JP2010207177A - Filtration molding for aquarium fish and production method thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide filtration moldings for aquarium fishes, preventing falling out of ion exchange resin powders supported on a support, and enabling recovery and reuse by preventing deformation of the support. <P>SOLUTION: There is provided a filtration molding 10 comprising a support 12 comprising a fiber material, ion exchange powders 14 supported on the support 12, and a covering layer 16 covering the surface of the support 12, is provided, wherein, the ratio of the surface area of the covering layer 16 to the total surface area of the support 12 is preferably in a range of 40-95%. The fineness of the fiber material of the support 12 is preferably in a range of 2-5 dtex on average. Further, the support 12 is preferably mat-like. Moreover, a surface protective layer comprising a fiber material is preferably equipped. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an ornamental fish filtration molded article suitable as a filter medium for filtering breeding water in an aquarium fish tank and a method for producing the same.

  Conventionally, artificial breeding of ornamental fish and the like has been actively performed using an aquarium fish tank. During the breeding process, excrement and residual food such as ornamental fish are produced. Therefore, breeding water is filtered by various methods for the purpose of maintaining water quality. For example, excrement and residual food are collected to some extent by physical filtration using wool or the like, and the remaining excrement and residual food are decomposed by biological filtration using a porous material.

  In this decomposition process, soluble ammonia nitrogen and nitrite nitrogen are generated. These are very toxic to ornamental fish and the like, and adversely affect the ornamental fish and the like. And this ammonia nitrogen and nitrite nitrogen are decomposed into nitrate nitrogen having low toxicity by nitrifying bacteria. Microorganisms that perform such nitrification are beneficial for water purification, but on the other hand, if such microorganisms grow too much, they will adversely affect ornamental fish and the like. Therefore, it is said that it is very difficult to maintain these balances and maintain the water quality for a long time.

  In addition, driftwood may be installed in the aquarium fish tank for the purpose of decoration or living as an ornamental fish. In this case, if the driftwood ash is not sufficiently extracted, the ash is eluted from the driftwood in the breeding water. This not only impairs the beauty, but also adversely affects ornamental fish and the like.

  Therefore, various materials and techniques for removing or decomposing harmful substances that adversely affect such ornamental fish have been proposed.

  For example, Patent Document 1 discloses an ornamental fish filter in which powdered activated carbon or zeolite is incorporated in a bag-like sheet body and filtration is performed using the adsorption action of the activated carbon or zeolite.

  Patent Document 2 discloses a technique for performing filtration in an aquarium fish tank using a filter medium in which a powder ion exchange resin is supported on a support made of fibers.

JP 2000-236774 A Japanese Patent Laid-Open No. 08-238040

  However, in the thing of patent document 1, in order to make adsorption | suction efficiency high, the fine powder of activated carbon with a small particle size is used. And if it is used as it is, the water becomes turbid, so it is necessary to use a bag for incorporating it so as not to flow out. Further, if the bag body is torn during handling or the like, there is a risk that it will be contaminated with activated carbon. In addition, the amount of use is large, and it is necessary to replace them regularly, which tends to increase costs.

  On the other hand, in the thing of patent document 2, at the time of handling, the powder ion exchange resin was easy to drop | omit from a fiber. And when it puts in water, since a fiber will swell, powder ion-exchange resin will fall out more easily and there was a possibility of making the inside of a water tank cloudy. Further, the fibers swollen in the water tank are in a state that does not remain in the form, and it is difficult to collect and wash and reuse the fibers. Furthermore, since the powder ion exchange resin is supported on the fiber by a wet method, it is necessary to dry the filter medium after the support. However, when spin dehydration is performed in the drying process, the fibers rub against each other and fluff is formed on the fiber surface. The appearance was bad.

  The problem to be solved by the present invention is to prevent the dropping of the ion exchange resin powder carried on the support, and to prevent the mold from being deformed and to enable recovery and reuse, and a filter molded body for ornamental fish. It is to provide a manufacturing method.

  In order to solve the above problems, a filter molded body for ornamental fish according to the present invention includes a support made of a fiber material, an ion-exchange resin powder carried on the support, and a coating layer covering the surface of the support. The gist is that

  At this time, the ratio of the surface area of the coating layer to the total surface area of the support is preferably in the range of 40 to 95%.

And the mass of the said coating layer per unit surface area of the said support body is good in the range of 40-120 g / m < ² >. At this time, the coating layer may contain a porous material. The porous material is preferably an adsorptive material. Furthermore, the coating layer may contain an adhesive.

  The thickness of the fiber material is preferably in the range of 2 to 5 dtex on average. The support is preferably in the form of a mat. At this time, the coating layer may be formed only on one surface of the mat-like support.

  The ion exchange resin may be one or more selected from an anion exchange resin and a cation exchange resin.

  The ornamental fish filtration molded body may further include a surface protective layer made of a fiber material.

  On the other hand, the method for producing a filter molded body for ornamental fish according to the present invention includes a step of forming a coating layer on the surface of a support made of a fiber material, and immersing the support in a liquid containing ion-exchange resin powder. The gist of the invention is to have a step and a step of drying the support infiltrated by the immersion.

  According to the filter molded body for ornamental fish according to the present invention, since the coating layer is provided on the surface of the support made of the fiber material, the ion-exchange resin powder carried on the support is separated from the support. Can be prevented. Moreover, since the surface of the support is reinforced by the coating layer, it is possible to prevent the support from being deformed. And thereby, a filtration molding can be collect | recovered and reused.

  At this time, when the ratio of the surface area of the coating layer covering the surface of the support is within the specific range, the effect of preventing the ion-exchange resin powder from dropping off and the effect of preventing the support from being deformed are excellent, and It is easy to come into contact with and has excellent filtration efficiency.

  And if the mass of the said coating layer per unit surface area of the said support body exists in the said specific range, shape | mold deformation | transformation of a support body can be prevented reliably. Further, when the coating layer contains a porous material, the porous material has continuous or independent pores in its structure and has a large specific surface area, so that it contains water when introduced into the breeding water. Therefore, the filtration molding can be quickly settled in the breeding water, and an excellent filtration effect can be expected from an early stage. Moreover, since the contact area with the breeding water is large, an excellent filtration effect can be expected.

  And when this porous material is an adsorptive material, it can actively adsorb harmful substances such as ammonia, nitrous acid and chlorine dissolved in the form of ions in the water tank. Therefore, a high filtration effect is obtained together with the adsorption effect by the ion exchange resin. Furthermore, since the coating layer can be hardened when the coating layer contains an adhesive, the effect of preventing the support from being deformed is excellent.

  And when the thickness of a fiber material exists in the range of 2-5 decitex on the average, while the load of ion-exchange resin powder can be made high, the dispersibility can be improved. Moreover, it is excellent also in water permeability. Thereby, the high filtration effect is acquired.

  At this time, if the support is mat-like, the effect of preventing the deformation of the mold is high. At this time, if the coating layer is formed only on one side surface of the mat-like support, the surface on which the coating layer is not formed is highly hydrophilic, so that the filtration molded body can quickly settle in the breeding water, and is excellent from an early stage. Filtration effect can be expected.

  And when an ion exchange resin contains an anion exchange resin and a cation exchange resin, since an aggregate is formed with an anion exchange resin and a cation exchange resin, water permeability is easy to be ensured.

  Further, when this filtration molded body is provided with a surface protective layer made of a fiber material, the ion exchange resin powder is detached so as to further cover the surface of the filtration molded body including the portion where the coating layer on the support surface is not formed. It is possible to further enhance the effect of suppressing the above.

  And, according to the method for producing an ornamental fish filtration molded body according to the present invention, the coating layer is formed on the surface of the support, so that the ion-exchange resin powder carried on the support is prevented from falling off and the support is not deformed. Can be produced. In addition, since the coating layer is formed on the surface of the support, it is difficult to form pills on the support surface even if rotational dehydration is performed in the drying process. Therefore, it is possible to produce a filtration molded article having an excellent appearance.

It is the perspective view (a) and sectional schematic diagram (b) showing the filtration molded object which concern on one Embodiment of this invention.

  Next, an embodiment of the present invention will be described in detail. As shown in FIG. 1, an ornamental fish filtration molded body 10 (hereinafter also referred to as a filtration molded body 10) according to an embodiment of the present invention includes a support 12 and ions supported on the support 12. An exchange resin powder 14 and a coating layer 16 covering the surface of the support 12 are provided.

  The support 12 is made of a fiber material. The fiber material is not particularly limited, and examples thereof include polyester fiber, nylon fiber, acrylic fiber, polyurethane fiber, and rayon fiber. These can be used alone or in combination of two or more. Among these, a polyester fiber is preferable from the viewpoint of easily containing water because a gap between fibers is easily formed even when the amount of fibers is increased.

  The thickness of the fiber material is 2 to 5 dtex on average (2 in the case of dtex and denier) from the viewpoints of water permeability, maintainability, cleanability, and easy adhesion of the ion exchange resin powder 14 uniformly and densely. -4 denier, hereinafter expressed in denier). Here, the thickness of the fiber material is expressed as an average even if the support 12 may be formed of fiber materials having the same thickness, or the support 12 may be formed of fiber materials having different thicknesses. Because it is good. The fiber may be prepared by mixing ultrafine cut fibers of 1 denier or less, cut fibers of 5 denier or more, and the like.

  When forming with fiber materials having different thicknesses, if the amount of fiber materials that are relatively thin is increased in mass ratio, the ion-exchange resin powder 14 is likely to enter between the fibers, so that the filtration performance of the filter molded body 10 is excellent in sustainability. . On the other hand, when a relatively thick fiber material is increased, the water permeability is excellent. Therefore, the ratio may be adjusted as appropriate in consideration of these balances. More preferably, the proportion of the relatively thin fiber material is increased from the viewpoint of excellent filtration performance sustainability.

  When the thickness of the fiber material is less than 2 denier on average, the gap between the fibers tends to be small. Therefore, the ion exchange resin powder 14 is likely to adhere uniformly and densely, but is difficult to permeate water. For this reason, the water transmission rate tends to decrease. In addition, when the gap between the fibers is reduced, excrement such as ornamental fish, residual food, and the like are easily deposited on the fibers and become clogged. As a result, the frequency of cleaning and replacement is increased, and the maintainability may be deteriorated.

  On the other hand, when the thickness of the fiber material exceeds 4 denier on average, the gap between the fibers tends to be large. Therefore, the water permeation rate is high, and the residence time of water containing pollutants such as excrement and residual bait tends to be short, so that purification is likely to be insufficient. Further, when the ion exchange resin powder 14 is attached to the fiber, the ion exchange resin powder 14 is likely to spill out from the gap between the fibers, and thus the ion exchange resin powder 14 is difficult to adhere. Furthermore, since the ion exchange resin powder 14 adheres to the portion where the fibers are densely packed, the gap between the fibers becomes large. As a result, the ion exchange resin powder 14 is difficult to be densely and uniformly dispersed in the support 12.

  The shape of the support 12 is molded into a predetermined shape from the viewpoint of being less likely to lose its shape during use, recovery, cleaning for removing dirt and the like that has been attached over a long period of time, and the like. preferable. More specifically, the shape of the support 12 is preferably a mat shape. The mat-like support may have a shape of one surface of a polygon such as a triangle, a quadrangle, or a pentagon, a circle, an ellipse, or the like, and can have various shapes. It can be adjusted as appropriate in consideration of the place of use, the size of the water tank, design and the like. Further, the size of the support 12 may be appropriately adjusted according to the degree of soiling of the breeding water, the size of the water tank, and the like. If the shape of the support 12 is a mat, it is easy to perform processing such as cutting to a desired size.

  The ion exchange resin powder 14 carried on the support 12 may be powdered in advance, or may be obtained by pulverizing granular ion exchange resin. The average particle diameter of the ion exchange resin powder 14 is not particularly limited. If the particle size is reduced, the surface area increases and the adsorption efficiency increases, but the handleability decreases. From this viewpoint, the average particle diameter of the ion exchange resin powder 14 is preferably 250 μm or less. More preferably, the average particle size is in the range of 1 to 25 μm.

  When the average particle size exceeds 250 μm, it is estimated that the filtering action is based only on the chemical ion exchange action by the ion exchange groups, and thus the filtration process may take time. On the other hand, when the average particle size is 250 μm or less, it is presumed that the surface activity becomes strong and the physical adsorption action appears, so that it can be expected that the filtration processing speed is increased. Furthermore, when the average particle size is in the range of 1 to 25 μm, it is easy to manufacture by mechanical pulverization and not only easy to use, but also exhibits excellent physical adsorption action similar to that of activated carbon. Due to the synergistic effect with the ion exchange action, an excellent filtration action can be exhibited. In addition, the filtration speed is remarkably increased. In addition, when the average particle size is less than 1 μm, the filtration processing speed is excellent and the physical adsorption action is obtained, but the production by mechanical pulverization is difficult and the cost tends to be high.

  As a method for pulverizing the granular ion exchange resin, a mechanical pulverization method may be used, but a method that does not impair the function of the ion exchange resin powder 14 as much as possible, for example, an airflow pulverization method, a freeze pulverization method, and the like. In this method, for example, a pulverizer “New Micron Cyclomat” manufactured by Masuno Seisakusho can be used.

  The ion exchange resin may be an anion exchange resin or a cation exchange resin. Moreover, an anion exchange resin and a cation exchange resin can also be used together. These can be used alone or in combination. Among these, it is preferable to contain both an anion exchange resin and a cation exchange resin from the viewpoint of more easily adsorbing ammonia nitrogen components and nitrite nitrogen components that adversely affect ornamental fish and the like. In addition, when an anion exchange resin and a cation exchange resin are used in combination, they form an aggregate, making it difficult to fill the gaps between the fibers of the support 12. Therefore, water permeability is easy to be secured. At this time, the ratio of the anion exchange resin to the cation exchange resin may be adjusted as appropriate, but the mass ratio is preferably in the range of 4: 1 to 1: 4. Although the clarification action is weak only with the cation exchange resin powder, the use of both the anion and cation exchange resin powders exhibits an excellent purification function for both the ammonia nitrogen component and the nitrite nitrogen component.

  The loading amount of the ion exchange resin powder 14 is not particularly limited. For example, the ion exchange amount of the ion exchange resin, the degree of soiling of the breeding water, the size of the water tank, the size of the filtration molded body 10, the handleability, and the like can be appropriately adjusted. From the viewpoint of handleability and the like, the supported amount is preferably in the range of 0.1 to 1 g / g (dry mass of support) per dry weight of the porous support.

  Specific examples of the ion exchange resin suitably used in the present invention include, for example, Diaion of Mitsubishi Chemical Corporation (registered trademark of Mitsubishi Chemical Corporation), Amberlite of Organo Corporation (registered by Rohm and Haas) Trademark). Examples of the anion exchange resin include Diaion PA316, WA30, Amberlite IRA900, IRA93, and the like. Examples of the cation exchange resin include Diaion PK216, WK11, Amberlite IRC120, IRC50, and the like. Examples of commercially available ion-exchange resin powders that have been powdered in advance include Diaion FMA manufactured by Mitsubishi Chemical Corporation and POWEX manufactured by Organo Corporation.

  Since the coating layer 16 covers the surface of the support 12, the ion exchange resin powder 14 carried on the support 12 is prevented from falling off the support 12. Further, since the shape of the support 12 is maintained, the support 12 is prevented from being deformed. On the other hand, since the support 12 is made of a fiber material, water easily enters the gaps between the fibers, and the support 12 is easy to contain water. However, since the covering layer 16 covers the surface, the water absorption of the support 12 It is easy to reduce the nature. Thereby, since time is required for contact with the support body 12 and breeding water, time until a filtration effect is exhibited will be required.

  Therefore, the coating layer 16 covering the surface of the support 12 may cover the entire surface of the support 12, but from the viewpoint of ensuring water permeability, a part of the entire surface of the support 12 is covered. It is preferable to coat. That is, it is preferable that a portion where the coating layer 16 is provided and a portion where the coating layer 16 is not provided are mixed on the surface of the support 12. Under the present circumstances, it is preferable that the ratio of the surface area of the coating layer 16 with respect to the total surface area of the support body 12 exists in the range of 40 to 95%. More preferably, it is in the range of 40 to 80%.

  When the ratio of the surface area of the coating layer 16 exceeds 95%, as described above, since it takes time to exhibit the filtration effect, the filtration efficiency tends to decrease. On the other hand, when the ratio of the surface area of the coating layer 16 is less than 40%, the effect of covering the support 12 with the coating layer 16, that is, the effect of preventing the ion exchange resin powder 14 from falling off or preventing the deformation of the support 12. Is prone to decline.

  The covering layer 16 can be formed in consideration of productivity and design. For example, when the support 12 is in the form of a mat, mass production is easy if it is formed on the upper and lower surfaces (surfaces having the maximum area) of the support 12. Further, a lattice-like pattern may be formed only on the side surface, the center of the upper and lower surfaces, or on the upper and lower surfaces.

  Moreover, when the support body 12 is mat-like, the coating layer 16 may be formed on only one of the upper and lower surfaces. In this case, since the surface on which the coating layer 16 is not formed has high hydrophilicity, the filtration molded body 10 can quickly settle in the breeding water, and an excellent filtration effect can be expected from an early stage.

The coating amount of the coating layer 16 is preferably in the range of 40 to 120 g / m ² per unit surface area of the support 12 from the viewpoint of preventing the support 12 from being deformed. If the coating amount of the coating layer 16 is less than 40 g / m ² , the shape tends to be lost in the dehydration process during mass production, or the support 12 is bent when the filter layer is laid down in a filter and used. The ion exchange resin powder 14 may be detached and the water in the water tank may become cloudy. In addition, when the coating amount of the coating layer 16 exceeds 120 g / m ² , the flexibility of the support 12 is extremely lowered and it is difficult to put it in a commercially available filter, or it is difficult to wash it during maintenance. It also lacks handling. For example, in the case of a support having a thickness of about 8 mm and a width of 50 to 100 mm, the support 12 having excellent shape retention can be obtained by setting the coating amount to 40 to 120 g / m ² .

  The covering layer 16 is not particularly limited as long as it can be formed into a film shape. Preferably, it contains a porous material. Since the porous material has continuous or independent pores in its structure and has a large specific surface area, it contains water when it is put into the breeding water. Therefore, when the porous material is contained, the filtration molded body 10 can be quickly settled in the breeding water, and an excellent filtration effect can be expected from an early stage. Moreover, since the contact area with the breeding water is large, an excellent filtration effect can be expected.

  And when this porous material is an adsorptive material, it can actively adsorb harmful substances such as ammonia, nitrous acid and chlorine dissolved in the form of ions in the water tank. Therefore, a high filtration effect is obtained together with the adsorption effect by the ion exchange resin. Furthermore, since the coating layer 16 can be hardened when the coating layer 16 contains an adhesive, the effect of preventing the deformation of the support 12 is excellent.

  Examples of the porous material include zeolite, activated carbon, bentonite, diatomaceous earth, calcium silicate hydrate and the like. Examples of the adsorptive material include charged materials (with ion exchange ability) such as zeolite, activated carbon, cristobalite, and barleystone.

  Examples of the adhesive (curing material) include acrylic ester (co) polymer, synthetic rubber, (modified) styrene-butadiene copolymer (SBR), and the like. More specifically, an acrylic acid ester copolymer aqueous emulsion (manufactured by Showa Polymer Co., Ltd., “Polysol FF08”), synthetic rubber latex (manufactured by DIC, “Lackstar”), and the like can be exemplified. Among these, an acrylic ester copolymer aqueous emulsion is preferable because it has a high effect of hardly inhibiting the porous portion of the porous material when used in combination with the porous material.

When the coating layer 16 contains a porous material, the content of the porous material in the coating layer 16 is preferably in the range of 30 to 115 g / m ² . More preferably, it is in the range of 40 to 110 g / m ² . When the content of the porous material is less than 30 g / m ² , a thin layer is formed on the surface, and the ion exchange resin powder 14 tends to flow out therefrom. On the other hand, when the content of the porous material exceeds 115 g / m ² , the water repellency tends to increase. Therefore, when it puts in breeding water, the water content of the support body 12 falls and the filtration effect is hard to be exhibited.

  The filtration molded body 10 may further include a surface protective layer. When the surface protective layer is provided, the surface of the filtration molded body 10 including the portion where the coating layer 16 on the surface of the support 12 is not formed is further covered, so that the effect of suppressing the detachment of the ion exchange resin powder 14 is further enhanced. Can do. The surface protective layer is preferably made of a fiber material. Examples of the fiber material include cellulose, polyester, and nylon. Among these, since cellulose has high hydrophilicity, it is preferable in that the filtration molded body 10 can quickly settle in the breeding water and an excellent filtration effect can be expected from an early stage. At this time, the fiber material is more preferably fibrillated (divided or fibrillated). The fibrillation can be performed by a known method. Examples of such a fiber material include cellulose fiber “Serish” manufactured by Daicel Chemical Industries.

  The filtration molded body 10 according to the present invention is suitable as a filter medium for filtering breeding water in an aquarium fish tank, for example, a suction port or a blowout port of a filter in an aquarium fish tank, or a filter interior. It can be installed and used where breeding water passes. At this time, the filter-molded body 10 may be used as it is, or may be used by being accommodated in a plastic case or the like having a mesh-like hole so that water can pass therethrough.

  In the filter molded body 10 according to the present invention, the mechanism is not sufficiently elucidated, but the charge of the ion exchange resin powder 14 and the purified microorganism are selectively combined, and the support 12 is used as a place for the growth of the purified microorganism. This is considered to be one of the reasons why the bioreactor effect superior to the conventional one can be exhibited.

  Next, a method for producing an ornamental fish filtration molded body according to the present invention (hereinafter sometimes referred to as the present production method) will be described. This manufacturing method has the process of forming a coating layer, the process of immersing a support body, and the process of drying a support body.

  In the step of forming the coating layer, first, a composition for forming a coating layer is prepared. In order to prepare the composition for forming a coating layer, for example, the porous material, the adhesive, and other components as necessary are mixed. Next, the obtained composition for forming a coating layer is applied to the support surface. The application method is not particularly limited, and various methods such as a roll coating method, a dipping method, and a spray coating method can be exemplified.

  In the step of immersing the support, first, the ion exchange resin powder is dispersed in a dispersion such as water, and then the support is immersed in the dispersion. Thereby, the ion exchange resin powder is dispersed in the fiber structure of the support. At this time, the dispersion may be stirred so that the ion-exchange resin powder is easily dispersed in the fiber structure of the support.

  Further, before the substrate is immersed in the dispersion, if the substrate is immersed in a liquid containing a fibrous material that is finer than the fiber material constituting the substrate, the minute amount is obtained. The fibrous material adheres to the fiber material of the support, and the fibers of the support are made denser. As a result, the ion exchange resin powder becomes more difficult to desorb from the support. Specifically, as such a fine fibrous material, for example, cellulose fiber “Serish” manufactured by Daicel Chemical Industries, Ltd. and the like can be mentioned.

  In the step of drying the support, the support infiltrated by the immersion is dried. In this case, first, the support can be dehydrated using a centrifuge or the like. Subsequently, it can dry by methods, such as a heating and ventilation. The drying temperature, the air flow rate, and the drying time can be appropriately determined. In addition, it is preferable to adjust a drying temperature in the temperature range which does not damage the fiber material which comprises a support body.

  And after immersing a support body in the liquid containing ion-exchange resin powder in this way, this can be dried, and ion exchange resin can be carry | supported by a support body. These operations can be repeated as necessary for reasons such as adjusting the amount of ion-exchange resin powder supported.

  When supporting both anions and cations as an ion exchange resin, the support is immersed in a liquid containing one (eg, anion exchange resin), dehydrated, and the other (eg, cation exchange resin). The anion and cation ions can be supported by a method of immersing the support in a liquid containing lysate and dehydrating it.

  Any of the step of forming the coating layer and the step of supporting the ion-exchange resin powder may be performed first. For example, when the step of forming the coating layer is performed first, it is more difficult to form pills in the step of drying the support.

  When forming a surface protective layer on the surface of the filtration molded body, after dispersing the material constituting the surface protective layer, for example, the above fiber material in a liquid such as water, the ion-exchange resin powder is supported in this liquid. And the support body in which the coating layer was formed is immersed. Next, dehydration and drying are performed. At this time, it is preferable to adjust the pH of the liquid within a range of 7 to 7.8 using a pH buffer that adjusts the pH to near neutral. If the treatment for forming the surface protective layer is carried out using a pH buffer that adjusts the pH to near neutral, the pH buffer can adhere to the filtration molded body, so the pH of the breeding water is maintained near neutral. Can provide a buffering action. If the pH of the breeding water can be maintained in the vicinity of neutrality, death of appreciation fish and the like due to rapid fluctuations in pH and increase in harmful components in water due to this can be prevented.

  According to the present production method described above, since the coating layer is formed on the support surface, it is possible to produce a filtration molded product that can prevent the ion-exchange resin powder from falling off and the support from being deformed. And the obtained filtration molded object is a thing suitable for reuse. That is, since dirt is attached to the surface of the filter molded body after long-term use, it is necessary to collect and wash the filter molded body after use. In this case, since the coating layer is formed on the surface of the support, for example, when dewatering is performed in the drying step after washing, it is difficult to form pills on the surface of the support. Therefore, it is possible to prevent deterioration in performance and appearance when reusing.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

(Example)
<Fabrication of filtration molding>
Artificial zeolite (manufactured by Chubu Electric Power Co., Ltd., “Cyculus”) and adhesive on the surface of a support (thickness 8 mm) formed from the fiber material shown in Table 1 in a mat shape with the application site and application amount shown in Table 1. A mixture of (acrylic ester copolymer aqueous emulsion, manufactured by Showa Polymer Co., Ltd., “Polysol FF08”) was spray-coated to form a coating layer. Subsequently, it cut-processed using the cutter and produced the 80 mm x 65 mm coating layer formation support body.

  Subsequently, the obtained coating layer forming support was immersed in 10 L of pretreated water containing 1% of microfibrous cellulose (manufactured by Daicel Chemical Industries, Ltd., “Serisch”), and then subjected to dehydration treatment. Next, it is immersed in 10 L of treated water containing 5% of an anion exchange resin powder (ion exchange resin powder having an average particle diameter of 15 μm prepared by air-flow grinding of “Diaion PA318” manufactured by Mitsubishi Chemical Corporation) for 5 to 10 minutes. After stirring, it was dehydrated with a centrifuge. Next, the cation exchange resin powder (Mitsubishi Chemical Co., Ltd., “Diaion PA218”, ion-exchange resin powder having an average particle diameter of 15 μm prepared by air-flow pulverization) is immersed in 10 L of treated water and is immersed for 1 to 5 minutes. After stirring, it was dehydrated with a centrifuge. Subsequently, it was blown and dried at a temperature of 80 ° C. or lower. As a result, the ion exchange resin was supported on the coating layer forming support to produce a filtration molded body according to the example.

  In addition, in the case of the surface protective layer “existing”, it was further immersed for 1 minute in 10 L of treated water containing 1% of microfibrous cellulose (manufactured by Daicel Chemical Industries, “Serisch”), followed by dehydration treatment. Subsequently, it blow-dried at the temperature of 80 degrees C or less, and produced the filtration molded object which concerns on an Example.

(Comparative Examples 1-2)
After carrying out pretreatment with microfibrous cellulose by the same method as in Example 1 on the support made of the fiber material described in Table 1, carrying both ion exchange resins by the same method as in Example 1, The filter body which concerns on Comparative Examples 1-2 was produced. The support of the filter body according to Comparative Examples 1 and 2 is not formed into a mat shape, and the coating layer is not formed on the surface of the support.

(Comparative Examples 3-6)
After coating each fiber of the fiber material shown in Table 1 with the same material as the coating material (artificial zeolite and adhesive) constituting the coating layer of the example, this fiber was molded into a mat shape. A support was prepared. Next, after pre-treatment with microfibrous cellulose by the same method as in Example 1, both ion exchange resins were supported by the same method as in Example 1, and the filtration molded bodies according to Comparative Examples 3 to 6 were obtained. Produced.

  Using each filter molded body or filter body, the desorption of the ion exchange resin, the shape after use, the possibility of reuse, and the adsorption effect were examined. In addition, mass production and handling were also investigated.

(Reference example)
As the filter medium, activated carbon (“Black Hole”, manufactured by Kyorin Co., Ltd.) was used instead of the above-mentioned filter molded body.

<Evaluation method>
(Desorption of ion exchange resin)
The test body formed by cutting the filter according to Example or Comparative Example into 2 cm square was put into 100 ml of distilled water, and a shaker with a rotational speed of 30 rpm (manufactured by Tokyo Rika Kikai Co., Ltd., multi shaker, hereinafter the same). Shake for 24 hours. Thereafter, the test specimen was gently taken out, and the turbidity and sedimentation due to the ion exchange resin powder in distilled water was visually evaluated. The case where there was almost no turbidity or sedimentation was judged as acceptable “◯”, the case where turbidity or sedimentation was slightly seen was regarded as acceptable “△”, and the case where turbidity or sedimentation was noticeable was regarded as unacceptable “x”.

(About the shape after use)
The test body formed by cutting the filter body according to Example or Comparative Example into 2 cm square was put in 100 ml of distilled water and shaken for 24 hours with a shaker having a water temperature of 16.5 to 17.0 ° C. and a rotation speed of 30 rpm. I let you. Then, the test body was taken out gently and it was visually evaluated whether the shape of the test body was maintained. If the shape of the test specimen is almost unchanged and the shape is maintained, it is acceptable (○). If the specimen is partially collapsed or slightly expanded, it is acceptable (△). Or the case where it was excessively expanded was regarded as a failure “x”.

(About the first adsorption effect)
Brown test water <1> was prepared by immersing a commercially available driftwood not taken from lye in water for 1 month to elute the lye component. In addition, 0.5 g of methylene blue (reagent) powder was completely dissolved in 50 ml of ethanol, and distilled water was added to make a 100 ml solution. This was diluted 200 times as a stock solution to prepare test water <2>.

  Subsequently, the test body formed by cutting the filter body according to the example or the comparative example into 2 cm square was put into test water <1>, and was shaken for 24 hours with a shaker having a rotation speed of 30 rpm. Thereafter, the test specimen was gently taken out, and the supernatant after standing was evaluated visually and based on the absorbance value by an absorption spectrophotometer (manufactured by JASCO Corporation, “UVIDEC-340”, measurement wavelength 300 nm). Moreover, the same operation was performed also with respect to test water <2>, and it evaluated by visual observation and the value of absorbance (measurement wavelength 665 nm). In any test water, it is transparent or almost transparent by visual inspection, and when the absorbance value is 70% or more, it is a pass “○”, and in any test water, it can be seen that it is visually colored. , When the absorbance value is 40-70%, “△”, in any test water, the color remains so as to be almost the same as the blank visually, and when the absorbance value is less than 40%, it is rejected. It was set as “x”.

(Adsorption effect during reuse)
With respect to the specimen subjected to the first adsorption effect test, the adsorption test was performed again using the new test solutions <1> and <2>. The evaluation was performed by visual observation and absorbance values as in the first evaluation of the adsorption effect.

(About mass productivity)
In the above examples or comparative examples, the coating layer forming support that has been processed up to the pretreatment water or the support that is not formed with the coating layer is cut into 8 × 7 cm, and the method in the above examples By the same method, the surface state of the filter body was visually evaluated after the operation of immersion, dehydration, and drying in treatment water containing ion-exchange resin powder was repeated three times. Pass if there is no fluff generation and almost no unevenness of ion exchange resin powder adherence, “Good” indicates pass of fluff generation and slight unevenness of ion exchange resin powder adherence, “Fair” A case where the occurrence of balls and the adhesion unevenness of the ion-exchange resin powder was large was regarded as a failure “x”.

(About handling)
The test body formed by cutting the filter body according to the example or the comparative example into 8 × 7 cm was gripped with a palm three times, and the flexibility was evaluated. After gripping, the test specimen returns to its original shape, and the shape is maintained as “Good”. If it is hard and difficult to grip, or the return is slow after bending, “Fair”. If it cannot be gripped, or it cannot be returned to its original position after being folded, it was judged as a failure “x”.

(About comprehensive evaluation)
If the ion exchange resin powder dropout evaluation, evaluation of the shape after use, evaluation of the first adsorption effect, whether or not it can be reused, and evaluation of the adsorption effect at the time of reuse are all “good” or better. In addition, the case where the mass productivity and the handling properties are excellent is designated as “◎”. On the other hand, any one of evaluation of drop-off of the ion exchange resin powder, evaluation of the shape after use, evaluation of the first adsorption effect, reusability, evaluation of the adsorption effect at the time of reuse has a rejection evaluation. The case was set as “x”.

  Area% represents the ratio of the surface area of the coating layer to the total surface area of the support, and the coating amount represents the mass of the coating layer per unit surface area of the support.

  In Comparative Examples 1 and 2, the ion exchange resin powder was easily detached from the support during handling. Further, when submerged in the aquarium fish tank, the support swelled and the desorption of the ion exchange resin powder proceeded. Furthermore, since the support body swelled into a muddy state when submerged in the aquarium fish tank, it was difficult to recover and reuse the used filter medium.

  In Comparative Examples 3 to 6, the ion-exchange resin powder was easily detached from the support both during handling and when submerged in the aquarium fish tank. In addition, when submerged in the aquarium fish tank, the support was deformed. Therefore, it is assumed that repeated reuse is difficult. Furthermore, since each of the fibers constituting the support is coated with a coating material, it is too hard and inferior in handling properties.

  Moreover, in the comparative example, when rotational dehydration was performed in the drying process of the support, the supports were rubbed, and pills were generated on the surface. Therefore, it was inferior to mass productivity.

  On the other hand, in the examples, rotational dehydration was performed in the drying process of the support, but no generation of pills was observed on the surface. Therefore, it was confirmed that the mass productivity was excellent.

  In addition, it was confirmed that the filtration molded body according to the example showed little desorption of the ion exchange resin powder both when handled and when submerged in the aquarium fish tank. Further, when submerged in the aquarium fish tank, the swelling of the support was suppressed and the shape was maintained. And it was able to confirm that the shape was maintained even if it pulled up from the tank for ornamental fish, and it can be reused. Further, the adsorption effect was excellent both in the initial stage and in the reuse, and it could be confirmed that it could be reused from this viewpoint.

  Looking at Examples 1-8, when the area ratio of the coating layer is 30%, there are relatively many portions that are not covered with the coating layer. Slightly inferior in effectiveness. When the area ratio of the coating layer is 96%, it is difficult to contain water when immersed, and the initial filtration efficiency is slightly inferior. On the other hand, when the area ratio of the coating layer was in the range of 40 to 95%, it was confirmed that the effect of preventing the ion-exchange resin powder from dropping from the support and the effect of preventing the deformation of the support were relatively high. Moreover, since it has an exposed surface which is not covered with a coating layer, it was confirmed that it was easy to contain water when it was immersed in water and was relatively excellent in initial filtration efficiency.

Looking at Examples 9 to 12, when the coating amount is in the range of 40 to 120 g / m ² , the shape of the support is maintained, and the effect of preventing shape loss is high. In particular, the coating amount is 45 to 70 g / m ² . In the range, the handling was further excellent.

  When Examples 2 and 13 to 16 were observed, it was confirmed that the adsorption effect was relatively high when the thickness of the fiber material of the support was within an average range of 2 to 4 denier. This is presumed to be because the fiber material forms a mesh having an appropriate size, so that the water transmission rate is maintained in an appropriate range and the amount of ion-exchange resin powder supported is high. On the other hand, if the thickness of the fiber material of the support exceeds an average of 4 deniers, the adsorption effect is slightly inferior. This is presumably because the mesh size of the fiber material is relatively large, the water permeation rate is likely to be too high, and the amount of ion-exchange resin powder supported is likely to decrease. Moreover, it was somewhat inferior in the desorption prevention effect of ion-exchange resin powder.

  When Examples 18-19 were seen, even when it had a surface protective layer, it has confirmed that the effect of this invention was high.

  It was also found that the effect of the effect of the present invention due to the number of times the ion exchange resin was immersed was small.

  Although the embodiments of the present invention have been described in detail above, the present invention is not limited to the above-described embodiments, and various modifications can be made without departing from the gist of the present invention.

DESCRIPTION OF SYMBOLS 10 Filtration molded object 12 Support body 14 Ion exchange resin powder 16 Coating layer

Claims (12)

A support made of fiber material;
An ion exchange resin powder carried on the support,
A filter molded body for ornamental fish, comprising a coating layer covering the surface of the support.   The ratio of the surface area of the said coating layer with respect to the total surface area of the said support body exists in the range of 40 to 95%, The filtration molded object for ornamental fish of Claim 1 characterized by the above-mentioned. The mass of the coating layer in a unit surface area per support, aquarium filtration molded product according to claim 1 or 2, characterized in that in the range of 40 to 120 g / m ^2.   The said coating layer contains the porous material, The filtration molded object for ornamental fish in any one of Claim 1 to 3 characterized by the above-mentioned.   5. The ornamental fish filtration molded article according to claim 4, wherein the porous material is an adsorbent material.   The said coating layer contains an adhesive agent, The filtration molded object for ornamental fish in any one of Claim 1 to 5 characterized by the above-mentioned.   The filter molded body for ornamental fish according to any one of claims 1 to 6, wherein the thickness of the fiber material is within a range of 2 to 5 dtex on average.   8. The ornamental fish filtration molded article according to any one of claims 1 to 7, wherein the support has a mat shape.   9. The ornamental fish filtration molded article according to claim 8, wherein the coating layer is formed only on one surface of the mat-like support.   The said ion exchange resin is 1 type (s) or 2 or more types selected from the anion exchange resin and the cation exchange resin, The filtration molded object for ornamental fish in any one of Claim 1 to 9 characterized by the above-mentioned.   The filter molded body for ornamental fish according to any one of claims 1 to 10, further comprising a surface protective layer made of a fiber material. Forming a coating layer on the surface of a support made of a fiber material;
Immersing the support in a liquid containing ion-exchange resin powder;
And a step of drying the support infiltrated by the immersion, a method for producing an ornamental fish filtration molded article.

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