JPH0696484B2 - Zeolite-activated carbon composite having antibacterial and antifungal and COD reducing functions and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a zeolite-activated carbon composite. More specifically, the present invention provides a novel zeolite-activated carbon composite having antibacterial and antifungal and COD reducing functions, and a method for producing the same. In addition to the above functions, the zeolite-activated carbon composite of the present invention further has a dehumidifying function and a dew condensation preventing function.

[Prior Art] As is well known, zeolite and activated carbon each have a wide range of applications. However, both of them are fusion-bonded in the presence of a heat-fusion fiber or a heat-fusion fiber and a binder to obtain a composite having excellent functional properties and physical properties, and the technique of the present invention utilizing this is completely known. Didn't.

[Object of the Invention] The present invention provides a completely new type of molded body which has never been hitherto, namely, a zeolite-activated carbon composite having an antibacterial and antifungal function and a COD lowering function, and a method for producing the same. The zeolite-activated carbon composite of the present invention also has a dew condensation preventing function and is excellent in mechanical strength and water resistance. Therefore, the zeolite-activated carbon composite of the present invention is suitable, for example, as an interior material for a humid room. The zeolite-activated carbon composite of the present invention can be used in an atmosphere of gas phase and liquid phase for the purpose of antibacterial (sterilization), mold prevention and / or reduction of COD. Since the composite of the present invention has a high strength, when actually used in a gas phase or a liquid phase, cracking, powder drop,
Since it does not cause pulverization or cracks, it is also suitable for interior purposes or industrial water treatment from this point.
Further, the present composite can be used in the field where dehumidification or prevention of dew condensation is required and exerts an effect. The present invention also provides an economical method for producing the above zeolite-activated carbon composite.

[Structure of the Invention] The present invention is a zeolite that holds metal ions having a bactericidal action, an activated carbon powder that does not hold the metal ions,
And a heat-fusible fiber having a softening point of 300 ° C. or lower as a main component, which is fused and bonded, and is a zeolite-activated carbon composite having antibacterial and antifungal and COD lowering functions. Further, the complex of the present invention can further contain a binder in addition to the above-mentioned constituent elements. Desirably, these novel zeolite-activated carbon composites have the functions of absorbing moisture and preventing dew condensation in addition to the above-mentioned functions.

Furthermore, the present invention, zeolite holding a metal ion having a bactericidal action, activated carbon powder particles not holding the metal ion, and a heat-fusible fiber having a softening point of 300 ° C. or lower, preferably a binder is further mixed. Then, there is provided a method for producing a zeolite-activated carbon composite, which comprises press-molding the mixture at a temperature equal to or higher than the softening point of the heat-fusible fiber.

In the present invention, it has been found that the heat- and pressure-bonded heat-fusible fibers do not adversely affect the antibacterial and antifungal functions, the COD lowering function, the adsorption ability, the dew condensation preventing function, etc. of the composite. . The heat-fusible fiber has a significant effect in strengthening the bond between the zeolite and the activated carbon powder or granules and significantly improving the compressive strength and bending fracture strength of the finally obtained zeolite-activated carbon composite. understood. Further, it was also found that the use of the heat-fusible fiber significantly improves the water resistance and physical properties of the zeolite-activated carbon composite. The zeolite-activated carbon composites of various compositions obtained by the present technology have excellent antibacterial and antifungal functions, and these functions have the advantage of being stably maintained over a long period of time.
In addition, the COD lowering function of the zeolite-activated carbon composite of the present invention is excellent. It was also confirmed that the zeolite-activated carbon composite of the present invention performs moisture absorption and dehumidification in a preferable state.
Therefore, the zeolite-activated carbon composite of the present invention has a wide range of uses in the fields of gas phase and liquid phase, which require antibacterial / mold prevention, COD reduction, etc., and the proportion of constituent components is adjusted depending on the field.
Further, the composite of the present invention was found to be extremely effective as an interior material required to have properties such as dew condensation prevention, antibacterial properties and mildew resistance in view of its function and physical property values.

Zeolite-activated carbon composite of the present invention is a mixture of zeolite and activated carbon powder particles and heat-fusible fibers that retain metal ions having a bactericidal action, and then the temperature above the softening point of the heat-fusible fibers. It is made by pressing the admixture. That is, in the method for producing a zeolite-activated carbon composite of the present invention, without adopting the wet forming method as found in the ordinary zeolite or activated carbon forming method,
Made by dry molding. That is, the feature of the present molding method is that water is not used, and the molding temperature of the zeolite-activated carbon composite is significantly lower in the present molding method than the firing temperature of a general zeolite or activated carbon molding. The present invention is characterized in that a composite having extremely high mechanical strength and water resistance can be obtained by using such a method.

The zeolite used as one of the composite materials in the present invention may be either natural or synthetic, and the shape thereof is preferably powdery or granular. Prior to molding, these zeolites are given antibacterial properties by the method described below. As natural zeolite, mordenite, clinoptilolite,
Chabazite and the like are exemplified as preferable examples of the raw material used in the present invention, such as A-type, X-type and Y-type zeolite, synthetic mordenite, and high-silica zeolite as the synthetic zeolite. By holding antibacterial or bactericidal metal ions against these zeolite materials,
The zeolite matrix is provided with antibacterial and antifungal functions. In general, the antibacterial or bactericidal metal ion is stably retained in the zeolite solid phase by carrying out an ion exchange reaction between the zeolite material and the antibacterial metal ion. In the present invention, the metal ion having a bactericidal action is one or more metal ions selected from the group consisting of silver, copper, zinc, mercury, tin, lead, bismuth, cadmium and chromium. It Preferably silver, copper or zinc is used. Preferably silver, copper or lead is used. Ion exchange with ions in zeolite may be carried out at room temperature or high temperature by a batch method or a column method using a solution of one or more kinds of metal ions belonging to the above group. The amount of antibacterial metal ion-exchanged into the zeolite phase can be easily adjusted by adjusting the concentration of salts in the aqueous solution phase. By carrying out such a wet ion exchange method, a uniform distribution of bactericidal metal ions in the zeolite solid phase is achieved, and an antibacterial zeolite having preferable properties can be prepared. Alternatively, an antibacterial zeolite material for molding may be prepared by appropriately mixing antibacterial zeolite prepared by ion exchange and a zeolite material (non-antibacterial), and containing a predetermined amount of metal ions having a bactericidal action as a whole. I can. It should be noted that a certain type of inorganic retention matrix other than zeolite, for example, a matrix such as amorphous aluminosilicate described in JP-A-62-70220 and 62-70221, a predetermined amount of antibacterial metal It is also possible to prepare a product in which the above is stably retained, and mix this with a predetermined amount of a zeolite material (non-antibacterial) to use as a zeolite material for molding.

Next, the activated carbon used as one of the composite materials in the present invention will be described. The shape thereof is preferably powdery or granular and has a large specific surface area with developed pores. For example, carbonaceous or coconut shell activated carbon is preferable as a material of the present invention in view of the flash point and other physical properties. The activated carbon having the above-mentioned shape is preferably used by previously mixing it with the powdery particles of zeolite holding the metal having the bactericidal action adjusted by the above method. The use ratio of the zeolite and the activated carbon used as the molding material in the present invention varies depending on the purpose of use of the finally obtained composite, but the zeolite is 2 to 98% relative to the total weight of the zeolite and the activated carbon (anhydrous basis). (Wt%) is suitable. For example, in order to increase the COD reduction rate of the aqueous solution phase, it is better to increase the content of activated carbon in the composite.

The content of the metal ion having a bactericidal action occupying in the zeolite-activated carbon composite of the present invention depends on the kind of the bactericidal metal that is actually used, a combination thereof (combined use), and a sterilization target. It is dominated by species such as bacteria and fungi. For example, when using only silver as the bactericidal metal ion, at least 5 ppm, when using only copper, at least 30 ppm, and when using only zinc, at least 60 ppm is contained in the zeolite-activated carbon composite of the present invention. The minimum requirement is to have antibacterial and antifungal effects. Further, by using two or more kinds of the above-mentioned bactericidal metal ions in combination, for example, silver-copper, silver-copper-zinc, etc., the synergistic effect of the bactericidal metal ions is exerted, and antibacterial and prevention against bacteria and mold are exhibited. The mold effect can be further enhanced.

Now, the zeolite and activated carbon containing metal ions having a bactericidal action adjusted by the above-mentioned method are preferably 10
It is dried (in air) near 0 ° -110 ° C, or heat-activated in a higher temperature range (nitrogen, if necessary,
It is used for molding under heating while being kept in an inert gas atmosphere such as carbon dioxide) to further reduce the water content. Usually, the zeolite and the activated carbon are dried at about 100 ° to 110 ° C to remove most of the adhered water on the surface of the zeolite and the activated carbon prior to the molding.
Therefore, even if water of crystallization remains in various zeolites, which are one of the constituent materials, it is not used in the molding step for producing the final composite of the present invention. In order to further impart a dew condensation preventing function to the zeolite-activated carbon composite having sterilizing ability, it is more preferable to use a porous zeolite material having a large water adsorption capacity and a large specific surface area. The composite of the present invention in which the above-mentioned natural or synthetic zeolite is made antibacterial and is combined with activated carbon exhibits not only the antibacterial and antifungal functions and the COD lowering function, but also the properties of moisture absorption and dew condensation prevention. Zeolite-containing activated carbon composite containing metal ions having bactericidal action, by adding a small amount of alumina, magnesia, silica gel, calcium chloride, water-absorbent resin powder, etc. as an adsorbent, to further improve the dew condensation prevention function. It is possible to raise it.

Next, the heat-fusible fiber used in the present invention will be described. The heat-fusible fibers include adhesive fibers (eg, non-crystalline polyester), composite fibers (eg, nylon 6/66; polyethylene / polypropylene; copolyester / polyester), and heat-fusible fibers (eg, copolyamide, copolyester, etc.). Thermoplastic copolymer fibers: polypropylene, polyethylene, polyamide, polybutylene terephthalate, polyethylene terephthalate and other homopolymer fibers). These fibers are added to the antibacterial zeolite and activated carbon in a necessary amount, and heat-bonded in a mixing process under heating or a pressure molding process under heating. Examples of heat-bondable fibers include polypropylene-based (single-component type) He
rculon T-151, Daiwabo PNS or PZS, polyethylene-based (single component type) Daiwabo BF, polypropylene-based (composite component) Chisso ES, Daiwabo NBF and Danak
lon ES, ester type (single component type) Diolen 51, Kadel
410, Grilene K-170, Hetrofil Melty (Unitika)
And bell combi (bell spinning), ester type (composite component type)
56, and nylon-based Heterofil, vinyl chloride-based MP Fiber, Vinylon-HH (both are trademarks), and the like. As the low melting point Bell Combi which is preferably used,
Bell Combi-4000 (single component type) with softening point 110 ° C and 4
080 (core-sheath type), Belcombi-3300 (single-component type) with a softening point of 130 ° C, and 3380 (core-sheath type), Belcombi-2000 (single-component type) with a softening point of 200 ° C, and 2080 (core-sheath) Type) is exemplified. Further, N-501 (polyester) having a softening point of 256 ° C. is also included. The above-mentioned commercially available Bell Combi has a diameter of 2 to
It is easily available with 6 denier and length of about several mm to several tens of mm. Generally, as the heat-fusible fiber suitable for the present invention, one having a softening point of 300 ° C. or lower is desirable. In the production of the zeolite-activated carbon composite having the antibacterial and antifungal functions, the COD lowering function and preferably the dew condensation preventing function of the present invention, one or two of the above-mentioned heat-fusible fibers are used.
The seeds and above are heat-sealed above their softening point and preferably below 300 ° C. In order to obtain a zeolite-activated carbon composite having excellent physical properties and having the above-mentioned functions, in general, the total weight of the zeolite having activated bactericidal metal ions and the powder of activated carbon (anhydrous basis) is used. 3 to 67%
It has been found to be extremely effective to use the heat-fusible fiber. In the present invention, when a zeolite that does not have a bactericidal metal ion is also used, the weight of the zeolite is included in the zeolite weight.

In the present invention, at least one of the above-mentioned heat-fusible fibers is used as the binder fiber when forming the zeolite-activated carbon composite having bactericidal metal ions.

Further, the following binder may be further added to the above components to perform pressure molding. As the binder, a liquid organic compound or a solid organic compound having the properties of the binder may be used as it is, or may be diluted with a suitable non-aqueous solvent or diluent so as to have an appropriate viscosity. The amount of the above-mentioned binder used is controlled by the ratio of zeolite and activated carbon, the type of heat-fusible fiber and the use ratio, but in order to maintain good bonding between particles, the total weight of zeolite and activated carbon (anhydrous basis) It is preferred to use 4 to 35% by weight of binder, based on In the production of the zeolite-activated carbon composite of the present invention, a mixture of zeolite-activated carbon retaining metal ions having a bactericidal action and a heat-fusible fiber or a mixture obtained by further adding a binder to the mixture is heat-fusible. Fiber softening point or higher, and preferably 300 ° C
Blended below. When using a mixture containing the latter binder, it is desirable that the binder used be heat resistant and low flammable. Examples of preferable binders having such properties include various polyesters such as Nipporan (trademark) manufactured by Nippon Polyurethane Industry Co., Ltd.
In particular, a series of Nipolan having a viscosity in the range of 100 to 3000 cp (75 ° C.) is suitable for the present invention. For example, liquid Nipporan N-
1004 [viscosity 600-900cp (75 ℃); acid value 2 or less; hydroxyl value
39-47; molecular weight about 2500] is very effective in shaping the composite as the binder used in the present invention. It has been confirmed by the present inventors that this has the effect of making the surface of the zeolite-activated carbon composite material smoother and at the same time imparting flexibility (plasticity) to the composite molded article, in addition to the function as a binder. Was done.

The zeolite-activated carbon composite of the present invention having the above-mentioned antibacterial and antifungal and COD lowering functions, and preferably additionally the functions of absorbing moisture and preventing dew condensation, is prepared as follows. Powdery or granular natural or synthetic zeolite that retains metal ions having a bactericidal action, or a mixture of this and zeolite that does not retain the above metal ions, and activated carbon (dried product or heat-activated product treated as described above). In the present invention, preferably 3 to 67% of the heat fusible fiber is added to the above mixture weight (anhydrous basis) and mixed. In this case, the hygroscopic agent as described above may be added as a minor component. As mentioned above, the mixing is preferably carried out at a temperature above the softening point of the heat-fusible fiber and below 300 ° C. The optimum temperature at the time of mixing depends on the kind of the heat-fusible fiber used, but usually 100 ° to 270 ° C. is the most preferable temperature range. The mixing step is usually performed in an air atmosphere, but when the temperature at the time of mixing is relatively high and the consumption of activated carbon is observed, the mixing may be performed in an inert gas atmosphere (for example, nitrogen, carbon dioxide gas, etc.). The above fibers are in a softened or melted state in the mixing step, and the fibers are in a preferable state in which they are entangled with zeolite particles and activated carbon particles. Further, a binder such as Nipporan N-1004 is added to the above mixture in an amount of 4 to 35%.
You may add and mix in the said temperature range. The mixture obtained above is further in the above temperature range, preferably 100 ° to 2
Finally, the zeolite-activated carbon composite of the present invention having an antibacterial and antifungal and COD reducing function is obtained by pressure molding at a temperature of 70 ° C. The molding pressure in this case depends on the strength required for the molded body and the apparent density, but is usually 2
Molding pressures in the range of up to 250 kg / cm ² are preferred. The zeolite-activated carbon composite of the present invention produced by the above method may further contain a non-combustible or flame-retardant lightweight material as a minor component. As the lightweight material used in this case, paper, pulp, wood powder, etc. are inflammable and have disadvantages.Inorganic fillers and lightweight materials such as silica, alumina, pearlite, rock wool, glass fiber, and carbon fiber. Etc. are preferred for the present invention. Further, pigments for coloring, fluorescent agents, inorganic chemical powders, metal powders, synthetic rubber for improving elasticity, high water absorption resin powders or fibers for improving water absorption should be further added as minor components. You can

The molded article of the present invention is structurally stable below the softening point of the heat-fusible fiber, for example, from 300 ° C or lower to extremely low temperature. In particular, it is very stable even at liquid nitrogen temperature (about -200 ° C), and the shrinkage rate is only 0.5%.

Next, the embodiments of the present invention will be described with reference to examples, but the present invention is not limited to the examples.

Example 1 Example 1 is a zeolite of the present invention having an antibacterial and antifungal and COD lowering function, which is obtained by press-molding a mixture of an antibacterial zeolite, activated carbon, a heat-fusible fiber and an organic binder. The present invention relates to an example of producing an activated carbon composite.

As antibacterial zeolite, A-type zeolite (NaZ)
Antibacterial properties obtained by ion exchange (at room temperature) with a mixed salt solution of AgNO ₃ , Cu (NO ₃ ) ₂ and Zn (NO ₃ ) ₂ and substituting a part of the sodium exchange groups with Ag, Cu and Zn. Zeolite (NaAgCuZu
Z) was used. This antibacterial zeolite [average particle size Dav = 3.
1 μm: Ag = 2.35%; Cu = 7.33%; Zn = 9.01% (anhydrous basis)] dry powder 350g 10% by weight of dried activated carbon (Fujisawa Yakuhin Co., Ltd. coconut shell activated carbon B-CW; Dav = 80μ
m) was added and both were mixed. 15% by weight of Velcombi-4080 [(trademark (Kanebo Co., Ltd.); softening point 110 ° C .; shape 3d × 5 mm (d is denier); core-sheath type] as a heat-fusible fiber) to the above mixture and Velcombi −4000
18% by weight of [softening point 110 ° C .; shape 6d × 5 mm; single component type] was added, and the resulting mixture was kneaded while being kept under heating at 170 ° to 180 ° C. By mixing under heating in the above temperature range, the heat-fusible fibers are softened or melted, and the fibers are entangled with the constituent particles of zeolite or activated carbon to form a preferable state in which the composite is firmly bonded. Further, to the above admixture, Nippon Polyurethane Industry Co., Ltd.'s Nipporan-1004 (trademark) was added as a binder in an amount of 10% by weight based on the total weight of the above zeolite and activated carbon (anhydrous basis). Continued under heating at ° ~ 180 ° C. Next, the mixture obtained in the above step is subjected to pressure molding at a pressure of 150 kg / cm ² at a temperature of 180 ° to 190 ° C. to obtain an antibacterial and antifungal and COD reducing function of the zeolite-activated carbon composite of the present invention. Test plate (shape; 50 x 50 mm; thickness 10 mm)
Was finally prepared. Content of bactericidal metal ion in the above test plate is Ag = 1.32%; Cu = 4.23%; Zn = 4.39%
Met.

Table 1 shows the molding conditions of Example 1 and the characteristics of the obtained molded body. Comparative Example 1 relates to a blank test. That is, in Comparative Example 1, instead of the antibacterial zeolite, the same type as in Example 1 except that a dry powder (Dav = 3 μm) of A-type Zeorio (NaZ; non-antibacterial) that does not retain bactericidal metal ions is used as a material. A mixture was prepared by adding 10% of activated carbon of the same type as used in Example 1 to this. Using this mixture and the heat-fusible fiber, molding was carried out in exactly the same manner as in Example 1 to obtain a zeolite-activated carbon composite test plate (50 × 50 mm; thickness 10 mm). The flexural strength of the dried composite (final product) was 219 kgf / cm ^{2 in} Example 1.
On the other hand, in Comparative Example 1 (blank test), it was 173 kgf / cm ² . All of these values are preferable values, indicating that the strength of the zeolite-activated carbon composite obtained by the method of the present invention is extremely excellent. The apparent density of the composite is in the range of 1.5 to 1.7 g / cm ³ in each example.
Next, a water immersion test was performed on the zeolite-activated carbon composite obtained in this example. The results are shown in Table 2.
It was found that the adsorbed amount of water was 9.66% 8 hours after the immersion of the molded article in water and 11.56% at 48 hours, which was almost saturated. It has been found that the composite of the present invention has extremely high water resistance without any occurrence of powder falling, cracking, crushing, etc. even when immersed in water for a long period of time.

Example 2 This example is a zeolite-activated carbon composite of the present invention (shape 50 × 50).
mm; thickness 10 mm). In Example 2, the same type of antibacterial zeolite (NaAgCuZnZ) as in Example 1 was used, and the amount of activated carbon (the same type as in Example 1) added was 100% by weight. Molding of the above mixture was carried out under exactly the same conditions as in Example 1, as shown in Table 1. The content of antibacterial metal in the obtained plate was Ag = 0.70%; Cu = 2.31% and Zn = 2.29%. The bending fracture strength and apparent density of the composite obtained in this example are 168 kgf / cm ² and 1.323 g / cm ³ , respectively,
In the water immersion test of the prototype plate, as shown in Table 2, the water absorption rate reached 19.29% at 24 hours and reached 20.05% near 48 hours after 48 hours. Comparative Example 2 relates to a blank test for comparison purposes. That is, Comparative Example 2
Then, instead of the antibacterial zeolite, an A-type zeolite (NaZ; which has the same kind as in Example 2 but does not retain bactericidal metal ions) is used.
A non-antibacterial fine powder dry product (Dav = 3 μm) was used as a raw material, to which 100% by weight of activated carbon of the same kind as used in Example 2 was added to prepare a mixture. Using this mixture and the heat-fusible fiber, molding was carried out in exactly the same manner as in Example 2 to finally obtain a zeolite-activated carbon composite test plate (50 × 50 mm; thickness 10 mm). The bending fracture strength and the apparent density of the molded body obtained in Comparative Example 2 were values close to those obtained in Example 2, as shown in Table 1.

Example 3 This example relates to a production example of the zeolite-activated carbon composite of the present invention, which is formed by pressure molding a mixture of antibacterial zeolite, activated carbon, and heat-fusible fiber.

As an antibacterial zeolite, N of Y-type zeolite (NaY)
A silver-tin-zeolite (NaAgSnY) obtained by partially replacing a ⁺ with Ag ⁺ and Sn ²⁺ was used. Antibacterial zeolite [D
av = 1.1 μm: Ag = 2.51%; Sn = 2.88% (anhydrous basis)] to 250 g of dry powder, 10% by weight of dried activated carbon (same quality as in Example 1) was added and mixed. To the above mixture, 20% by weight of Belcombi 4000 (softening point 110 ° C.) and 12% by weight of N-501 (softening point 256 ° C.) were added as heat-fusible fibers,
Mixing was carried out while heating at around 260 ° C (nitrogen gas atmosphere). Next, pressure molding was carried out at 150 kg / cm ² under the above temperature, and a test plate of the zeolite-activated carbon composite of the present invention having an antibacterial and antifungal and COD lowering function (shape: 50 × 50 mm; thickness 10 mm ) Was adjusted. The content of antibacterial metal in this test plate was Ag = 1.71% and Sn = 1.92%. The bending fracture strength of the test plate was 170 kgf / cm ² , and the apparent density was 1.347 g / cm ³ , as shown in Table 1.

Example 4 This example relates to another structural example of the zeolite-activated carbon composite of the present invention obtained by press-molding a mixture of antibacterial zeolite, activated carbon, heat fusible fibers and a binder.

As an antibacterial zeolite, natural mordenite [SiO ₂ / Al ₂
O ₃ = about 10 (molar ratio)] in which the ion-exchangeable metal is Ag ⁺
The antibacterial silver-mordenite (Ag-mordenite) obtained by partially substituting with was used. To 300 g of dry powder (150 to 200 mesh) of the antibacterial mordenite [Ag = 3.24%; (anhydrous basis)], 20% by weight of dried activated carbon (same quality as in Example 1) was added and mixed. 1 each of Belcombi 4080 and 4000 as heat fusible fibers for the above mixture
Add 5 or 18% by weight, and add Nipolan 100 as a binder.
10% by weight of 4 was added, and mixing and molding were carried out in the same manner as in Example 1 to prepare a test plate (shape: 50 × 50 mm; thickness 10 mm) of the zeolite-activated carbon composite of the present invention. . The content of antibacterial metal in this test plate is Ag = 1.81
%Met. The bending fracture strength of the test plate is 177 kgf / cm ² , as shown in Table 1, and the apparent density is 1.629 g / cm ^3.
Met.

Comparative Example 4 is for comparison purposes with Example 4,
Natural mordenite that does not retain germicidal metals (antibacterial: 1
50-200 mesh) was used. The molding conditions are exactly the same as in Example 4, as shown in Table 1.

Antibacterial and antifungal function test Next, the antibacterial and antifungal function test of the zeolite-activated carbon composite of the present invention will be described. For this purpose, tests were carried out on the measurement of mortality and the formation of stunting zones. When measuring the mortality of bacteria, a liquid (1 small sample obtained by cutting the zeolite-activated carbon composite of the present invention) of 1 ml of a bacterial suspension (10 ⁴ cells / 1 ml) was immersed ( (Including 200 mg of test piece per ml) Pour into 9 ml of the mixture, act at 37 ℃ for 24 hours, 0.1 ml of Mueller H
The cells were dispersed in inton medium, and after 48 hours at 30 ° C., the number of surviving individuals was measured to determine the mortality rate. When measuring the killing rate of fungi, a solution containing 100 mg of a test sample (small test piece obtained by cutting the molded article of the present invention) and 10 ⁴ spores per 1 ml was prepared and left at 30 ° C. for 24 hours. , 0.1 ml thereof was dispersed in Sabouraud agar medium, and the number of surviving individuals was measured after 48 hours at 30 ° C. to determine the mortality rate.

In the above-mentioned antibacterial test, Staphylococcus aureus and Pseudomonas aeruginosa were used as bacteria.
Aspergillus flavus (Aspergillus flavus) and Aspergillus niger (Aspergillus niger) were used as molds (fungi).

The mortality measurement results are shown in Table 3. The zeolite-activated carbon composite (containing AgCuZnZ) produced in Example 1 was Staph.
Both ylococcus aureus and Aspergillus niger showed 100% mortality, and the complex (containing AgCuZnZ) produced in Example 2 was Pseudomonas aeruginosa and Aspergill.
All of them showed 100% mortality against us flavus. From this, it is clear that the complex of the present invention has excellent antibacterial and antifungal functions. On the other hand, Comparative Example 1
Complex (blank test) has no effect on Staphylococcus aureus with 0% mortality and Aspergillus nige
It has almost no effect on fungi such as r. The subject (for blank test) of Comparative Example 2 is Pseudomonas aeruginosa.
It was proved that it had no effect against the fungus, and that it exhibited almost no fungicidal ability against fungi such as Aspergillus flavus. The complex of the present invention (containing AgSnY) produced as a trial in Example 3 exhibits an excellent effect against bacteria such as Staphylococcus aureus. Furthermore, the complex of the present invention (containing Ag-mordenite) produced as a trial in Example 4 was Aspergillus flavus.
Gives 100% mortality to such molds. on the other hand,
The composite of Comparative Example 4 (blank test) shows almost no effect against the above molds. From the above results, it is clear that the zeolite-activated carbon composite of the present invention exerts an extremely excellent effect on bacteria and fungi.

Next, the presence or absence of formation of a growth arrest zone was determined as a typical bacterium.
It investigated using Staphylococcus aureus. The complex obtained in Example 1 and Comparative Example 1 was used as a test object. The above bacteria were suspended in physiological saline at 10 ⁸ cells / ml, and Mueller Hinton
The mixture was dispersed in a medium with a 0.1 ml conradi stick and the complex was placed on the medium. After 18 hours at 37 ° C, the presence or absence of a zone of inhibition was observed. The formation of the inhibition zone was clearly confirmed in the subject of Example 1 (containing AgCuZnZ), but the formation of the inhibition zone was not observed in the subject of Comparative Example 1. The antibacterial effect of the zeolite-activated carbon composite of the present invention is clearer than the above test.

Dew condensation prevention function test Next, the dew condensation prevention function of the zeolite-activated carbon composite of the present invention will be described. Small test pieces (25 × 25 mm; thickness 10 mm) were prepared by cutting the molded articles produced in Examples 1 and 2. After reactivating by heating the above test piece in vacuum at 200 ° C for 3 hours, change the moisture absorption rate with time in a humidity chamber at a temperature of 25 ° C and relative humidity (RH) of 25% or 90%. It was measured in the atmosphere. Curves 1 and 2 in FIG. 1 relate to the subject of Example 2, and curves 3 and 4 relate to the subject of Example 2. Curves 1 and 3 are 25
℃, RH = 90%, curves 2 and 4 are 25 ℃,
It is a moisture absorption curve under the condition of RH = 53%. The zeolite of the present invention can be used in both relatively humid atmospheres (curves 1 and 3) and in relatively low humidity atmospheres (curves 2 and 4).
It is clear from FIG. 1 that the activated carbon composite has excellent hygroscopicity. Further, the small test pieces (shape 25 × 25 mm; thickness 10 mm) of the molded articles obtained in the above Examples 1 and 2 were saturated with water, and then subjected to a dehumidification test in an atmosphere of 25 ° C. and RH = 35%. went. It was confirmed that dehumidification was performed at a preferable rate for all the test pieces. From the above test, it is clear that the zeolite-activated carbon composite of the present invention has a satisfactory dew condensation preventing function.

COD reduction and sterilization test Next, the zeolite-activated carbon composite of the present invention is effective as a gas phase or liquid phase deodorant, a free chlorine removing agent in water, and the COD (or BOD) in water using this composite. ) It is also effective for removing contributing components.

The zeolite-activated carbon composite of the present invention was tested using model wastewater to show that it has both a COD lowering function and a bactericidal function.

Sewage water was diluted with water and E. coli was inoculated to prepare two types of model wastewater.

Model wastewater A: COD = 50 mg / l, E. coli number about 10 ⁶ cells / ml Model wastewater B: COD = 83 mg / l, E. coli number about 10 ⁶ cells / ml Test 1 Zeolite-activated carbon composite prepared in Example 2 above Body plate (50 x 50 x 10 mm, Ag0.70%, Cu2.31%, Zn2.29
%) Was cut to make 50 small pieces of 10 × 10 × 10 mm, which were put in 400 ml of model wastewater A. This was stirred (350 rpm) at 20-25 ° C for 20 hours. Next, the COD removal rate was measured, and the killing rate of E. coli in the model wastewater was calculated. The results are shown in Table 4.

Test 2 The zeolite-activated carbon composite plate (50 × 50 × 10 mm, Ag1.81%) prepared in Example 4 above was cut to 10 × 10 ×.
Make 60 pieces of 10mm and put them in 400ml of model wastewater B,
The same test as in Test 1 was performed.

From this result, the composite of the present invention is an antibacterial zeolite and activated carbon, which are fused and solidified by a heat-fusible fiber and a binder, but both have excellent COD removal rate and bactericidal effect. It is clear that

The features of the zeolite-activated carbon composite of the present invention are summarized below.

(A) The zeolite-activated carbon composite of the present invention exhibits excellent antibacterial and antifungal and COD lowering functions.

(B) The zeolite-activated carbon composite of the present invention reversibly absorbs or dehumidifies depending on the humidity of the atmosphere.

(C) Since the composite of the present invention retains the functions described in (a) and (b), it is possible to prevent or suppress the formation of dew condensation and the formation of mold by using this. .

(D) Since the composite is strongly bonded by the heat-fusible fiber, the strength is extremely high, and cracks, powder drops, cracks and the like occur during use as seen in ordinary zeolite molded products. No phenomenon is seen.

(E) The treatment temperature for obtaining the composite of the present invention is lower than that during ordinary wet molding of zeolite or activated carbon, and it is possible to manufacture the composite extremely economically.

(F) The bending fracture strength of the molded article is governed by the molding pressure, the amount of the heat-fusible fiber and the binder added, and other factors, but in general, the molded article has extremely high strength and elasticity. The body is obtained.

(G) The water resistance of this composite is great. The flexural fracture strength of the composite obtained by immersing it in water to saturate it and then drying it is about the same as that at the time of production. In addition, even if the composite is immersed in water and saturatedly adsorbed, cracks and powdering of the molded body,
No phenomenon such as cracking is observed. Further, at that time, the elution of the zeolite component and the antibacterial metal ion forming the molded body into water is extremely small. Furthermore, the swelling property of this composite is very small, and the elongation of length when saturated with water is about 0.5%.

(H) The molded product of the present invention is structurally stable from a high temperature of 300 ° C. to a low temperature region. At liquid nitrogen temperature, the shaped body is very stable and its shrinkage is less than 0.5%.

(I) The composite of the present invention is also excellent in heat insulation and soundproofing.

(J) In view of the characteristics of the zeolite-activated carbon composite of the present invention, the composite of the present invention is suitable, for example, as an interior material and as a deodorant or a COD reducing agent.

[Brief description of drawings]

FIG. 1 is a graph showing a moisture absorption rate curve of a test piece of the zeolite-activated carbon composite of the present invention at a temperature of 25 ° C. and RH = 53% or 99%.

Continuation of the front page (51) Int.Cl. ⁵ Identification number Reference number within the agency FI Technical indication location C02F 1/28 A 1/50 101 (72) Inventor Satoshi Ando 5-1 Kurono Nishi, Joto-ku, Osaka City, Osaka Prefecture 2-604 (72) Inventor Akira Dono 1-6-4-402 Tomobuchi-cho, Miyakojima-ku, Osaka-shi, Osaka (72) Inventor Kazuo Sawada 1-10-129, Higashiota, Ibaraki-shi, Osaka (56) References JP-A-60-100504 (JP, A) JP-A-56-63910 (JP, A) JP-A-59-137553 (JP, A)

Claims (20)

[Claims] 1. A zeolite containing a metal ion having a bactericidal action, a powder or granular material of activated carbon which does not hold the metal ion, and a heat-fusible fiber having a softening point of 300 ° C. or less as main components, Zeolite-activated carbon composite having antibacterial and antifungal and COD lowering functions which are bonded to each other. 2. The zeolite-activated carbon composite according to claim 1, further comprising a polyester binder. 3. The zeolite-activated carbon composite according to claim 1 or 2, further comprising a zeolite having metal ions having a bactericidal action and a zeolite having no metal ions having a bactericidal action. 4. The zeolite in the zeolite-activated carbon composite is contained in the range of 2 to 98% by weight based on the total weight (anhydrous basis) of the zeolite and activated carbon.
Item 3. The zeolite-activated carbon composite according to Item 2 or 3. 5. The zeolite-activated carbon composite according to claim 1, further comprising a non-combustible or flame-retardant filler and / or a lightweight material. 6. The zeolite-activated carbon composite according to claim 1, further comprising an inorganic hygroscopic agent as a minor component. 7. The zeolite-activated carbon composite according to any one of claims 1 to 6, wherein the heat-fusible fiber is a polyester fiber. 8. The total weight of zeolite and activated carbon powders holding metal ions having a bactericidal action (anhydrous basis).
The zeolite-activated carbon composite according to any one of claims 1 to 7, which contains 3 to 67% by weight of the heat fusion fiber. 9. The method according to claim 1, wherein the zeolite containing metal ions having a bactericidal action and 4 to 35% by weight of a polyester-based binder based on the weight (anhydrous basis) of the activated carbon powder and granules. Item 8. The zeolite-activated carbon composite according to any one of items 8. 10. A metal ion having a bactericidal action is silver, copper,
The zeolite according to any one of claims 1 to 9, which is one or more metal ions selected from the group consisting of zinc, mercury, tin, lead, bismuth, cadmium and chromium. Activated carbon complex. 11. A zeolite having a metal ion having a bactericidal action, a powder or granular material of activated carbon not having the metal ion, and a heat-fusible fiber having a softening point of 300 ° C. or less are mixed, and then heat-bonded. A method for producing a zeolite-activated carbon composite, which comprises press-molding the above mixture at a temperature equal to or higher than the softening point of the functional fiber. 12. The method according to claim 11, wherein a polyester binder is further mixed in addition to the powder and granules of zeolite and activated carbon retaining metal ions having a bactericidal action and the heat-fusible fiber. 13. The method according to claim 12, wherein the zeolite having a metal ion having a bactericidal action is mixed with the zeolite having no metal ion having a bactericidal action. 14. The zeolite according to any one of claims 11 to 13, wherein the zeolite is added in the range of 2 to 98% by weight based on the total weight of zeolite and activated carbon (anhydrous basis). -A method for producing an activated carbon composite. 15. A mixture of non-combustible or flame-retardant filler and / or lightweight material, which is further mixed.
The method according to any one of the items. 16. An inorganic hygroscopic agent is further added as a small amount component and mixed, and the mixture is mixed.
Method described in one. 17. The method according to claim 11, wherein the pressure molding is performed at a temperature of 300 ° C. or lower. 18. The method according to any one of claims 11 to 17, wherein the heat fusible fiber is a polyester fiber. 19. A weight ratio of zeolite-activated carbon powder granules (anhydrous basis) that retains metal ions having a bactericidal action.
~ 67% by weight of the heat fusible fiber.
The method according to any one of items 11 to 18. 20. A zeolite containing metal ions having a bactericidal action and 4 to 35% by weight of a polyester binder of the activated carbon powder granule weight (anhydrous basis). The method according to any one.