JP2013013862A - Biofiltration material for cleaning treatment of organic wastewater - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a biofiltration material for eliminating organic matter in water cleaning treatment by chemically bonding biocompatible particles with biocompatibility to a base material.SOLUTION: A surface treatment comprising at least one method selected from acid, alkali, ozone, ozone water, ozone bubbling, plasma, corona discharge and ultraviolet irradiation is applied onto the organic or inorganic base material to produce a reactive functional group such as a hydroxy group or a carboxyl group, and a calcium phosphate sintered body (hydroxyapatite) which is biocompatible particles, is chemically bonded to the produced reactive functional group.

Description

  The present invention relates to a filter medium for an organic wastewater purification system using biological filtration.

  Conventionally, various methods have been studied as organic matter removal methods in water purification treatment, and these can be broadly classified into decomposition, adsorption, and filtration. Among these, for filtration, a method using a filter such as a hollow fiber having fine pores is mainly used. For adsorption, a method of removing an object by a porous substrate such as activated carbon or a method of removing by a reaction with a surface functional group is used.

  For the decomposition, a method using a chemical reaction, a method using direct decomposition by light, etc., a method using biological filtration using biological activity, etc. are mainly used. In the method using chemical reaction, oxidative decomposition using chlorine, ozone, hydrogen peroxide, or the like, or a method using acid or alkali is used. In photolysis, a method of directly decomposing organic matter by irradiating with high energy ultraviolet rays is used. In biological filtration, a method is used in which organic matter is decomposed by microorganisms such as bacteria attached to a substrate such as resin or ceramics.

JP 2006-219541 A Japanese Patent Laid-Open No. 11-090137

  In the conventional method using adsorption or filtration, the filter base material needs to be discarded along with its lifetime in principle, and the environmental load in filter production and disposal is a big problem as well as running cost.

  In addition, most of the methods using a decomposition reaction use chemical agents such as chlorine, ozone, UV, etc., which is not preferable for living organisms and the environment including humans. In addition, there is a concern that the powerful UV used for photolysis also has a harmful effect on biological systems. Furthermore, it is difficult to say that both of them are preferably used from the viewpoint of running cost and environmental load over a long period of time as well as short-term and environmentally in recent years.

  In addition, biological filtration, in which microorganisms such as bacteria are supported on a substrate and water is purified using the biodegradation action of the microorganism, is also used in some cases, but filter substrates are usually made of synthetic resin or ceramics. Since it is an inorganic material such as glass, there is a problem that the affinity of organisms such as bacteria is low. Therefore, in the prior art, it has been difficult to create an environment in which microorganisms can live and to quickly establish useful microorganisms. For this reason, considerable time is required until the effect is exhibited after the purification material is installed and replaced, and there has been a problem such as a decrease in filtration capacity at the time of start-up or replacement of the purification material. In addition, since the degree of microbial activity at the time of cleaning the cleaning material is low, there has been a problem that the filtration ability is lowered due to the dropout of useful microorganisms that have been fixed. Furthermore, it is very difficult to keep the useful microorganisms in a fixed state. If the biodegradation action of the microorganisms decreases or the microorganisms die, etc. Contaminants contained in the sorghum rot, and on the contrary, it may cause odors and toxic substances, which is often a problem.

  Furthermore, in the past, it has been studied to apply a biocompatible material to the surface of the purification material, which uses a method such as welding or coating. For example, in the case of welding, there is a problem that the material is exposed to a high temperature and thus biocompatibility is impaired, and in the case of an organic base material, the base material itself cannot withstand the processing temperature and cannot be used. In addition, in the method using a binder such as paint, there is a problem that the surface of the biocompatible material is covered with another material such as a binder and the effectiveness is reduced, and there is an influence on a living thing by the binder component.

  An object of this invention is to provide the biological filter which solved the trouble of such a prior art.

  In order to achieve the above-mentioned object, the present invention described in claim 1 provides a biofilter characterized in that a base material and biocompatible particles having biocompatibility are chemically bonded. The filter medium of the present invention is characterized in that particles having biocompatibility are first chemically bonded to the surface thereof.

  Here, the biocompatible particle is a material that does not have a harmful effect in contact with a tissue such as a living organism or a cell, and that a biological tissue such as a cell or a microorganism such as a bacterium is easily activated. The present applicant has been paying attention to the biocompatible material from an early stage and has continued research.

  The filter medium of the present invention can be used regardless of whether it is liquid or gas because a biocompatible material having such properties (having no harmful effects on the living body and being easy to settle) is attached to the surface. It is possible to fix microorganisms quickly, to prevent falling off, and to maintain a fixed state, so that a stable purification performance can be exhibited quickly.

  And it is preferable that the base material used by this invention does not show toxicity with respect to a biological body itself. For example, examples of organic base materials include polyester resins typified by polyethylene terephthalate, polyamide resins typified by nylon, polysaccharides typified by cellulose, silicone resins, polyolefin resins typified by polyethylene, and polyurethane. Examples include resins, acrylic resins, methacrylic resins, vinylon resins represented by polyvinyl alcohol, and the like. Furthermore, in the case of an inorganic base material, examples include metals such as stainless steel, natural minerals such as ceramics, glass, and zeolite.

  Moreover, although the shape is not limited, it is preferable that the surface area be as large as possible as in the case of a normal biological filter. For example, a sponge shape, a hook shape, or the like can be given as an example.

  In the invention described in claim 1, as described in claim 2, a step of performing a surface treatment to generate a reactive functional group on the surface of the base material is reacted with the biocompatible particles. It is preferable to include being produced by a direct reaction step.

  Usually, there are a few functional groups that serve as reaction sites on the surface of the substrate for both organic and inorganic systems, but by actively forming functional groups that serve as reaction sites, more biocompatible particles can be obtained. This is because it is possible to bond to the substrate surface more firmly. Moreover, it is because it becomes possible to bond more biocompatible particles to the surface of the base material more firmly by including a process for promoting a binding reaction such as heating, stirring, and aging.

  In the invention described in claim 2, as described in claim 3, the reactive functional group is a hydroxy group, carboxyl group, amino group, sulfonic acid group, sulfo group, thiol group, cyano group, hydrosilyl group. It is preferable that

  In the invention of the second aspect, as described in the fourth aspect, the method for generating the reactive functional group is from acid, alkali, ozone, ozone water, ozone bubbling, plasma, corona discharge, and ultraviolet treatment. It is preferable to include at least one method selected from the group consisting of:

  In the invention described in claim 4, as described in claim 5, it is preferable that the method for generating the reactive functional group is ozone water.

  In the invention described in claim 2, as described in claim 6, it is preferable that the biocompatible particles are a calcium phosphate sintered body.

  In the invention described in claim 2, as described in claim 7, it is preferable that the calcium phosphate sintered body is hydroxyapatite.

  Hydroxyapatite has a hydroxyl group on its surface, so it can form more chemical bonds with the reactive functional groups on the substrate surface, thereby ensuring more reliable and stronger adhesion to the substrate surface. This is because they can be combined.

In the invention of the second aspect, as described in the eighth aspect, the biocompatible particles preferably have an average particle diameter of 20 nm to 50 μm.
Since the specific surface area, which is the ratio of the surface area to the volume, increases as the particle size decreases, the particle can increase the effective area that can be used by useful microorganisms, thereby improving the purification efficiency. Because it becomes. However, since the size of the virus is usually about 20 nm or more, particles larger than this are preferable for engraftment. However, when the particle size is increased, the above-described effect of increasing the specific surface area is diminished, and furthermore, the weight ratio with respect to the bonded area is increased, which may cause problems such as dropout. In consideration of a typical sponge-like wrinkle size of about 100 μm, it is preferably 50 μm or less.

  The present invention is a filter medium in which bioaffinity particles having biocompatibility are chemically bonded to the surface of a substrate as described above, and unlike conventional chemicals such as chlorine and ozone, which have an adverse effect on the ecosystem It can be purified without using UV or the like. In addition, the microorganisms can be quickly fixed, the dropout hardly occurs, and the fixed state can be maintained, so that a stable purification performance can be exhibited quickly.

  As a result, even when a new purification system is set up, useful microorganisms such as bacteria that have a purification ability can be quickly established and propagated on the surface of the substrate, thereby quickly exerting the purification action. It is possible to reduce the impact on the living organisms and ecosystems due to the lack of purification capacity at the time of new startup, which has become a problem.

  In general, the cleaning material needs to be periodically cleaned or replaced. In this case as well, a decrease in purification capacity becomes a problem as in the case of new startup. Therefore, instead of cleaning and replacing all the purification materials at the same time, only a part of them is cleaned or replaced by dividing it into a plurality. However, even if it does in this way, the reduction | decrease in the purification capability accompanying washing | cleaning and replacement | exchange will occur, and the influence by rise time becomes a problem in the conventional purification | cleaning material. In contrast, the filter medium provided by the present invention provides quick recovery of the purification capacity.

  Furthermore, since the base material and the biocompatible particles are directly bonded, it is possible to eliminate the influence on the living body and the reduction of the effective surface area due to the conventionally used binder. The effective surface area can be increased by using fine particles. Furthermore, since the particles are independently bonded to the surface of the base material, unlike coating and application, the flexibility of the base material is not impaired, and dropout due to deformation is unlikely to occur.

It is a figure which shows the result of having observed the HAp composite_body | complex formed in the polyester-made base material as Example 1 with the scanning electron microscope, (a) is 2000 times, (b) shows the result observed at the magnification of 10000 times. . It is a figure which shows the result of having observed the HAp composite_body | complex which immersed the polyester base material of HAp coating of Example 1 in the pure water for 1 week using the scanning electron microscope, (a) is 2000 times, (b) is 10,000. The results observed at double magnification are shown. It is a figure which shows the result of having observed with a scanning electron microscope the HAp composite_body | complex of Example 1 which processed with the probe ultrasonic wave in 1: 1 ethanol and a pure water liquid, (a) is 2000 times, ( b) shows the result of observation at a magnification of 10,000 times. It is a figure which shows the result of having observed the HAp composite_body | complex formed in the polyurethane-made base material as Example 2 with the scanning electron microscope, (a) is 2000 times, (b) shows the result observed by the magnification of 10000 times. . It is a figure which shows the result of having observed the HAp composite_body | complex formed in the polyurethane-made base material of Example 2 with the scanning electron microscope, (a) is 2000 times, (b) shows the result observed by the magnification of 10000 times. . It is a figure which shows the result of having observed the HAp composite_body | complex formed in the inorganic type base material as Example 3 with the scanning electron microscope, (a) is 2000 times, (b) shows the result observed by the magnification of 10000 times. . It is a figure which shows the result of having observed the HAp composite_body | complex formed in the inorganic type base material of Example 3 with the scanning electron microscope, (a) shows the result observed at 2000 times, (b) at the magnification of 10,000 times. . It is a figure which shows the result of having observed the HAp composite_body | complex formed in the polyester-made base material as a comparative example 1 with the scanning electron microscope, (a) is 2000 times, (b) shows the result observed at the magnification of 10000 times. . It is a figure which shows the result of having observed the HAp composite_body | complex formed in the polyester base material of the comparative example 1 using the scanning electron microscope, (a) is 2000 times, (b) is the result observed at the magnification of 10000 times. Show. It is a figure which shows the result of having observed the HAp composite_body | complex formed in the polyurethane-made base material as a comparative example 2 with the scanning electron microscope, (a) is 2000 times, (b) shows the result observed by the magnification of 10000 times. . It is a figure which shows the result of having observed the HAp composite using the scanning electron microscope which immersed the polyurethane base material HAp composite of the comparative example 2 in the pure water for 1 week, (a) is 2000 times, (b). Indicates the result of observation at a magnification of 10,000 times.

One implementation process of the present invention will be described as follows.
The biofilter material manufacturing technology according to the present invention includes a surface treatment step for surface-treating the base material, and a binding step for binding the calcium phosphate to the surface of the base material after the surface treatment step. The process should just be a process which makes the surface of the said base material and ozone water contact.

    In the present specification, the “calcium phosphate complex” means a structure formed by binding calcium phosphate to the surface of a substrate. In the present specification, “ozone water” means water in which ozone is dissolved. Further, in the present specification, the “surface treatment” means a treatment for modifying the surface of the substrate. For example, the surface of the substrate is brought into contact with ozone water to generate a hydroxyl group or the like on the surface of the substrate. Processing.

  Various substrates can be selected as the substrate used in the production method according to the present invention. For example, specific examples of the resin substrate include, for example, polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate (hereinafter referred to as “PET”), silicone polymers (which may be silicone rubber), polyethylene glycol, poly Alkylene glycol, polyglycolic acid, polylactic acid, polyamide, polyurethane, polysulfone, polyether, polyetherketone, polyamine, polyurea, polyimide, polyethylene, polypropylene, polytetrafluoroethylene, polyacrylic acid, polymethacrylic acid, polymethacrylic acid Synthetic polymers such as methyl, polyacrylonitrile, polystyrene, polyvinyl alcohol, polyvinyl chloride; cellulose, amylose, amylopectin, chitin, chitosan, etc. Sugars, polypeptides such as collagen, hyaluronic acid, chondroitin, mucopolysaccharide such as chondroitin sulfate, although natural polymers such as silk fibroin and the like, but is not limited thereto. Among the base materials exemplified here, polyester and polyolefin are preferable from the viewpoint of being suitable as a biofiltration filter material and from the viewpoint of cost.

  The shape of the base material applicable to the manufacturing method according to the present invention is not particularly limited. Depending on the application to be used, substrates of various shapes can be appropriately selected. For example, it may be a fiber, a sheet, a tube, a bowl, a porous body, or a more complicated shape.

[Calcium phosphate]
The calcium phosphate used in the production method according to the present invention is not particularly limited, but is preferably hydroxyapatite (Ca ₁₀ (PO ₄ ) ₆ (OH) ₂ ), more preferably a hydroxyapatite sintered body (also called hydroxyapatite ceramics). . In particular, the hydroxyapatite sintered body is stable for a long period of time, has high safety, and is used for medical purposes because of its high biocompatibility.

  In addition, it does not specifically limit as a method to manufacture a hydroxyapatite sintered compact, For example, the conventionally well-known method currently disclosed by Unexamined-Japanese-Patent No. 2004-51952, Unexamined-Japanese-Patent No. 2005-146120, WO2009-0570502 etc. Can be manufactured.

[Surface treatment process]
The surface treatment step included in the production method according to the present invention is a step of surface-treating the substrate, and may be a step capable of forming a reactive functional group on the surface of the substrate.

  The present inventors have found that the binding of calcium phosphate and the substrate can be performed very simply by subjecting the substrate to surface treatment using ozone water. For example, even if the base material has a complicated shape, the surface of the base material can be easily and uniformly infused with ozone water simply by infiltrating the base material with ozone water or by spraying the base material with ozone water. Can be contacted. Therefore, the operation can be performed easily and efficiently.

  The present inventors have also found that calcium phosphate and a substrate can be bonded with a strong adhesive strength and a high coverage by performing a surface treatment with ozone water. Conventionally, when a substrate coated with calcium phosphate is subjected to ultrasonic cleaning, the calcium phosphate may be peeled off. This is due to the weak adhesive strength between the calcium phosphate and the substrate. However, when calcium phosphate was bonded to a substrate surface-treated with ozone water, it was possible to prevent the calcium phosphate from peeling off when ultrasonically cleaned. Further, by performing surface treatment of the substrate using ozone water, various substrates can be coated with calcium phosphate at a uniform high coverage.

  It is considered that such excellent adhesive strength and coverage are realized because ozone water can introduce radicals into any base material. For example, even if it is a base material whose surface is terminated with an oxygen group or an alkyl group such as polyester, or a base material that does not have an oxygen group on its surface such as polyolefin, radicals can be introduced satisfactorily. be able to.

  Conventionally, it has been difficult to efficiently introduce radicals into a substrate whose surface is terminated with oxygen groups, but the present inventors have found that radicals can be efficiently introduced into oxygen groups using ozone water.

  Further, the present invention is superior to the method using a radical initiator such as APS in the following points. That is, if ozone water is used, the cleaning process and waste water treatment can be simplified, which is excellent in that the influence of residual components can be eliminated. Also, some radical initiators have been pointed out as explosive hazards, which can be cumbersome. However, ozone water is easy to handle and safe because there is no danger of explosion. Furthermore, since ozone decomposes naturally over time and becomes harmless oxygen, there is almost no environmental load. Therefore, the present invention is excellent in terms of simplicity and safety.

  Furthermore, since the present invention does not require the use of an auxiliary agent such as a silane coupling agent, the process is simplified, and further, concerns about the influence of the auxiliary agent on the living body and the environment can be eliminated.

  The ozone water used in the surface treatment step is not limited as long as it is water in which ozone is dissolved, and may be manufactured using a conventionally known method and apparatus. For example, you may manufacture by the method of aeration of ozone in water. In addition, as a device for dissolving ozone in water, a conventionally known stirrer, bubble cylinder, pressure injector, Benchery injector, static mixer, or the like may be used. As a method for producing ozone water, the non-profit organization Japan Ozone Association, edited by the Ozone Handbook, Hidetoshi Sugimitsu, Kosuge Publishing, and the basics and application of ozone can be referred to.

  The concentration of ozone in the ozone water used in the production method according to the present invention is not particularly limited, but it is preferably 1 ppm or more and 50 ppm or less, in order to bind calcium phosphate to the surface of the base material with strong adhesive strength and high coverage. Is preferably 10 ppm to 35 ppm.

  The temperature of the ozone water is not particularly limited, but it is preferably 20 ° C. or higher and 60 ° C. or lower, and more preferably 20 ° C. or higher and 40 ° C. or lower, in order to bind calcium phosphate to the surface of the substrate with strong adhesive strength and high coverage. Further, room temperature (for example, 25 ° C.) is more preferable.

  Although it does not specifically limit as time to contact the surface of a base material and ozone water, 5 minutes or more and 30 minutes or less are preferable in order to couple | bond calcium phosphate with the surface of a base material with strong adhesive strength and high coverage. More preferably, the time is from 20 minutes to 20 minutes.

  The method for bringing the surface of the base material into contact with ozone water is not particularly limited. For example, the base material may be immersed in ozone water. Moreover, you may stir the said ozone water during immersion.

[Bonding process]
The binding step included in the production method according to the present invention may be a step of binding the calcium phosphate to the reactive functional group formed by the surface treatment step.
For example, a functional group introduction step of introducing a reactive functional group that facilitates the binding of calcium phosphate to the surface of the base material is performed, and the base material after the functional group introduction is brought into contact with calcium phosphate.

  Examples of such a functional group are preferably a hydroxyl group and a carboxyl group, but are not limited thereto.

  There is no particular limitation on the method for bonding the calcium phosphate with the base material on which the reactive functional group is formed by the surface treatment. For example, the substrate may be immersed in a liquid in which calcium phosphate is suspended. Moreover, you may stir the said liquid during immersion. In addition, after immersion, the substrate may be allowed to stand under reduced pressure conditions, preferably under vacuum conditions, or may be further heated under reduced pressure conditions or vacuum conditions. As heating temperature, 50 to 200 degreeC is preferable, and 80 to 150 degreeC is more preferable.

[Washing process]
In the production method according to the present invention, a washing step of washing the calcium phosphate complex obtained by the binding step may be performed. The washing process may be performed according to the intended use.

  What is necessary is just to select suitably according to the grade of the target washing | cleaning as a concrete washing | cleaning method. For example, ultrasonic cleaning may be performed. Since the calcium phosphate composite obtained by the production method according to the present invention has an extremely strong adhesive strength between the substrate and calcium phosphate, peeling of calcium phosphate can be satisfactorily suppressed even when ultrasonic cleaning is performed. The ultrasonic cleaning may be performed by a conventionally known method.

  The manufacturing method of the calcium-phosphate composite filter base demonstrated above can be utilized for various uses. For example, it can be used for purification of living water such as aquariums, aquaculture and fish pets, purification of organic wastewater such as food factories, and production of filters for purifying natural water such as rivers and lakes.

  Examples will be shown below, and the embodiments of the present invention will be described in more detail. Of course, the present invention is not limited to the following examples, and it goes without saying that various aspects are possible in detail. Further, the present invention is not limited to the above-described embodiments, and various modifications can be made within the scope shown in the claims, and the present invention is also applied to the embodiments obtained by appropriately combining the disclosed technical means. It is included in the technical scope of the invention. Moreover, all the literatures described in this specification are used as reference.

<Example 1: Direct compounding to a polyester substrate>
In this example, a polyester substrate (hereinafter referred to as “polyester substrate”) was used.
Further, a hydroxyapatite sintered body (hereinafter referred to as “HAp”, and a composite of a base material and HAp is referred to as “hydroxyapatite composite” or “HAp composite”) was used as calcium phosphate. In addition, about HAp, it manufactured in accordance with the method as described in WO2009-0570502.

[Ozone water treatment]
First, ozone water was manufactured using the gas melt | dissolution module (Japan Gore-Tech company make, model: GT-01T). Specifically, ozone water was produced by contacting pure water (flow rate 600 mL / min, pressure 0.1 MPa) and ozone gas (flow rate 500 mL / min, pressure 0.03 to 0.05 MPa) in a gas dissolution module. .
Next, the polyester base material was put in a PFA container, and ozone water was circulated through the container. That is, the ozone water was poured and extracted while maintaining the state in which the polyester base material was immersed in the ozone water in the container.

In this example, the concentration of ozone water was 10 to 13 ppm and the temperature was 25 ° C. Moreover, the time for the polyester base material to be immersed in the ozone water was 20 minutes. Hereinafter, the time for immersing the substrate in ozone water is referred to as “ozone water treatment time”.
Next, after all ozone water was extracted, the polyester base material was recovered, washed with pure water, and then washed with ethanol.

[Combination of HAp]
The polyester base material was put into 1000 mL of a HAp dispersion (concentration: 1 Wt%, solvent: ethanol), and left to stand for 30 minutes for complexation. Next, after taking out the polyester base material, ultrasonic cleaning for 1 minute in ethanol was performed by replacing ethanol three times. Then, it dried under reduced pressure for 1 hour in the vacuum desiccator.

[Observation using a scanning electron microscope]
The HAp complex obtained in this example was observed using a scanning electron microscope (manufactured by JEOL Ltd., model: JSM-5510). FIG. 1 is a diagram showing the results of observing the HAp complex obtained in this example with a scanning electron microscope. (A) shows the results of observing at 2000 times and (b) at 10000 times. .

  As shown in FIG. 1, the surface of the polyester substrate was covered with HAp with a uniform and high coverage. From this, it was shown that the substrate can be coated with HAp uniformly and at a high coverage by performing surface treatment of the substrate using ozone water.

  Next, the HAp-coated polyester base material was immersed in pure water for 1 week.

[Observation using a scanning electron microscope]
FIG. 2 is a diagram showing the HAp complex immersed in pure water for one week using the above-described scanning electron microscope. (A) is observed at a magnification of 2000 times, and (b) is observed at a magnification of 10,000 times. Results are shown.

  As shown in FIG. 2, the surface of the polyester substrate was covered with HAp with a uniform and high coverage. Compared to FIG. 1, the HAp coverage is equivalent, and it can be said that HAp does not fall off even if immersed in pure water for one week. That is, it was confirmed that the binding force between the HAp complex and the substrate was strong.

  Next, the HAp complex was treated with probe ultrasonic waves (manufactured by SONIFIER450 BRANSON SONIC POWER CONPANY) for 5 minutes in a 1: 1 ethanol / pure water mixture.

[Observation using a scanning electron microscope]
FIG. 3 is a diagram showing the results of observing the HAp complex treated with probe ultrasound in a 1: 1 ethanol / pure water mixed solution using the above-mentioned scanning electron microscope, (a) 2000 times and (b) show the results observed at a magnification of 10,000 times.

  As shown in FIG. 3, the surface of the polyester substrate was covered with HAp with a uniform and high coverage. Compared with FIG. 1, the HAp coverage is the same, and it can be said that HAp does not fall off even when probe sonication is performed. That is, the binding force of the HAp composite substrate can withstand the stress caused by the probe ultrasonic waves.

<Example 2: Direct compounding to a polyurethane-based substrate>
In this example, a polyurethane substrate (hereinafter referred to as “polyurethane substrate”) was used as the substrate. The same procedure as in Example 1 was performed until the production of the HAp complex.

[Observation using a scanning electron microscope]
FIG. 4 is a diagram showing the results of observing the HAp complex obtained in this example using the above-described scanning electron microscope, where (a) is observed at a magnification of 2000 times and (b) is observed at a magnification of 10,000 times. The results are shown. As shown in FIG. 4, the surface of the polyurethane substrate was covered with HAp with a uniform and high coverage. From this, it was shown that the base material can be coated with HAp uniformly and at a high coverage rate by subjecting the polyurethane base material to surface treatment using ozone water.

  Next, the HAp-coated polyurethane substrate was immersed in pure water for 1 week.

[Observation using a scanning electron microscope]
FIG. 5 is a diagram showing the results of observing the HAp complex obtained in this example using the above-mentioned scanning electron microscope, where (a) is observed at a magnification of 2000 times and (b) is observed at a magnification of 10000 times. The results are shown. As shown in FIG. 5, the surface of the polyurethane base material was covered with HAp with a uniform and high coverage. Compared with FIG. 4, the HAp coverage is equivalent, and it can be said that HAp does not fall off even if immersed in pure water for one week. That is, it was confirmed that the binding force between the HAp composite and the base material is strong even when the base material is polyurethane.

<Example 3: Direct compounding to a silica substrate>
In this example, an HAp composite was produced on an inorganic (silica) base material (hereinafter referred to as a silica base material) by the same method as in Example 1.

[Observation using a scanning electron microscope]
FIG. 6 is a diagram showing the results of observing the HAp complex obtained in this example using the scanning electron microscope described above, (a) is observed at a magnification of 2000 times, and (b) is observed at a magnification of 10000 times. The results are shown. As shown in FIG. 6, it was confirmed that an HAp composite having a uniform and high coverage can be obtained not only with a resin system but also with an inorganic base material.

  Next, the HAp-coated silica substrate was immersed in pure water for 1 week.

[Observation using a scanning electron microscope]
FIG. 7 is a diagram showing the results of observing the HAp complex obtained in this example using the above-described scanning electron microscope, where (a) is observed at a magnification of 2000 times and (b) is observed at a magnification of 10000 times. The results are shown. As shown in FIG. 7, the surface of the silica substrate was covered with HAp with a uniform and high coverage. Compared to FIG. 6, the HAp coverage is equivalent, and it can be said that HAp does not fall off even if immersed in pure water for one week. That is, it was confirmed that the binding force between the HAp composite and the base material is strong even when the base material is inorganic.

<Comparative Example 1: Direct compounding to a polyester substrate (no ozone treatment)>
In this comparative example, a HAp composite was produced in the same manner as in Example 1 except that ozone treatment was not performed. That is, in this example, the HAp composite was directly produced on the substrate without performing ozone treatment.

[Observation using a scanning electron microscope]
FIG. 8 is a diagram showing the results of observing the HAp complex obtained in this Comparative Example with the above-described scanning electron microscope, where (a) is observed at a magnification of 2000 times and (b) is observed at a magnification of 10000 times. Indicates. As shown in FIG. 8, the amount of HAp coating on the surface of the polyester substrate was small.

[Observation using a scanning electron microscope]
FIG. 9 is a diagram showing the results of observing the HAp complex obtained in this example with the above-described scanning electron microscope. (A) is the result of 2,000 times, and (b) is the result of being observed at a magnification of 10000 times. Indicates. As shown in FIG. 9, HAp particles were dropped on the surface of the polyester base material. That is, when immersed in pure water for 1 week, the bonding force between the polyester base material and the HAp particles was weak, so that the dropping occurred.

<Comparative Example 2: Direct compounding onto a polyurethane substrate (no ozone treatment)>
In this comparative example, a HAp composite was produced on a polyurethane substrate in the same manner as in Example 2 except that the ozone water treatment was not performed. That is, in this example, the HAp complex was directly produced on the substrate to produce the HAp complex.

[Observation using a scanning electron microscope]
FIG. 10 is a diagram showing the results of observing the HAp complex obtained in this example with the above-described scanning electron microscope. (A) is 3000 times, and (b) is 20000 times magnification. Indicates.

  As shown in FIG. 10, the surface of the base material was covered with HAp with a uniform and high coverage.

  Next, the polyurethane base material HAp composite not subjected to ozone treatment was immersed in pure water for one week.

[Observation using a scanning electron microscope]
FIG. 11 is a diagram showing the results of observing the HAp complex obtained in this example with the above-described scanning electron microscope. (A) is a result of 2,000 times, and (b) is a result of being observed at a magnification of 10000 times. Indicates. As shown in FIG. 11, almost no HAp complex was seen on the surface of the polyurethane substrate, and the HAp particles were dropped by being immersed in pure water for 1 week. That is, the bonding strength between the polyurethane base material not subjected to ozone treatment and the HAp particles is weak.

Claims (8)

  A biological filter material for organic wastewater purification treatment, wherein a base material and biocompatible particles having biocompatibility are chemically bonded.   The organic wastewater purification treatment according to claim 1, comprising a step of performing a surface treatment to generate a reactive functional group on the surface of the substrate and a reaction step of reacting the biocompatible particles. Biological filter media.   3. The organic wastewater purification treatment according to claim 2, wherein the reactive functional group is a hydroxy group, a carboxyl group, an amino group, a sulfonic acid group, a sulfo group, a thiol group, a cyano group, or a hydrosilyl group. Biological filter media.   The method for generating the reactive functional group includes at least one method selected from the group consisting of acid, alkali, ozone, ozone water, ozone bubbling, plasma, corona discharge, and ultraviolet treatment. Biological filter material for organic wastewater purification treatment according to 1.   The biological filter material for organic wastewater purification treatment according to claim 4, wherein the method for generating the reactive functional group is ozone water.   The biological filter material for organic wastewater purification treatment according to any one of claims 2 to 5, wherein the biocompatible particles are a calcium phosphate sintered body.   The biological filter material for organic wastewater purification treatment according to claim 6, wherein the calcium phosphate sintered body is hydroxyapatite.   The biological filter material for organic wastewater purification treatment according to any one of claims 1 to 7, wherein the biocompatible particles have an average particle size of 20 nm to 50 µm.