84, and the solution S A tank 86 as a solution storage unit for storing a sufficient amount of the processed product X to be hydrophilized, a waste liquid storage unit (not shown) having a capacity sufficient to store the solution S discharged through the waste solution pipe 85, Disposed in the middle of the liquid pipe 84 and disposed in the waste liquid pipe 85 and a liquid supply valve 87 for adjusting whether or not the solution S in the tank 86 is guided to the container 81, and the flow rate of the solution S guided to the container 81. A waste liquid valve 88 is provided for adjusting whether or not the solution S in the container 81 is discharged to the waste liquid storage unit and the flow rate of the discharged solution S.
The container 81 and the solution control means 83 function as solution contact means for bringing the solution S into contact with the object to be processed X in such a manner that the object to be processed X is immersed in the solution S.

The holding member 82 holds the workpiece X so that the workpiece X can be held in position even when the flow of the solution S occurs in the container 81.
One end of the holding member 82 is supported and fixed to the container 81.
When the flow of the solution S occurs in the container 81, the holding member 82 has a shape that does not hinder the flow. Therefore, the exchange of the solution in the container 81 is performed satisfactorily.

  The mask 89 is located between the KrI excimer lamp L and the workpiece X, and is composed of a chromium film or the like that is a light shielding material that blocks ultraviolet light emitted by the KrI excimer lamp L at a predetermined position. Pattern 89a.

  Therefore, the hydrophilization device 80 can be replaced with the solution S by providing the solution control means 83 as compared with the hydrophilization device 30 shown in FIG. It is possible to carry out a patterned hydrophilization.

In the hydrophilization device 80 having such a configuration, the workpiece X is held by the holding member 82 and placed in the container 31, and then the liquid supply valve 87 is opened, and the solution S in the tank 86 is The portion to be hydrophilized of the workpiece X, here the entire upper surface in the state shown in FIG. 17, is filled in the container 81 to such an extent that it is sufficiently immersed. The KrI excimer lamp L is caused to emit light, and ultraviolet rays are irradiated toward the workpiece X.
When passing through the mask 89, the ultraviolet light is partially blocked by the pattern 89a according to the shape of the pattern 89a, and partially irradiated to the solution S positioned on the upper surface of the workpiece X.

  Nitrous oxide dissolved in the solution S in the ultraviolet irradiation region is dissociated to generate atomic oxygen (O). This atomic oxygen strongly oxidizes the workpiece X, and the hydrophilicity of the workpiece X Is done. Oxidizing the surface of the substrate or sheet, which is the object to be processed X, introduced the above-mentioned polar functional group into the surface, and formed the above-described molecular level fine irregularities, resulting in a rough surface. It will be in such a state and hydrophilization will be performed.

  Thereby, for example, a label or the like can be easily and satisfactorily attached to a sheet or the like. It becomes possible to perform printing on the surface of the workpiece X that has been made hydrophilic. The surface of the object to be treated X that has been made hydrophilic has an anti-fogging / anti-fouling function, and the feeling of use under use conditions that require such a function is improved. Moreover, even if it gets dirty, it is easily removed by washing with water.

  Since the diffusion movement distance of atomic oxygen is extremely small, the surface of the workpiece X irradiated with ultraviolet light is hydrophilized, but the atomic oxygen cannot move to the region where the ultraviolet light is blocked by the mask 89, For this reason, in the region where the ultraviolet light is blocked by the mask 89, the hydrophilicity by atomic oxygen is not performed. In this manner, when the workpiece X is a substrate such as a silicon wafer, an oxide film having a desired pattern is formed.

  Since nitrous oxide is consumed in the process of hydrophilization, the liquid supply valve 87 and the waste liquid valve 88 are appropriately opened and closed to replace the solution S in the sealed space, and the amount of nitrous oxide in the solution S in the container 81 and Keep the concentration in a range suitable for hydrophilization. In order to keep the concentration of nitrous oxide in the solution S in the container 81 within a range suitable for hydrophilization, the liquid supply valve 87 and the waste liquid valve 88 are appropriately adjusted to open and close so that the flow rates thereof are appropriate.

  A concentration detecting means for detecting the concentration of nitrous oxide in the solution S in the container 81, and a liquid supply valve when the nitrous oxide concentration detected by the concentration detecting means falls below a predetermined concentration suitable for hydrophilization 87, a control means for driving the waste liquid valve 88 is provided in the solution control means 83, and feedback control is performed to keep the amount and concentration of nitrous oxide in the container 81 within a range suitable for hydrophilization. it can. In this case, in order to keep the concentration of nitrous oxide in the solution S in the container 81 within a range suitable for hydrophilization, the liquid supply valve 87 and the waste liquid valve 88 are appropriately opened and closed by control means so that the flow rates thereof are appropriate. adjust.

  When the desired hydrophilization is performed, the hydrophilization is terminated, and the hydrophilized workpiece X is obtained. After the hydrophilization, the solution S adhering to the workpiece X is removed as necessary by drying or blowing air. The solution S in the container 81 is appropriately discharged by opening the waste liquid valve 88 to the waste liquid storage unit.

By such hydrophilization, a desired hydrophilization of the surface of the workpiece X is performed. Since nitrous oxide is safe, it is not always necessary to treat nitrous oxide dissolved in the solution S after hydrophilization. Moreover, even if the concentration of nitrous oxide in the solution S is lowered, it is possible to ensure sufficient hydrophilic performance.
Such a solution control means 83 can be similarly applied to the hydrophilization devices 40, 50, and 60 described with reference to FIGS.

Also in the hydrophilization apparatuses 40, 50, and 60 shown in FIGS. 13 to 15, a patterned hydrophilization is provided by disposing a mask in the same manner as the mask 89 between the KrI excimer lamp L and the workpiece X. It can be performed.
In this case, in the hydrophilization apparatuses 40 and 50, it is necessary to irradiate ultraviolet rays in a state where the workpiece X is held in position.

  Moreover, in the hydrophilization apparatus 60, the to-be-processed object X is wound up intermittently by a winding mechanism, and an ultraviolet-ray is irradiated when the to-be-processed object X stops. If the operation of performing hydrophilic treatment when stopping winding and winding up the workpiece X with a length equal to or longer than the pattern length after hydrophilization is repeated, the workpiece X that has been hydrophilicized in the same pattern continuously. Can be obtained. After the pattern is formed, if the workpiece X is cut between the patterns, a large number of workpieces X having the same pattern can be obtained.

In order to carry out the patterned hydrophilization, the mask S is not used, but the solution S is attached to the workpiece X in a desired pattern by using a printing technique or the like, and the patterning of the application of the solution S is performed. It is possible to irradiate at least a site where the solution S is attached to the workpiece X by performing ultraviolet rays.
Note that the hydrophilization apparatus 70 shown in FIG. 16 can also be said to perform patterned hydrophilization when it is used to hydrophilize part of the surface of the object to be processed.

  The hydrophilization device 70 shown in FIG. 16 is intended for an object to be processed that is mainly difficult to transport, such as an upper surface of a desk, a floor, or a wall. Such a hydrophilizing device 70 is suitable for hydrophilizing a relatively large portion. On the other hand, it may be required to make a relatively small portion hydrophilic in a spot manner.

FIG. 18 shows a hydrophilizing apparatus in view of such circumstances.
The hydrophilization device 90 is intended for an object (not shown) that is mainly required to be hydrophilized in the form of a spot, such as an artificial artificial tooth, and the nitrous oxide solution S is to be treated. Irradiating ultraviolet light so as to be positioned on the locus of the solution S in the injection direction of the solution S disposed inside the injection unit 91 and injected by the injection unit 91 KrI excimer lamp L.
The object to be treated may be any material as long as it is required to be made hydrophilic in a spot shape as well as the artificial tooth implanted.

The injection means 91 includes a nozzle unit 92 that is used by a user performing hydrophilic treatment and is connected to the nozzle unit 92, and stores a sufficient amount of the solution S to hydrophilize the object to be processed. The storage unit and a pump (not shown) that applies a predetermined pressure to the solution S stored in the solution storage unit and sends the solution S to the nozzle unit 92.
The injection means 91 functions as a solution contact means for bringing the solution S into contact with the object to be processed.

  The nozzle portion 92 integrally includes a KrI excimer lamp L. The nozzle unit 92 includes a grip 93 held by the user, an injection port 94 for injecting the solution, a trigger (not shown) for switching whether or not the solution S is to be injected from the nozzle unit 92, and operating the trigger to operate the solution S The first flow path 95 extending from the ultraviolet light irradiation position of the KrI excimer lamp L toward the injection port 94, which is filled with the solution S when being injected from the injection port 94, is located inside the grip 93. A second flow path 96 that feeds the solution S pumped from the solution storage section into the first flow path 95, and an injection mode such as a flow diameter of the solution S that is attached to the injection opening 94 and injected from the injection opening 94 And a diaphragm not shown.

The trigger can be operated with the user holding the grip 93. The trigger is configured so that the flow rate of the solution S can be adjusted according to the operation amount.
The KrI excimer lamp L is configured to light up when the trigger is operated so that the solution S is emitted.
The pump applies a pressure sufficient to inject the solution S from the injection port 94 to the solution S and pumps it to the nozzle portion 92.

  In the hydrophilizing device 90 having such a configuration, the user holds the grip 93 and directs the injection port 94 toward the hair that is the object to be processed, operates the trigger, and injects an appropriate amount of the solution S onto the object to be processed. At the same time, the KrI excimer lamp L emits light and is irradiated with ultraviolet rays. The attachment range of the solution S on the object to be processed is easily set to an appropriate state by the user adjusting the position of the nozzle portion 92, the emission direction of the solution S, and the aperture.

  Nitrous oxide dissolved in the solution S in the ultraviolet irradiation region is dissociated to generate atomic oxygen (O). This atomic oxygen strongly oxidizes the object to be processed, and the object to be processed becomes hydrophilic. Done. Oxidizing the surface of the above-mentioned housing, which is the workpiece X, introduces the above-mentioned polar functional groups into the surface, and forms the above-mentioned fine irregularities at the molecular level, resulting in a rough surface. In this state, hydrophilization is performed.

  Thereby, for example, the wettability of artificial teeth with saliva is improved, and the feeling of use is improved. It has an antifouling function, makes it difficult to get dirty, and even if it gets dirty, it is easily removed by washing with water. In addition, when the object to be processed is not an artificial tooth, it is possible to print on the surface of the object X that has been hydrophilized so that the label can be easily and satisfactorily attached. It becomes. The surface of the object to be treated X that has been made hydrophilic has an anti-fogging / anti-fouling function, and the feeling of use under use conditions that require such a function is improved.

The injection amount of the solution S is adjusted according to the amount of nitrous oxide consumed in the process of hydrophilization.
When the desired hydrophilization is performed, the hydrophilization is finished, and a hydrophilized workpiece is obtained. If necessary, the solution S adhering to the object to be processed is removed by drying or blowing air.

  In the case where it is required to make a comparatively small portion hydrophilic in a spot manner, such as the hydrophilicity of an artificial tooth, the desired hydrophilicity of the surface of the object to be processed is performed. Since nitrous oxide is safe, it is not always necessary to treat nitrous oxide dissolved in the solution S after hydrophilization.

In the hydrophilizing device 90, the solution S is attached to only necessary portions to perform the hydrophilization, so that the hydrophilization is efficiently performed. Since the amount of consumption of the solution S is small and the hydrophilicity is obtained while the solution S is substantially exchanged, even if the concentration of nitrous oxide in the solution S is lowered, sufficient hydrophilicity performance is ensured. Is possible.
Further, since the ultraviolet light is irradiated only in the emission direction of the solution S, it is possible to irradiate only the necessary part with the ultraviolet light, and the influence by irradiating the other part with the ultraviolet light is avoided.
In addition, it can be said that the hydrophilization apparatus 90 also performs patterned hydrophilization when using this to hydrophilize a part of the surface of the workpiece. For example, when the object to be processed is a sheet like the object X to be processed in the hydrophilizing apparatus 60, or when the object to be processed is the top surface, floor, wall, etc. of the object to be processed X in the hydrophilizing apparatus 70. is there.

  Here, the mode of contact of the solution S with the workpiece X during irradiation with ultraviolet light will be described. The above-described hydrophilizing devices 30, 40, 50, 60, and 80 allow the workpiece X to be placed in the solution S. The above-described hydrophilization devices 70 and 90 are for wetting a portion to be hydrophilized of the object to be treated with the solution S. With respect to the latter contact mode, the hydrophilization apparatus 90 is configured to wet the portion to be hydrophilized of the workpiece X by injecting the solution S with the solution S. The apparatus 90 is not limited to the apparatus that continuously attaches the solution S to the object to be hydrophilized, and the apparatus that injects the solution S in the form of a mist to adhere to the object to be hydrophilized.

Such a hydrophilizing apparatus is shown in FIG.
The hydrophilizing apparatus 100 includes a table 101 that holds the workpiece X on its upper surface, and a suction unit (not shown) that sucks the workpiece X by generating a negative pressure between the table 101 and the workpiece X. A rotating shaft 102 that rotatably supports the table 101, a motor (not shown) that rotationally drives the rotating shaft 102, a KrI excimer lamp L disposed above the table 101, and a workpiece X on the table 101. The solution spraying means 103 for spraying the solution S, and the solution S sprayed on the workpiece X by the solution spraying means 103 disposed so as to cover the table 101 are prevented from scattering to the outside and the excess solution S is removed. A container 104 to be stored, a waste liquid pipe 105 for discharging the solution S stored in the container 104 to the outside, and a capacity sufficient to store the solution S discharged through the waste liquid pipe 105 And the waste reservoir (not shown) which are I, and the solution S in 104 disposed in the waste liquid pipe 105 and a waste valve 106 which switches whether to discharge the waste liquid reservoir.

The solution spraying means 103 mists the solution S in the tank 107 as a solution storage unit that stores a sufficient amount of the solution S to hydrophilize the workpiece X, and the solution S in the tank 107 onto the workpiece X on the table 101. And a nozzle 108 sprayed in a shape. The tank 107 is maintained at a higher pressure than the atmosphere inside. The nozzle 108 is rotatably provided in the tank 107.
The solution spraying means 103 functions as a solution contact means for bringing the solution S into contact with the workpiece X.
The suction means vacuum-sucks the workpiece X so that the workpiece X is held on the table 101 even when the table 101 rotates.
The object to be processed X in this example is a sheet such as a semiconductor substrate such as a silicon wafer, a substrate such as a printed wiring board, a plastic such as polycarbonate, a resin or the like, which has a relatively simple shape such as a flat plate shape.

  In the hydrophilizing apparatus 100 having such a configuration, the workpiece X is placed on the table 101 and is held by operating the suction means, and the nozzle 108 is rotated to a predetermined position suitable for spraying the solution S. Then, while rotating the table 101, the solution S is sprayed from the nozzle 108 to uniformly adhere to the workpiece X, and then the KrI excimer lamp L is emitted to emit ultraviolet light. The adhesion amount of the solution S on the workpiece X is adjusted by adjusting the ejection amount and ejection time of the solution S from the nozzle 108.

Nitrous oxide dissolved in the solution S in the ultraviolet irradiation region is dissociated to generate atomic oxygen (O). This atomic oxygen strongly oxidizes the object to be processed, and the object X is made hydrophilic. Is done. Oxidizing the surface of the substrate or sheet, which is the object to be processed X, introduced the above-mentioned polar functional group into the surface, and formed the above-described molecular level fine irregularities, resulting in a rough surface. In this state, the hydrophilic treatment, here, the hydrophilic treatment is performed.
The adhesion amount of the solution S is adjusted according to the amount of nitrous oxide consumed in the process of hydrophilization.

  As a result, for example, labeling on a sheet or the like can be easily and satisfactorily performed, and when a resin substrate used for a printed wiring board or the like is made hydrophilic, plating is performed well, resulting in high quality. A printed wiring board is provided. It becomes possible to perform printing on the surface of the workpiece X that has been made hydrophilic. The surface of the object to be treated X that has been made hydrophilic has an anti-fogging / anti-fouling function, and the feeling of use under use conditions where such a function is required is improved. Moreover, even if it gets dirty, it is easily removed by washing with water.

  When the desired hydrophilization is performed, the hydrophilization is terminated, and the hydrophilized workpiece X is obtained. After the hydrophilization, the solution S adhering to the workpiece X is removed as necessary by drying or blowing air. The removal of the solution S may be performed by rotating the table 101.

The solution S collected in the container 104 is discharged to the waste liquid storage section through the waste liquid pipe 105 by opening the waste liquid valve 106 at an appropriate time.
The nozzle 108 can occupy a predetermined position only when it is necessary for spraying the solution S when it is necessary to take care not to interfere with the irradiation of ultraviolet light.

  As an aspect in which the solution S is attached to the workpiece X, there can be mentioned another method by so-called spin coating. In this case, for example, in the hydrophilization apparatus 100, instead of the solution spraying means 103, a solution flowing means for dropping the solution S onto the object to be processed X held on the table 101 is provided. While rotating the table 101 while holding the object to be processed X, the solution S is dropped by the solution flow-down means so that the solution S is uniformly attached to the object to be processed X, and then the KrI excimer lamp L emits light. And irradiate with ultraviolet rays. The adhesion amount of the solution S on the workpiece X can be adjusted by adjusting the flow rate and the flowing time of the solution S from the solution flowing means.

  Also in these hydrophilizing apparatuses 100, patterned hydrophilization can be performed by performing the patterning of the application of the mask 89 and the solution S described with respect to the hydrophilizing apparatus 80 shown in FIG. In this case, the table 101 is not rotated at the time of ultraviolet irradiation other than the spraying of the solution S and the spin coating, and the workpiece X is held in a fixed position.

  If the application of the solution S is performed by spraying or spin coating, the consumption of the solution S can be reduced, and the solution S can be hydrophilized while being substantially exchanged, so that the nitrous oxide in the solution S can be reduced. Even if the concentration is lowered, it is possible to ensure sufficient hydrophilization performance. However, when spraying, if the droplets are too small, nitrous oxide is dissipated into the atmosphere before the solution S reaches the workpiece X, but the solution S is substantially free from the workpiece X. Since the hydrophilization is performed while exchanging, even if the concentration of nitrous oxide in the solution S is somewhat lowered due to dissipation, it is possible to ensure sufficient hydrophilization performance. However, the size of the droplet is adjusted as appropriate so that the amount of dissipation does not become too large.

  Hereinafter, the sterilization of the substance according to the second embodiment of the present invention will be described in detail with reference to the drawings.

  Since the sterilization of the substance using the sterilization method in the second embodiment can be performed by using the hydrophilizing device 30 shown in FIG. 10 as a substance sterilization apparatus, in this example, the sterilization method shown in FIG. A method for sterilizing the workpiece X will be described with reference to FIG.

Here, the substance to be sterilized can be, for example, a salmon plate constituting salmon, which is one of the fish paste products.
The salmon is formed by placing fish surimi on a sardine and steaming it with steam.

  Since this slat is a plate for placing food (salmon), it needs to be sterilized to prevent spoilage, but the surface not in contact with the slat does not need to be sterilized. In addition, since the potato is sterilized by steam when steamed, the risk of microbial growth is considered to be relatively low.

However, the surface that is in contact with the salmon is in a state where the fish meat surimi and the salmon plate come into contact with each other before steaming. There is a risk that microorganisms will propagate in the meantime.
In particular, in food production, it is hygienically important to suppress the growth of microorganisms and reduce the number of initial germs as much as possible during the period from production to sterilization.

  The workpiece X is, for example, a mortar plate with microorganisms attached to its surface. Here, the microorganism is not particularly limited, and examples thereof include bacteria, yeast, and fungi.

  In the sterilization apparatus 30 shown in FIG. 10, after placing the workpiece X on the protrusion 31 a and placing it in the container 31, the solution S is a portion where the workpiece X should be sterilized, here The container 31 is filled to the extent that the entire upper surface of the plate in the state shown in FIG. 10 is sufficiently immersed. The KrI excimer lamp L is caused to emit light, and the entire solution S located on the upper surface of the workpiece X is irradiated with ultraviolet rays.

Nitrous oxide dissolved in the solution S in the ultraviolet irradiation region is dissociated to generate atomic oxygen (O), and the atomic oxygen strongly oxidizes the microorganisms attached to the workpiece X, Is sterilized. The timing of sterilization can be adjusted according to the desired degree of sterilization. However, when a sterilized state is desired, the sterilization should be performed by terminating the irradiation of ultraviolet light when all the microorganisms are sterilized. A board is obtained.
After sterilization, the sterilized microorganism may remain attached to the object to be processed X. For example, in order to wash the sterilized microorganism, sterilized water or the like is processed. It may be brought into contact with X and washed away.
Moreover, in order to remove the solution S adhering to the workpiece X, the solution S may be dried or sterilized air may be blown.

  By such sterilization, a high degree of sterilization is performed to reliably kill microorganisms, such as fungi, which have adhered to the surface of the mortar board at room temperature without requiring a bactericidal agent. Since nitrous oxide is safe, it is not always necessary to treat nitrous oxide dissolved in the solution S after sterilization.

  The ultraviolet light emitted by the KrI excimer lamp L is highly straight, but the parts to be sterilized are compared, such as when the workpiece X is plate-shaped and only the upper surface is to be sterilized, as shown in FIG. In the case of a simple shape, it is easy to irradiate ultraviolet light, and desired sterilization can be performed.

  However, when the part to be sterilized is relatively complicated, such as when the shape of the workpiece X is complicated, the ultraviolet light is used except for a special case where the workpiece X is a substance that transmits ultraviolet light. In some cases, it is difficult to irradiate a desired part with light because of its high straightness, and sterilization cannot be performed sufficiently. Even when the workpiece X has a simple shape such as a plate shape as in the example shown in FIG. 10, it is difficult to sterilize the whole.

  Even in the example shown in FIG. 10, when the workpiece X is a substance that transmits ultraviolet light from the KrI excimer lamp L, for example, glass tableware or a cup, or the bottom of the container 31 is mirror-finished, In the case where the ultraviolet light is sufficiently guided to the entire object to be processed X by the reflection by the mirror surface, the entire object to be processed X can be sterilized.

  However, in general, it is difficult to sterilize the entire surface of the workpiece X having a three-dimensional shape with the configuration shown in FIG. 10 without changing the state of the workpiece X. This is remarkable, for example, when the workpiece X is a substance having irregularities on the surface.

  Next, a substance sterilization apparatus in view of such circumstances will be described.

  Since the sterilization method in this example can be implemented by using the hydrophilization device 40 shown in FIG. 13 as a substance sterilization device, the hydrophilization device 40 shown in FIG. A method for sterilizing the workpiece X will be described with reference to FIG.

Here, the substance to be sterilized can be, for example, a denture that is one of medical instruments.
Dentures are inserted into the user's mouth and chew foods and the like while replacing lost teeth.

Since this denture is a device that is inserted into the user's mouth for a long time, the microorganisms present in the patient's mouth propagate with food meals attached during meals as nutrients. There is a fear.
In particular, dentures are used while being kept at the body temperature of the user, so it is likely to be a suitable condition for the growth of microorganisms, and the propagated microorganisms can cause tooth decay and periodontal disease, so the dentures are always clean. It is important to keep on.
Dentures have a relatively complex shape such as irregularities along the gums.

  In the sterilizer 40 shown in FIG. 13, after the dentures, which are the object to be treated X, are put into the main body 43 from the openings 42, the solution S is poured from the openings 42 to fill the main body 43, thereby the entire dentures. Soak. After the solution S is poured from the opening 42 to fill the main body 43, the workpiece X may be put into the main body 43 from the opening 42. The opening 42 is closed with a lid 44 in a state where the entire workpiece X is immersed.

  When the KrI excimer lamp L is caused to emit light, a plurality of KrI excimer lamps L disposed on the side and the bottom irradiate ultraviolet light from the side and below, and ultraviolet light is provided on the inner surfaces of the main body 43 and the lid 44. The entire surface of the solution S positioned on the surface of the workpiece X is irradiated with ultraviolet rays by being reflected by the mirror surface.

  Nitrous oxide dissolved in the solution S in the ultraviolet irradiation region is dissociated to generate atomic oxygen (O), and this atomic oxygen strongly oxidizes microorganisms attached to the denture that is the object to be treated X. The dentures are sterilized. The timing of the sterilization end can be adjusted according to the desired degree of sterilization. However, especially when a sterilized state is desired, the sterilized denture is obtained by terminating the irradiation of ultraviolet light when all the microorganisms are sterilized. Is obtained.

After sterilization, the sterilized microorganism may remain attached to the object to be processed X. For example, in order to wash the sterilized microorganism, sterilized water or the like is processed. It may be brought into contact with X and washed away.
Moreover, in order to remove the solution S adhering to the workpiece X, the solution S may be dried or sterilized air may be blown.

  By such sterilization, microorganisms such as fungi attached to the surface of the object to be processed X having a relatively complicated shape with irregularities on the surface are surely killed at room temperature without requiring a sterilizing agent. Advanced sterilization is performed. Since nitrous oxide is safe, it is not always necessary to treat nitrous oxide dissolved in the solution S after sterilization.

  When it is necessary to hold the workpiece X in the main body 43, a holding member in which the shape, position, and material that transmits the ultraviolet light are appropriately selected is provided in the main body 43. By doing so, the holding can be performed. Such a holding member can be omitted when the specific gravity of the workpiece X is almost equal to the specific gravity of the solution S and is floated in the solution S. Therefore, a regulator for adjusting the specific gravity can be dissolved in the solution S.

  According to the sterilization apparatus 40, the surface of the workpiece X having a relatively complicated shape with irregularities on the surface can be sterilized, but the workpiece X is placed inside like a cylinder, a bottle, or a cup. When the space has a certain shape, it is difficult to sterilize the inner surface constituting the space with the structure shown in FIG. 11 except in a special case where the workpiece X is a substance that transmits ultraviolet light. It is.

  Next, a substance sterilization apparatus in view of such circumstances will be described.

  Since the sterilization method in this example can be implemented by using the hydrophilizing device 50 shown in FIG. 14 as a substance sterilizing device, the hydrophilizing device 50 shown in FIG. A method for sterilizing the workpiece X will be described with reference to FIG.

  The substance to be sterilized here is, for example, a beverage container, and can be a milk bottle that is one of the return bottles.

Milk bottles are sold after sterilized milk is filled inside and covered.
Since this milk bottle is generally a return bottle, after it is used once, it is washed, filled with milk, and put on the market again.

  However, since the milk bottle is filled with milk, it is necessary to sterilize the inside sufficiently, and an unspecified number of people hold it by hand and bring its milk into contact with the milk bottle. Since it is a drink, the outer surface of the milk bottle must also be kept hygienic.

  The workpiece X is a milk bottle.

  In the sterilization apparatus 50 shown in FIG. 14, after the workpiece X is put into the main body 53 from the opening 52, the solution S is poured from the opening 52 to fill the main body 53. And a KrI excimer lamp L is inserted into the workpiece X. After the solution S is poured from the opening 52 to fill the inside of the main body 53, the workpiece X is put into the main body 53 from the opening 52 and the whole is immersed, and a KrI excimer lamp L is inserted into the processing object X. Also good. After the workpiece X is put into the main body 53 through the opening 52, a KrI excimer lamp L is inserted into the workpiece X, and the solution S is poured from the opening 52 to fill the main body 53, so that the workpiece X is filled. It may be immersed.

The opening 52 is closed with a lid 54 in a state where the entire workpiece X is immersed.
If the KrI excimer lamp L to be inserted into the workpiece X is integrated with the lid 54 and the opening 52 is closed with the lid 54, the KrI excimer lamp L may be inserted into the workpiece X.

  When the KrI excimer lamp L is caused to emit light, a plurality of KrI excimer lamps L disposed on the side and bottom of the main body 53 are irradiated with ultraviolet light from the side and below, and are disposed inside the workpiece X. The KrI excimer lamp L emits ultraviolet light from the inside, and the ultraviolet light is reflected by the mirror surfaces provided on the inner surfaces of the main body 53 and the lid 54, so that the ultraviolet light is positioned on the outer surface and the inner surface of the workpiece X. The entire solution S is irradiated.

  Nitrous oxide dissolved in the solution S in the ultraviolet irradiation region is dissociated to generate atomic oxygen (O), and the atomic oxygen strongly oxidizes the microorganisms attached to the object X to be treated. The processing object X is sterilized. The timing of sterilization can be adjusted according to the desired degree of sterilization. However, when a sterilized state is desired, the irradiation of ultraviolet light is terminated when all the microorganisms are sterilized. Processed product X is obtained.

After sterilization, the sterilized microorganism may remain attached to the object to be processed X. For example, in order to wash the sterilized microorganism, sterilized water or the like is processed. It may be brought into contact with X and washed away.
Moreover, in order to remove the solution S adhering to the workpiece X, the solution S may be dried or sterilized air may be blown.

  By such sterilization, the microorganisms, such as fungi, that have adhered to the inner and outer surfaces of the object to be processed X having a space inside can be surely killed at room temperature without requiring a sterilizing agent. Sterilization is performed.

Even if the internal space is narrow and cannot be wiped, advanced sterilization can be performed if the KrI excimer lamp L can be inserted and irradiated with ultraviolet rays.
Further, for example, even a hollow object such as a hole pipette into which the KrI excimer lamp L cannot be inserted can highly sterilize the inside if the ultraviolet light is transmitted.
Since nitrous oxide is safe, it is not always necessary to treat nitrous oxide dissolved in the solution S after sterilization.

  In addition, when it is necessary to hold the workpiece X in the main body 53, a holding member in which the shape, position, and material that transmits the ultraviolet light are appropriately selected is provided in the main body 53. By doing so, the holding can be performed. Such a holding member can be omitted when the specific gravity of the workpiece X is almost equal to the specific gravity of the solution S and is floated in the solution S. Therefore, a regulator for adjusting the specific gravity can be dissolved in the solution S.

  According to the sterilizers 40 and 50, the workpieces X that can be stored in the containers 41 and 51 and can be immersed in the solution S inside the containers 41 and 51, and can be sterilized in this state, can be irradiated with ultraviolet light. . However, if the object to be treated X is a relatively large object, or if it is an object that needs to be expanded to increase the surface area in order to sterilize it by irradiating it with ultraviolet rays, such as a cloth, it is sterilized. In this case, it is necessary to make the containers 41 and 51 very large, resulting in an increase in size of the sterilizers 40 and 50.

  Next, a substance sterilization apparatus in view of such circumstances will be described.

  The sterilization method in this example can be carried out by using the hydrophilizing device 60 shown in FIG. 15 as a substance sterilizing device. Therefore, the hydrophilizing device 60 shown in FIG. A method for sterilizing the workpiece X will be described with reference to FIG.

  Here, the substance to be sterilized can be, for example, a used sheet laid on a hospital bed.

Sheets are laid on the bed to prevent the futon and the bed from getting dirty.
In particular, hospital bed sheets come into contact with patients undergoing medical treatment, so saliva scattered by coughing and sneezing, blood from injured parts, etc. may adhere, Need to sterilize.

  However, the sheets are rich in flexibility, and in the ultraviolet light from the KrI excimer lamp L having high linearity, a shadowed portion is likely to occur.

  The object to be processed X may be any plastic sheet, cloth, etc., as long as it is in the form of a sheet and can be wound by a winding mechanism. Here, the object to be processed X is laid on a hospital bed. An explanation will be given taking the used sheets as an example.

  In the sterilization apparatus 60 shown in FIG. 15, the solution X is positioned between the KrI excimer lamps L after the workpiece X is wound around the roller 62 and can be wound by the winding mechanism. The container 61 is filled to such an extent that the workpiece X is immersed. Then, the workpiece X is fed by the winding mechanism. Then, after being immersed in the solution S, a part of the solution S supplied to the wound workpiece X is scraped off by the blade 63 as necessary, and the supply amount of the solution S is equalized. Thereafter, the workpiece X sent between the KrI excimer lamps L is sterilized by receiving irradiation of ultraviolet rays from the lamps.

  Nitrous oxide dissolved in the solution S in the ultraviolet irradiation region is dissociated to generate atomic oxygen (O), and the atomic oxygen strongly oxidizes and decomposes organic substances attached to the workpiece X. The processing object X is sterilized.

  The winding speed of the workpiece X by the winding mechanism is adjusted so that the microorganism is oxidized while the workpiece X moves between the KrI excimer lamps L, and a desired degree of sterilization is obtained. When the winding of the workpiece X by the winding mechanism is finished, the sterilization is finished, and the sterilized workpiece X is obtained.

After sterilization, the sterilized microorganism may remain attached to the object to be processed X. For example, in order to wash the sterilized microorganism, sterilized water or the like is processed. It may be brought into contact with X and washed away.
Moreover, in order to remove the solution S adhering to the workpiece X, the solution S may be dried or sterilized air may be blown.
When drying is performed, this may be performed while winding.

  By such sterilization, a high degree of sterilization that reliably kills microorganisms such as fungi adhering to the surface of the workpiece X at room temperature without using a bactericide is performed. Since nitrous oxide is safe, it is not always necessary to treat nitrous oxide dissolved in the solution S after sterilization. In addition, when the to-be-processed object X is a cloth and is a woven fabric, sterilization is performed within a range irradiated with ultraviolet rays.

  The moving means for moving the object to be processed X may be a configuration provided with a transport member such as a belt for moving the object to be processed X in a mode in which the object to be processed X is placed or fixed, instead of the winding mechanism described above. If it is such a structure, the to-be-processed object X will not be restricted to a sheet-like thing, but a comparatively big thing can be sterilized as the to-be-processed object X. According to this configuration, a plurality of workpieces X can be continuously sterilized while being transported by the transport member. In order to sterilize the entire workpiece X while being transported by such a transport member, the position and shape of the transport member, the use of a material that transmits ultraviolet rays, the position and number of KrI excimer lamps L can be selected as appropriate. .

In such a sterilization apparatus 60, when the workpiece X is a relatively large object, or when it is necessary to expand the surface area to sterilize by irradiating with ultraviolet rays, such as a cloth. However, the size of the container 61 is not greatly affected by the workpiece X, and the increase in size is suppressed.
Moreover, the to-be-processed object X which can be conveyed easily and can be immersed in the solution S inside the container 61 and can be irradiated with ultraviolet light in this state can be sterilized.
However, when the workpiece X is not easily transportable, such as a desk, floor, or wall, sterilization may be difficult or impossible.

  Next, a substance sterilization apparatus in view of such circumstances will be described.

  Since the sterilization method in this example can be implemented by using the hydrophilizing device 70 shown in FIG. 16 as a substance sterilizing device, the hydrophilizing device 70 shown in FIG. A method for sterilizing the workpiece X will be described with reference to FIG.

  Here, the substance to be sterilized can be, for example, the floor of a food factory.

  The floor of the food factory is one of the places where workers are likely to get dirty because it is a place where workers walk, but it needs to be kept hygienic because it is also a place where food is handled.

  However, in general, the floor of food factories is larger than the floors of households, and in order to ensure safety even if it is mixed with food, it is desirable to refrain from using drugs that affect the human body. Is.

  In the sterilization apparatus 70 shown in FIG. 16, the container 71 is brought into close contact with the portion to be sterilized using the elasticity of the rubber 76, and the object to be processed, the container main body 74, and the glass 75 are sealed. After forming the space, the suction pump is operated to fill the sealed space with the solution S. In this state, the KrI excimer lamp L is caused to emit light, and ultraviolet light is applied to the solution S located on the site where the object to be processed is to be sterilized.

Nitrous oxide dissolved in the solution S in the ultraviolet irradiation region is dissociated to generate atomic oxygen (O), and the atomic oxygen strongly oxidizes the microorganisms attached to the object to be treated. Items are sterilized.
Since nitrous oxide is consumed during the sterilization process, the solution S in the sealed space may be replaced by appropriately driving the suction pump.

  Concentration detection means for detecting the concentration of nitrous oxide in the solution S in the sealed space, and the suction pump is driven when the nitrous oxide concentration detected by the concentration detection means falls below a predetermined concentration suitable for sterilization And a control means that performs the feedback control to keep the concentration of the nitrous oxide of the solution S in the sealed space within a range suitable for sterilization.

  When the number of microorganisms adhering to the object to be processed X reaches a desired state, the sterilization is finished and a sterilized object to be processed is obtained. After the sterilization, the supply pipe 72 is removed from the solution storage unit or the container 71, etc. so that the solution S is not supplied from the solution storage unit to the container 71. The solution S is discharged to the waste liquid storage unit, and the container 71 is detached from the object to be processed.

After sterilization, the sterilized microorganism may remain attached to the object to be processed X. For example, in order to wash the sterilized microorganism, sterilized water or the like is processed. It may be brought into contact with X and washed away.
Moreover, in order to remove the solution S adhering to the workpiece X, the solution S may be dried or sterilized air may be blown.

  By such sterilization, for example, in addition to the floor surface of a food factory, microorganisms such as fungi that have adhered to the surface of an object to be treated that are difficult to transport, such as the upper surface of a desk, floor, wall, etc. Advanced sterilization that reliably kills at room temperature is performed without the need for a bactericidal agent. Since nitrous oxide is safe, it is not always necessary to treat nitrous oxide dissolved in the solution S discharged to the waste liquid storage unit.

  When the close contact state between the container 71 and the object to be processed is maintained and the leakage of the solution S does not become a problem, sterilization may be performed while moving the sterilizer 70, particularly the container 71. Since the time for discharging the solution S before the container 71 is moved becomes unnecessary and sterilization can be performed continuously, sterilization can be performed efficiently.

When the container 71 and the object to be processed are in close contact with each other, the ultraviolet light is prevented from leaking from the sealed space, and the influence of the ultraviolet light on the outside can be avoided.
In the examples shown in FIGS. 13 and 14, since the inside of the containers 41 and 51 is sealed, the influence due to leakage of ultraviolet light to the outside is avoided.

  In view of the fact that nitrous oxide is consumed during the sterilization process as in the sterilization apparatus 70, configuring the solution S to be replaceable is extremely excellent in exhibiting high sterilization performance. Even if the concentration of nitrous oxide in the solution S is lowered, sufficient sterilization performance can be ensured. In the configuration examples shown in FIGS. 10, 13 to 15, the solution S can be replaced in the sterilization process.

  For example, a sterilization apparatus configured so that the solution S can be replaced during the sterilization process will be described below. Since the sterilization method in this example can be carried out by using the hydrophilizing device 80 shown in FIG. 17 as a material sterilizing device, the hydrophilizing device 80 shown in FIG. A method for sterilizing the workpiece X will be described with reference to FIG. Moreover, this sterilizer 80 corresponds to the sterilizer 30 in FIG.

  In the sterilizing apparatus 80 shown in FIG. 17, after the workpiece X is held by the holding member 82 and placed in the container 31, the liquid supply valve 87 is opened, and the solution S in the tank 86 is treated. The portion to be sterilized of the object X, here, the entire upper surface in the state shown in FIG. 17 is filled in the container 81 to such an extent that it is sufficiently immersed. The KrI excimer lamp L is caused to emit light, and the entire solution S located on the upper surface of the workpiece X is irradiated with ultraviolet rays.

Nitrous oxide dissolved in the solution S in the ultraviolet irradiation region is dissociated to generate atomic oxygen (O), and the atomic oxygen strongly oxidizes the microorganisms attached to the object X to be treated. The processing object X is sterilized.
Since nitrous oxide is consumed during the sterilization process, the liquid supply valve 87 and the waste liquid valve 88 are appropriately opened and closed to replace the solution S in the sealed space, and the amount and concentration of nitrous oxide in the solution S in the container 81 In a range suitable for sterilization. In order to keep the concentration of nitrous oxide in the solution S in the container 81 within a range suitable for sterilization, the liquid supply valve 87 and the waste liquid valve 88 are appropriately adjusted to open and close so that their flow rates are appropriate.

  A concentration detecting means for detecting the concentration of nitrous oxide in the solution S in the container 81, and a liquid supply valve 87 when the nitrous oxide concentration detected by the concentration detecting means falls below a predetermined concentration suitable for sterilization. A control means for driving the waste liquid valve 88 can be provided in the solution control means 83, and feedback control can be performed to keep the amount and concentration of nitrous oxide in the container 81 in a range suitable for sterilization. In this case, in order to keep the concentration of nitrous oxide in the solution S in the container 81 within the range suitable for sterilization, the liquid supply valve 87 and the waste liquid valve 88 are appropriately adjusted to be opened and closed by the control means so that the flow rates thereof are appropriate. To do.

When the number of microorganisms adhering to the workpiece X reaches a desired state, the sterilization is finished, and the sterilized workpiece X is obtained.
After sterilization, the sterilized microorganism may remain attached to the object to be processed X. For example, in order to wash the sterilized microorganism, sterilized water or the like is processed. It may be brought into contact with X and washed away.
Moreover, in order to remove the solution S adhering to the workpiece X, the solution S may be dried or sterilized air may be blown.
The solution S in the container 81 is appropriately discharged by opening the waste liquid valve 88 to the waste liquid storage unit.

By such sterilization, a high degree of sterilization that reliably kills microorganisms such as fungi adhering to the surface of the workpiece X at room temperature without using a bactericide is performed. Since nitrous oxide is safe, it is not always necessary to treat nitrous oxide dissolved in the solution S after sterilization. Even if the concentration of nitrous oxide in the solution S is lowered, sufficient sterilization performance can be ensured.
Such a solution control means 83 can be similarly applied to the sterilizers 40, 50, 60 described with reference to FIGS.

  The sterilizer 70 shown in FIG. 16 is intended for objects to be processed that are difficult to transport, such as the upper surface of a desk, floor, and wall. Such a sterilizer 70 is suitable for sterilizing a relatively large portion. On the other hand, it may be required to sterilize relatively small portions such as elevators and intercom buttons that are touched by an unspecified number of people.

  Next, a substance sterilization apparatus in view of such circumstances will be described.

  Since the sterilization method in this example can be implemented by using the hydrophilizing device 90 shown in FIG. 18 as a substance sterilizing device, the hydrophilizing device 90 shown in FIG. A method for sterilizing the workpiece X will be described with reference to FIG.

  In the sterilizer 90 shown in FIG. 18, the user holds the grip 93 and directs the injection port 94 toward the object to be processed, operates the trigger, and injects and attaches an appropriate amount of the solution S to the object to be processed. The KrI excimer lamp L is caused to emit light and irradiated with ultraviolet rays. The attachment range of the solution S on the object to be processed is easily set to an appropriate state by the user adjusting the position of the nozzle portion 92, the emission direction of the solution S, and the aperture.

Nitrous oxide dissolved in the solution S in the ultraviolet irradiation region is dissociated to generate atomic oxygen (O), and the atomic oxygen strongly oxidizes the microorganisms attached to the object to be treated. Items are sterilized.
The injection amount of the solution S is adjusted according to the amount of nitrous oxide consumed in the sterilization process.

When the number of microorganisms adhering to the site to be sterilized reaches a desired state, sterilization is completed, and a sterilized object to be processed is obtained.
After sterilization, the sterilized microorganism may remain attached to the object to be processed X. For example, in order to wash the sterilized microorganism, sterilized water or the like is processed. It may be brought into contact with X and washed away.
Moreover, in order to remove the solution S adhering to the workpiece X, the solution S may be dried or sterilized air may be blown.

  In such a sterilization, in the case where it is required to sterilize a relatively small portion such as a sterilization of a push button, microorganisms such as fungi attached to the surface of such an object to be processed are Advanced sterilization that reliably kills at room temperature is performed without the need for a bactericidal agent. Since nitrous oxide is safe, it is not always necessary to treat nitrous oxide dissolved in the solution S after sterilization.

In the sterilizer 90, sterilization is efficiently performed because the solution S is attached to only necessary portions to perform sterilization. Since the amount of consumption of the solution S is small and the sterilization is performed while the solution S is substantially exchanged, even if the concentration of nitrous oxide in the solution S is lowered, sufficient sterilization performance can be ensured. It is.
Further, since the ultraviolet light is irradiated only in the emission direction of the solution S, it is possible to irradiate only the necessary part with the ultraviolet light, and the influence by irradiating the other part with the ultraviolet light is avoided.

  Here, the mode of contact of the solution S with the workpiece X during irradiation with ultraviolet light will be described. The sterilizers 30, 40, 50, 60, and 80 described above immerse the workpiece X in the solution S. The above-described sterilization apparatuses 70 and 90 wet the part to be sterilized with the solution S. Regarding the latter contact mode, the sterilization apparatus 90 has a configuration in which the part to be sterilized of the workpiece X is wetted with the solution S by injecting the solution S. As described above, the solution S is not limited to be continuously adhered to the object to be sterilized, but may be one in which the solution S is sprayed in a mist state and adhered to the object to be sterilized.

  Next, a sterilizing apparatus for such a substance will be described.

  Since the sterilization method in this example can be implemented by using the hydrophilizing apparatus 100 shown in FIG. 19 as a substance sterilizing apparatus, the hydrophilizing apparatus 100 shown in FIG. A method for sterilizing the workpiece X will be described with reference to FIG.

Here, the substance to be sterilized can be a dish dish, for example.
In many cases, food is placed on the dish, and therefore it is preferable to sterilize for hygiene purposes.
Further, if washing can be performed simultaneously with sterilization, in addition to microbial cleanliness, a clean state can be achieved.

  In the sterilization apparatus 100 shown in FIG. 19, the workpiece X is placed on the table 101 and the suction means is operated and held, the nozzle 108 is rotated to a predetermined position suitable for spraying the solution S, After the table 101 is rotated, the solution S is sprayed from the nozzle 108 to uniformly adhere to the workpiece X, and then the KrI excimer lamp L is emitted to irradiate ultraviolet rays. The adhesion amount of the solution S on the workpiece X is adjusted by adjusting the ejection amount and ejection time of the solution S from the nozzle 108.

Nitrous oxide dissolved in the solution S in the ultraviolet irradiation region is dissociated to generate atomic oxygen (O), and this atomic oxygen strongly oxidizes microorganisms and dirt attached to the object to be treated. The processing object X is sterilized and cleaned.
And since the to-be-processed object X is rotating, the water flow of the solution S generate | occur | produces toward radial direction outward with a centrifugal force, and the effect which wash | cleans the disinfected microorganism and the decomposed dirt can also be acquired.
When the number of microorganisms adhering to the workpiece X reaches a desired state, the sterilization is finished, and the sterilized workpiece X is obtained.

After sterilization, sterilized microorganisms and decomposed dirt may remain attached to the workpiece X, so in order to wash the sterilized microorganisms and decomposed dirt, For example, sterilized water or the like may be brought into contact with the workpiece X and washed away.
Moreover, in order to remove the solution S adhering to the workpiece X, the solution S may be dried or sterilized air may be blown.

The solution S collected in the container 104 is discharged to the waste liquid storage section through the waste liquid pipe 105 by opening the waste liquid valve 106 at an appropriate time.
The nozzle 108 can occupy a predetermined position only when it is necessary for spraying the solution S when it is necessary to take care not to interfere with the irradiation of ultraviolet light.

  As an aspect in which the solution S is attached to the workpiece X, there can be mentioned another method by so-called spin coating. In this case, for example, in the sterilization apparatus 100, instead of the solution spraying means 103, a solution flowing means for dropping the solution S onto the object to be processed X held on the table 101 is provided. While rotating the table 101 while holding the object to be processed X, the solution S is dropped by the solution flow-down means so that the solution S is uniformly attached to the object to be processed X, and then the KrI excimer lamp L emits light. And irradiate with ultraviolet rays. The adhesion amount of the solution S on the workpiece X can be adjusted by adjusting the flow rate and the flowing time of the solution S from the solution flowing means.

  If the application of the solution S is performed by spraying or spin coating, the consumption of the solution S can be reduced, and sterilization is performed while the solution S is substantially exchanged. Therefore, the concentration of nitrous oxide in the solution S Even if it is made low, it is possible to ensure sufficient sterilization performance. However, when spraying, if the droplets are too small, nitrous oxide is dissipated into the atmosphere before the solution S reaches the workpiece X, but the solution S is substantially free from the workpiece X. Since sterilization is performed while exchanging, even if the concentration of nitrous oxide in the solution S is somewhat lowered due to dissipation, sufficient sterilization performance can be ensured. However, the size of the droplet is adjusted as appropriate so that the amount of dissipation does not become too large.

  Hereinafter, the cleaning of the substance according to the third embodiment of the present invention will be described with reference to the drawings.

  The cleaning method in this example can be implemented by using the hydrophilizing device 30 shown in FIG. 10 as a substance cleaning device, so that the hydrophilizing device 30 shown in FIG. A method for cleaning the workpiece X will be described with reference to FIG.

  The workpiece X in this example is a flat dish having a relatively simple shape such as a flat plate shape, but may be a substrate such as a silicon wafer.

  An organic substance (not shown) adheres to the surface of the workpiece X (the same applies to each configuration example described below). Examples of organic substances include oils and proteins that are decomposed by an oxidation reaction. The organic substance is assumed to be a thin film-like soil having a thickness of several nanometers to several hundred micrometers attached on the surface of the workpiece X. This is because it is difficult to wash such dirt simply by washing with water or wiping with a cloth. However, it is of course possible to clean organic matter that is thicker than this thickness. When the object to be processed X is a substrate, when organic substances are included in particles or the like adhering in a circuit manufacturing process or the like, the particles and the like are also targets to be decomposed by an oxidation reaction.

  In the cleaning apparatus 30 shown in FIG. 10, after the workpiece X is placed on the protrusion 31 a and placed in the container 31, the solution S is a portion to be cleaned of the workpiece X, here The container 31 is filled to the extent that the entire upper surface in the state shown in FIG. 10 is sufficiently immersed. The KrI excimer lamp L is caused to emit light, and the entire solution S located on the upper surface of the workpiece X is irradiated with ultraviolet rays.

  Nitrous oxide dissolved in the solution S in the ultraviolet irradiation region is dissociated to generate atomic oxygen (O), and the atomic oxygen strongly oxidizes and decomposes organic substances attached to the workpiece X. Then, the workpiece X is cleaned. That is, the organic substance is oxidized and decomposed into water, carbon dioxide, etc., and removed from the dish or substrate as the object X to be processed. Thereby, for example, the plate is in the same state as a new one, and the substrate is subjected to the next process in a clean state, and a clean product is obtained. Such removal includes not only the case where the organic matter is completely decomposed into water, carbon dioxide, etc., but also the case where the organic matter is separated from the workpiece X in the process of being decomposed into water, carbon dioxide, etc. Including. When all the organic substances are removed from the object to be processed X, the cleaning is finished, and the cleaned object X is obtained.

  After cleaning, if there is a possibility that organic waste debris peeled off from the workpiece X in the process of being decomposed may be reattached to the workpiece X, such decomposition waste is completely removed from the workpiece X. For example, the object to be treated X is washed with the solution S or water as necessary. Moreover, the solution S adhering to the to-be-processed object X is removed by drying or blowing air as needed. The blowing of air is also effective for removing the debris.

  By such cleaning, dirt that has adhered to the surface of the workpiece X, which is difficult to clean simply by wiping with water or wiping with a cloth, such as oil film and particles, is completely decomposed, Cleaning is performed. Since nitrous oxide is safe, it is not always necessary to treat nitrous oxide dissolved in the solution S after washing.

  The ultraviolet light emitted from the KrI excimer lamp L is highly straight, but the part to be cleaned has a relatively simple shape, such as when the workpiece X is plate-shaped and only the upper surface is to be cleaned as shown in FIG. In this case, it is easy to irradiate ultraviolet light, and desired cleaning can be performed.

  However, when the portion to be cleaned is relatively complicated, such as when the shape of the workpiece X is complicated, the ultraviolet light is used except for special cases such as when the workpiece X is a substance that transmits ultraviolet light. Because of its high straightness, it may be difficult to irradiate the desired part with light, and cleaning may not be performed sufficiently. Even in the case where the workpiece X has a simple shape such as a plate shape as in the example shown in FIG. 10, it is difficult to clean the whole object.

  Also in the example shown in FIG. 10, when the workpiece X is a substance that transmits ultraviolet light from the KrI excimer lamp L, for example, it is a lens such as an optical device or a spectacle lens, or the bottom of the container 31 is mirror-finished. When the ultraviolet light is sufficiently guided to the entire object to be processed X by reflection by the mirror surface, the entire object to be processed X can be cleaned.

  However, in general, it is difficult to clean the entire surface of the workpiece X having a three-dimensional shape with the configuration shown in FIG. 10 without changing the state of the workpiece X. This is remarkable, for example, when the workpiece X is a substance having irregularities on the surface.

  Next, a cleaning apparatus in view of such circumstances will be described.

  The cleaning method in this example can be carried out by using the hydrophilizing device 40 shown in FIG. 13 as a substance cleaning device, so that the hydrophilizing device 40 shown in FIG. A method for cleaning the workpiece X will be described with reference to FIG.

  Moreover, although the to-be-processed object X in this example is a housing | casing of an electrical product which makes comparatively complicated shape with an unevenness | corrugation on the surface, for example, it is not restricted to this.

  In the cleaning apparatus 40 shown in FIG. 13, after the workpiece X is put into the main body 43 from the opening 42, the solution S is poured from the opening 42 to fill the main body 43. Soak. After the solution S is poured from the opening 42 to fill the main body 43, the workpiece X may be put into the main body 43 from the opening 42. The opening 42 is closed with a lid 44 in a state where the entire workpiece X is immersed.

  When the KrI excimer lamp L is caused to emit light, a plurality of KrI excimer lamps L disposed on the side and the bottom irradiate ultraviolet light from the side and below, and ultraviolet light is provided on the inner surfaces of the main body 43 and the lid 44. The entire surface of the solution S positioned on the surface of the workpiece X is irradiated with ultraviolet rays by being reflected by the mirror surface.

  Nitrous oxide dissolved in the solution S in the ultraviolet irradiation region is dissociated to generate atomic oxygen (O), and the atomic oxygen strongly oxidizes and decomposes organic substances attached to the workpiece X. Then, the workpiece X is cleaned. That is, the organic matter is oxidized, decomposed into water, carbon dioxide, etc., and removed from the workpiece X. In this removal, not only when the organic substance is completely decomposed into water, carbon dioxide, etc., but also the organic substance is separated from the object to be treated X in the process of being decomposed into water, carbon dioxide, etc. Including. When all the organic substances are removed from the object to be processed X, the cleaning is finished, and the cleaned object X is obtained.

  After cleaning, if there is a possibility that organic waste debris peeled off from the workpiece X in the process of being decomposed may be reattached to the workpiece X, such decomposition waste is completely removed from the workpiece X. For example, the object to be treated X is washed with the solution S or water as necessary. Moreover, the solution S adhering to the to-be-processed object X is removed by drying or blowing air as needed. The blowing of air is also effective for removing the debris.

  Due to such cleaning, the surface of the workpiece X having a relatively complicated shape with irregularities on the surface, which is attached to the surface of the workpiece X, is difficult to clean by simply washing with water or wiping with a cloth, For example, the oil film is completely decomposed and advanced cleaning is performed. Since nitrous oxide is safe, it is not always necessary to treat nitrous oxide dissolved in the solution S after washing. When the workpiece X is a casing of an electrical product, it is subjected to an assembly process such as assembling parts inside after cleaning.

  When it is necessary to hold the workpiece X in the main body 43, a holding member in which the shape, position, and material that transmits the ultraviolet light are appropriately selected is provided in the main body 43. By doing so, the holding can be performed. Such a holding member can be omitted when the specific gravity of the workpiece X is almost equal to the specific gravity of the solution S and is floated in the solution S. Therefore, a regulator for adjusting the specific gravity can be dissolved in the solution S.

  According to the cleaning device 40, the surface of the workpiece X having a relatively complicated shape with irregularities on the surface can be cleaned. However, the workpiece X is placed inside like a cylinder, a bottle, or a cup. When a certain shape of the space is formed and it is necessary to clean this part, the inner surface constituting the space is shown in FIG. 11 except for a special case where the workpiece X is a substance that transmits ultraviolet light. It is difficult to clean with the configuration.

  Next, a cleaning apparatus in view of such circumstances will be described.

  The cleaning method in this example can be implemented by using the hydrophilizing device 50 shown in FIG. 14 as a substance cleaning device. Therefore, the hydrophilizing device 50 shown in FIG. A method of cleaning the workpiece X will be described with reference to FIG.

  The workpiece X in this example is a bin. Examples of the bottle include a milk bottle to be recycled.

  In the cleaning apparatus 50 shown in FIG. 14, after the workpiece X is put into the main body 53 from the opening 52, the solution S is poured from the opening 52 to fill the main body 53, thereby the entire processing target X. And a KrI excimer lamp L is inserted into the workpiece X. After the solution S is poured from the opening 52 to fill the inside of the main body 53, the workpiece X is put into the main body 53 from the opening 52 and the whole is immersed, and a KrI excimer lamp L is inserted into the processing object X. Also good. After the workpiece X is put into the main body 53 through the opening 52, a KrI excimer lamp L is inserted into the workpiece X, and the solution S is poured from the opening 52 to fill the main body 53, so that the workpiece X is filled. It may be immersed.

The opening 52 is closed with a lid 54 in a state where the entire workpiece X is immersed.
If the KrI excimer lamp L to be inserted into the workpiece X is integrated with the lid 54 and the opening 52 is closed with the lid 54, the KrI excimer lamp L may be inserted into the workpiece X.

  When the KrI excimer lamp L is caused to emit light, a plurality of KrI excimer lamps L disposed on the side and bottom of the main body 53 are irradiated with ultraviolet light from the side and below, and are disposed inside the workpiece X. The KrI excimer lamp L emits ultraviolet light from the inside, and the ultraviolet light is reflected by the mirror surfaces provided on the inner surfaces of the main body 53 and the lid 54, so that the ultraviolet light is positioned on the outer surface and the inner surface of the workpiece X. The entire solution S is irradiated.

  Nitrous oxide dissolved in the solution S in the ultraviolet irradiation region is dissociated to generate atomic oxygen (O), and the atomic oxygen strongly oxidizes and decomposes organic substances attached to the workpiece X. Then, the workpiece X is cleaned. That is, the organic matter is oxidized, decomposed into water, carbon dioxide, etc., and removed from the workpiece X. In this removal, not only when the organic substance is completely decomposed into water, carbon dioxide, etc., but also the organic substance is separated from the object to be treated X in the process of being decomposed into water, carbon dioxide, etc. Including. When all the organic substances are removed from the object to be processed X, the cleaning is finished, and the cleaned object X is obtained.

  After cleaning, if there is a possibility that organic waste debris peeled off from the workpiece X in the process of being decomposed may be reattached to the workpiece X, such decomposition waste is completely removed from the workpiece X. For example, the object to be treated X is washed with the solution S or water as necessary. Moreover, the solution S adhering to the to-be-processed object X is removed by drying or blowing air as needed. The blowing of air is also effective for removing the debris.

  Due to such cleaning, dirt that is attached to the inner and outer surfaces of the object to be processed X having a space inside, and that is difficult to clean by simply wiping with water or wiping with a cloth, such as an oil film, for example Is completely decomposed and highly cleaned. For example, in the case where the object to be processed X is a milk bottle to be recycled, the milk remaining inside after use is removed, and it becomes an extremely clean state, which is suitable for side recycling.

Even if the internal space is thin and cannot be wiped, advanced cleaning can be performed if the KrI excimer lamp L can be inserted and irradiated with ultraviolet rays.
Further, for example, even a hollow object such as a hole pipette into which the KrI excimer lamp L cannot be inserted can highly clean the inside if the ultraviolet light is transmitted.
Since nitrous oxide is safe, it is not always necessary to treat nitrous oxide dissolved in the solution S after washing.

  In addition, when it is necessary to hold the workpiece X in the main body 53, a holding member in which the shape, position, and material that transmits the ultraviolet light are appropriately selected is provided in the main body 53. By doing so, the holding can be performed. Such a holding member can be omitted when the specific gravity of the workpiece X is almost equal to the specific gravity of the solution S and is floated in the solution S. Therefore, a regulator for adjusting the specific gravity can be dissolved in the solution S.

  According to the cleaning devices 40 and 50, the object to be processed X that can be stored in the containers 41 and 51 and can be immersed in the solution S in the containers 41 and 51 and can be irradiated with ultraviolet light in this state can be cleaned. . However, if the object to be processed X is a relatively large object, or if it is an object that needs to be expanded to increase the surface area to be cleaned by irradiating with ultraviolet rays, such as a cloth, this is cleaned. In this case, it is necessary to make the containers 41 and 51 very large, resulting in an increase in the size of the cleaning devices 40 and 50.

  Next, a cleaning apparatus in view of such circumstances will be described.

  The cleaning method in this example can be carried out by using the hydrophilizing device 60 shown in FIG. 15 as a substance cleaning device. Therefore, the hydrophilizing device 60 shown in FIG. A method of cleaning the workpiece X will be described with reference to FIG.

  In addition, the processing object X in this example may be any material such as a plastic sheet, a cloth, etc., as long as it is in the form of a sheet and can be wound by a winding mechanism, for example, a sheet used in a hospital or the like. , Pillows and bed covers.

  In the cleaning apparatus 60 shown in FIG. 15, the solution S is positioned between the KrI excimer lamps L after the workpiece X is wound around the roller 62 and can be wound by the winding mechanism. The container 61 is filled to such an extent that the workpiece X is immersed. Then, the workpiece X is fed by the winding mechanism. Then, after being immersed in the solution S, a part of the solution S supplied to the wound workpiece X is scraped off by the blade 63 as necessary, and the supply amount of the solution S is equalized. Thereafter, the workpiece X sent between the KrI excimer lamps L is subjected to a cleaning process by being irradiated with ultraviolet rays from the lamps.

  Nitrous oxide dissolved in the solution S in the ultraviolet irradiation region is dissociated to generate atomic oxygen (O), and the atomic oxygen strongly oxidizes and decomposes organic substances attached to the workpiece X. Then, the workpiece X is cleaned. That is, the organic matter is oxidized, decomposed into water, carbon dioxide, etc., and removed from the workpiece X. In this removal, not only when the organic substance is completely decomposed into water, carbon dioxide, etc., but also the organic substance is separated from the object to be treated X in the process of being decomposed into water, carbon dioxide, etc. Including.

  The winding speed of the workpiece X by the winding mechanism is adjusted so that the organic matter is decomposed and the cleaning is sufficiently performed while the workpiece X moves between the KrI excimer lamps L. When the winding of the workpiece X by the winding mechanism is completed, the workpiece X is removed from the workpiece X and the cleaning is completed, and the cleaned workpiece X is obtained. For example, when the object to be processed X is a sheet or the like used in a hospital or the like, body fluid such as blood and dirt such as sweat are removed, and a clean state is obtained.

  After cleaning, if there is a possibility that organic waste debris peeled off from the workpiece X in the process of being decomposed may be reattached to the workpiece X, such decomposition waste is completely removed from the workpiece X. For example, the object to be treated X is washed with the solution S or water as necessary. Moreover, the solution S adhering to the to-be-processed object X is removed by drying or blowing air as needed. The blowing of air is also effective for removing the debris. When drying is performed, this may be performed while winding.

  By such cleaning, dirt that has adhered to the surface of the workpiece X, which is difficult to clean by simply wiping with water or wiping with a cloth, such as an oil film, is completely decomposed, and advanced cleaning is performed. Done. Since nitrous oxide is safe, it is not always necessary to treat nitrous oxide dissolved in the solution S after washing. In addition, when the to-be-processed object X is a cloth and is a textile, washing | cleaning is performed in the range irradiated with an ultraviolet-ray.

  The moving means for moving the object to be processed X may be a configuration provided with a transport member such as a belt for moving the object to be processed X in a mode in which the object to be processed X is placed or fixed, instead of the winding mechanism described above. With such a configuration, the workpiece X is not limited to a sheet shape, and a relatively large object can be cleaned as the workpiece X. According to this configuration, a plurality of objects to be processed X can be continuously washed while being conveyed by the conveying member. In order to clean the entire workpiece X while being transported by such a transporting member, the position and shape of the transporting member, the use of a material that transmits ultraviolet rays, the position and number of KrI excimer lamps L can be selected as appropriate. .

In such a cleaning device 60, when the object to be processed X is a relatively large object, or when it is necessary to expand the surface area of the object to be cleaned by irradiating with ultraviolet rays, such as a cloth. However, the size of the container 61 is not greatly affected by the workpiece X, and the increase in size is suppressed.
In addition, the workpiece X that can be easily transported and immersed in the solution S inside the container 61 and can be irradiated with ultraviolet light in this state can be cleaned.
However, when the workpiece X is not easily transportable, such as a desk, floor, or wall, cleaning may be difficult or impossible.

  Next, a cleaning apparatus in view of such circumstances will be described.

  The cleaning method in this example can be implemented by using the hydrophilizing device 70 shown in FIG. 16 as a substance cleaning device, so that the hydrophilizing device 70 shown in FIG. A method of cleaning the workpiece X will be described with reference to FIG.

  In the cleaning apparatus 70 shown in FIG. 16, the container 71 is brought into close contact with the portion to be cleaned of the object using the elasticity of the rubber 76, and the object to be processed, the container body 74, and the glass 75 are hermetically sealed. After forming the space, the suction pump is operated to fill the sealed space with the solution S. In this state, the KrI excimer lamp L is caused to emit light, and ultraviolet light is applied to the solution S located on the site where the object to be processed is to be cleaned.

Nitrous oxide dissolved in the solution S in the ultraviolet irradiation region is dissociated to generate atomic oxygen (O), and the atomic oxygen strongly oxidizes and decomposes organic substances attached to the object to be processed, The workpiece is cleaned. That is, the organic substance is oxidized, decomposed into water, carbon dioxide, etc., and removed from the object to be processed. This removal includes not only the case where the organic substance is completely decomposed into water, carbon dioxide and the like, but also the separation of the organic substance from the object to be processed in the process of being decomposed into water, carbon dioxide and the like. .
Since nitrous oxide is consumed in the cleaning process, the solution S in the sealed space may be replaced by appropriately driving the suction pump.

  Concentration detection means for detecting the concentration of nitrous oxide in the solution S in the sealed space, and the suction pump is driven when the nitrous oxide concentration detected by the concentration detection means falls below a predetermined concentration suitable for cleaning And a control unit that performs the feedback control to keep the nitrous oxide concentration of the solution S in the sealed space within a range suitable for cleaning.

  When all the organic substances are removed from the object to be processed, the cleaning is finished, and the cleaned object to be processed is obtained. After the cleaning, the liquid supply pipe 72 is removed from the solution storage unit or the container 71, and the solution S is not supplied from the solution storage unit to the container 71. The solution S is discharged to the waste liquid storage unit, and the container 71 is detached from the object to be processed.

  Necessary for completely removing the debris from the object to be treated when there is a possibility that the organic substance debris from the object to be treated is reattached to the object to be treated in the process of decomposition. Depending on the condition, the object to be treated is washed with the solution S or water. Moreover, the solution S adhering to a to-be-processed object is removed by drying or blowing air as needed. The blowing of air is also effective for removing the debris.

  By such cleaning, it is difficult to clean by simply rinsing with water or wiping with cloth, which has adhered to the surface of the object to be processed, such as the top surface of the desk, floor, or wall, which is difficult to transport. Dirt, such as oil film, dirt, mold, etc., is completely decomposed and advanced cleaning is performed. Since nitrous oxide is safe, it is not always necessary to treat nitrous oxide dissolved in the solution S discharged to the waste liquid storage unit.

  When the tight contact state between the container 71 and the object to be processed is maintained, and the leakage of the solution S does not become a problem, cleaning may be performed while moving the cleaning device 70, particularly the container 71. Since the time for discharging the solution S before the container 71 is moved becomes unnecessary and the cleaning can be performed continuously, the cleaning can be performed efficiently.

When the container 71 and the object to be processed are in close contact with each other, the ultraviolet light is prevented from leaking from the sealed space, and the influence of the ultraviolet light on the outside can be avoided.
In the examples shown in FIGS. 13 and 14, since the inside of the containers 41 and 51 is sealed, the influence due to leakage of ultraviolet light to the outside is avoided.

  In view of the fact that nitrous oxide is consumed in the course of cleaning as in the cleaning device 70, the configuration in which the solution S can be replaced is extremely excellent in exhibiting high cleaning performance. Even if the concentration of nitrous oxide in the solution S is lowered, sufficient cleaning performance can be ensured. In the configuration examples shown in FIGS. 10, 13 to 15, the solution S can be replaced in the cleaning process.

  For example, a cleaning apparatus configured so that the solution S can be replaced in the cleaning process will be described below.

  The cleaning method in this example can be carried out by using the hydrophilizing device 80 shown in FIG. 17 as a substance cleaning device. Therefore, the hydrophilizing device 80 shown in FIG. A method of cleaning the workpiece X will be described with reference to FIG. The cleaning device 80 corresponds to the cleaning device 30.

  In the cleaning apparatus 80 shown in FIG. 17, after the workpiece X is held by the holding member 82 and placed in the container 31, the liquid supply valve 87 is opened, and the solution S in the tank 86 is treated. The portion to be cleaned of the object X, here, the entire upper surface in the state shown in FIG. 17 is filled into the container 81 to such an extent that it is sufficiently immersed. The KrI excimer lamp L is caused to emit light, and the entire solution S located on the upper surface of the workpiece X is irradiated with ultraviolet rays.

  Nitrous oxide dissolved in the solution S in the ultraviolet irradiation region is dissociated to generate atomic oxygen (O), and the atomic oxygen strongly oxidizes and decomposes organic substances attached to the workpiece X. Then, the workpiece X is cleaned. That is, the organic matter is oxidized, decomposed into water, carbon dioxide, etc., and removed from the workpiece X. Thereby, for example, the plate is in the same state as a new one, and the substrate is subjected to the next process in a clean state, and a clean product is obtained. Such removal includes not only the case where the organic matter is completely decomposed into water, carbon dioxide, etc., but also the case where the organic matter is separated from the workpiece X in the process of being decomposed into water, carbon dioxide, etc. Including.

  Since nitrous oxide is consumed during the cleaning process, the solution supply valve 87 and the waste solution valve 88 are appropriately opened and closed to replace the solution S in the sealed space, and the amount and concentration of nitrous oxide in the solution S in the container 81 Keep in a range suitable for cleaning. In order to keep the concentration of nitrous oxide in the solution S in the container 81 within a range suitable for cleaning, the liquid supply valve 87 and the waste liquid valve 88 are appropriately adjusted to open and close so that the flow rates thereof are appropriate.

  A concentration detecting means for detecting the concentration of nitrous oxide in the solution S in the container 81, and a liquid supply valve 87 when the nitrous oxide concentration detected by the concentration detecting means falls below a predetermined concentration suitable for cleaning. The solution control means 83 is provided with a control means for driving the waste liquid valve 88, and feedback control is performed to keep the amount and concentration of nitrous oxide in the container 81 within a range suitable for cleaning. In this case, in order to keep the concentration of nitrous oxide in the solution S in the container 81 within a range suitable for cleaning, the supply valve 87 and the waste liquid valve 88 are appropriately opened and closed by the control means so that the flow rates thereof are appropriate. To do.

  When all the organic substances are removed from the object to be processed X, the cleaning is finished, and the cleaned object X is obtained. After cleaning, if there is a possibility that organic waste debris peeled off from the workpiece X in the process of being decomposed may be reattached to the workpiece X, such decomposition waste is completely removed from the workpiece X. For example, the object to be treated X is washed with the solution S or water as necessary. Moreover, the solution S adhering to the to-be-processed object X is removed by drying or blowing air as needed. The blowing of air is also effective for removing the debris. The solution S in the container 81 is appropriately discharged by opening the waste liquid valve 88 to the waste liquid storage unit.

By such cleaning, dirt that has adhered to the surface of the workpiece X, which is difficult to clean by simply wiping with water or wiping with a cloth, such as an oil film, is completely decomposed, and advanced cleaning is performed. Done. Since nitrous oxide is safe, it is not always necessary to treat nitrous oxide dissolved in the solution S after washing. Even if the concentration of nitrous oxide in the solution S is lowered, sufficient cleaning performance can be ensured.
Such a solution control means 83 can be similarly applied to the cleaning apparatuses 40, 50, 60 described with reference to FIGS.

  The cleaning apparatus 70 shown in FIG. 16 is intended for an object to be processed that is mainly difficult to transport, such as an upper surface of a desk, a floor, or a wall. Such a cleaning device 70 is suitable for cleaning a relatively large portion. On the other hand, it may be required to spot-clean relatively small parts such as tooth cleaning.

  Next, a cleaning apparatus in view of such circumstances will be described.

  The cleaning method in this example can be carried out by using the hydrophilizing device 90 shown in FIG. 18 as a substance cleaning device. Therefore, the hydrophilizing device 90 shown in FIG. A method for cleaning the workpiece X will be described with reference to FIG.

  In the cleaning apparatus 90 shown in FIG. 18, the user holds the grip 93 and directs the injection port 94 toward the object to be processed such as a tooth, operates the trigger, and injects an appropriate amount of the solution S onto the object to be processed. At the same time, the KrI excimer lamp L emits light and is irradiated with ultraviolet rays. The attachment range of the solution S on the object to be processed is easily set to an appropriate state by the user adjusting the position of the nozzle portion 92, the emission direction of the solution S, and the aperture.

  Nitrous oxide dissolved in the solution S in the ultraviolet irradiation region is dissociated to generate atomic oxygen (O), and the atomic oxygen strongly oxidizes and decomposes organic substances attached to the object to be processed, The workpiece is cleaned. That is, the organic substance is oxidized, decomposed into water, carbon dioxide, etc., and removed from the object to be processed. This removal includes not only the case where the organic substance is completely decomposed into water, carbon dioxide and the like, but also the separation of the organic substance from the object to be processed in the process of being decomposed into water, carbon dioxide and the like. .

The injection amount of the solution S is adjusted according to the amount of nitrous oxide consumed in the cleaning process.
When all organic substances such as coloring components adhering to the teeth are removed, the cleaning is completed, and a cleaned object to be processed is obtained. Necessary for completely removing the debris from the object to be treated when there is a possibility that the organic substance debris from the object to be treated is reattached to the object to be treated in the process of decomposition. Depending on the condition, the object to be treated is washed with the solution S or water. In this case, if such cleaning is performed by injecting the solution S using the cleaning device 90, it is possible to perform cleaning by spot injection only to that portion while observing the state of reattachment of the organic matter, which is extremely easy. Cleaning is performed. Moreover, the solution S adhering to a to-be-processed object is removed by drying or blowing air as needed. The blowing of air is also effective for removing the debris.

  When such a cleaning requires spot cleaning of a relatively small portion such as a tooth cleaning, the surface adhered to the surface of the object to be treated is simply washed with water or wiped with a cloth. Stain is difficult to clean, for example, coloring components are completely decomposed, and advanced cleaning is performed. Since nitrous oxide is safe, it is not always necessary to treat nitrous oxide dissolved in the solution S after washing.

In the cleaning device 90, cleaning is performed efficiently because the solution S is attached to only necessary portions and cleaning is performed. Since the amount of consumption of the solution S is small and the cleaning is performed while the solution S is substantially exchanged, even if the concentration of nitrous oxide in the solution S is lowered, sufficient cleaning performance can be ensured. It is.
Further, since the ultraviolet light is irradiated only in the emission direction of the solution S, it is possible to irradiate only the necessary part with the ultraviolet light, and the influence by irradiating the other part with the ultraviolet light is avoided.

  Here, the mode of contact of the solution S with the workpiece X during irradiation with ultraviolet light will be described. The cleaning devices 30, 40, 50, 60, and 80 described above immerse the workpiece X in the solution S. The cleaning devices 70 and 90 described above wet the part to be cleaned of the object to be cleaned with the solution S. With respect to the latter contact mode, the cleaning device 90 is configured to wet the portion to be cleaned of the workpiece X with the solution S by injecting the solution S. As described above, the solution S is not limited to be continuously adhered to the object to be cleaned, but may be one in which the solution S is sprayed in the form of a mist to adhere to the object to be cleaned.

  Next, such a cleaning apparatus will be described.

  Since the cleaning method in this example can be implemented by using the hydrophilizing apparatus 100 shown in FIG. 19 as a substance cleaning apparatus, the hydrophilizing apparatus 100 shown in FIG. A method for cleaning the workpiece X will be described with reference to FIG.

  The workpiece X in this example assumes a substrate such as a silicon wafer, but may be a flat dish. In the case where an organic substance is contained in particles or the like adhering to the workpiece X in a circuit manufacturing process or the like, the particles or the like are also subject to decomposition by an oxidation reaction.

  In the cleaning apparatus 100 shown in FIG. 19, the workpiece X is placed on the table 101, the suction means is operated and held, the nozzle 108 is rotated to a predetermined position suitable for spraying the solution S, After the table 101 is rotated, the solution S is sprayed from the nozzle 108 to uniformly adhere to the workpiece X, and then the KrI excimer lamp L is emitted to irradiate ultraviolet rays. The adhesion amount of the solution S on the workpiece X is adjusted by adjusting the ejection amount and ejection time of the solution S from the nozzle 108.

  Nitrous oxide dissolved in the solution S in the ultraviolet irradiation region is dissociated to generate atomic oxygen (O), and the atomic oxygen strongly oxidizes and decomposes organic substances attached to the object to be processed, The workpiece X is cleaned. That is, the organic matter is oxidized, decomposed into water, carbon dioxide, etc., and removed from the workpiece X. Thereby, for example, the substrate is subjected to the next process in a clean state, and a clean product is obtained, and the plate is in the same state as a new product. Such removal includes not only the case where the organic matter is completely decomposed into water, carbon dioxide, etc., but also the case where the organic matter is separated from the workpiece X in the process of being decomposed into water, carbon dioxide, etc. Including.

  The adhesion amount of the solution S is adjusted according to the amount of nitrous oxide consumed in the cleaning process.

  When all the organic substances are removed from the object to be processed X, the cleaning is finished, and the cleaned object X is obtained. After cleaning, if there is a possibility that organic waste debris peeled off from the workpiece X in the process of being decomposed may be reattached to the workpiece X, such decomposition waste is completely removed from the workpiece X. For example, the object to be treated X is washed with the solution S or water as necessary. Moreover, the solution S adhering to the to-be-processed object X is removed by drying or blowing air as needed. The blowing of air is also effective for removing the debris. The removal of the solution S may be performed by rotating the table 101.

  By such cleaning, dirt that has adhered to the surface of the workpiece X, which is difficult to clean simply by wiping with water or wiping with a cloth, such as oil film and particles, is completely decomposed, Cleaning is performed. Since nitrous oxide is safe, it is not always necessary to treat nitrous oxide dissolved in the solution S after washing.

The solution S collected in the container 104 is discharged to the waste liquid storage section through the waste liquid pipe 105 by opening the waste liquid valve 106 at an appropriate time.
The nozzle 108 can occupy a predetermined position only when it is necessary for spraying the solution S when it is necessary to take care not to interfere with the irradiation of ultraviolet light.

  As an aspect in which the solution S is attached to the workpiece X, there can be mentioned another method by so-called spin coating. In this case, for example, in the cleaning apparatus 100, instead of the solution spraying means 103, a solution flowing means for dropping the solution S onto the object to be processed X held on the table 101 is provided. While rotating the table 101 while holding the object to be processed X, the solution S is dropped by the solution flow-down means so that the solution S is uniformly attached to the object to be processed X, and then the KrI excimer lamp L emits light. And irradiate with ultraviolet rays. The adhesion amount of the solution S on the workpiece X can be adjusted by adjusting the flow rate and the flowing time of the solution S from the solution flowing means.

  If the application of the solution S is performed by spraying or spin coating, the consumption of the solution S can be reduced, and the cleaning is performed while the solution S is substantially exchanged. Therefore, the concentration of nitrous oxide in the solution S Even if it is lowered, it is possible to ensure sufficient cleaning performance. However, when spraying, if the droplets are too small, nitrous oxide is dissipated into the atmosphere before the solution S reaches the workpiece X, but the solution S is substantially free from the workpiece X. Since cleaning is performed while exchanging, even if the concentration of nitrous oxide in the solution S is somewhat lowered due to dissipation, sufficient cleaning performance can be ensured. However, the size of the droplet is adjusted as appropriate so that the amount of dissipation does not become too large.

Hereinafter, decolorization of a substance according to a fourth embodiment of the present invention will be described with reference to the drawings.
Since the decolorization method in this example can be carried out by using the hydrophilization device 30 shown in FIG. 10 as a substance decolorization device, the hydrophilization device 30 shown in FIG. A method for decolorizing the workpiece X will be described with reference to FIG.

A symbol X indicates an object to be processed as a substance to be decolorized.
The workpiece X in the present example is a dish such as a handkerchief, a towel, or a dish serving, which has a relatively simple shape such as a flat plate shape.

  The workpiece X has a colored body (not shown) such as a dye or a pigment. The colored body is an object integrated with the object to be processed X in any manner, such as an object attached to the surface of the object to be processed X, an object soaked in the object to be processed X, an object included as a component of the object to be processed X Although it may be present (the same applies to each configuration example described below), it must be in contact with the solution S and irradiated with ultraviolet light to be decolorized. The colored body is decomposed by oxidation, and examples thereof include synthetic dyes such as mauve and indigo, and natural dyes such as calsamon, shikonin, alizarin, crocin, tannin, carotene, and anthocyan. Also included are handkerchiefs, towels, dish stains, and dirt that are decomposed by oxidation.

  In the decoloring apparatus 30 shown in FIG. 10, after the workpiece X is placed on the protrusion 31a and placed in the container 31, the solution S is a portion where the workpiece X should be decolored, here. The container 31 is filled to the extent that the entire upper surface in the state shown in FIG. 10 is sufficiently immersed. The KrI excimer lamp L is caused to emit light, and the entire solution S located on the upper surface of the workpiece X is irradiated with ultraviolet rays.

  Nitrous oxide dissolved in the solution S in the ultraviolet irradiation region is dissociated to generate atomic oxygen (O), and this atomic oxygen strongly oxidizes and decomposes the colored body of the workpiece X, Decolorization of the workpiece X is performed. That is, the colored body is oxidized, decomposed into water, carbon dioxide, or the like, or eluted into the solution S, and removed from the handkerchief, towel, or dish as the workpiece X. As a result, for example, handkerchiefs, towels, and dishes are bleached, and the product is in the same state as a new product. As described above, the colored body that is difficult to separate by simply washing with water or wiping with cloth is decomposed or separated from the object X, and decolorization is performed. When the desired decolorization is performed, the decolorization is finished, and the decolorized workpiece X is obtained.

After the decolorization, if there is a possibility that the colored body separated from the object to be processed X in the process of decoloring is reattached to the object to be processed X, such a colored object is removed from the object to be processed X. In order to remove the material, the object to be processed X is washed with the solution S, water, or the like as necessary. Moreover, the solution S adhering to the to-be-processed object X is removed by drying or blowing air as needed. The blowing of air is also effective for re-removing the colored body once separated.
Since nitrous oxide is safe, it is not always necessary to treat nitrous oxide dissolved in the solution S after decolorization.

  The ultraviolet light emitted by the KrI excimer lamp L is highly straight, but the part to be decolored has a relatively simple shape, for example, when the workpiece X is plate-shaped and only the upper surface is decolored as shown in FIG. In this case, it is easy to irradiate with ultraviolet light, and desired decolorization can be performed.

  However, when the part to be decolored is relatively complicated, such as when the shape of the workpiece X is complicated, the ultraviolet light is used except for a special case where the workpiece X is a substance that transmits ultraviolet light. Because of the high straightness, it may be difficult to irradiate a desired part with light, and decoloration may not be performed sufficiently. Even in the case where the workpiece X has a simple shape such as a plate shape as in the example shown in FIG. 10, it is difficult to decolor the whole.

  Also in the example shown in FIG. 10, when the workpiece X is a substance that transmits ultraviolet light from the KrI excimer lamp L, or the bottom of the container 31 is mirror-finished, and the entire workpiece to be processed X is reflected by this mirror surface. In the case of a configuration that sufficiently guides light, the entire workpiece X can be decolorized.

  However, in general, it is difficult to decolor the entire surface of the workpiece X having a three-dimensional shape with the configuration shown in FIG. 10 without changing the state of the workpiece X. This is remarkable, for example, when the workpiece X is a substance having irregularities on the surface.

  Next, a decoloring apparatus in view of such circumstances will be described.

  Since the decolorization method in this example can be implemented by using the hydrophilizing device 40 shown in FIG. 13 as a substance cleaning device, the hydrophilizing device 40 shown in FIG. A method for decolorizing the workpiece X will be described with reference to FIG.

The workpiece X is a stuffed toy having a relatively complicated shape with irregularities on the surface, for example, but is not limited thereto.
The colored body is a stain or stain of the stuffed toy X, which is decomposed by oxidation.

  In the decoloring apparatus 40 shown in FIG. 13, after the workpiece X is put into the main body 43 from the opening 42, the solution S is poured from the opening 42 to fill the main body 43, whereby the entire workpiece X is processed. Soak. After the solution S is poured from the opening 42 to fill the main body 43, the workpiece X may be put into the main body 43 from the opening 42. The opening 42 is closed with a lid 44 in a state where the entire workpiece X is immersed.

  When the KrI excimer lamp L is caused to emit light, a plurality of KrI excimer lamps L disposed on the side and the bottom irradiate ultraviolet light from the side and below, and ultraviolet light is provided on the inner surfaces of the main body 43 and the lid 44. The entire surface of the solution S positioned on the surface of the workpiece X is irradiated with ultraviolet rays by being reflected by the mirror surface.

  Nitrous oxide dissolved in the solution S in the ultraviolet irradiation region is dissociated to generate atomic oxygen (O), and this atomic oxygen strongly oxidizes and decomposes the colored body of the workpiece X, Decolorization of the workpiece X is performed. That is, the colored body is oxidized and decomposed into water, carbon dioxide, or the like, or eluted into the solution S and removed from the stuffed toy X. As a result, for example, the color generated in the stuffed toy due to dirt is decolored, and this is a memorable item, and such a request can be met. As described above, the colored body that is difficult to separate by simply washing with water or wiping with cloth is decomposed or separated from the object X, and decolorization is performed. When the desired decolorization is performed, the decolorization is finished, and the decolorized workpiece X is obtained.

  After the decolorization, if there is a possibility that the colored body separated from the object to be processed X in the process of decoloring is reattached to the object to be processed X, such a colored object is removed from the object to be processed X. In order to remove the material, the object to be processed X is washed with the solution S, water, or the like as necessary. Moreover, the solution S adhering to the to-be-processed object X is removed by drying or blowing air as needed. The blowing of air is also effective for re-removing the colored body once separated.

  By such decolorization, a desired decolorization of the workpiece X having a relatively complicated shape with irregularities on the surface is performed. Since nitrous oxide is safe, it is not always necessary to treat nitrous oxide dissolved in the solution S after decolorization.

  When it is necessary to hold the workpiece X in the main body 43, a holding member in which the shape, position, and material that transmits the ultraviolet light are appropriately selected is provided in the main body 43. By doing so, the holding can be performed. Such a holding member can be omitted when the specific gravity of the workpiece X is almost equal to the specific gravity of the solution S and is floated in the solution S. Therefore, a regulator for adjusting the specific gravity can be dissolved in the solution S.

  According to the decoloring apparatus 40, it is possible to decolor the surface of the workpiece X having a relatively complicated shape with irregularities on the surface, but the workpiece X is placed inside like a cylinder, a bottle, or a cup. When the space has a certain shape, it is difficult to decolor the inner surface forming the space with the structure shown in FIG. 11 except in a special case where the workpiece X is a substance that transmits ultraviolet light. It is.

  Next, a decoloring apparatus in view of such circumstances will be described.

  The decolorization method in this example can be carried out by using the hydrophilizing device 50 shown in FIG. 14 as a substance cleaning device. Therefore, the hydrophilizing device 50 shown in FIG. A method for decolorizing the workpiece X will be described with reference to FIG.

The object to be processed X has a bottle shape, but may be a part of clothes such as trousers or a jacket, particularly a hem portion. The workpiece X may be any shape as long as it has a space inside and needs to decolor this part and the outer surface.
When the object to be processed X is a garment such as trousers or a jacket, the colored body is a stain or dirt on the hem and is decomposed by oxidation.

  In the decolorizing apparatus 50 shown in FIG. 14, after the workpiece X is put into the main body 53 from the opening 52, the solution S is poured from the opening 52 to fill the main body 53, and thereby the entire workpiece X is processed. And a KrI excimer lamp L is inserted into the workpiece X. After the solution S is poured from the opening 52 to fill the inside of the main body 53, the workpiece X is put into the main body 53 from the opening 52 and the whole is immersed, and a KrI excimer lamp L is inserted into the processing object X. Also good. After the workpiece X is put into the main body 53 through the opening 52, a KrI excimer lamp L is inserted into the workpiece X, and the solution S is poured from the opening 52 to fill the main body 53, so that the workpiece X is filled. It may be immersed.

The opening 52 is closed with a lid 54 in a state where the entire workpiece X is immersed.
If the KrI excimer lamp L to be inserted into the workpiece X is integrated with the lid 54 and the opening 52 is closed with the lid 54, the KrI excimer lamp L may be inserted into the workpiece X.

  When the KrI excimer lamp L is caused to emit light, a plurality of KrI excimer lamps L disposed on the side and bottom of the main body 53 are irradiated with ultraviolet light from the side and below, and are disposed inside the workpiece X. The KrI excimer lamp L emits ultraviolet light from the inside, and the ultraviolet light is reflected by the mirror surfaces provided on the inner surfaces of the main body 53 and the lid 54, so that the ultraviolet light is positioned on the outer surface and the inner surface of the workpiece X. The entire solution S is irradiated.

  Nitrous oxide dissolved in the solution S in the ultraviolet irradiation region is dissociated to generate atomic oxygen (O), and this atomic oxygen strongly oxidizes and decomposes the colored body of the workpiece X, Decolorization of the workpiece X is performed. That is, the colored body is oxidized, decomposed into water, carbon dioxide, or the like, or eluted into the solution S, and removed from the hem portion of clothes such as trousers and jackets as the object to be processed X. Thereby, the decolorization of the front and back of the hem portion is performed at a time. As described above, the colored body that is difficult to separate by simply washing with water or wiping with cloth is decomposed or separated from the object X, and decolorization is performed.

  When the desired decolorization is performed, the decolorization is finished, and the decolorized workpiece X is obtained. After the decolorization, if there is a possibility that the colored body separated from the object to be processed X in the process of decoloring is reattached to the object to be processed X, such a colored object is removed from the object to be processed X. In order to remove the material, the object to be processed X is washed with the solution S, water, or the like as necessary. Moreover, the solution S adhering to the to-be-processed object X is removed by drying or blowing air as needed. The blowing of air is also effective for re-removing the colored body once separated.

By such decolorization, desired decolorization of the inner and outer surfaces of the object to be processed X having a space inside and an opening in the space is performed.
Even if the internal space is narrow, if the KrI excimer lamp L can be inserted and ultraviolet irradiation can be performed, the decolorization can be performed satisfactorily.
In addition, for example, even a hollow object such as a hole pipette into which a KrI excimer lamp L cannot be inserted can satisfactorily decolorize the interior if ultraviolet light is transmitted.
Since nitrous oxide is safe, it is not always necessary to treat nitrous oxide dissolved in the solution S after decolorization.

  In addition, when it is necessary to hold the workpiece X in the main body 53, a holding member in which the shape, position, and material that transmits the ultraviolet light are appropriately selected is provided in the main body 53. By doing so, the holding can be performed. Such a holding member can be omitted when the specific gravity of the workpiece X is almost equal to the specific gravity of the solution S and is floated in the solution S. Therefore, a regulator for adjusting the specific gravity can be dissolved in the solution S.

  According to the decoloring devices 40 and 50, the processing object X that can be stored in the containers 41 and 51 and can be immersed in the solution S inside the containers 41 and 51 and can be irradiated with ultraviolet light in this state can be decolorized. . However, if the workpiece X is a relatively large object, or if it is an object that needs to be expanded to increase the surface area in order to decolorize by irradiating it with ultraviolet rays, such as a cloth, it is decolorized. In this case, it is necessary to make the containers 41 and 51 very large, resulting in an increase in the size of the decolorizing devices 40 and 50.

  Next, a decoloring apparatus in view of such circumstances will be described.

  The decolorization method in this example can be carried out by using the hydrophilizing device 60 shown in FIG. 15 as a substance cleaning device. Therefore, the hydrophilizing device 60 shown in FIG. A method for decolorizing the workpiece X will be described with reference to FIG.

  The object to be processed X may be any sheet as long as it can be wound by a winding mechanism, such as a plastic sheet such as a plastic film, a cloth, a sheet, a pillow, Examples include a bed cover.

  In the decoloring apparatus 60 shown in FIG. 15, the solution S is positioned between the KrI excimer lamps L after the workpiece X is wound around the roller 62 and can be wound by the winding mechanism. The container 61 is filled to such an extent that the workpiece X is immersed. Then, the workpiece X is fed by the winding mechanism. Then, after being immersed in the solution S, a part of the solution S supplied to the wound workpiece X is scraped off by the blade 63 as necessary, and the supply amount of the solution S is equalized. Thereafter, the workpiece X sent between the KrI excimer lamps L is decolored by receiving ultraviolet rays from the lamps.

  Nitrous oxide dissolved in the solution S in the ultraviolet irradiation region is dissociated to generate atomic oxygen (O), and this atomic oxygen strongly oxidizes and decomposes the colored body of the workpiece X, Decolorization of the workpiece X is performed. That is, the colored body is oxidized and decomposed into water, carbon dioxide or the like, or eluted into the solution S and removed from the workpiece X. As described above, the colored body that is difficult to separate by simply washing with water or wiping with cloth is decomposed or separated from the object X, and decolorization is performed.

  The winding speed of the workpiece X by the winding mechanism is adjusted so that the colored body is decomposed and desired decolorization is performed while the workpiece X moves between the KrI excimer lamps L. When the winding of the workpiece X by the winding mechanism is finished, the decoloring is finished, and the decolored workpiece X is obtained. For example, when the object to be processed X is a sheet or the like used in a hospital or the like, body fluid such as blood, stains such as sweat, and dirt are removed by decolorization, resulting in a clean state.

  After the decolorization, if there is a possibility that the colored body separated from the object to be processed X in the process of decoloring is reattached to the object to be processed X, such a colored object is removed from the object to be processed X. In order to remove the material, the object to be processed X is washed with the solution S, water, or the like as necessary. Moreover, the solution S adhering to the to-be-processed object X is removed by drying or blowing air as needed. The blowing of air is also effective for re-removing the colored body once separated. When drying is performed, this may be performed while winding.

  By such decolorization, desired decolorization of the workpiece X is performed. Since nitrous oxide is safe, it is not always necessary to treat nitrous oxide dissolved in the solution S after decolorization. In addition, when the to-be-processed object X is a cloth and it is a textile fabric, decoloring is performed in the range irradiated with ultraviolet rays. Therefore, in order to completely decolorize such a fabric, it is desirable that the fabric is thin.

  The moving means for moving the object to be processed X may be a configuration provided with a transport member such as a belt for moving the object to be processed X in a mode in which the object to be processed X is placed or fixed, instead of the winding mechanism described above. If it is such a structure, the to-be-processed object X will not be restricted to a sheet-like thing, but a comparatively big thing can be used as the to-be-processed object X, and this can be decolored. According to this configuration, the plurality of workpieces X can be continuously decolored while being transported by the transport member. In order to decolorize the entire object to be processed X while being transported by such a transporting member, the position and shape of the transporting member, the use of a material that transmits ultraviolet rays, the position and number of the KrI excimer lamps L can be selected as appropriate. .

In such a decoloring apparatus 60, when the object to be processed X is a relatively large object, or when it is an object that needs to be expanded to increase the surface area in order to decolorize by irradiating with ultraviolet rays, such as a cloth. However, the size of the container 61 is not greatly affected by the workpiece X, and the increase in size is suppressed.
Moreover, it can carry out and can be immersed in the solution S inside the container 61, and it can decolorize about the to-be-processed object X which can irradiate an ultraviolet light in this state.
However, when the workpiece X is not easily transportable, such as a desk, floor, or wall, decolorization may be difficult or impossible.

  Next, a decoloring apparatus in view of such circumstances will be described.

  Since the decolorization method in this example can be implemented by using the hydrophilization device 70 shown in FIG. 16 as a substance cleaning device, the hydrophilization device 70 shown in FIG. A method for decolorizing the workpiece X will be described with reference to FIG.

  In the decoloring apparatus 70 shown in FIG. 16, the container 71 is brought into close contact with the portion to be decolorized using the elasticity of the rubber 76, and the object to be processed, the container body 74, and the glass 75 are hermetically sealed. After forming the space, the suction pump is operated to fill the sealed space with the solution S. In this state, the KrI excimer lamp L is caused to emit light, and ultraviolet light is applied to the solution S located on the portion where the object to be processed is to be decolorized.

Nitrous oxide dissolved in the solution S in the ultraviolet irradiation region is dissociated to generate atomic oxygen (O), and this atomic oxygen strongly oxidizes and decomposes the colored body of the object to be processed, The processed product is decolorized. That is, the colored body is oxidized and decomposed into water, carbon dioxide or the like, or eluted into the solution S and removed. As a result, for example, the color generated on the wall due to stains, dirt, mold, graffiti, etc. is removed. As described above, the colored body that is difficult to separate by simply washing with water or wiping with cloth is decomposed or separated from the object X, and decolorization is performed.
Since nitrous oxide is consumed in the process of decolorization, the solution S in the sealed space may be replaced by appropriately driving the suction pump.

  Concentration detection means for detecting the concentration of nitrous oxide in the solution S in the sealed space, and the suction pump is driven when the nitrous oxide concentration detected by the concentration detection means falls below a predetermined concentration suitable for decolorization And a control means that performs the feedback control to keep the concentration of nitrous oxide in the solution S in the sealed space within a range suitable for decolorization.

  When the desired decolorization is performed, the decolorization is finished, and a decolored workpiece is obtained. After decolorization, the suction pump is driven after the liquid supply pipe 72 is removed from the solution storage unit or the container 71 so that the solution S is not supplied from the solution storage unit to the container 71. The solution S is discharged to the waste liquid storage unit, and the container 71 is detached from the object to be processed. When there is a possibility that the colored body separated from the object to be processed X in the process of decoloring is reattached to the object to be processed X, such a colored object is removed from the object to be processed X. Therefore, the processing object X is washed with the solution S, water, or the like as necessary. Moreover, the solution S adhering to a to-be-processed object is removed by drying or blowing air as needed. The blowing of air is also effective for re-removing the colored body once separated.

  By such decolorization, desired decolorization of an object to be processed that is difficult to transport, such as the upper surface of a desk, a floor, or a wall, is performed. Since nitrous oxide is safe, it is not always necessary to treat nitrous oxide dissolved in the solution S discharged to the waste liquid storage unit.

  When the tight contact state between the container 71 and the object to be processed is maintained and the leakage of the solution S does not become a problem, decolorization may be performed while moving the decoloring device 70, particularly the container 71. Since the time for discharging the solution S before the container 71 is moved becomes unnecessary and decolorization can be performed continuously, decolorization can be performed efficiently.

When the container 71 and the object to be processed are in close contact with each other, the ultraviolet light is prevented from leaking from the sealed space, and the influence of the ultraviolet light on the outside can be avoided.
In the examples shown in FIGS. 13 and 14, since the inside of the containers 41 and 51 is sealed, the influence due to leakage of ultraviolet light to the outside is avoided.

  In consideration of the fact that nitrous oxide is consumed in the process of decoloration as in the decolorization apparatus 70, the configuration in which the solution S can be replaced is extremely excellent in exhibiting high decolorization performance. Even if the concentration of nitrous oxide in the solution S is lowered, it is possible to ensure sufficient decolorization performance. Also in the configuration examples shown in FIGS. 10, 13 to 15, the solution S can be configured to be exchangeable during the decolorization process.

  For example, a decoloring apparatus configured so that the solution S can be replaced during the decoloring process will be described below.

  Since the decolorization method in this example can be implemented by using the hydrophilizing device 80 shown in FIG. 17 as a substance cleaning device, the hydrophilizing device 80 shown in FIG. A method for decolorizing the workpiece X will be described with reference to FIG. Further, the decoloring device 80 corresponds to the decoloring device 30 in FIG.

In the decoloring apparatus 80 having such a configuration, the workpiece X is held by the holding member 82 and placed in the container 31, and then the liquid supply valve 87 is opened to allow the solution S in the tank 86 to pass through. The portion to be decolorized of the processed product X, here, the entire upper surface in the state shown in FIG. 17 is filled in the container 81 to such an extent that it is sufficiently immersed. The KrI excimer lamp L is caused to emit light, and ultraviolet rays are irradiated toward the workpiece X.
When passing through the mask 89, the ultraviolet light is partially blocked by the pattern 89a according to the shape of the pattern 89a, and partially irradiated to the solution S positioned on the upper surface of the workpiece X.

  Nitrous oxide dissolved in the solution S in the ultraviolet irradiation region is dissociated to generate atomic oxygen (O), and this atomic oxygen strongly oxidizes and decomposes the colored body of the workpiece X, Decolorization of the workpiece X is performed. That is, the colored body is oxidized, decomposed into water, carbon dioxide, or the like, or eluted into the solution S, and removed from the handkerchief, towel, or dish as the workpiece X. As a result, for example, handkerchiefs, towels, and dishes are bleached, and the product is in the same state as a new product. As described above, the colored body that is difficult to separate by simply washing with water or wiping with cloth is decomposed or separated from the object X, and decolorization is performed.

  Since the diffusion transfer distance of atomic oxygen is extremely small, the color of the workpiece X is decolored in the region irradiated with ultraviolet light, but the atomic oxygen cannot move to the region where the ultraviolet light is blocked by the mask 89. For this reason, decolorization by atomic oxygen is not performed in the region where the ultraviolet light is blocked by the mask 89. In this way, a decoloring region having a desired pattern is formed. Therefore, for example, when the object to be processed X is a cloth such as a handkerchief or a towel, a fabric having a pattern of such a color difference is produced by utilizing the difference in color between the decolored area and the non-bleached area. Is possible.

  Since nitrous oxide is consumed in the process of decolorization, the liquid supply valve 87 and the waste liquid valve 88 are appropriately opened and closed to replace the solution S in the sealed space, and the amount and concentration of nitrous oxide in the solution S in the container 81 Keep in a range suitable for decolorization. In order to keep the concentration of nitrous oxide in the solution S in the container 81 within a range suitable for decolorization, the liquid supply valve 87 and the waste liquid valve 88 are appropriately adjusted to open and close so that the flow rates thereof are appropriate.

  A concentration detecting means for detecting the concentration of nitrous oxide in the solution S in the container 81, and a liquid supply valve 87 when the nitrous oxide concentration detected by the concentration detecting means falls below a predetermined concentration suitable for decolorization. The solution control means 83 is provided with a control means for driving the waste liquid valve 88, and feedback control is performed to keep the amount and concentration of nitrous oxide in the container 81 within a range suitable for decolorization. In this case, in order to keep the concentration of nitrous oxide of the solution S in the container 81 within a range suitable for decolorization, the liquid supply valve 87 and the waste liquid valve 88 are appropriately adjusted to be opened and closed by the control means so that the flow rates thereof are appropriate. To do.

  When the desired decolorization is performed, the decolorization is finished, and the decolorized workpiece X is obtained. After the decolorization, if there is a possibility that the colored body separated from the object to be processed X in the process of decoloring is reattached to the object to be processed X, such a colored object is removed from the object to be processed X. In order to remove the material, the object to be processed X is washed with the solution S, water, or the like as necessary. Moreover, the solution S adhering to the workpiece X is removed by drying or blowing air as necessary. The blowing of air is also effective for re-removing the colored body once separated. The solution S in the container 81 is appropriately discharged by opening the waste liquid valve 88 to the waste liquid storage unit.

By such decolorization, desired decolorization of the workpiece X is performed. Since nitrous oxide is safe, it is not always necessary to treat nitrous oxide dissolved in the solution S after decolorization. Even if the concentration of nitrous oxide in the solution S is lowered, it is possible to ensure sufficient decolorization performance.
Such a solution control means 83 can be similarly applied to the decoloring devices 40, 50, 60 described with reference to FIGS.

Also in the decoloring apparatuses 40, 50, and 60 shown in FIGS. 13, 14, and 15, patterning is performed by disposing a mask between the KrI excimer lamp L and the workpiece X in the same manner as the mask 89. Decolorization can be performed. By utilizing the difference in color between the decoloring region and the non-bleaching region, it is possible to manufacture the workpiece X having such a color difference as a pattern.
In this case, in the decoloring apparatuses 40 and 50, it is necessary to irradiate the ultraviolet rays with the workpiece X held in position.

  Moreover, in the decoloring apparatus 60, the to-be-processed object X is intermittently wound up by a winding mechanism, and an ultraviolet-ray is irradiated when the to-be-processed object X stops. If the operation of performing decolorization when stopping the winding and winding the workpiece X by a length longer than the pattern length after decoloring is repeated, the workpiece X that has been decolored in the same pattern is obtained continuously. Can do. After the pattern is formed, if the workpiece X is cut between the patterns, a large number of workpieces X having the same pattern can be obtained.

In order to perform patterned decolorization, instead of using the mask 89, the solution S is attached to the object to be processed X in a desired pattern by using a printing technique or the like, and patterning of application of the solution S is performed. Further, ultraviolet rays may be irradiated to at least a portion where the solution S is attached to the workpiece X.
Note that the decoloring apparatus 70 shown in FIG. 16 can also be said to perform patterned decolorization when using this to decolor a part of the surface of the object to be processed.

  The decoloring apparatus 70 shown in FIG. 16 is intended for an object to be processed that is mainly difficult to transport, such as a desk top, a floor, or a wall. Such a decoloring device 70 is suitable for decolorizing a relatively large portion. On the other hand, it may be required to decolorize a relatively small portion in a spot manner.

  Next, a decoloring apparatus in view of such circumstances will be described.

  Since the decolorization method in this example can be implemented by using the hydrophilizing device 90 shown in FIG. 18 as a substance cleaning device, the hydrophilizing device 90 shown in FIG. A method for decolorizing the workpiece X will be described with reference to FIG.

  In the decoloring apparatus 90 shown in FIG. 18, the user holds the grip 93 and directs the injection port 94 toward the object to be processed such as teeth, operates the trigger, and injects an appropriate amount of the solution S onto the object to be processed. At the same time, the KrI excimer lamp L emits light and is irradiated with ultraviolet rays. The attachment range of the solution S on the object to be processed is easily set to an appropriate state by the user adjusting the position of the nozzle portion 92, the emission direction of the solution S, and the aperture.

Nitrous oxide dissolved in the solution S in the ultraviolet irradiation region is dissociated to generate atomic oxygen (O), and this atomic oxygen strongly oxidizes and decomposes the colored body of the object to be processed, The processed product is decolorized. That is, the colored body is oxidized and decomposed into water, carbon dioxide, or the like, or eluted into the solution S and removed from the tooth or the like as the object to be processed. As a result, for example, the tooth color is bleached and bleaching is performed, and it is possible to meet the demand for whitening the teeth, which is important for beauty. In this way, a colored body that is difficult to separate by simply washing with water or wiping with a cloth is decomposed or separated from the object to be decolorized.
The injection amount of the solution S is adjusted according to the amount of nitrous oxide consumed in the decolorization process.

  When the desired decolorization is performed, the decolorization is finished, and a decolorized workpiece is obtained. When there is a possibility that the colored body separated from the object to be processed remains attached to the object to be processed in the process of decolorization, etc., in order to remove the colored object from the object to be processed. If necessary, the object to be treated is washed with the solution S or water. In this case, if the cleaning is performed by injecting the solution S using the decolorizing device 90, the cleaning can be performed by spot injection only to the portion while observing the state of reattachment of the colored body. Cleaning is performed. Moreover, the solution S adhering to the to-be-processed object X is removed by drying or blowing air as needed. The blowing of air is also effective for re-removing the colored body once separated.

  When it is required to decolorize a relatively small portion by spotting, a desired decoloring of the surface of the workpiece is performed. For example, as described above, when the object to be processed is a tooth, tooth bleaching is performed well. Since nitrous oxide is safe, it is not always necessary to treat nitrous oxide dissolved in the solution S after decolorization.

In the decoloring device 90, since the solution S is attached to only necessary portions and decolorization is performed, decolorization is performed efficiently. Since the consumption of the solution S can be reduced and the decolorization is performed while the solution S is substantially exchanged, even if the concentration of nitrous oxide in the solution S is lowered, sufficient decolorization performance can be ensured. It is.
Further, since the ultraviolet light is irradiated only in the emission direction of the solution S, it is possible to irradiate only the necessary part with the ultraviolet light, and the influence by irradiating the other part with the ultraviolet light is avoided.
In addition, it can be said that the decoloring apparatus 90 also performs patterned decolorization when using this to decolor a part of the workpiece. For example, the object to be processed is a sheet like the object X to be processed in the decoloring device 60, or the upper surface of the desk, the floor, the wall, etc. like the object X to be processed in the decoloring device 70.

  Here, the mode of contact of the solution S with the workpiece X during irradiation with ultraviolet light will be described. The above-described decoloring devices 30, 40, 50, 60, and 80 immerse the workpiece X in the solution S. The decoloring devices 70 and 90 described above wet the part to be decolored of the workpiece with the solution S. Regarding the latter contact mode, the decoloring device 90 is configured to wet the portion to be decolored of the workpiece X by injecting the solution S with the solution S. However, as the ejection mode, the decoloring device 90 As described above, the solution S is not limited to the material to be continuously adhered to the object to be decolored, but may be the one in which the solution S is ejected in a mist shape and adhered to the object to be decolored.

  Next, such a decoloring apparatus will be described.

  Since the decolorization method in this example can be implemented by using the hydrophilizing device 100 shown in FIG. 19 as a substance cleaning device, the hydrophilizing device 100 shown in FIG. A method for decolorizing the workpiece X will be described with reference to FIG.

  In the decoloring apparatus 100 having such a configuration, the workpiece X is placed on the table 101 and is held by operating the suction means, and the nozzle 108 is rotated to a predetermined position suitable for spraying the solution S. After the table 101 is rotated, the solution S is sprayed from the nozzle 108 to uniformly adhere to the workpiece X, and then the KrI excimer lamp L is emitted to irradiate ultraviolet rays. The adhesion amount of the solution S on the workpiece X is adjusted by adjusting the ejection amount and ejection time of the solution S from the nozzle 108.

Nitrous oxide dissolved in the solution S in the ultraviolet irradiation region is dissociated to generate atomic oxygen (O), and this atomic oxygen strongly oxidizes and decomposes the colored body of the object to be processed, The processed product X is decolorized. That is, the colored body is oxidized, decomposed into water, carbon dioxide, or the like, or eluted into the solution S and removed from the dish as the object to be processed X. As a result, for example, the color generated on the plate by the pigment is decolored, and the state is the same as a new product. As described above, the colored body that is difficult to separate by simply washing with water or wiping with cloth is decomposed or separated from the object X, and decolorization is performed.
The adhesion amount of the solution S is adjusted according to the amount of nitrous oxide consumed in the decolorization process.

  When the desired decolorization is performed, the decolorization is finished, and the decolorized workpiece X is obtained. After the decolorization, if there is a possibility that the colored body separated from the object to be processed X in the process of decoloring is reattached to the object to be processed X, such a colored object is removed from the object to be processed X. In order to remove the material, the object to be processed X is washed with the solution S, water, or the like as necessary. Moreover, the solution S adhering to the to-be-processed object X is removed by drying or blowing air as needed. The blowing of air is also effective for re-removing the colored body once separated. The removal of the solution S may be performed by rotating the table 101. Since nitrous oxide is safe, it is not always necessary to treat nitrous oxide dissolved in the solution S after decolorization.

The solution S collected in the container 104 is discharged to the waste liquid storage section through the waste liquid pipe 105 by opening the waste liquid valve 106 at an appropriate time.
The nozzle 108 can occupy a predetermined position only when it is necessary for spraying the solution S when it is necessary to take care not to interfere with the irradiation of ultraviolet light.

  As an aspect in which the solution S is attached to the workpiece X, there can be mentioned another method by so-called spin coating. In this case, for example, in the decoloring apparatus 100, instead of the solution spraying means 103, a solution flowing means for dropping the solution S onto the object to be processed X held on the table 101 is provided. While rotating the table 101 while holding the object to be processed X, the solution S is dropped by the solution flow-down means so that the solution S is uniformly attached to the object to be processed X, and then the KrI excimer lamp L emits light. And irradiate with ultraviolet rays. The adhesion amount of the solution S on the workpiece X can be adjusted by adjusting the flow rate and the flowing time of the solution S from the solution flowing means.

  Also in these decoloring apparatuses 100, patterned decoloring can be performed by performing the patterning of the application of the mask 89 and the solution S described with respect to the decoloring apparatus 80 shown in FIG. In this case, the table 101 is not rotated at the time of ultraviolet irradiation other than the spraying of the solution S and the spin coating, and the workpiece X is held in a fixed position.

  If the solution S is applied by spraying or spin coating, the consumption of the solution S can be reduced, and decolorization is performed while the solution S is substantially exchanged. Therefore, the concentration of nitrous oxide in the solution S Even if it is lowered, it is possible to ensure sufficient decolorization performance. However, when spraying, if the droplets are too small, nitrous oxide is dissipated into the atmosphere before the solution S reaches the workpiece X, but the solution S is substantially free from the workpiece X. Since decolorization is performed while exchanging, even if the concentration of nitrous oxide in the solution S is somewhat lowered due to dissipation, it is possible to ensure sufficient decolorization performance. However, the size of the droplet is adjusted as appropriate so that the amount of dissipation does not become too large.

  Hereinafter, manufacture of a substance having a function different from that of the original substance according to the fifth embodiment of the present invention will be described with reference to the drawings.

  FIG. 20 shows a substance manufacturing apparatus for manufacturing a substance having a function different from that of the original substance to which the present invention is applied.

  The production apparatus 110 includes a tray-shaped reactor 114 that stores a nitrous oxide solution 111, and krypton-iodine as a light source that is disposed above the reactor 114 and irradiates ultraviolet rays toward the inside of the reactor 114. The dielectric barrier discharge lamp used, that is, the KrI excimer lamp L is included.

  In order to produce ε-caprolactone, the solution 111 is a solution in which nitrous oxide is dissolved in cyclohexanone, or after dissolving cyclohexanone in a solvent such as methanol, ethanol, n-hexane, cyclohexane, and the like. Is melted. Nitrous oxide is dissolved in the solution 111 at a concentration of about 1000 ppm.

  In the manufacturing apparatus 110 having such a configuration, the KrI excimer lamp L emits light and the entire solution 111 is irradiated with ultraviolet light.

  Nitrous oxide dissolved in the solution 111 in the ultraviolet irradiation region is dissociated to generate atomic oxygen (O), and this atomic oxygen strongly oxidizes cyclohexanone dissolved in the solution 111, Synthesis of ε-caprolactone is performed. The production is finished when the desired amount of ε-caprolactone is obtained.

  Such manufacturing makes it possible to produce ε-caprolactone quickly and less wastefully by making the reaction field relatively small, and it is also necessary to take countermeasures against corrosion and repair in systems where corrosion countermeasures and repairs were difficult. Not only will there be a high degree of synthesis of ε-caprolactone. Since nitrous oxide is safe, it is not always necessary to treat nitrous oxide dissolved in the solution 111 after production.

  As described above, a functional substance can be obtained by irradiating the solution 111 containing the predetermined substance and nitrous oxide with ultraviolet light, but the predetermined substance is oxidized in a smaller reaction system. A method for obtaining a functional substance is described below.

  In recent years, an apparatus (microreactor) that forms a microspace of 1 μm to several μm on a glass or plastic substrate using a microfabrication technique to produce a chemical reaction or a functional substance has attracted attention.

  According to this microreactor, only a necessary amount of a necessary substance can be produced as needed, and therefore, it is expected as a production system with less burden on the environment.

  FIG. 21 is a schematic view showing an example of the microreactor 126. The microreactor 126 is formed by forming a flow path on a plastic substrate 127 having a length of 7 cm, a width of 3 cm, and a thickness of 5 mm by using a micro-processing technique, so that two substances can be mixed.

  The microreactor 126 includes a first liquid storage unit 121 in which a first liquid is stored and a second liquid storage unit 122 in which a second liquid is stored. The liquid supplied from the supply pipe 128 joins at the joining part 123 and is mixed while flowing through the reaction part 124 so that the substances react with each other and reach the reactant storage part 125. The reactant stored in the reactant reservoir 125 is taken out through the delivery pipe 129.

  The reaction of the substance in the microreactor thus formed is expected to enable miniaturization of the apparatus because the reaction rate is very high.

  However, when an acid solution is supplied to the liquid storage unit so as to perform an oxidation reaction in the microreactor, all the acid solution channels are exposed to the acid solution and are likely to deteriorate.

  In addition, the acid solution may dissolve the wall surface of the flow path, and the dissolved product on the wall surface is mixed with the reaction product, which may cause a reduction in the purity of the reaction product.

  Therefore, by using a nitrous oxide solution as an oxidant when producing a functional substance in this microreactor, atomic oxygen is generated only when an oxidation reaction is necessary, and an oxidation reaction is performed in other channels. It is possible to suppress deterioration due to oxidation of the microreactor 126 without causing it to occur.

  That is, in the manufacturing apparatus 130 shown in FIG. 22, the ultraviolet light irradiated from the KrI excimer lamp L is interposed between the microreactor 126 and the KrI excimer lamp L with the light blocking body 131 having the slit 132 interposed therebetween. Only the portion of the slit 132 is passed through so as to hit only a predetermined portion of the microreactor 126.

  In the manufacturing apparatus 130, the predetermined substance is cyclohexanone, the nitrous oxide solution is a solution of nitrous oxide in a solvent such as methanol, ethanol, n-hexane, cyclohexane, and the functional substance is ε-caprolactone. Can also be interpreted as

  Therefore, for example, by supplying a nitrous oxide solution to the first liquid storage unit 121 and supplying a predetermined substance in the form of a solution to the second liquid storage unit 122, the solutions are merged at the merge unit 123. , And mixed while flowing through the reaction section 124.

  The predetermined position of the reaction unit 124 is irradiated with the ultraviolet light 113 that has passed through the slit 132 provided in the light blocking body 131, and the ultraviolet light 113 on the microreactor 126 is irradiated with the ultraviolet light 113. A given substance can be oxidized by a nitrous oxide solution to produce a functional substance.

  In FIG. 22, the supply pipe 128 connected to the first liquid storage part 121 and the second liquid storage part 122 and the delivery pipe 129 connected to the reactant storage part 125 are omitted.

  According to this manufacturing apparatus 130, the oxidation reaction of the substance can be performed quickly, the contamination of impurities is small, and a necessary amount of a functional substance can be produced as necessary. It can be used as a production system with few.

  Next, a manufacturing apparatus focused on removing impurities will be described with reference to the schematic diagram of FIG.

  In the production of substances, a high degree of purification may be required. Therefore, it is possible to obtain a functional substance with a high degree of purification by separating the predetermined substance from the mixture of the predetermined substance and impurities and irradiating only the predetermined substance with ultraviolet light. A simple manufacturing apparatus.

  Here, in FIG. 23, the manufacturing apparatus 140 is configured using a high-performance liquid chromatograph generally used as an analytical instrument.

  That is, the manufacturing apparatus 140 includes a solvent bottle 145 containing the nitrous oxide solution 141, a pump 146 that delivers the nitrous oxide solution 141, a column 65 that is a separation means, and a detector 67 that detects the separated substance. The KrI excimer lamp L for irradiating the ultraviolet light 113, the three-way valve 69 for switching the flow path, the waste liquid bottle 143 for storing the waste liquid, and the product storage bottle 144 for storing the manufactured functional substance are respectively piped. 142 is connected.

  The nitrous oxide solution 141 is obtained by dissolving nitrous oxide gas in a solvent having a composition suitable for separation of a predetermined substance.

  Further, the pump 146 includes an introduction port 64, and a liquid mixture of a predetermined substance and impurities can be introduced into the nitrous oxide solution from the introduction port 64.

  In addition, a cell 68 made of quartz glass is disposed between the pipe 142 connecting the detector 67 and the three-way valve 69, and the nitrous oxide solution 141 flowing in the cell 68 is irradiated with ultraviolet light. 113 can be irradiated.

  In the manufacturing apparatus 140 configured as described above, first, the nitrous oxide solution 141 stored in the solvent bottle 145 is supplied to the pump 146.

  In the pump 146, predetermined substances and contaminants are introduced from the introduction port 64, mixed in the nitrous oxide solution 141 flowing in the pump 146, and pushed out from the pump 146.

  The nitrous oxide solution 141 containing the predetermined substance and impurities pushed out from the pump 146 reaches the column 65.

  In the column 65, the predetermined substance and the contaminants are separated while flowing through the column 65, and are discharged at each timing.

  Predetermined substances and contaminants discharged from the column 65 at each timing reach the detector 67.

  The detector 67 is set to be able to detect that the predetermined substance has reached the detector 67, and the nitrous oxide solution 141 flowing in the detector 67 contains the predetermined substance or contains impurities. Can be determined.

  The nitrous oxide solution 141 that has flowed out of the detector 67 flows in a cell 68 that is disposed immediately below the KrI excimer lamp L.

  The nitrous oxide solution 141 that has passed through the cell 68 reaches the three-way valve 69 and is distributed so as to reach the waste liquid bottle 143 or the product storage bottle 144.

  Here, when it is determined by the detector 67 that the predetermined substance is flowing, the KrI excimer lamp L is turned on and the three-way valve 69 is adjusted so that the liquid that has passed through the cell 68 is the product storage bottle 144. As a result, a predetermined substance is oxidized in the cell 68 to generate a functional substance, and a highly purified functional substance can be stored in the product storage bottle.

  On the other hand, when it is determined by the detector 67 that foreign substances are flowing, the three-way valve 69 is adjusted so that the liquid that has passed through the cell 68 reaches the waste liquid bottle 143, thereby having functionality. Substances and contaminants can be prevented from being mixed.

  Note that the lighting of the KrI excimer lamp L and the adjustment of the three-way valve 69 may be performed manually, or may be electrically controlled according to a signal transmitted from the detector 67.

  In this manner, by configuring the manufacturing apparatus 140, a highly purified functional substance can be obtained from a predetermined substance including impurities.

  Next, FIG. 24 shows an example of obtaining a highly purified functional substance by another chromatography.

  FIG. 24 shows a substance manufacturing apparatus 150 to which a separation technique by so-called thin layer chromatography is applied.

  This thin-layer chromatography is generally a chromatography using a thin-layer plate in which an adsorbent such as silica gel, alumina, or cellulose is fixed in a thin film on a plate of glass, plastic, aluminum or the like.

  When one end of the thin layer plate thus prepared is immersed in the solvent, the solvent moves toward the other end in the gap between the adsorbents by capillary action.

  Here, if a sample exists on a thin layer board, a sample will also move with the movement of a solvent. Depending on the strength of adsorption of each component contained in the sample to the adsorbent on the thin layer plate and the difference in solubility in the solvent, each component constituting the sample moves on the thin layer plate according to its characteristics. To do. Therefore, each component has a different moving distance during a predetermined time, and can be separated into each component. Thin layer chromatography is a technique that enables separation and identification of substances by utilizing the difference in the movement distance of each component during a predetermined time.

  Here, the manufacturing apparatus 150 according to the present invention includes a KrI excimer lamp L that irradiates the ultraviolet light 113 and a glass developing tank 156 so that the ultraviolet light 113 can enter the developing tank 156. .

  Further, the developing tank 156 contains the nitrous oxide solution 152 and the thin layer plate 153, and the thin layer plate 153 leans against the wall surface of the developing tank 156, while its lower part is placed in the nitrous oxide solution 152. It is soaked.

  The thin layer plate 153 is not particularly limited as long as it can be used for thin layer chromatography, but in this example, a silica gel powder fixed to a glass plate with a constant thickness is used. Is used.

  The nitrous oxide solution 152 is a mixture of a predetermined substance and impurities so as to be separable.

  In the manufacturing apparatus 150 configured as described above, a stock solution spot 154 is created by dropping a liquid mixture of a predetermined substance and impurities on the thin layer plate 153 before being immersed in the nitrous oxide solution 152. In FIG. 24, the stock solution spots 154 are created at four locations. However, if more functional substances are to be obtained, the number of stock solution spots 154 may be increased.

  Moreover, the position where the stock solution spot 154 is created is preferably a height that does not immerse in the nitrous oxide solution 152 stored in the developing tank 156 and is as low as possible.

  In addition, as shown in FIG. 24, when the stock solution spots 154 are created at a plurality of locations, the work can be facilitated when the functional substances are collected by creating them so as to be arranged in the horizontal direction as much as possible.

  The thin layer plate 153 on which the stock solution spot 154 is formed is stored in the developing tank 156 so that the lower part is immersed in the nitrous oxide solution 152 and left for a predetermined time.

  The leaving time is a time for which the predetermined substance is reliably separated from the impurities, and is preferably as short as possible. By setting the time as short as possible, the degree of purification of the functional substance can be increased.

  The thin layer plate 153 disposed in the development tank 156 wets the surface of the thin layer plate 153 with the nitrous oxide solution 152 from the bottom to the top while sucking up the nitrous oxide solution 152, and this water flow Predetermined substances and contaminants contained in the stock solution spot 154 are caused to flow upward.

  Here, since the nitrous oxide solution 152 has a composition capable of separating a predetermined substance and contaminants, a predetermined substance spot 155 and a contaminant spot 157 are formed on the thin layer plate 153, respectively. It will be.

  After the material spot 155 and the contaminant spot 157 are reliably separated from each other, the KrI excimer lamp L is turned on, and the thin layer plate 153 is irradiated with the ultraviolet light 113, so that it is included in the predetermined material spot. The nitrous oxide solution 152 reacts with a predetermined substance to generate a functional substance.

  After the predetermined substance changes to a functional substance, the irradiation with the ultraviolet light 113 is stopped, and the thin layer plate 153 is taken out from the developing tank 156.

  The recovery of the functional substance can be performed by scraping the silica gel powder of the predetermined substance spot 155 irradiated with the ultraviolet light 113 from the glass plate.

  By using such a manufacturing apparatus 150, it is possible to separate a predetermined substance from foreign substances and oxidize the predetermined substance to obtain a functional substance having a high degree of purification.

  In Examples 1 to 5 described above, from the viewpoint of improving the adhesion of the nitrous oxide solution to the object to be treated, a thickener for improving the viscosity may be added to the solution. As the thickener, those that do not lose the function of generating atomic oxygen and do not consume the generated atomic oxygen are preferable. By improving the viscosity of the solution, for example, in the case of hydrophilizing a substance, when hydrophilizing a substance that easily repels the solution, the hydrophilizing devices 70 and 90 are used to hydrophilize walls and artificial teeth. In such a case, even when these form a vertical surface and the solution easily flows down, the solution remains on the object to be processed and the hydrophilicity is favorably performed. Therefore, the liquid contact target can be expanded and the liquid contact time can be expanded, and hydrophilicity can be achieved under various conditions.

  In the case of decolorizing a substance, since the viscosity is high, even if a solution is attached, color bleeding hardly occurs, so that the coloring range on the substance is difficult to be widened and good decolorization is performed. For example, when the solvent is water and the colored body is a dye, or when the solvent is an organic substance and the colored body is a pigment, the colored body easily dissolves in the solution, and color bleeding tends to occur. If the viscosity is high, movement of the solution is difficult to occur, so that color bleeding is also difficult to occur, and the colored body does not adhere to other parts of the object to be processed at the time of decolorization, and the decolorization is performed well. Even in the case of patterning, since the colored body does not adhere to other parts of the object to be processed during decolorization, good patterning is performed.

  Hereinafter, a method for oxidizing an object using a nitrous oxide solution to which a thickener is added, which is a sixth embodiment of the present invention, will be described with reference to the drawings.

  The substance oxidizing method in this example can be implemented by using the hydrophilizing apparatus 30 shown in FIG. 10 as the substance oxidizing apparatus. Therefore, the hydrophilizing apparatus 30 shown in FIG. A method for oxidizing the workpiece X will be described with reference to FIG.

  The solution S is a nitrous oxide-containing viscous aqueous solution (hereinafter sometimes simply referred to as a solution) containing nitrous oxide and a thickener. In this solution S, nitrous oxide is dissolved at a concentration of about 1000 ppm. The thickener was methylcellulose, and its concentration was 0.1 weight percent. As described above, even if the thickener is added and the viscosity of the solution is increased, the nitrous oxide-containing solution having a relatively low viscosity can be used in the same manner as the nitrous oxide-containing solution. Is possible.

  A symbol “X” indicates an object to be processed. The workpiece X in this example is a plate such as a plate, a handkerchief, a towel, or a dish for serving dishes, which has a relatively simple shape such as a flat plate shape. The to-be-processed object X has a substance to be oxidized such as an organic substance in the portion to be oxidized. As the form of existence, any form may be used as long as the substance to be oxidized is present, for example, when it is attached, penetrated, or contained as a component of the workpiece X (each configuration described below) The same applies to the example), but it must be in contact with the solution S and irradiated with ultraviolet light to be oxidized. For example, the object to be treated X may be a so-called soiled object such as a handkerchief or towel with a substance to be oxidized attached, or a dish with a stain.

  The object oxidation apparatus having such a configuration is suitable for the case where the entire surface of the oxide is oxidized. Further, when the solution S is provided with a retention property by containing a thickener, the solution is prevented from flowing and excessive oxidation is performed. Therefore, it is suitable for the case where a relatively light oxidation treatment, in other words, a thin oxidation treatment, is performed on the entire surface of the oxide.

  In the oxidizer 30 shown in FIG. 10, after the workpiece X is placed on the protrusion 31a and placed in the container 31, the solution S is added to the portion to be oxidized of the workpiece X, here FIG. The container 31 is filled in such a manner that the entire upper surface in the state shown in FIG. The KrI excimer lamp L is caused to emit light, and the entire solution S located on the upper surface of the workpiece X is irradiated with ultraviolet rays.

  Nitrous oxide dissolved in the solution S in the ultraviolet irradiation region is dissociated to generate atomic oxygen (O), and this atomic oxygen strongly oxidizes an oxidizable substance such as an organic substance attached to the workpiece X. Oxidized and decomposed to oxidize the workpiece X. That is, an oxidizable substance such as an organic substance is oxidized and decomposed into water, carbon dioxide, or the like, or eluted into the solution S and removed from the object to be processed X such as a plate, a handkerchief, a towel, or a dish. As a result, an object such as a plate, a handkerchief, a towel, or a plate is subjected to an oxidation treatment such as bleaching or decolorization. As described above, the organic matter that is difficult to separate by simply washing with water or wiping with cloth is decomposed or separated from the workpiece X, and is subjected to oxidation treatment such as bleaching or decolorization. Is given. When the process is performed until a desired state is obtained, the process ends and the workpiece X is obtained. The organic substance here is an organic substance-containing substance, and includes not only dirt but also all objects to be removed including organic substances such as ink, coating film, adhesive, and glue to be removed.

  After the oxidation treatment, the object to be treated X may be subjected to a cleaning treatment as necessary. As the cleaning liquid, for example, solution S or water can be used. If washed, there is an advantage that even if the material separated from the workpiece X by the oxidation treatment is reattached to the workpiece X, it can be removed reliably. Moreover, the solution S adhering to the to-be-processed object X is removed by drying or blowing air as needed. The blowing of air is also effective for re-removal of the oxidized material once separated. Since nitrous oxide is safe, it is not always necessary to treat nitrous oxide dissolved in the solution S after the oxidation treatment.

  By the way, it was previously described that the UV absorption spectrum of the aqueous nitrous oxide solution shows a peak in the vicinity of 190 nm. In the oxidation method and the oxidation apparatus according to the embodiment of the present invention, a thickener is contained in the nitrous oxide-containing solution. Therefore, the thickener used by dissolving in a solution is preferably one having a low property of absorbing ultraviolet light having a wavelength of around 190 nm, that is, having as low an absorbance as possible. Then, the light absorbency about the light of the predetermined wavelength of various thickeners was measured.

  In measuring the absorbance, first, a 0.1 wt% aqueous solution of each thickener was prepared. For the prepared aqueous solution, the absorbance was measured using a synthetic quartz cell (optical path length: 10 mm) and an absorptiometer (UV-1700, manufactured by Shimadzu Corporation). Since the peak of the UV absorption spectrum of the aqueous nitrous oxide solution is around 190 nm, the absorbance was measured for three wavelengths of 190 nm, 200 nm, and 210 nm. The measurement results are shown in Table 2 below.

  As a result, as shown in Table 2, from the viewpoint of not absorbing ultraviolet light and not inhibiting photodissociation, the organic thickener is preferably methylcellulose, and the inorganic thickener is laponite or hydrophilic. Sex fumed silica gel was preferred. In the absorbance measurement here, the measurement was performed with the content of the thickener constant. Even if the content is the same, the viscosity of the aqueous solution containing the thickener differs depending on the type of the thickener. Therefore, when selecting a thickener from the viewpoint of efficient photodissociation, the absorbance of each thickener per unit content as shown in Table 2 and the nitrous oxide content used A thickener may be selected in consideration of the viscosity necessary for the solution.

  The ultraviolet light emitted by the KrI excimer lamp L is highly straight, but the parts to be oxidized are compared, for example, when the workpiece X is plate-shaped and only the upper surface is to be oxidized as shown in FIG. In the case of a simple shape, it is easy to irradiate ultraviolet light, and a desired oxidation treatment can be performed.

  However, when the part to be subjected to the participation process is relatively complicated, such as when the shape of the object to be processed X is complicated, except for special cases such as the object X being a substance that transmits ultraviolet light, Due to the high linearity of the ultraviolet light, it may be difficult to irradiate the desired part with light, and the oxidation treatment may not be sufficiently performed. Even in the case where the workpiece X has a simple shape such as a plate shape as in the example shown in FIG. 10, it is not always easy to perform the oxidation treatment on the whole.

  In the example shown in FIG. 10 as well, when the workpiece X is a substance that transmits ultraviolet light from the KrI excimer lamp L, or the bottom of the container 31 is mirror-finished, and the entire workpiece to be processed X is reflected by this mirror surface. In the case of a structure that sufficiently guides light, the entire object to be processed X can be oxidized.

  However, in general, it is difficult to oxidize the entire surface of the workpiece X having a three-dimensional shape with the configuration shown in FIG. 10 without changing the state of the workpiece X. This is remarkable, for example, when the workpiece X is a substance having irregularities on the surface.

  Next, the oxidation apparatus in view of such circumstances will be described.

  Since the method for oxidizing a substance in this example can be implemented by using the hydrophilizing apparatus 40 shown in FIG. 13 as an oxidizing apparatus for the substance, the hydrophilizing apparatus 40 shown in FIG. A method for oxidizing the workpiece X will be described with reference to FIG.

  This oxidation apparatus can be applied as an oxidation apparatus for various types of workpieces X. In this example, the workpiece X was a metal or resin part provided with a flat line part, a convex part, a ridge line part, and a valley line part constituting the corner part. However, the workpiece X is not limited to this.

  In the oxidation apparatus 40 shown in FIG. 13, after the workpiece X is put into the main body 43 from the opening 42, the solution S is poured from the opening 42 to fill the main body 43. Soak. After the solution S is poured from the opening 42 to fill the main body 43, the workpiece X may be put into the main body 43 from the opening 42. The opening 42 is closed with a lid 44 in a state where the entire workpiece X is immersed.

  When the KrI excimer lamp L is caused to emit light, a plurality of KrI excimer lamps L disposed on the side and the bottom irradiate ultraviolet light from the side and below, and ultraviolet light is provided on the inner surfaces of the main body 43 and the lid 44. The entire surface of the solution S positioned on the surface of the workpiece X is irradiated with ultraviolet rays by being reflected by the mirror surface. Thereby, the oxidation treatment is performed on the workpiece X having a relatively complicated shape with irregularities on the surface.

  Nitrous oxide dissolved in the solution S in the ultraviolet irradiation region is dissociated to generate atomic oxygen (O), and this atomic oxygen strongly oxidizes and decomposes the substance to be treated X. The object to be processed X is subjected to oxidation treatment. That is, the participation target substance on the surface of the workpiece X is oxidized and decomposed into water, carbon dioxide or the like, or eluted into the solution S and removed from the workpiece X. As a result, the surface of the workpiece X is oxidized. More specifically, on the surface of the workpiece X, roughening treatment, frictional force improvement treatment, corrosion resistance treatment, anticorrosion treatment, hydrophilic treatment, fine recess formation treatment, reflectance reduction treatment, irregular reflection improvement treatment, Treatments such as adhesion prevention treatment, difficult adsorption enhancement treatment, water retention enhancement treatment, fungi removal treatment such as sterilization treatment, matting treatment, and fading treatment are performed. Moreover, the color of the surface can be changed. For example, a color change process, a decoloring process, a bleaching process, etc. can be performed. In addition, information such as characters on the surface can be subjected to oxidation treatment. For example, an erasing process for erasing information such as characters, or a description process for displaying information by making the shape of the oxidized portion a shape that allows information such as characters to be recognized, especially when the information is a symbol or the like A rendering process can be performed. In addition, a surface-coated material or the like can be a processing target. For example, it is possible to perform a removal treatment or a peeling treatment of the coated material. These variations of the oxidation treatment can be applied to the oxidation apparatus that will be described later, but will not be described in the following description.

  According to the oxidation apparatus 40, the object to be processed X that can be stored in the container 41 and immersed in the solution S in the container 41 and can be irradiated with ultraviolet light in this state can be oxidized. However, when the object to be processed X is a relatively large object, or when the surface area needs to be expanded to oxidize such as decoloring by irradiating ultraviolet rays like a cloth, In order to subject this to an oxidation treatment, it is necessary to make the container 41 extremely large, which leads to an increase in the size of the oxidizer 40.

  Next, a substance oxidation apparatus in view of such circumstances will be described.

  The substance oxidizing method in this example can be implemented by using the hydrophilizing apparatus 60 shown in FIG. 15 as the substance oxidizing apparatus. Therefore, the hydrophilizing apparatus 60 shown in FIG. A method for oxidizing the workpiece X will be described with reference to FIG.

  The object to be processed X may be any sheet as long as it can be wound by a winding mechanism, such as a plastic sheet such as a plastic film, a cloth, a sheet, a pillow, Examples include a bed cover.

  In the oxidizer 60 having such a configuration, the solution X is placed between the KrI excimer lamps L after the workpiece X is wound around the roller 62 and can be wound up by the winding mechanism. The container 61 is filled to such an extent that the workpiece X to be processed is immersed. Then, the workpiece X is fed by the winding mechanism. Then, after being immersed in the solution S, a part of the solution S supplied to the wound workpiece X is scraped off by the blade 63 as necessary, and the supply amount of the solution S is equalized. Thereafter, the workpiece X sent between the KrI excimer lamps L is oxidized by being irradiated with ultraviolet rays from the lamps.

  Then, the nitrous oxide dissolved in the solution S in the ultraviolet irradiation region is dissociated to generate atomic oxygen (O), and this atomic oxygen strongly oxidizes the substance to be processed X to be processed. Decomposition is performed, and the object X is oxidized. That is, the substance to be oxidized is oxidized and decomposed into water, carbon dioxide or the like, or eluted into the solution S and removed from the workpiece X. As described above, the substance to be treated, which is difficult to separate by simply washing with water or wiping with a cloth, is decomposed or separated from the object to be treated X and oxidized. .

  The winding speed of the workpiece X by the winding mechanism is adjusted so that the target substance is decomposed and the desired oxidation treatment is performed while the workpiece X moves between the KrI excimer lamps L. . When the winding of the workpiece X by the winding mechanism is finished, the oxidation treatment is finished, and the workpiece X subjected to the oxidation treatment is obtained. For example, when the object to be processed X is a sheet or the like used in a hospital or the like, body fluid such as blood, stains such as sweat, and dirt are decolored or removed by an oxidation process, and a clean state is obtained.

  The moving means for moving the object to be processed X may be configured to include a transporting member such as a belt for moving the object to be processed X in a manner in which the object to be processed X is placed or fixed, instead of the winding mechanism described above. With such a configuration, the workpiece X is not limited to a sheet shape, and a relatively large article can be oxidized as the workpiece X. According to this configuration, the plurality of workpieces X can be continuously oxidized while being transported by the transport member. In order to oxidize the entire object to be processed X while being transported by such a transporting member, the position and shape of the transporting member, the use of a material that transmits ultraviolet rays, the position and number of KrI excimer lamps L are appropriately selected. it can.

  In addition, in the case of using the nitrous oxide-containing viscous solution as the solution S as in the oxidation apparatus of this embodiment, the supply amount of the solution S supplied to the workpiece X can be equalized while reducing the amount supplied. Since it is easy, it can be said that it is suitable as a method and apparatus for performing oxidation treatment only on the surface layer of the workpiece X. Further, the nitrous oxide-containing viscous solution may be reused by providing a collecting means such as a receiving tray for recovering the nitrous oxide-containing viscous solution removed by the reduction or equalization. Thereby, efficient utilization of a nitrous oxide-containing viscous solution is possible.

  In such an oxidizer 60, the object to be processed X is a relatively large object, or a substance that needs to be expanded to oxidize by being irradiated with ultraviolet rays like a cloth. However, the size of the container 61 is not greatly affected by the workpiece X, and the increase in size is suppressed. Further, the object to be treated X that can be easily transported and immersed in the solution S inside the container 61 and can be irradiated with ultraviolet light in this state can be oxidized.

  Next, an oxidation apparatus suitable for the case where the workpiece X is not easily transportable such as a desk, a floor, or a wall will be described.

  The substance oxidizing method in this example can be implemented by using the hydrophilizing apparatus 70 shown in FIG. 16 as the substance oxidizing apparatus. Therefore, the hydrophilizing apparatus 70 shown in FIG. A method for oxidizing the workpiece X will be described with reference to FIG.

  In the oxidizer 70 shown in FIG. 16, the container 71 is brought into close contact with the portion to be oxidized of the object by using the elasticity of the rubber 76, and the object to be processed, the container body 74, and the glass 75 are sealed. After forming the space, the suction pump is operated to fill the sealed space with the solution S. In this state, the KrI excimer lamp L emits light, and ultraviolet light is irradiated to the solution S located on the site where the object to be processed is to be oxidized.

  Nitrous oxide dissolved in the solution S in the ultraviolet irradiation region is dissociated to generate atomic oxygen (O), and this atomic oxygen strongly oxidizes and decomposes the substance to be treated, An oxidation treatment is performed on the workpiece. That is, the substance to be oxidized is oxidized and decomposed into water, carbon dioxide or the like, or eluted into the solution S and removed. As a result, for example, the color generated on the wall due to stains, dirt, mold, graffiti, etc. is removed. In addition, since nitrous oxide is consumed during the oxidation process, the solution S in the sealed space may be replaced by appropriately driving the suction pump.

  Concentration detection means for detecting the concentration of nitrous oxide in the solution S in the sealed space, and the suction pump is driven when the nitrous oxide concentration detected by the concentration detection means falls below a predetermined concentration suitable for oxidation And a control means that performs the feedback control to keep the concentration of the nitrous oxide of the solution S in the sealed space in a range suitable for oxidation.

  When the desired oxidation is performed, the oxidation is terminated and an oxidized object to be processed is obtained. After the oxidation, the supply pipe 72 is removed from the solution storage unit or the container 71, and the solution S is not supplied from the solution storage unit to the container 71. The solution S is discharged to the waste liquid storage unit, and the container 71 is detached from the object to be processed.

  By such oxidation, desired oxidation of a workpiece such as a desk top, a floor, or a wall, which is mainly difficult to transport, is performed. Since nitrous oxide is safe, it is not always necessary to treat nitrous oxide dissolved in the solution S discharged to the waste liquid storage unit.

  When the tight contact state between the container 71 and the object to be processed is maintained and the leakage of the solution S does not become a problem, the oxidation of the oxidizer 70, particularly the container 71, may be performed while moving. Since the time for discharging the solution S before the container 71 is moved becomes unnecessary and the oxidation can be performed continuously, the oxidation can be performed efficiently.

  When the container 71 and the object to be processed are in close contact with each other, the ultraviolet light is prevented from leaking from the sealed space, and the influence of the ultraviolet light on the outside can be avoided. In the example shown in FIG. 13, since the inside of the container 41 is sealed, the influence due to leakage of ultraviolet light to the outside is avoided.

  Moreover, when the solution S used is a nitrous oxide-containing viscous solution as in the oxidation apparatus of this embodiment, leakage of the solution S is more reliably prevented.

  Considering that nitrous oxide is consumed in the course of the oxidation treatment as in the oxidation apparatus 70, configuring the solution S to be replaceable is extremely excellent in exhibiting high oxidation performance. Even if the concentration of nitrous oxide in the solution S is lowered, sufficient oxidation performance can be ensured. Also in the configuration examples shown in FIGS. 10, 13, and 14 described above, the solution S can be configured to be exchangeable during the oxidation process.

  In addition, the oxidizer 70 shown in FIG. 16 can also be said to perform a patterned process when it is used to oxidize part of the surface of the object to be processed.

  The oxidizer 70 shown in FIG. 16 is intended for an object to be processed that is mainly difficult to transport, such as a desk top, a floor, or a wall. Such an oxidizer 70 is suitable for performing an oxidation process on a relatively large portion. On the other hand, it may be required to oxidize a relatively small portion in a spot manner.

  Next, the oxidation apparatus in view of such circumstances will be described.

  The substance oxidizing method in this example can be carried out by using the hydrophilizing apparatus 90 shown in FIG. 18 as the substance oxidizing apparatus. Therefore, the hydrophilizing apparatus 90 shown in FIG. A method for oxidizing the workpiece X will be described with reference to FIG.

  In the oxidizer 90 shown in FIG. 18, the user holds the grip 93 and directs the injection port 94 toward the object to be processed such as teeth, operates the trigger, and jets an appropriate amount of the solution S onto the object to be processed. At the same time, the KrI excimer lamp L emits light and is irradiated with ultraviolet rays. The attachment range of the solution S on the object to be processed is easily set to an appropriate state by the user adjusting the position of the nozzle portion 92, the emission direction of the solution S, and the aperture.

  Nitrous oxide dissolved in the solution S in the ultraviolet irradiation region is dissociated to generate atomic oxygen (O), and this atomic oxygen strongly oxidizes and decomposes the substance to be treated, For example, decolorization of the workpiece is performed. That is, the substance to be oxidized is oxidized and decomposed into water, carbon dioxide, or the like, or eluted into the solution S, and the tooth or the like, which is the object to be processed, is oxidized. As a result, for example, the tooth color is bleached and bleaching is performed, and it is possible to meet the demand for whitening the teeth, which is important for beauty. The ejection amount of the solution S is adjusted according to the amount of nitrous oxide consumed in the oxidation process.

  The oxidation apparatus 90 is an apparatus suitable for the case where the oxidation treatment is performed by attaching the solution S to only necessary portions. Since the amount of consumption of the solution S is small and the oxidation is performed while the solution S is substantially exchanged, even if the concentration of nitrous oxide in the solution S is lowered, sufficient oxidation performance can be ensured. It is. Further, since the ultraviolet light is irradiated only in the jetting direction of the solution S, it is possible to irradiate only the necessary part with the ultraviolet light, and the influence of irradiating the other part with the ultraviolet light is avoided. The oxidation apparatus 90 can also be said to perform patterned oxidation when it is used to oxidize part of the object to be processed. For example, when the object to be processed is a sheet like the object X to be processed in the oxidation apparatus 60, the upper surface, the floor, the wall, or the like of the desk is similar to the object X to be processed in the oxidation apparatus 70.

  Here, the mode of contact of the solution S with the workpiece X during irradiation with ultraviolet light will be described. The above-described oxidation apparatuses 30, 40, and 60 immerse the workpiece X in the solution S. In addition, the above-described oxidizers 70 and 90 wet the portion to be oxidized of the object to be treated with the solution S. Regarding the latter contact mode, the oxidation device 90 is configured to wet the portion to be oxidized of the workpiece X by the solution S by jetting the solution S. However, as the jet mode, the oxidation device 90 may be used. As described above, the solution S is not limited to be continuously adhered to the oxide, but may be a solution in which the solution S is ejected in a mist state to adhere to the oxide.

  Further, if the solution S is a nitrous oxide-containing viscous solution, when the solution S is attached to the surface of the workpiece X by the jetting means, the solution S may be attached to the portion to be oxidized in a state where it is difficult to flow down. it can. Further, since the ejection is used, even when the portion to be oxidized exists at a position where it is difficult to supply the solution S by immersion, the solution S can be attached to the portion to be oxidized. Therefore, the oxidation apparatus of this embodiment and the oxidation method used in the apparatus are, for example, an object to be oxidized in a position where an oxidation target part exists on an inclined surface or a vertical surface, or a position where the solution S is difficult to be supplied. It can be said that this is suitable as an apparatus and method for oxidizing the workpiece X having a portion.

  In addition, when the ultraviolet light source and the part to be processed are in the atmosphere, the place where the viscous solution is not applied is oxidized by ozone generated in the atmosphere. Therefore, in lamps other than the KrI excimer lamp, The portion where the generated ozone is in direct contact, that is, the portion where the viscous liquid is not applied, may undergo oxidation. However, if a KrI excimer lamp is used, the generation of ozone is less, so the viscous solution Depending on the presence or absence of coating, an oxidation treatment in which an oxidized portion and a non-oxidized portion are clearly separated can be performed. Therefore, the oxidation method and the oxidation apparatus of the present embodiment and the oxidation method and the oxidation apparatus described below are suitable as a method of applying the solution only to a portion where the oxidation treatment is desired and performing the oxidation treatment only on the portion. .

  As described above, the oxidizer shown in FIG. 18 uses the ejection means as the means for supplying the solution S, but the supply means may be an application means as described below.

  FIG. 25 shows an oxidizer having a brush 160 as an applicator for applying the solution S and a KrI excimer lamp L for irradiating ultraviolet rays toward the surface of the workpiece X. Here, the brush 160 is a solution supply means for bringing the solution S into contact with the workpiece X. Thus, the oxidation apparatus using an applicator such as the brush 160 is suitable as an oxidation apparatus that performs an oxidation treatment on the surface of the workpiece X. The structure for supporting the brush 160 and the mechanism for moving the brush are omitted here.

  The KrI excimer lamp L is configured to irradiate ultraviolet light toward the surface on which the solution S of the workpiece X is applied. In order to uniformly irradiate the solution application surface with ultraviolet light, the irradiation direction of the KrI excimer lamp L is more preferably orthogonal to the surface to which the solution S is applied.

  In the oxidation apparatus having such a configuration, after supplying the solution S to the brush 160, the solution S is applied to the oxidized portion of the workpiece X with the brush 160. Thereafter, the KrI excimer lamp L is caused to emit light, and the oxidized portion of the workpiece X is irradiated with ultraviolet light. An oxidation process is performed on the portion to be oxidized to which the solution S is applied, and a process such as decolorization is performed. Note that the mechanism for the oxidation treatment has already been described and is omitted here.

  Although various things can be considered as to-be-processed object X, a board | plate material can be mentioned, for example. It is conceivable that the surface of the plate material is subjected to an oxidation treatment to be bleached or decolorized.

  Further, the solution S applied by the brush 160 includes a thickener and has a higher viscosity than that not included. Therefore, the applied solution S has a property of staying at the applied position or a property of being easily retained. When the solution S having such characteristics is used, the application region and the non-application region can be clearly distinguished. Therefore, it can apply | coat so that an application | coating area | region may be made into a specific shape, or the shape which shows information, such as a character. After applying in this way, when the applied region is irradiated with ultraviolet light, the applied region is oxidized. For example, in the case of decoloring processing, the specific shape and character information become obvious. In addition, when characters or figures are described with materials containing organic substances such as ink, the solution S is applied to the portions such as characters, and then the ink is oxidized by irradiation with ultraviolet light. be able to. If this is a decoloring process, information such as characters and figures can be erased.

  Further, the supply means for the solution S may be, for example, a printing means in addition to a spraying means or a coating means such as a brush.

  FIG. 26 includes a print unit 161 that applies the solution S by the offset printing method, and a KrI excimer lamp L that irradiates the surface of the workpiece X with ultraviolet rays. The KrI excimer lamp L is the same as the oxidizer described with reference to FIG.

  The print unit 161 uses an offset printing method sometimes referred to as so-called lithographic printing, and includes a roll 162 for attaching a lithographic plate used in the offset printing method, and a plate 163 attached to the roll 162. Have Note that the offset printing method used in the print unit 161 is a method widely used as a printing machine, and therefore detailed description of the structure is omitted here.

  The solution S containing nitrous oxide used in the oxidation apparatus of this embodiment is basically an aqueous solution. Therefore, if the solution is to be applied to the entire portion to be oxidized of the object to be treated, a plate having a hydrophilic treatment applied to the corresponding portion is used, and the solution is supplied to the portion to which the hydrophilic treatment has been applied. Thus, the solution S can be supplied from the plate to the portion to be oxidized. Further, when the solution S containing the thickener is hydrophobic and oleophilic in comparison with water, the shape of the solution application region is changed by replacing the ink in a normal printing machine with the solution. The solution can be applied in an arbitrary pattern shape. For example, such a case is conceivable when the thickener contained in the solution S is an organic thickener.

  In the oxidation apparatus having such a configuration, the solution S is supplied to the solution benefit unit 163a of the plate 163 of the print unit 161, and the plate 163 is pressed against the workpiece X such as a plate material. Then, the solution S is applied in a predetermined pattern from the plate 163 toward the workpiece X. Thereafter, the KrI excimer lamp L is caused to emit light, and the workpiece X is irradiated with ultraviolet light. Then, an oxidation process is performed on the portion to be oxidized to which the solution S is applied, and an oxidation process such as decolorization is performed.

  Note that the mechanism for the oxidation treatment has already been described and is omitted here. As described above, various materials such as a thin film such as a film can be considered as the workpiece X other than paper. Moreover, the solution used in this embodiment is a highly viscous solution containing a thickener and has a property of staying at the applied position. The usage mode suitable for such a case is as described above. Therefore, the description thereof is omitted here. Note that the method of supplying the solution S by a printing method is suitable as a method of supplying a small amount of solution, but the oxidation apparatus of the present embodiment and the method used in the apparatus use a lithographic plate, It is particularly suitable as a method for applying a small amount of solution S.

  Further, according to the offset printing type solution supply means used in the present embodiment, a precise coating pattern can be realized, so that the solution S can be applied to an area corresponding to graphic or character information. Also, the printing method solution supply means is suitable as a means for supplying a relatively small amount of solution, and it is easy to adjust the supply amount, and is suitable for a case where a small amount of solution is to be applied evenly over the entire oxidized region. In addition, it is suitable as a method for continuously applying to a band-like portion to be oxidized at a high speed, and is suitable as an apparatus for performing an oxidation treatment on a thin object such as paper or film.

  When the printing method solution supply means is used in the oxidation apparatus, the printing unit may use a printing method other than the offset printing method.

  FIG. 27 includes a print unit 164 that applies the solution S by a relief printing method, and a KrI excimer lamp L that irradiates ultraviolet rays toward the surface of the workpiece X. The KrI excimer lamp L is the same as the oxidizer described with reference to FIG.

  This printing unit 164 uses a relief printing method also called so-called letterpress printing, and has a roll 165 for attaching a relief plate used in the relief printing method, and a relief plate 166 attached to the roll 165. Note that the relief printing method used in the print unit 164 is a method widely used as a printing machine, and therefore, detailed description of the structure is omitted here. Since the structure other than this is the same as that of the oxidation apparatus using the offset printing type print unit 164, the same components are denoted by the same reference numerals, and the description thereof is omitted.

  In the oxidizer having such a configuration, the solution S is supplied to the convex portion 166a of the relief plate 166 of the print unit 164, and the relief plate 166 is pressed against the workpiece X such as a plate material. Then, the solution S is applied in a predetermined pattern from the relief plate 166 toward the workpiece X. Thereafter, the KrI excimer lamp L is caused to emit light, and the workpiece X is irradiated with ultraviolet light. Then, an oxidation process is performed on the portion to be oxidized to which the solution S is applied, and an oxidation process such as decolorization is performed.

  Note that the mechanism for the oxidation treatment has already been described and is omitted here. In addition, when the solution has a property of staying at the position where the solution is applied, it is as described above that there are various suitable usage modes, and thus description thereof is omitted here. However, the oxidation apparatus of the present embodiment and the method used in the apparatus use a relief plate, and when supplying the solution S to the oxidation target portion by coating, applying pressure to the solution supply portion. It is suitable as a method for supplying the solution S. Therefore, it is suitable for a case where a small amount of the solution S is pressed into not only the surface but also the inside of the workpiece X.

  The effect obtained when using the printing solution supply means, such as the ability to realize a precise coating pattern, has already been described in the description of the oxidation apparatus using the offset printing method solution supply means. A description of the points is omitted here.

  FIG. 28 includes a print unit 167 that applies the solution S by an intaglio printing method and a KrI excimer lamp L that irradiates the surface of the workpiece X with ultraviolet rays. The KrI excimer lamp L is the same as the oxidizer described with reference to FIG.

  This print unit 167 uses an intaglio printing method also called so-called gravure printing, and has a roll 168 for attaching an intaglio used in the intaglio printing method, and an intaglio 169 attached to the roll 168. Since the intaglio printing method used in the print unit 167 is a method widely used as a printing machine, the detailed description of the structure is omitted here. Since the structure other than this is the same as that of the oxidation apparatus using the offset printing type print unit, the same components are denoted by the same reference numerals, and the description thereof is omitted.

  In the oxidation apparatus having such a configuration, the solution S is supplied to the recess 169a of the intaglio 169 of the print unit 167, and the intaglio 169 is pressed against the workpiece X such as a plate material. Then, the solution S is applied in a predetermined pattern from the intaglio 169 to the plate material that is the workpiece X. Thereafter, the KrI excimer lamp L is caused to emit light, and the workpiece X is irradiated with ultraviolet light. Then, an oxidation process is performed on the portion to be oxidized to which the solution S is applied, and an oxidation process such as decolorization is performed.

  Note that the mechanism for the oxidation treatment has already been described and is omitted here. In addition, when the solution has a property of staying at the position where the solution is applied, it is as described above that there are various suitable usage modes, and thus description thereof is omitted here. However, since the oxidation apparatus of the present embodiment and the method used in the apparatus use the intaglio 169, the intaglio is basically suitable as a method for supplying a small amount of the solution S. The solution S filled in the concave portion 169a of 169 is supplied to the workpiece X. Therefore, a larger amount of the solution S can be supplied as compared with the above oxidation apparatus in which the solution supply means uses a lithographic plate or a relief plate. Therefore, the oxidation apparatus of this embodiment and the oxidation method used in the apparatus are suitable as a method for supplying a relatively large amount of the solution S among the printing methods.

  The effect obtained when using the printing solution supply means, such as the ability to realize a precise coating pattern, has already been described in the description of the oxidation apparatus using the offset printing method solution supply means. A description of the points is omitted here.

  FIG. 29 includes a print unit 170 that applies the solution S by stencil printing and a KrI excimer lamp L that irradiates ultraviolet rays toward the surface of the workpiece X. The KrI excimer lamp L is the same as the oxidizer described with reference to FIG.

  This printing unit 170 uses a stencil printing method also called screen printing or lithographic printing. Both end support members 172 and 172 for fixing the cylindrical stencil 171 used in the stencil printing method and the both end support A stencil 171 attached to the members 172 and 172 and a squeegee 173 for supplying the solution S to the stencil 171 are provided. Since the stencil printing method used in the printing unit 170 is a method widely used as a printing machine, the detailed description of the structure is omitted here. Briefly, in stencil printing, since it is necessary to supply the solution S to the inside of the cylindrical stencil 171, a solution supply window 172a communicating with the inside of the stencil 171 is formed on both end support members 172 and 172. ing. Further, the squeegee 173 in the stencil 171 is directly fixed to the arm 174 that supports the both end support members 172 and 172 via a fixture (not shown), and is fixed in a rotating state even if the stencil 171 rotates. Yes. The rotating means of the stencil 171 is not shown. Since the structure other than this is the same as that of the oxidation apparatus using the offset printing type print unit, the same components are denoted by the same reference numerals, and the description thereof is omitted.

  In the oxidation apparatus having such a configuration, the solution S is supplied to the inside of the cylindrical stencil 171 of the print unit 170 and the stencil 171 is pressed against the workpiece X such as a plate material. Then, the solution S is applied to the object to be processed from the stencil 171 in a predetermined pattern. Thereafter, the KrI excimer lamp L is caused to emit light, and the oxidized portion of the workpiece X is irradiated with ultraviolet light. Then, an oxidation process is performed on the portion to be oxidized to which the solution S is applied, and an oxidation process such as decolorization is performed.

  Note that the mechanism for the oxidation treatment has already been described and is omitted here. In addition, when the solution has a property of staying at the position where the solution is applied, it is as described above that there are various suitable usage modes, and thus description thereof is omitted here. However, since the oxidation apparatus of the present embodiment and the method used in the apparatus use a stencil, although it is basically suitable as a method for supplying a small amount of the solution S, The solution S filled in the holes is supplied to the object to be processed. Therefore, a larger amount of the solution S can be supplied as compared with the above oxidation apparatus in which the solution supply means uses a lithographic plate or a relief plate. Therefore, the oxidation apparatus of this embodiment and the oxidation method used in the apparatus are suitable as a method for supplying a relatively large amount of the solution S among the printing methods. Furthermore, compared with the solution supply means using an intaglio, the solution supply means using a stencil has the advantage that it is easier to supply a small amount of solution.

  The effect obtained when using the printing solution supply means, such as the ability to realize a precise coating pattern, has already been described in the description of the oxidation apparatus using the offset printing method solution supply means. A description of the points is omitted here.

  As described above, the embodiments of various oxidation methods and oxidation apparatuses have been described. However, by adding the following steps and means to each oxidation method and oxidation apparatus, higher quality oxidation treatment can be performed.

  For example, after the oxidation treatment, that is, after completion of the ultraviolet irradiation, a cleaning means such as a showering device for cleaning the workpiece X with the solution S, water, or the like may be provided as necessary. You may provide drying means, such as a dryer which dries the solution S adhering to the to-be-processed object X as needed. A cleaning means such as an air jet that cleans the surface of the workpiece X by blowing air or the like may be provided. Foreign matter such as that generated by oxidation treatment may adhere to or remain on the surface of the workpiece X. By performing such treatment, foreign matter can be removed.

  More specifically, the oxidation apparatus shown in FIG. 15 may include a dryer that dries the workpiece X in a state of being wound by the winding mechanism. In addition, the oxidizer 90 shown in FIG. 18 may use a jetting unit that jets the solution S to the portion to be oxidized as a cleaning unit. In the oxidation apparatus 90, the solution can be spot-sprayed only at the site while observing the state of the re-adhesion of the substance to be oxidized on the portion to be oxidized, so that the portion to be oxidized can be cleaned very easily.

  When it is necessary to hold the workpiece X to be contacted with the solution and to be irradiated with ultraviolet rays, the holding member appropriately selected the shape, position, and material that transmits the ultraviolet light that does not affect the irradiation with ultraviolet light. May be provided. The holding member can be omitted when the specific gravity of the object to be processed and the specific gravity of the solution S are substantially equal and the object to be processed is in a state of floating in the solution. Therefore, the adjusting agent for adjusting the specific gravity of the solution S can be dissolved in the solution S.

  You may provide the solution adjustment means like the said blade 63 which adjusts the quantity of the solution S supplied to the to-be-oxidized part of the to-be-processed object. By adjusting the amount of the solution by the solution adjusting means, the supply amount of the solution S can be made uniform or the supply amount can be reduced for the entire oxidized portion.

  In Examples 1 to 6 described above, when an object to be processed is oxidized using an aqueous solution in which nitrous oxide is dissolved, ultraviolet light is applied after the aqueous solution is sufficiently adhered to the object to be processed. Irradiation is necessary. However, when the physical property of the object to be processed is hydrophobic, the aqueous solution may not be sufficiently attached to the object to be processed. For example, when the object to be processed is a cleaned surface of fluorine such as a silicon wafer, even if an aqueous solution in which nitrous oxide is dissolved is attached to the surface of the silicon wafer by spraying or spin coating, the aqueous solution will be repelled. This causes the problem that the oxidation reaction does not proceed.

  Therefore, from the viewpoint of improving the adhesion of the nitrous oxide solution to the object to be treated, an organic solvent having high wettability may be used as a solvent for dissolving nitrous oxide. Thereby, efficient oxidation treatment is enabled for the hydrophobic object to be treated. In addition, a substance whose surface is oxidized can be provided at a low cost.

  In this example, as an organic solvent for dissolving nitrous oxide, hexane, cyclohexane, methylhydrogen polysiloxane, cyclic dimethylsiloxane, tetramethylorthosilicate, perfluoropolyether, perfluorohexane, trimethyl phosphate, triethyl phosphate, An organic solvent containing at least one of tributyl phosphate is used.

Since these organic solvents have high wettability to hydrophobic objects, atomic oxygen (O) generated by decomposition of nitrous oxide (N ₂ O) by irradiation with ultraviolet light is efficiently treated. React with things. Therefore, the surface of the hydrophobic object can be efficiently oxidized.

  For example, (1) silicon wafer with a natural oxide film of about 10 mm and (2) silicon wafer from which the natural oxide film has been removed with dilute hydrofluoric acid (contact angle measurement device, Kyowa Interface Science Co., Ltd.) As a result of using the Contact-Angle meter CA-D type) (1) The contact angle of a silicon wafer with a natural oxide film of about 10 mm is 20.0 °, and (2) the natural oxide film is diluted with The contact angle of the silicon wafer removed with acid was measured to be 74.7 °, and it was determined that the substance (1) was hydrophilic and the substance (2) was hydrophobic.

  The contact angle is measured by dropping a solution droplet on a solid surface and measuring the angle between the end of the droplet and the solid surface. The more wet the substance is, the smaller the droplet becomes and the smaller the contact angle. In addition, as the substance is harder to wet, the droplet has a shape closer to a sphere and the contact angle becomes larger.

  For example, when the same contact angle was measured using 1,4-butane sultone, the contact angle of the substance (1) was 8.1 °, and the contact angle of the substance (2) was 17.6 °. It was done. As described above, it was confirmed that the wettability was improved for the silicon wafer (2), which was determined to be hydrophobic, from which the natural oxide film was removed with dilute hydrofluoric acid.

  Furthermore, as an organic solvent other than 1,4-butane sultone, an attempt was made to measure the contact angle for perfluorohexane, tetramethyl orthosilicate, methyl hydrogen polysiloxane, dimethyl sulfate, trimethyl phosphate, and tributyl phosphate. Both the substance of (1) and the substance of (2) will spread thinly and spread on the surface as soon as the droplet is dropped, so the contact angle is too small and the contact angle value It was not possible to actually measure.

  These solutions show that the wettability is good for (1) a silicon wafer having a natural oxide film of about 10 cm and (2) a silicon wafer from which the natural oxide film has been removed with dilute hydrofluoric acid.

  Therefore, nitrous oxide is dissolved in these organic solvents with good wettability, this solution is kept in contact with the object to be treated, and the solution is efficiently irradiated by irradiating the solution with ultraviolet light in that state. It is thought that things can be oxidized.

  FIG. 30 is a chart comparing the transmittance (% T) of ultraviolet light (wavelength 191 nm to 240 nm) of water and air with each organic solvent.

  Since the organic solvent shown in FIG. 30 has a relatively high transmittance of ultraviolet light having a shorter wavelength than 240 nm, nitrous oxide can absorb most of the irradiated ultraviolet light. Therefore, since nitrous oxide is easily decomposed, the oxidation reaction of the object to be processed can be performed with high efficiency.

Furthermore, by using a solvent that is not easily decomposed by atomic oxygen (O) generated when nitrous oxide is irradiated with ultraviolet light, the object to be treated can be oxidized efficiently. Examples of organic solvents that are hardly decomposed by atomic oxygen (O) include, for example, a fluorine compound having a strong bonding force between carbon and fluorine, a silicon compound in which silicon is already bonded to oxygen, a sulfur compound for the same reason, The phosphoric acid condensate of a phosphorus compound etc. can be mentioned.
The dissolution ratio of nitrous oxide in these organic solvents may be several thousand ppm or more.

The characteristics of the oxidation reaction performed by irradiating the nitrous oxide solution with ultraviolet light are as described above.
Hereinafter, embodiments of the present invention having such characteristics will be described with reference to the drawings.

  Since the treatment method oxidation method in this example can be implemented by using the hydrophilization apparatus 30 shown in FIG. 10 as the treatment object oxidation apparatus, the hydrophilic treatment apparatus 30 shown in FIG. The method for oxidizing the workpiece X will be described with reference to FIG.

  The object to be processed X in the present embodiment is hydrophobic and is, for example, a silicon wafer obtained by removing the natural oxide film with dilute hydrofluoric acid as described above, but may be another substrate, It may be other than such a substrate. Further, the workpiece X has a relatively simple shape such as a flat plate shape.

  The solution S is an organic solution using an organic solvent as a nitrous oxide solvent, and nitrous oxide is dissolved in the solution S at a concentration of several thousand ppm. The solution S is at least one of hexane, cyclohexane, methylhydrogen polysiloxane, cyclic dimethylsiloxane, tetramethylorthosilicate, perfluoropolyether, perfluorohexane, trimethyl phosphate, triethyl phosphate, and tributyl phosphate. Nitrous oxide is dissolved in an organic solvent with high wettability containing water.

  In the oxidation apparatus 30 shown in FIG. 10, first, the workpiece X is placed on the protrusion 31a in the container 31, and then the solution S is a portion where the workpiece X should be oxidized, here shown in FIG. It is dropped so that the whole upper surface in the state gets wet. The solution S is hydrophobic, but is made of an organic solvent. Therefore, the solution X wets the treatment X well, adheres uniformly to the entire upper surface, and is applied. Although FIG. 10 shows a state in which the entire workpiece X is immersed, the workpiece X does not necessarily have to be immersed. Next, in this state, the KrI excimer lamp L emits light, and the solution S on the upper surface of the workpiece X is irradiated with ultraviolet light.

  Nitrous oxide dissolved in the solution S in the ultraviolet light irradiation region is dissociated to generate atomic oxygen (O), and this atomic oxygen strongly oxidizes the workpiece X, Oxidation takes place. When the object to be processed X is a silicon wafer, an oxidation process is performed on the surface of the substrate, for example, an oxide film is formed on the surface. Since the surface of the workpiece X is well wetted by the solution S, the oxidation treatment is performed well. After oxidation, the solution S adhering to the workpiece X is dried and removed as necessary. Further, the solution S may be removed by blowing air. Since nitrous oxide is safe, it is not always necessary to treat nitrous oxide dissolved in the solution S after oxidation.

  Since the ultraviolet light emitted from the KrI excimer lamp L has high straightness, the part to be oxidized is relatively simple, for example, when the workpiece X is plate-shaped as shown in FIG. In the case of a shape, it is easy to irradiate ultraviolet light, and oxidation can be performed in a desired range and thickness.

  The oxidizer 30 consumes nitrous oxide during the oxidation process. Considering this, by configuring the solution S to be replaceable, higher oxidation performance can be exhibited. Even when the concentration of nitrous oxide in the solution S is set low, sufficient oxidation performance can be ensured. Also in the configuration example shown in FIG. 10 described above, the solution S can be configured to be exchangeable during the oxidation process.

  For example, FIG. 31 shows an oxidizer configured such that the solution S can be exchanged in the course of oxidation. FIG. 31 has a mask 89 as a shielding means integrally provided in a detachable manner at the lower part of the KrI excimer lamp L in FIG. 17, and FIG. 17 except that the mask 89 is provided. It is the same composition as. The oxidizer 80 corresponds to the oxidizer 30 shown in FIG.

  The mask 89 is located between the KrI excimer lamp L and the workpiece X, and blocks a predetermined portion of the ultraviolet light emitted by the KrI excimer lamp L using a light shielding material such as a chromium film. The pattern 89a is configured as described above.

  In contrast to the oxidizer 30 shown in FIG. 10, the oxidizer 80 shown in FIG. 31 has a configuration in which the solution S can be exchanged by including the solution control means 83. By providing it, it is possible to perform patterned oxidation.

  In the oxidizer 80 configured as described above, the workpiece X is held by the holding member 82 and placed in the container 31, and then the liquid supply valve 87 is opened to fill the container 81 with the solution S in the tank 86. . At this time, the solution S is dropped so that the entire upper surface of the workpiece X is wet. The solution S is hydrophobic, but is made of an organic solvent. Therefore, the solution X wets the treatment X well, adheres uniformly to the entire upper surface, and is applied. Although FIG. 10 shows a state in which the entire workpiece X is immersed, the workpiece X does not necessarily have to be immersed. Next, the KrI excimer lamp L is caused to emit light, and ultraviolet light is irradiated toward the workpiece X. The irradiated ultraviolet light is partially blocked by the pattern 89a when passing through the mask 89, and the transmitted ultraviolet light is applied to the solution S on the upper surface of the workpiece X.

  Nitrous oxide dissolved in the solution S in the ultraviolet light irradiation region is dissociated to generate atomic oxygen (O). This atomic oxygen strongly oxidizes the workpiece X, and the workpiece X Is oxidized. When the object to be processed X is a silicon wafer, an oxidation process is performed on the surface of the substrate, for example, an oxide film is formed on the surface. Since the surface of the workpiece X is well wetted by the solution S, the oxidation treatment is performed well. Since the diffusion distance of atomic oxygen is extremely small, the surface of the workpiece X irradiated with ultraviolet light is oxidized, but atomic oxygen cannot move to the region where the ultraviolet light is blocked by the mask 89. Therefore, oxidation with atomic oxygen is not performed in a region where ultraviolet light is blocked by the mask 89. In this manner, when the workpiece X is a substrate such as a silicon wafer, an oxide film having a desired pattern is formed.

  Since nitrous oxide is consumed during the oxidation process, the liquid supply valve 87 and the waste liquid valve 88 are appropriately opened and closed to replace the solution S in the sealed space, and the amount and concentration of nitrous oxide in the solution S in the container 81 Is controlled within a range suitable for oxidation.

  At this time, concentration detecting means for detecting the concentration of nitrous oxide in the solution S in the container 81, and supply when the nitrous oxide concentration detected by the concentration detecting means falls below a predetermined concentration suitable for oxidation. A control means for driving the liquid valve 87 and the waste liquid valve 88 is provided in the solution control means 83, and feedback control is performed to keep the amount and concentration of nitrous oxide in the container 81 in a range suitable for oxidation. Can do. In this case, in order to keep the concentration of nitrous oxide in the solution S in the container 81 within a range suitable for oxidation, the liquid supply valve 87 and the waste liquid valve 88 are appropriately opened and closed by the control means so that the flow rates thereof are appropriate. Take control.

  When the desired oxidation is completed, the solution S adhering to the workpiece X is removed by drying or blowing air as necessary. The solution S in the container 81 is appropriately discharged by opening the waste liquid valve 88 to the waste liquid storage unit.

  By such oxidation, desired oxidation of the surface of the workpiece X is performed. Since nitrous oxide is safe, it is not always necessary to treat nitrous oxide dissolved in the solution S after oxidation. Even if the concentration of nitrous oxide in the solution S is lowered, sufficient oxidation performance can be ensured.

  In order to perform patterned oxidation, instead of using the mask 89, the solution S is attached to the object to be processed X in a desired pattern using a printing technique or the like, and ultraviolet light is applied to the solution in the object X. You may make it irradiate to the adhesion site | part of S. In this case, by using a solution obtained by dissolving nitrous oxide in an organic solvent having high wettability as the solution S, it is possible to effectively oxidize a hydrophobic object.

  Next, an embodiment of an oxidizer used for spot-oxidizing a small portion of an object to be processed will be described.

  Since the method for oxidizing the object to be processed in this example can be implemented by using the hydrophilizing apparatus 90 shown in FIG. 18 as the apparatus for oxidizing the object to be processed, the hydrophilizing apparatus 90 shown in FIG. The method for oxidizing the workpiece X will be described with reference to FIG.

  The oxidizer 90 is intended for a hydrophobic object that is mainly required to be partially oxidized.

  In the oxidizer 90 configured as shown in FIG. 18, the user holds the grip 93 and directs the injection port 94 toward the workpiece, operates the trigger, and sprays an appropriate amount of the solution S onto the workpiece. At the same time, the KrI excimer lamp L is caused to emit light and is irradiated with ultraviolet light. The adhesion range of the solution S on the object to be processed can be easily set to an appropriate state by the user adjusting the position of the nozzle portion 92, the injection direction of the solution S, and the restriction. By using an organic solvent having high wettability as the solvent of the solution S, the solution S can be satisfactorily adhered even to the treatment object having hydrophobicity, and the oxidation treatment of the treatment object can be effectively performed. it can. That is, the solution S is hydrophobic, but is made of an organic solvent. Therefore, the solution S is wetted satisfactorily and adheres uniformly to the desired portion and is applied.

  Nitrous oxide dissolved in the solution S in the ultraviolet light irradiation region is dissociated by irradiation with ultraviolet light to generate atomic oxygen (O). The object to be processed can be oxidized by the atomic oxygen. Since the surface of the workpiece X is well wetted by the solution S, the oxidation treatment is performed well. Further, the injection amount of the solution S may be adjusted according to the amount of nitrous oxide consumed in the oxidation process. When the desired oxidation treatment is completed, the solution S adhering to the object to be treated is removed or dried by blowing air as necessary.

  As described above, a relatively small portion can be oxidized as necessary by applying an appropriate amount of the solution S to the necessary portion of the object to be treated by spraying and irradiating with ultraviolet light. Since the amount of consumption of the solution S is small and the oxidation is performed while the solution S is substantially exchanged, even if the concentration of nitrous oxide in the solution S is lowered, sufficient oxidation performance can be ensured. It is. Since nitrous oxide is a safe substance, it is not essential to treat nitrous oxide dissolved in the solution S after oxidation. Further, by irradiating the ultraviolet light only in the spraying direction of the solution S, it is possible to avoid the influence caused by irradiating other portions with the ultraviolet light.

  Note that in the case where only a part of the surface of the object to be processed is oxidized using the oxidation apparatus 90, patterned oxidation can be performed. For example, even if the object to be processed is a sheet shape, a top surface of a desk, a floor, a wall or the like, it can be oxidized using the oxidation apparatus 90.

  Although the oxidizer 90 is configured to wet the object to be processed continuously by injection of the solution S, the injection of the solution S may be performed in the form of a mist. Next, an oxidation apparatus for injecting the solution S in such a manner and coating the surface of the workpiece X thinly to oxidize the workpiece X will be described.

  Since the method for oxidizing the object to be processed in this example can be implemented by using the hydrophilizing apparatus 100 shown in FIG. 19 as an oxidizing apparatus for the object to be processed, the hydrophilizing apparatus 100 shown in FIG. The method for oxidizing the workpiece X will be described with reference to FIG.

  In the oxidation apparatus 100 having such a configuration, the workpiece X is placed on the table 101 and is held by operating the adsorption means, and the nozzle 108 is rotated to a predetermined position suitable for spraying the solution S. The solution S is sprayed from the nozzle 108 while rotating the table 101. Since the solution S is in the form of fine droplets, and the treatment object X is hydrophobic, it uses an organic solvent. It adheres to the entire surface and is applied. After the solution S is uniformly attached to the workpiece X, the KrI excimer lamp L is emitted and irradiated with ultraviolet light. The adhesion amount of the solution S on the workpiece X can be adjusted by adjusting the ejection amount and ejection time of the solution S from the nozzle 108.

  Nitrous oxide dissolved in the solution S in the ultraviolet light irradiation region is dissociated to generate atomic oxygen (O), and this atomic oxygen strongly oxidizes the workpiece X, Oxidation takes place. When the object to be processed X is a silicon wafer, an oxidation process is performed on the surface of the substrate, for example, an oxide film is formed on the surface. By using an organic solvent having high wettability for the solution S, the surface of the workpiece X is well wetted by the solution S, so that the oxidation treatment is performed well. Thus, the oxidation treatment can also be effectively performed on the workpiece X having hydrophobicity.

  A more effective oxidation treatment can be performed by adjusting the adhesion amount of the solution S according to the amount of nitrous oxide consumed in the oxidation process. When the desired oxidation is completed, the table 101 is rotated as necessary to remove the solution S adhering to the workpiece X. The solution S collected in the container 104 is discharged to the waste liquid storage section through the waste liquid pipe 105 by opening the waste liquid valve 106 at an appropriate time. When it is necessary to consider that the nozzle 108 does not hinder the irradiation of ultraviolet light, a structure in which the nozzle 108 protrudes to a predetermined position only when necessary for spraying the solution S can be employed.

  As an aspect in which the solution S is attached to the workpiece X, there can be mentioned another method by so-called spin coating. In this case, for example, instead of the solution spraying means 103 in the oxidizer 100, a solution flowing means for dropping the solution S onto the workpiece X held on the table 101 is provided. While rotating the table 101 while holding the object to be processed X, the solution S is dropped by the solution flow-down means so that the solution S is uniformly attached to the object to be processed X, and then the KrI excimer lamp L emits light. And irradiate with ultraviolet light. The adhesion amount of the solution S on the workpiece X can be adjusted by adjusting the flow rate and the flowing time of the solution S from the solution flowing means.

  Also in these oxidizers 100, patterned oxidation can be performed by performing the patterning of the application of the mask 89 and the solution S described with respect to the oxidizer 80 shown in FIG. In this case, the table 101 is not rotated at the time of ultraviolet light irradiation other than during spraying of the solution S and spin coating, and the workpiece X is held in a fixed position.

  If the solution S is applied by spraying or spin coating, the amount of consumption of the solution S can be reduced, and the oxidation is performed while the solution S is substantially exchanged. Therefore, the concentration of nitrous oxide in the solution S Even if it is made low, it is possible to ensure sufficient oxidation performance. However, when spraying, if the droplets are too small, nitrous oxide is dissipated into the atmosphere before the solution S reaches the workpiece X, but the solution S is substantially free from the workpiece X. Since oxidation is performed while exchanging, even if the concentration of nitrous oxide in the solution S is somewhat lowered due to dissipation, sufficient oxidation performance can be ensured. However, the size of the droplet is adjusted as appropriate so that the amount of dissipation does not become too large.

  The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited to the specific embodiments, and various modifications can be made within the scope of the gist of the present invention described in the claims. Deformation / change is possible.

  For example, in the first embodiment, the object to be processed is a plate-like object, an object having an uneven surface, an object having a space inside and having an opening in the space, a sheet-like object, a relatively large object, and the like. It can be a thing.

  In addition to silicon, aluminum alloy, copper alloy, and iron alloy, the material to be treated includes aromatic resin, aliphatic resin, oxygen-containing polymer compound, nitrogen-containing polymer compound, halogen-containing polymer compound, and ceramic. Materials etc. can be used.

  In addition, the hydrophilicity of the surface of the substance is made hydrophilic in each of the above examples, but may be hydrophobized or the like. When the mode of hydrophilization is hydrophobization, the physical property of the substance needs to be hydrophobized by oxidation, and such a material is selected as the substance.

  In Example 2, the object to be treated may be any kind of fish such as fry for use in aquaculture, seed before seeding such as seed pods, tableware, food packaging containers, medical instruments, and vegetables.

  For example, in order to sterilize the fry for use in aquaculture, the fish can be sterilized by immersing the fry as the object to be processed X in the solution S of the sterilizer 30 shown in FIG. In this case, the protrusion 31a provided on the bottom of the container 31 is not necessarily required.

Then, by turning on the KrI excimer lamp L, nitrous oxide in the solution S is dissociated to generate atomic oxygen, and this atomic oxygen oxidizes and sterilizes microorganisms adhering to the fish surface. Become.
Irradiation ultraviolet light may affect the fish body, so the irradiation time and intensity of the ultraviolet light will adversely affect the fish body while reducing the number of microorganisms adhering to the fish surface to the desired level. It is preferable that the degree is not so large.

  In this way, by sterilizing juvenile fish to be cultivated in advance, fish diseases caused by microorganisms can be prevented, and there is no risk of adverse effects on nature and the human body.

  Here, an example of sterilizing fry with the sterilizer 30 has been described. However, as with the sterilizer 40, a plurality of KrI excimer lamps L may be provided so that the fish body is uniformly irradiated with ultraviolet light. The mode of the sterilizer can be selected as appropriate.

The target to be sterilized is not limited to fry, but may be adult fish or fish after landing. In particular, in the case of a fish after landing, the fish body may be sterilized by immersing the fish body in the solution S as shown in FIG. 10, but using the sterilizer 90 shown in FIG. 18 while spraying the solution S on the fish body. You may make it sterilize by irradiating with ultraviolet light.
Next, sterilization of seeds before sowing will be described using seed pods as an example. For example, in order to sterilize the seed pod, the seed pod can be sterilized by immersing the seed pod as the workpiece X in the solution S of the sterilizer 30 shown in FIG. In this case, the protrusion 31a provided on the bottom of the container 31 is not necessarily required.

Then, by turning on the KrI excimer lamp L, nitrous oxide in the solution S is dissociated to generate atomic oxygen, and this atomic oxygen oxidizes and sterilizes microorganisms adhering to the surface of the seed pod. Become.
Irradiation ultraviolet light may affect the growth of seed pods after sowing, so the irradiation time and irradiation intensity of ultraviolet light, while reducing the microorganisms adhering to the surface of the seed pods to the desired level, It is preferable that the seeds are not adversely affected.

  Thus, by sterilizing the seed pods in advance, it is possible to prevent seedling growth inhibition by microorganisms, and there is no possibility of adversely affecting the nature and the human body.

Here, an example in which the seed sterilizer is sterilized by the sterilizer 30 has been described. However, as in the sterilizer 40, a plurality of KrI excimer lamps L may be provided so that the seed potato is uniformly irradiated with ultraviolet light. 18 may be sterilized by irradiating with ultraviolet light while spraying the solution S on the fish body using the sterilizing apparatus 90 shown in FIG. That is, the aspect of the sterilizer can be selected as appropriate.
In addition, the target to be sterilized is not limited to seed rice (rice), but may be plant seeds or bulbs (underground stems).

  Next, taking a teacup as an example, sterilization of tableware will be described. For example, in order to sterilize a teacup, the teacup can be sterilized by immersing the teacup as the object X in the solution S of the sterilizer 30 shown in FIG. In this case, the protrusion 31a provided on the bottom of the container 31 is not necessarily required.

Then, by turning on the KrI excimer lamp L, nitrous oxide in the solution S is dissociated to generate atomic oxygen, and this atomic oxygen oxidizes and sterilizes microorganisms adhering to the teacup surface; Become.
The irradiation time and irradiation intensity of the ultraviolet light can be appropriately adjusted at the time when the microorganisms adhering to the teacup surface have decreased to a desired level.

  Thus, by sterilizing teacups in advance, food poisoning caused by microorganisms can be prevented, and there is no risk of adverse effects on nature and the human body.

Here, an example of sterilizing teacups with the sterilizer 30 has been described. However, as with the sterilizer 40, a plurality of KrI excimer lamps L may be provided so that the teacups are uniformly irradiated with ultraviolet light. The sterilization apparatus 90 shown in FIG. 18 may be used to sterilize by irradiating ultraviolet light while spraying the solution S onto the teacup. That is, the aspect of the sterilizer can be selected as appropriate.
The object to be sterilized is not limited to teacups (Seto), but may be cups (glass), blades (metal), or cutting boards (made of wood or resin).

  Next, sterilization of food packaging containers will be described using a paper pack beverage as an example. In general, a paper pack beverage is a sheet-like paper wound in a roll, continuously supplied in a sterilizing liquid, immersed in the sterilizing liquid through a predetermined time, and after the sterilizing liquid is dried, It is manufactured by appropriately folding and filling it with a sterilized beverage.

  Therefore, in order to sterilize the wrapping paper of the paper pack beverage using the nitrous oxide solution as an alternative to the sterilizing solution, the sheet-shaped packaging is used as the object to be processed X in the solution S of the sterilizing apparatus 60 shown in FIG. By immersing the paper, the wrapping paper can be sterilized.

Then, by turning on the KrI excimer lamp L, nitrous oxide in the solution S is dissociated to generate atomic oxygen, and this atomic oxygen oxidizes and sterilizes microorganisms adhering to the surface of the packaging paper. It becomes.
The irradiation time and irradiation intensity of ultraviolet light can be appropriately adjusted so that the microorganisms adhering to the surface of the packaging paper are in a sterilized state.

  Thus, by pre-sterilizing the packaging paper, it is possible to prevent the paper pack beverage from being spoiled by microorganisms and causing food poisoning and the like, and there is no possibility of adversely affecting the nature and human body.

Here, an example of sterilizing packaging paper with the sterilizer 60 has been described. However, as in the sterilizer 40, a plurality of KrI excimer lamps L are arranged, for example, so-called milk bottles filled with milk or the like are irradiated with ultraviolet light. You may make it irradiate uniformly. That is, the aspect of the sterilizer can be selected as appropriate.
The target to be sterilized is not limited to wrapping paper (paper) but may be a bottle (glass), a plastic bottle (resin), or the like.

  Next, sterilization of a medical instrument will be described using a dental mirror as an example. For example, in order to sterilize the dental mirror, the dental mirror can be sterilized by immersing the dental mirror as the workpiece X in the solution S of the sterilizing apparatus 30 shown in FIG. In this case, the protrusion 31a provided on the bottom of the container 31 is not necessarily required.

Then, by turning on the KrI excimer lamp L, nitrous oxide in the solution S is dissociated to generate atomic oxygen, and this atomic oxygen oxidizes and sterilizes microorganisms attached to the surface of the dental mirror. It becomes.
The irradiation time and irradiation intensity of the ultraviolet light can be appropriately adjusted according to the time when the microorganisms adhering to the dental mirror surface are reduced to a desired level.

  Thus, by sterilizing the dental mirror in advance, it is possible to prevent infection of microorganisms from person to person, and there is no possibility of adversely affecting nature and the human body.

Here, an example of sterilizing a dental mirror with the sterilizer 30 has been described. However, as in the sterilizer 40, a plurality of KrI excimer lamps L are arranged so that the dental mirror is uniformly irradiated with ultraviolet light. Alternatively, the sterilization apparatus 90 shown in FIG. 18 may be used to sterilize by irradiating with ultraviolet light while spraying the solution S on the dental mirror. That is, the aspect of the sterilizer can be selected as appropriate.
The target to be sterilized is not limited to a dental mirror (stainless steel) but may be a thermometer (glass) or a syringe (resin).

  Next, sterilization of vegetables will be described using radishes as an example. Since radish is a root vegetable, there are many cases where a large amount of soil-derived microorganisms are attached to the surface. For example, in order to sterilize the surface of the radish, the radish can be sterilized by immersing the radish as the workpiece X in the solution S of the sterilizer 30 shown in FIG. In this case, the protrusion 31a provided on the bottom of the container 31 is not necessarily required.

  Then, by turning on the KrI excimer lamp L, nitrous oxide in the solution S is dissociated to generate atomic oxygen, which oxidizes and sterilizes the microorganisms attached to the surface of the radish. Become.

The irradiation time and irradiation intensity of ultraviolet light can be appropriately adjusted according to the time when the microorganisms adhering to the surface of the radish are reduced to a desired level.
Thus, by sterilizing radishes in advance, it can be used as a sanitary food, it does not wither due to osmotic pressure like other fungicides, and there is no risk of adverse effects on nature and the human body. .

  Here, an example of sterilizing radishes with the sterilizer 30 has been described. However, as with the sterilizer 40, a plurality of KrI excimer lamps L may be provided to irradiate the radishes uniformly with ultraviolet light. The sterilization apparatus 90 shown in FIG. 18 may be used to sterilize by irradiating with ultraviolet light while spraying the solution S on the radish. That is, the aspect of the sterilizer can be selected as appropriate.

The target to be sterilized is not limited to radish (root vegetables) but may be cabbage (leaf) or apple (fruit).
Furthermore, the object to be sterilized is not limited to vegetable foods such as vegetables and fruits. For example, it may be used for sterilizing animal foods such as eggs, livestock meat, fish meat, and processed foods such as sausages and konjac. It may be used.

  Moreover, in order to improve the bactericidal effect of the nitrous oxide solution, it may be used by mixing with other bactericides. As a disinfectant that can be mixed, any disinfectant that does not lose its disinfecting ability even in the presence of atomic oxygen generated from nitrous oxide can be used, and examples thereof include hydrogen peroxide.

  In Example 4, the object to be processed is a plate-like object, an object with irregularities on the surface, an object with a space inside and an opening in this space, a sheet-like object, a relatively large object, and other objects. can do.

  As for patterning, as described above, the object to be processed can be locally decolored by locally irradiating the solution with ultraviolet light. If the light is collected and irradiated to the object to be processed, the light intensity of the ultraviolet light can be increased, and the irradiation region can be narrowed down to, for example, the order of a micrometer or less.

  When patterning, it is desirable that the ultraviolet light is a parallel light beam in order to transfer the pattern formed on the mask at a reduction ratio of 1: 1. Further, projection type exposure can also be performed. In this case, a lens system is provided between the KrI excimer lamp and the object to be processed, and the mask pattern is enlarged or reduced so that an image is formed on the surface of the object to be processed. By so doing, decolorization can be performed by enlarging or reducing the pattern formed on the mask.

  In the fifth embodiment, substances are produced by oxidizing cyclohexane to produce ε-caprolactone, oxidizing allyl methacrylate to produce glycidyl methacrylate, or oxidizing chitosan to produce low molecular chitosan. There is no particular limitation as long as it obtains a functional substance by oxidizing a predetermined substance.

  In particular, this example is a reaction that oxidizes alcohol to produce aldehyde, ketone, carboxylic acid, etc., a reaction that oxidizes amine to produce amine oxide, a reaction that oxidizes sulfide or sulfoxide to produce sulfone, aromatic Reactions that oxidize compounds to generate carboxylic acids, reactions that oxidize benzene derivatives to generate carboxylic acids, reactions that oxidize halogen compounds to generate carboxylic acids, oxidize alkenes, aldehydes, carboxylic acids, alcohols, ethers, It can be applied to reactions that produce ketones, reactions that oxidize aryl to produce aldehydes, reactions that oxidize alkynes to produce aldehydes and alkenes, and reactions that oxidize ketones to produce carboxylic acid derivatives.

  In the sixth embodiment, the object to be processed is a plate-like object, an object with irregularities on the surface, an object with a space inside and an opening in this space, a sheet-like object, a relatively large object or other object It can be.

  As for patterning, as described above, the object to be processed can be oxidized locally by irradiating the solution with ultraviolet light locally. If the light is collected and irradiated to the object to be processed, the light intensity of the ultraviolet light can be increased, and the irradiation region can be narrowed down to, for example, the order of a micrometer or less.

  When patterning, it is desirable that the ultraviolet light is a parallel light beam in order to transfer the pattern formed on the mask at a reduction ratio of 1: 1. Further, projection type exposure can also be performed. In this case, a lens system is provided between the KrI excimer lamp and the object to be processed, and the mask pattern is enlarged or reduced so that an image is formed on the surface of the object to be processed. By doing so, the pattern formed on the mask can be enlarged or reduced, and oxidation can be performed.

  In the seventh embodiment, the object to be processed is a plate-like object, an object with irregularities on the surface, a space in the interior, an object having an opening in this space, a sheet-like object, a relatively large object, or other It can be a thing.

  In addition, the material of the object to be processed is silicon, silicon substrate, aluminum, copper, iron, zinc, titanium, tantalum, silver, zirconium, tungsten, chromium, molybdenum, nickel, hafnium, ruthenium, niobium, yttrium, scandium, neodymium, Lanthanum, cerium, cobalt, vanadium, manganese, gallium, germanium, indium, tin, rhodium, palladium, cadmium, antimony, mercury cadmium tellurium, gallium aluminum arsenic, indium gallium arsenide, indium gallium phosphide, indium phosphide, indium antimony, gallium arsenide , Gallium antimony, gallium phosphide, and alloys containing these can be used.

  Further, a substrate such as a circuit board such as a semiconductor substrate such as a silicon wafer can be used as the object to be processed. That is, the object to be processed may be a silicon substrate itself, or a molybdenum, aluminum or other conductor film formed on the surface of a silicon substrate, glass substrate or the like, and a conductor film pattern is formed on a semiconductor or insulator. be able to. Alternatively, a printed circuit board in which a copper foil is formed on an insulating substrate may be used as an object to be processed, and the printed circuit board may be patterned without using a photosensitive film such as a photoresist.

  As for patterning, as described above, the surface of the object to be processed can be locally processed by locally irradiating the solution with ultraviolet light, and further, for example, a synthetic quartz lens is used. If the ultraviolet light is collected by the lens and irradiated to the object to be processed, the light intensity of the ultraviolet light can be increased, and the irradiation region can be narrowed down to, for example, the order of a micrometer or less. If a silicon substrate is used as an object to be processed, a minute region on the surface can be processed to a predetermined depth.

  When patterning, it is desirable that the ultraviolet light is a parallel light beam in order to transfer the pattern formed on the mask at a reduction ratio of 1: 1. Further, projection type exposure can also be performed. In this case, a lens system is provided between the KrI excimer lamp and the object to be processed, and the mask pattern is enlarged or reduced so that an image is formed on the surface of the object to be processed. By doing so, the pattern formed on the mask can be enlarged or reduced, and oxidation can be performed.

  As can be seen from these, the oxidation method and the oxidation apparatus of the object to be processed according to the present invention can be used as a production method and a production apparatus for various devices such as semiconductor circuits, and the oxidation according to the present invention. The resulting material can be such various devices.

  The effects described in the embodiments of the present invention are only the most preferable effects resulting from the present invention, and the effects of the present invention are limited to those described in the embodiments of the present invention. is not.

  Although various reforming methods and reformers have been described above, nitrous oxide gas supply, nitrous oxide dissolution method, concentration detection, and waste liquid treatment in these reformers can be performed as follows. .

  Nitrous oxide gas can be supplied by a gas cylinder of compressed gas such as liquefied gas filled in a high-pressure vessel, and can be installed in the vicinity of the reformer. It can also be supplied from a large high-pressure vessel in a factory or factory using a centralized pipe. A small container such as a cassette type gas cylinder may be mounted and supplied to the reformer, or a nitrous oxide generator is provided in the reformer, in the vicinity of the reformer, or in the workplace, and Nitrogen oxide may be directly supplied to a tank or a processing tank in the reformer.

  Nitrous oxide gas can be generated as follows. As an industrial method, (1) an ammonia oxidation method in which ammonia is heated at 200 ° C. to 500 ° C. in the presence of a metal oxide catalyst using oxygen or air, and (2) ammonium nitrate is thermally decomposed or nitric acid Practical scale of ammonium nitrate decomposition method that produces soda by heating ammonium sulfate mixture, (3) sulfamic acid and nitric acid react while supplying sulfamic acid divided into two or more stages or adding sulfuric acid Can be used.

  In the case of small-scale production, nitrous oxide can be generated by passing ozone gas and nitrogen gas through a glass capillary used for gas chromatography, etc., which is suitable for efficiently generating a small amount of nitrous oxide gas. ing.

  As a method of dissolving nitrous oxide gas in a solvent, (1) a gas diffusion plate or a gas diffusion tube made of a porous material made of plastic or ceramic is installed so as to be immersed in the solvent, and the above-described gas cylinder or generator A method of supplying nitrous oxide gas to the diffuser plate or diffuser tube and bubbling in the solvent from the above, (2) Using the ejector, the pressurized solvent is ejected from the nozzle of the ejector, and the generated negative Nitrous oxide gas and solvent are brought into contact with and dissolved by using pressure to absorb and dissolve nitrous oxide gas into the solvent, pressurized plate tower, packed tower, shower tower, bubble tower, etc. Stirring and dissolving the solvent in contact with the pressurized nitrous oxide gas in a pressure vessel, and stirring and mixing the pressurized solvent and nitrous oxide gas in a small pressure vessel (3) A porous membrane hollow fiber made of a hydrophobic resin such as polytetrafluoroethylene, utilizing the hydrophobicity of the resin and the gas permeability of the pores. By dissolving the gas in the liquid, or by dissolving the gas that has permeated the resin in the liquid using a non-porous gas permeable membrane hollow fiber using the gas dissolution / diffusion mechanism inside the resin, at any pressure There is a dissolution method using a hollow fiber membrane in which nitrous oxide gas is dissolved in a solvent without generating bubbles.

Further, these methods can be used in combination with an ultrasonic wave or a magnetic field having a gradient to improve the amount of nitrous oxide gas dissolved in the solvent and the dissolution rate.
Considering the concentration of nitrous oxide gas and the amount of nitrous oxide-containing liquid required for the reformer according to the present invention, nitrous oxide gas can be used as a method for efficiently and efficiently dissolving nitrous oxide gas in a solvent in a short time. It is preferable to use a thread membrane.

The concentration control and detection method of nitrous oxide in the solvent will be described.
Nitrous oxide in the solvent can be maintained at a substantially constant concentration by dissolving the nitrous oxide gas in the solvent by the above-mentioned predetermined method and controlling the dissolution time and gas supply pressure. is there. Therefore, there is an advantage that it is not always necessary to detect, record and manage the nitrous oxide concentration in the solvent in the reformer.

  However, when it becomes necessary to strictly control the concentration, the nitrous oxide concentration can be detected and managed as follows. (1) Electrolysis of nitrous oxide using an electrolytic cell having a working electrode and a counter electrode, if necessary, two or more electrolytic electrodes of a regenerative electrode, an ion exchange membrane that partitions the electrodes, and an electrolytic solution containing halogen ions (2) An ultraviolet ray having a predetermined wavelength is irradiated to a cell stored in a nitrous oxide-containing solvent and used as a light source across the cell. A spectrophotometric method for measuring absorbance with a light receiving system arranged at an opposite position, (3) a TN (total nitrogen) analysis method defined in JIS K0102, (4) an inert gas in a nitrous oxide-containing solvent The nitrous oxide dissolved in the solvent is moved into the gas phase by, for example, pumping and diffusing, and the non-dispersive infrared absorption method, ultraviolet absorption altitude method, and oxygen ion conductive solid decomposition products are used. Measuring sensor How to measure the nitrous oxide concentration in the gas phase using, and the like can be used. When supplying the solution of the wet etching apparatus of the present invention, it can be used for solution management in a container in which an object to be processed is immersed.

The nitrous oxide waste liquid treatment will be described.
Only about several hundred ppm of nitrous oxide remains in the solvent after the treatment, and the amount of nitrous oxide in the waste liquid is very small due to mixing with the rinse water after treatment and wastewater from other processes. Become. Therefore, basically, there is an advantage that it is not necessary to provide a mechanism for decomposing and removing nitrous oxide in the reformer.

  In addition, when performing neutralization treatment, activated sludge treatment, electrolytic treatment, etc. to treat components other than nitrous oxide in the waste liquid, nitrous oxide does not hinder these treatments. It is possible to carry out sludge treatment and the like without treating nitrous oxide in the waste liquid. Furthermore, when transporting waste liquid containing nitrous oxide to other workplaces or waste disposal sites, nitrous oxide does not cause abnormal decomposition like oxidants such as hydrogen peroxide. It has the advantage that nitrous oxide in the waste liquid does not have to be treated before transport.

  However, when it is necessary to decompose nitrous oxide in the reformer and reduce nitrous oxide emissions from the reformer due to the relationship with other processes or the environmental management of the entire workplace. There are the following methods for decomposing nitrous oxide in wastewater. (1) A method of decomposing waste water by irradiating it with ultraviolet rays for a certain period of time, (2) A method of electrolysis using a noble metal such as platinum as an anode, (3) A method of reductive decomposition by reaction with hydrogen gas in the presence of a catalyst, (4) Microbial decomposition using microorganisms that breathe using oxygen in nitrous oxide in an anaerobic state, and these methods can be applied to a reformer as necessary.

The present invention is a method for modifying a substance that modifies the substance by irradiating the solution with ultraviolet light in a state in which the solution containing nitrous oxide (N ₂ O) is in contact with the substance. Thus, it is possible to provide a method for modifying a substance that is easy to handle and can modify the substance itself or the surface of the substance or the deposit on the substance surface with high efficiency. Further, the present invention resides in a substance reforming apparatus that modifies the substance itself or the substance surface or deposits on the substance surface by using such a substance modification method. It is possible to provide an apparatus for modifying a substance that is easy and can highly efficiently modify the substance itself, the substance surface, or a deposit on the substance surface. In addition, since the present invention resides in a modified substance obtained by performing reforming using such a substance reforming method or such substance reforming apparatus, it is possible to provide a highly efficient modified substance. it can. Furthermore, according to the present invention, the nitrous oxide-containing solution that comes into contact with the object also contains a thickener, and since it has the property of easily staying at the contact position when brought into contact with the object, It is possible to oxidize by bringing the solution into contact with only the portion to be oxidized. Further, since the nitrous oxide-containing solution supplied by the solution supply means of the object oxidation apparatus according to the present invention contains a thickener, the solution brought into contact with the object tends to stay at the contact position. Therefore, it is possible to oxidize by bringing the solution into contact with only the portion to be oxidized.

Claims (23)

A method for modifying a substance, wherein the substance is modified by irradiating the solution with ultraviolet light in a state where a solution containing nitrous oxide (N ₂ O) is in contact with the substance.   The method for modifying a substance according to claim 1, wherein the modification is hydrophilization.   The method for modifying a substance according to claim 1, wherein the modification is sterilization.   2. The method for modifying a substance according to claim 1, wherein the modification is cleaning performed by decomposing and removing organic substances by oxidation.   The method for modifying a substance according to claim 1, wherein the modification is decolorization.   6. The method for modifying a substance according to claim 5, wherein a decoloring time of the substance is controlled by an irradiation time of the ultraviolet light.   6. The method for modifying a substance according to claim 5, wherein a decoloring region of the substance is controlled by the irradiation region of the ultraviolet light.   A method of modifying a substance, wherein the modification has a function different from that of the original substance.   9. The method for modifying a substance according to claim 8, wherein the original substance is an alcohol or a ketone.   9. The method for modifying a substance according to claim 8, wherein the original substance is an organic compound having at least one unsaturated bond.   9. The method for modifying a substance according to claim 8, wherein the original substance is a polysaccharide.   9. The method for modifying a substance according to claim 8, wherein the substance having a function different from that of the original substance is carboxylic acid.   A method for reforming a substance, wherein the reforming according to any one of claims 8 to 12 is obtained in a microreactor.   Irradiation with ultraviolet light is performed after separating the functional substance different from the original substance from the solution containing the nitrous oxide and the functional substance different from the original substance. 14. The method for modifying a substance according to claim 8, wherein the substance is modified.   15. The method for modifying a substance according to claim 8, wherein an irradiation time of the ultraviolet light is controlled in order to obtain a substance having a function different from that of the original substance.   The method for modifying a substance according to claim 1, wherein the solution contains a thickener.   The method for modifying a substance according to any one of claims 1 to 16, wherein a krypton-iodine (KrI) excimer lamp is used as the ultraviolet light source.   A substance obtained by the method for modifying a substance according to any one of claims 1 to 17. A solution contact means for bringing a solution containing nitrous oxide (N ₂ O) into contact with the substance, and a light source for irradiating the solution with ultraviolet light in a state where the solution and the substance are brought into contact with each other by the solution contact means. An apparatus for modifying a substance configured to hydrophilize the substance by irradiation with the ultraviolet light. A solution contact means for bringing a solution containing nitrous oxide (N ₂ O) into contact with the substance, and a light source for irradiating the solution with ultraviolet light in a state where the solution and the substance are brought into contact with each other by the solution contact means. An apparatus for modifying a substance configured to sterilize the substance by irradiation with the ultraviolet light. A solution contact means for bringing a solution containing nitrous oxide (N ₂ O) into contact with an organic substance attached to the substance, and the solution is irradiated with ultraviolet light in a state where the solution and the organic substance are brought into contact with each other by the solution contact means. A substance reforming apparatus comprising a light source and configured to wash the substance by irradiation with the ultraviolet light. A solution contact means for bringing a solution containing nitrous oxide (N ₂ O) into contact with the substance, and a light source for irradiating the solution with ultraviolet light in a state where the solution and the substance are brought into contact with each other by the solution contact means. An apparatus for modifying a substance configured to decolorize the substance by irradiation with the ultraviolet light. A solution contact means for bringing a solution containing nitrous oxide (N ₂ O) into contact with the substance, and a light source for irradiating the solution with ultraviolet light in a state where the solution and the substance are brought into contact with each other by the solution contact means. An apparatus for modifying a substance configured to produce a substance having a function different from that of the substance by irradiation with the ultraviolet light.

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