JPS60181002A - Antimicrobial composition containing zeolite as carrier and production thereof - Google Patents

Abstract

PURPOSE:The titled composition, obtained by fixing antimicrobial silver, copper or zinc ions on ion exchange groups of zeolite by exchange reaction, stable in various media, and having improved prolonged duration of effect and water and heat resistance, etc. CONSTITUTION:A particulate antimicrobial composition, containing natural or synthetic zeolite as a carrier, ion exchangeable metal, contained in the above- mentioned zeobite, and substituted by a metal selected from silver, copper and zinc, and having preferably <=2.6mum average particle diameter in the state of containing water of crystallization or anhydrous state. The content of the antimicrobial metal is 0.0006-4% silver, 0.03-10% copper and 0.04-14% zinc based on the anhydrous state. The above-mentioned composition is obtained by reacting zeolite with a solution containing the above-mentioned metal ions at <=7pH, adding a binder to the metal-substituted zeolite, wet kneading the resultant mixture with water or an aqueous solution of urea, molding the kneaded mixture into a given shape, drying the molded material, and firing the dried material within a temperature region below the thermal decomposition starting temperature of the zeolite.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to antimicrobial compositions and methods for forming the same. More specifically, the present invention relates to a novel inorganic zeolite carrier using natural or synthetic zeolite, which has excellent properties not only in terms of water resistance and heat resistance, but also in terms of antibacterial activity and sustainability of antibacterial effects. The present invention provides an antibacterial composition and a method for producing the same. Various organic and inorganic disinfectants are commercially available, and the present invention belongs to the latter field.

(Prior art) It is well known that metal ions, such as zinc ions, copper ions, silver ions, etc., have antibacterial properties.Silver ions are generally widely used as disinfectants and disinfectants in the form of silver nitrate aqueous solutions. However, when used in the form of a solution, it is inconvenient to handle, and its uses are naturally limited.On the other hand, silver and halogen arsenic can be physically adsorbed onto activated carbon alumina, silica gel-based materials, cellulose, or nonwoven fabrics. It has also been used to sterilize liquids by putting it into containers or filling it into columns of appropriate shapes.

However, in the latter case of adsorption onto a stationary phase, there are drawbacks in terms of the holding capacity of the bactericidal metal to the adsorbed substance mentioned above and its leakage into the liquid phase. For example, when an aqueous solution of silver nitrate is brought into contact with activated carbon to retain silver in the active phase, if the concentration of silver nitrate in the aqueous solution phase is increased, the amount of silver adsorbed into the active phase will increase in proportion to the above concentration. As is clear from the silver adsorption isotherm, there is a limit to the amount of silver adsorption. In addition, as the amount of silver retained in the active secondary phase increases, when such silver-containing activated carbon is brought into contact with a solution, the silver in the solid phase may leak out into the liquid phase at an early stage.・The tendency to increase the amount of silver increases, and it is often observed that the amount of silver eluted into the liquid to be sterilized ultimately exceeds the permissible amount. In order to prevent such silver elution phenomenon as much as possible, for example, a bactericidal agent is commercially available in which the silver content in silver-containing activated carbon for the purpose of sterilization is suppressed to a small amount of about several hundred ppm. However, the use of such disinfectants is not necessarily satisfactory in terms of bactericidal power and sustainability of the bactericidal effect. Regarding silver regulations, the public health authorities of the U.S., S., and A.
PI)b or less. Judging from these regulatory values, when using silver-containing sterilizers, a new type of silver is used to minimize the leakage of silver into the solution, keep it below the regulatory value, and maximize the sterilizing effect over a long period of time. There is an urgent need to develop a retaining material. Furthermore, antibacterial compositions can be added to natural fibers, synthetic fibers, non-woven fabrics, pigments, sheets, plastics, textiles, etc. to maintain their antibacterial properties, or antibacterial compositions can be sprayed onto walls, building materials, etc. In order to maintain antibacterial properties in water, the particle size of the antibacterial composition is required to be extremely small.The same is required when using the antibacterial composition in the form of an emulsion or suspension.Next, the particle size of the antibacterial composition is required to be extremely small. When sterilizing antibacterial compositions and solutions, the molding strength of antibacterial compositions and the elution of metal ions become problems.

As a result of extensive research into inorganic antibacterial compositions for the purpose of improving commercially available disinfectants, the present inventor has found that various antibacterial compositions consisting of fine particles using natural or synthetic zeolite as carriers have been developed. It is stable in the medium of 1. We discovered that it has many advantages compared to known disinfectants in terms of antibacterial activity, durability of antibacterial effect, water resistance, heat resistance, etc., and has the potential to be used in a wider range of fields. The present invention was also achieved by discovering a new method for molding the composition.

The details of the invention will be explained below.

(Structure of the invention) This invention provides natural zeolite or synthetic zeolite,
Or crystal water formed by using both of them as a carrier and in which a part or substantially all of the ion-exchangeable metal contained in the zeolite is replaced by at least one metal selected from the group consisting of silver, copper, and zinc. A particulate antibacterial composition containing or anhydrous; using a natural iolide or a synthetic zeolite, or both as a carrier, in which a portion or substantially all of the ion-exchangeable metal contained in the zeolite is silver or copper. and at least one selected from the group consisting of silver, copper and zinc; and at least one selected from the group consisting of silver, copper and zinc.
A zeolite substituted with the metal is obtained by reacting the ion with a natural zeolite, a synthetic zeolite, or both in a solution containing metal ions with a pH of 7 or less, and this metal-substituted zeolite! Add an inorganic binder and/or an organic binder to the mixture and perform wet mixing with water or an aqueous urea solution, mold the resulting mixture into a predetermined shape, then dry this wet molded product, The present invention also relates to a method for producing the above-mentioned molded antibacterial composition, which is characterized by firing under normal pressure or reduced pressure in a temperature range below the onset of thermal decomposition of zeolite.

(Specific explanation of the structure) The antibacterial composition of the present invention uses zeolite as an antibacterial metal holding material, but whether it is a natural product or a synthetic product, Moreover, there is no problem even if these two are used in combination.

The reason why zeolite is used to support at least one of the antibacterial metal ions used in this application, such as copper, zinc, and silver ions, is based on the following.

Zeolite, which exhibits molecular sieve action, is porous and has an extremely large specific surface area, and is composed of aluminosilicate with a three-dimensional skeleton structure containing pores and cavities of different sizes depending on the type of zeolite. When an antibacterial metal is retained in a zeolite having such a structure by an ion exchange method, the latter antibacterial metal is stably bonded to the zeolite matrix, is uniformly distributed, and has extremely high activity against bacteria. It is possible to prepare an antibacterial composition with multi-±L properties and a large specific surface area. When an antibacterial composition prepared in this manner is used for sterilization, the contact area is large, and the antibacterial silver, copper and zinc ions are retained in a highly active manner in the zeolite carrier, resulting in increased bactericidal activity. However, it was confirmed that the bactericidal effect was sustained over a long period of time.

Furthermore, by using zeolite as a holding material (carrier),
This has the advantage of providing a porous antibacterial composition that is both thermally and chemically stable. In other words, the antibacterial composition of the present invention is extremely stable thermally, with no change in composition observed between 100°C and 200°C, and even when the temperature is raised to around 500°C and maintained in an almost anhydrous state, it remains stable. The crystal structure is stable, and X-ray diffraction does not show any phenomenon in which some of the bonds of silver, zinc, or copper bonded to the zeolite matrix are broken and converted into metal oxides. Continue heating to 600
As is well known, silver salts, in which very small amounts of metal oxides are only visible by X-ray diffraction, are easily discolored by sunlight, etc. when the temperature reaches around ℃. It has been found that when ions are fixed to a zeolite matrix by an ion exchange reaction, weather resistance is significantly increased and discoloration can be prevented to a minimum.

When antibacterial silver, copper, or zinc ions are immobilized on the ion exchange groups of zeolite (in zeolite) by an exchange reaction, the metals in the zeolite matrix are easily dissociated to form AgZ -* Ag +Z, CuZ2. -+Cu
+2Z: Since antibacterial metal ions such as ZnZ2→Zn +2Z are easily generated, there is an advantage that the antibacterial effect can be maximized. Therefore, compared to known antibacterial agents used in the form of metallic silver or silver halide, the amount of antibacterial metal contained in the antibacterial composition of the present invention is lower in order to achieve the same antibacterial effect. There are advantages to being able to do it. Next, since the antibacterial composition of the present invention is completely composed of inorganic substances, it is thermally, chemically, and mechanically stable. Therefore, it also has excellent solvent resistance and chemical resistance. In addition, this antibacterial composition is insoluble in water, and has the advantage that the constituent antibacterial metals and alumina, silicon dioxide, metal oxides, etc. contained in the zeolite matrix hardly dissolve out during long-term use. . That is, during actual sterilization, the elution of antibacterial silver, copper, or zinc into the aqueous solution phase is extremely small, and all of them are maintained in the liquid phase below the pollution regulation value, so they are completely harmless.

The shape of the molded product of the molded antibacterial composition of the present invention includes seed shapes such as pellets, tablets, moon plates, cylinders, and honeycombs. One of the notable advantages of the present invention is that the molded product obtained by the molding method of the present invention has high mechanical strength and high defect density. When the molded antibacterial agent of the present invention having such advantages is used for purposes such as water sterilization, the shape of the molded product remains unchanged for a long period of time, as will be clear from the examples below, and the antibacterial agent It has been found that the leakage of silver, copper, or zinc, which are active metal components, into the aqueous solution phase is slight, and that all of the above components are suppressed to below the pollution regulation value in the aqueous solution phase.

The zeolite crystals used in the present invention will be explained in further detail. Zeolite L is xM, -0” At203・y
It is expressed by the general formula of SiO2.Zn20. M is usually 1
~1 for a divalent metal. X and y represent the coefficients of the metal oxide and silicon dioxide, respectively, and 2 represents the number of crystal water molecules in the zeolite. M in the above formula represents ion exchange characteristics, and causes an exchange reaction with the antibacterial metal ions of copper, copper, and zinc used in the present invention at room temperature to high temperature, and produces the amount required in the present invention. It is possible to retain the above-mentioned antibacterial metal ions in the zeolite matrix. Natural and synthetic zeolites that can be used in the present invention each have a unique ion exchange capacity that varies depending on the type.

Both the natural and synthetic zeolites described below have the ability to retain antimicrobial metal ions of silver, copper, and zinc in the amounts required by the present invention. Examples of natural zeolites suitable for the present invention include Chabazite.
e) is 5 meq/ge mordenite (mod
enite) is 2.6 meq/jj, erionite (Er1onite) is 3.8 meq/g, clinopcilolite (clinopcilolite)
indicates an exchange capacity of 2.6 meq/g. Although many impurities are present in these natural zeolites, this does not affect the preparation of the antimicrobial composition of the present invention. On the other hand, as a synthetic zeolide, for example, 8-type zeolide is 7 meq/fi.

The X-type zeolide has an exchange capacity of 6.4 meq/9, and the Y-type zeolide has an exchange capacity of 5.0 meq/9.
These zeolites are suitable for use in the zeolite matrix of the present invention.

However, the above values are approximate values of exchange capacity per unit weight (based on anhydrous zeolite), and these values are sufficient to retain the predetermined amounts of silver, copper, and zinc in the present application. Silver, copper, zinc and the above ions (,
For example, A-type ionite, X-type ionite,
Ion-exchangeable metal ions and Ag s C contained in type zeolide, Y-type zeolide and chabasite
The activity of the zeolite is increased by performing ion exchange with u or Zn2+ at room temperature to high temperature using the Z-edge method or the column method to stably and uniformly retain the required amount of metal ions with bactericidal ability in the zeolite skeleton. It is easy to prepare an antibacterial composition that can exhibit excellent antibacterial ability.

Next, the selective adsorption of antibacterial ions such as silver, copper, and zinc varies somewhat depending on the type of zeolite, but the above antibacterial metal ions have a greater adsorption ability for ceolide than other metal ions. There are advantages to having In particular, the adsorption of silver ions to zeolite is extremely high. This fact shows that when the antibacterial composition containing the zeolite of the present invention as a carrier is used in liquids or water containing various metal ions for the purpose of sterilization, the antibacterial ions of Ag and CuZn used in the present invention are present in the zeolite matrix. This means that it is strongly bound and remains stable for a long time, resulting in a long-lasting bactericidal effect. For example, the order of selective adsorption of monovalent metal ions to synthetic 8-type zeolide is Ag”>
Tt+>Na+>K+') Nu, ;">Rh")
The order of selective adsorption of monovalent metal ions to X-type zeolide is Ag+>Tt+>
Cs+>Rb+)K+>Na+)t, t+, and further for Y-type zeolide. The order of selective adsorption of monovalent metal ions is Ag+>CB+>Rb+>N
The order is H4+〉K+〉Na)LiO. The selective adsorption of silver ions to the above three synthetic zeolites is maximum.

From this, it is clear how stable the antibacterial silver ions held in the zeolite matrix are. Therefore, as in the present invention, it is natural that the elution of antibacterial silver retained in zeolite into the aqueous solution phase is suppressed to a very small extent and is below the regulatory value for silver, as is clear from the examples described below. it is conceivable that. As an example of natural zeolite, the order of selective adsorption of monovalent metal ions to chabasite is Ag+>Rh'')NH4+>Na+)Ls
The order is +. Similar to the synthetic zeolite mentioned above, chabasite also has the highest adsorption ability for silver ions. Next, the order of selective adsorption of divalent metal ions to 8-type zeolide is Zn'') Sr2+) Ba2+) Ca''〉Co
The order is 2+〉Ni2+〉Cd2+〉Hg24゛゛゛>Mg2+, and from this it is clear that the adsorption of antibacterial zn2+ ions is superior compared to other divalent ions. . Considering this fact, it is presumed that even if an antibacterial zinc composition using zeolite as a carrier is used for sterilization purposes in water, most of the antibacterial ions will be stably retained in the zeolite matrix. .

Regarding the zeolite material used in the present invention, as mentioned above, it is preferable to use a natural product or a synthetic product, but when antibacterial metal ions are adsorbed and retained by an ion exchange reaction, the ratio of the zeolite used is It is desirable that the surface area is large and that the shape is powdery or granular in order to promote the reaction. Most commercially available synthetic zeolites are sodium-type powders on the micron order, while natural zeolites are usually available in the form of powders (e.g. 100 to 200 mesh), lumps, blocks, etc. . As mentioned above, it is desirable for the zeolite material to have a large specific surface area, but the specific surface area of commercially available anhydrous active substitutes for 8-type zeolide, X-type zeolide, and Y-type zeolide is as follows: It is within the range of 400 to 1000 m2/9, and these are suitable as the material of the present invention. On the other hand, natural zeolide also has a specific surface area of 100 to 500. m2
Zeolite materials in the range of /9 are available, and natural mordenite, chabasite, etc. are particularly suitable as the zeolite material of the present invention.

In the present invention, the above-mentioned zeolite is made into a powder or granular product in advance before being loaded with antibacterial ions. Furthermore, if necessary, the antibacterial composition used in the present invention is ground into a finer powder to have an average particle size of 2.6 μm or less, and the antibacterial metal is added to the fine zeolite powder by an ion exchange reaction. It is preferable to carry it. Or particle size 2. &μ
After holding antibacterial metals using powdered or granular zeolite with a particle diameter of 2.0 m or more, fine pulverization is performed to reduce the average particle size to 2.
．． It is also preferable to adjust the antibacterial composition to 6 μm or less. Antibacterial compositions have been prepared and antibacterial tests have been conducted over a long period of time. In other words, natural zeolites are mainly mordenite, chanogusite,
Synthetic zeolides mainly include A-type zeolide, Various antibacterial compositions were prepared by holding silver, copper, and zinc as antibacterial metals, either alone or in combination of two or more, in various proportions, and antibacterial tests were conducted. As a result, it was found that the fine antibacterial composition of the present invention and its molded product have excellent antibacterial effects against bacteria and fungi. As a result of various tests, it was found that the antibacterial activity mainly depends on the type of antibacterial metal and the holding medium, but also on the structure of the zeolite matrix. The aforementioned natural and synthetic zeolites used as carriers in the present invention alone do not exhibit any antibacterial ability. It has also been found that the usual impurities contained in natural zeolites have little effect on the antibacterial activity of the antibacterial composition of the present invention. Incidentally, the average particle diameter of the antibacterial composition of the present invention is preferably 2.6 μm or less.

The average particle diameter of 2.6 μm or less in this invention is a value expressed based on the dry state of the antibacterial composition at 100° to 110°C. When the antibacterial composition of the present invention is used in the form of an emulsion, slurry, suspension, etc. using water or other medium, or when used as a spray, the particle size of the antibacterial composition is extremely small and the particles are dispersed. Excellent characteristics are required. When used in such a state, the preferred average particle size of the antibacterial composition containing water of crystallization or anhydrous state of the present invention is 2.4 μm or less, and most preferably 1.6/Am or less. Further, products in which the antibacterial composition of the present invention is added to natural fibers, nonwoven fabrics, pigments, sheets, paper, plastics, coating compositions for various paints, filtration media, air filters, underlay sheets, polymeric materials, etc.
Alternatively, when applying antibacterial properties to the surface of the above materials by attaching them to the surface of the material using an adhesive, etc., particles with a fine particle size are required. It is preferable to maintain the size of the sterilizing composition so as to increase the effective surface area during sterilization to increase the sterilizing effect under activated conditions.

The average particle diameter of the present invention is 2.6 μm or less (100° to 11
It is not a very difficult problem to prepare antibacterial compositions containing water of crystallization (0° C. dry basis) or in an anhydrous state.

When preparing the antibacterial composition of the present invention using synthetic zeolite as a carrier by ion exchange, it is relatively easy to obtain zeolite in the form of fine powder. For example, A-type zeolide with an average particle diameter of 3 to 10 μm and X-type zeolide with an average particle diameter of 4 to 15 μm are easily available.

Therefore, after using these synthetic zeolites to prepare an antibacterial material by supporting the required amount of antibacterial silver, copper, or zinc on the zeolite using the ion exchange method, the antibacterial material is prepared using a ball mill,... By pulverizing with a pulverizer or the like, an antibacterial composition having an average particle size of around 2.6 μm can be obtained. Furthermore, when an antibacterial composition with an average particle size of 2.6 μm or less is required, wet pulverization or the like may be performed, for example. The average particle diameter of the antibacterial composition of the present invention using natural theolide as a carrier is 07~? Adjusting to about 6 μm is
For example, it is relatively easy to carry out wet pulverization. Furthermore, in order to prevent the coalescence of the primary particles of the antibacterial composition with an average particle diameter of 2311 m or less of the present invention as much as possible and maintain a good dispersion state, ultrasonic waves may be used, or organic to inorganic A dispersant may be used.

Next, the appropriate amount of antibacterial metal supported by the zeolite solid phase in the antibacterial composition of the present invention will be explained.

The exchange capacity of the natural or synthetic zeolites described above as suitable zeolite materials for the present invention is sufficient to retain the antimicrobial metals required in the present invention. Silver is added to sodium-type synthetic zeolite by ion exchange.
It is easily possible to maintain ~20% (anhydrous basis). ψ1j is made by using ion exchange method to maintain silver at 20% or more (anhydrous standard) in 8-type to It is easy to maintain it close to the anhydrous standard). On the other hand, it is possible to retain about 10 to 15 silver (on an anhydrous basis) in natural zeolites such as clinoptilolite and chabasite by an ion exchange method.

Therefore, the antibacterial composition of the present invention can contain the metal in the amount described above. However, from economical or practical point of view, the silver content in zeolite should be 0.0006 to 4.
It is preferable to use 1 (anhydrous standard), and the reason for this is based on the following.

The present inventor uses various natural or synthetic zeolites to
By supporting these with silver in various proportions, the average particle diameter was 1.8.
An antibacterial composition containing water of crystallization below μm and ld but in an anhydrous state was prepared and subjected to an antibacterial test using the disk method and a measurement of the killing rate against fungi. In this case, the test bacterium is Staphylococcus aureus (5taph
ylococcu+s aureus)s Bacillus 5ubtilis, Escherichia coli
t), Pseudomonas aeruginosa (Pseudomonas aeruginosa)
onasaeruginosa), Candida albicans
, Aspergillus flatus
flavus), Asp
ergillus niger) etc. were used.

, A-type, X-type and Y-type as synthetic zeolite carriers.
, - type zeolide sodium type is used, and clinoptilolite and chabasite are used as natural zeolite carriers, and these materials hold silver at 4% or more (anhydrous basis) and have an average particle size of 1. When various antibacterial compositions with 8/zm or less were prepared and antibacterial tests were conducted,
All compositions with silver content of 4% or more have excellent antibacterial activity against the above-mentioned test bacteria.
The killing rate of Aspergillus flarus reached 99-100% when using any of the antibacterial compositions. Furthermore, even when the silver content was in the range of 01 to 4% (anhydrous standard), almost the same antibacterial effect as that when the silver content was 4% or more was obtained. Also, from an economic point of view, it is advantageous to lower the upper limit of silver content. Furthermore, the silver content decreased and
Even with antibacterial compositions containing 8-type zeolide, Y-type zeo-6-lite, natural mordenite, etc. containing about 2 to 0.04% (anhydrous basis) and having an average particle diameter of 18 μm or less, Staphylococcus spp. aureus (5taphyl
ococusaureus), Escherichia coli (F, scherichiacoli), Pseudomonas aeruginosa (Pseudomonas ae)
ruginosa), Kandig 0 albicans (C
andida albicans), while the antibacterial effect against Aspe.
rgillus flavug) mortality rate is still 84~
It was found that the rate reached 94%. The silver content is further reduced from the above value to 0.0006~0. OO07% (
The antibacterial composition maintained on an anhydrous basis was also found to have an antibacterial effect against the several types of bacteria mentioned above.
), values of 10 to 19% were also obtained. However, it has been found that in antibacterial compositions containing silver below the above-mentioned value, the antibacterial effect decreases rapidly as the silver content decreases.

From the above test results, it is preferable that the silver-containing antibacterial composition of the present invention has a content of 0.0O06'%. Next, for antibacterial compositions containing copper with an average particle size of 18 μm or less in a crystal water-containing state or in an anhydrous state, it is recommended that the copper content in the zeolite be 0.03 to 10% (anhydrous standard). preferable. Regarding the copper-containing antibacterial composition, as with the silver-containing antibacterial composition described above, a number of antibacterial compositions were prototyped using various preparation conditions, and the antibacterial activity of these compositions was evaluated. For example, an average particle size of 8-type zeolide containing copper of about 20 parts (anhydrous standard) is 1.
The killing rate of the antibacterial composition of 8 μm or less against Aspe'rgillus flavue is l. Astakurugirasu when it drops by 2 balls and reaches 5-6% (anhydrous standard)
Pergillus flavus (A!pergillus flavus)
The mortality rate for copper is 95-99%, and
When the copper content was 2%, the killing rate against the above bacteria was reduced to 52 to 70%.In addition, the antibacterial composition of the present invention containing 1 to 2% copper was effective against Escherichia coli (Escheri=chiac).
olt) and Pseudomonas aeruginosa (Pseu
It was confirmed that the antibacterial effect was still remarkable against 'domonas aerugjnosa)'. Also copper from 05~
The antibacterial composition of the present invention having an average particle size of 1.8 μm or less prepared from natural clinoptilolite containing 0.6% (anhydrous basis)
When the mortality rate against S. llus flavus was measured, it was 37-47%. Furthermore, the copper content has been increased to 0.03%.
An antibacterial effect was also observed against 2 to 3 bacteria even when the antibacterial composition was maintained at It has been found that when the copper content is less than 0.03%, the antibacterial effect decreases drastically as the copper content decreases.

Based on the above reasons, in the present invention, the copper content is reduced to 0.03%.
~10 inches (anhydrous standard) is preferable. Next, in the antibacterial composition of the present invention which contains zinc and has an average particle diameter of 1.8 μm or less, the amount of zinc contained in the zeolite is 0.04 to 14% (anhydrous standard).
It is preferable that As for antibacterial compositions containing zinc, as with the antibacterial compositions containing silver and copper mentioned above, a large number of antibacterial compositions were produced using different preparation conditions, and the antibacterial activity of these compositions was investigated. An evaluation was conducted.

For example, As pergillus 5, an antibacterial composition containing 14% zinc (anhydrous basis) in Y-type zeolide and having an average particle size of 18 n or less,
HaVII! ! ), the mortality rate is 100%.

Even if zinc was maintained above the 2-dimension value, the mortality rate remained unchanged.

Aapergillus frag, an antibacterial composition with an average particle size of 18 μm or less, containing 11.28% (anhydrous) zinc in Y-type zeolide.
The killing rate against lavuIr was 100%, and in the antibacterial evaluation, it was particularly effective against Staphylococcus aureus and Etschierichia coli (T':5cherichjac).
It was confirmed that it has a significant antibacterial effect against oli. Furthermore, an antibacterial composition with an average particle size of 18 μm or less was prepared by retaining zinc in natural chapazite. In this case, the composition of Aspergillus flag (Asper) containing 0.93% and 0.11% zinc (anhydrous basis) was used.
The mortality rates against (Gillus flavus) were 86% and 35%, respectively. Aspergillus fragus, an antibacterial composition with an average particle size of 18 μm or less, containing 0.04% zinc (anhydrous basis) using the same natural zeolite as above.
), the mortality rate was 21%. Furthermore, various tests were conducted using the above natural zeolite with a zinc content of 0.04% or less, and it was found that the antibacterial activity decreased significantly as the zinc content decreased.

Based on such test results, the average particle diameter of the present invention is 18 μm.
In the following antibacterial compositions, the amount of zinc contained in the zeolite used is preferably 14% to 0.04%.

Next, as mentioned above, the antibacterial composition of the present invention includes silver, copper,
It is also possible to support two or more types of antibacterial metals selected from the group of zinc.

It can be prepared in accordance with the method for preparing the antibacterial composition of the present invention containing a single antibacterial metal.

Now, in order to show a uniform distribution of multiple or more antibacterial metals in zeolite and achieve a uniform antibacterial effect, it is necessary to prepare a mixed solution of metal salts having multiple or more antibacterial activities as shown in the following procedure [+lJ]. prepared in advance and subjected to ion exchange with a natural or synthetic zeolite suitable for the present invention as described above.
It may be carried out at room temperature to high temperature. In this case, the amount of each metal in the zeolite phase can be easily adjusted by adjusting the concentration of each metal in the aqueous phase. Among the antibacterial compositions of the present invention, the antibacterial activity of the antibacterial composition containing silver is greater than that containing zinc or copper.

Therefore, when preparing a composite antibacterial composition containing silver with an average particle size of 2.6 μm or less, the silver content should be as small as possible, and the content of zinc and copper should be increased compared to that of silver. is also economically advantageous. Such a composite antibacterial composition is also suitable for use in multi-purpose sterilization.

The antimicrobial compositions of the present invention containing one or more antimicrobial metals remain highly structurally stable whether kept dry (containing water of crystallization), saturated with water, or anhydrous. They are stable and have good antibacterial effects in all cases. When the dry antibacterial composition is heated and activated to form an anhydride, it has the advantage of not only high antibacterial activity but also high adsorption capacity for water and various gases. Therefore, the excellent heat-activated antibacterial composition has the distinctive advantage of not only having an antibacterial effect but also the ability to adsorb and remove harmful gases and dehumidify. It is expected that the field of application of the antibacterial composition of the present invention will be further expanded by taking advantage of such properties.

Next, a method for producing the molded antibacterial composition of the present invention will be described. Since the gist of the configuration of this invention has already been described, related explanations will be supplemented here. First, the method for preparing the material for molding will be described. A solution containing one or more metal salts selected from the group of silver, copper, and zinc as antibacterial metals, and ions of natural or synthetic zeolite powder to granules suitable for the present invention as described above. An antibacterial composition made of metal-substituted zeolite can be obtained by carrying out the exchange reaction at room temperature to high temperature using a patch method or a column method. Incidentally, during the above ion exchange reaction, it is necessary to adjust the - of the aqueous solution phase containing the antibacterial metal salt to 7 or less. By adjusting the pH, a predetermined amount of antibacterial metal is uniformly distributed in the zeolite phase, and at the same time some silver oxides, copper and zinc hydroxides, or precipitates of basic salts are deposited on the surface and fine particles of the zeolite. It is possible to prevent a phenomenon in which the antibacterial activity of the antibacterial composition of the present invention decreases due to precipitation in the pores. The natural or synthetic zeolites used as materials for the present invention, especially the latter commercially available products, contain modest amounts of free alkali, which may cause some of the antimicrobial metals to be converted into oxides and hydroxides. , basic salts, etc., and to prevent them from precipitating into the zeolite phase as much as possible, it is necessary to maintain -1 of the aqueous solution phase at 7 or less during ion exchange. The zeolite substituted with metal by the above ion exchange method is filtered and then washed with water to remove excess metal ions.

Next, the zeolite carrying the required amount of antibacterial metal is pulverized through a drying process. To this, an inorganic binder and/or an organic binder are added, and wet mixing is carried out in the presence of water or a urine solution, and the resulting mixture is shaped into an appropriate shape by a molding machine. For example, −ξlet, tablet,
Molded into spheres, columns, plates, cylinders, etc. The moisture content during wet mixing is controlled by the physical properties of the powder used and the shape of the desired molded product1, but during normal molding,
A moisture content of 17-40% is a preferred range. in this case,
The moisture required during mixing is provided by adding water or an aqueous urea solution. By using an aqueous urea solution, the urea decomposes during firing of the molded body made of the antibacterial composition, generating gases such as NH3, CO2, and H2O, and foaming violently. It has the effect of becoming porous and activating. Preferred inorganic bonds used in the present invention include montmorinonite (bentonite), kaolin, diatomaceous earth, colloidal silica, and colloidal alumina.

Examples of organic binders include microcrystalline celluloses such as methylcellulose, carboxymethylcellulose, and hydroxyethylcellulose.

The above-mentioned inorganic and organic binders may be used alone or in combination, but when molding an antibacterial composition using the monosynthetic zeolide of the present invention as a carrier, in order to obtain a predetermined strength of the molded product, It is particularly desirable to use only an inorganic binder or to use a combination of organic and inorganic binders. −
When molding the antibacterial composition using the natural zeolite of Rikiki's invention as a carrier, it is preferable to use only an organic binder or to use a combination of organic and inorganic binders. The amount of the above binder actually used is controlled by the physical properties of the antibacterial composition, but if an inorganic binder is used alone or in combination during normal molding, 10
A preferable range is 45° to 45°. On the other hand, when only an organic binder is used, the additive amount is 1-1% based on the material, and when an organic-inorganic binder is used in combination, the former is added at 1-5% based on the material. This is a preferable range. Next, the antibacterial molded body molded into a predetermined shape by the above method has a 900~
I], after drying at 0°C, it is finally fired at a temperature below the onset of thermal decomposition of the antibacterial composition. The firing temperature range varies depending on the composition of the material used, but in the case of normal firing in the present invention, a suitable range is 340° to 580°C, and the most preferable range is 390° to 50°C. . This firing is done under normal pressure or reduced pressure.

It can be carried out with The reason why the furnace is evacuated and firing is performed under reduced pressure is as follows. When the amount of antibacterial metals in the molded body of the antibacterial composition of the present invention increases by performing calcination under reduced pressure, it is effective to minimize the conversion of a part of the metals into oxides. be. Further, among the zeolite materials used in the present invention, the structure of X-type zeolide tends to deteriorate in heat, especially in a heated atmosphere containing water vapor. By performing the calcination of the antibacterial metal amount of the present invention using X-type zeolide as a carrier under reduced pressure, gases generated from the composition can be quickly removed and the antibacterial composition can be maintained in a stable state. It was confirmed that there is an advantage of being fired.

The antibacterial molded product prepared by this molding method has a high apparent density, excellent mechanical strength, and high antibacterial activity, as shown in the examples below. When the molded body of the present invention was brought into contact with various liquids for the purpose of sterilization, it was confirmed that the elution of antibacterial components from the molded body into the aqueous solution phase was minimal, and sterilization was carried out under favorable conditions.

Next, embodiments of the present invention will be explained with reference to Examples, but the present invention is not limited to these Examples.

Example 1 This example relates to a method for preparing an antibacterial composition of the present invention in which silver is retained in natural zeolite. Natural clinoptilolite from the United States (main ingredient: StO + 72.2%)
: At,,05. l 2.9chi; Mg0.

Q, 5%: CaO, 0.8%; Na2O, 3,
7%; K2O.

4.4%: Fe2O3,0.7%) IO(
1~200 meters, 7 units of fine powder, 01M for 5kg
Approximately 3 t of silver nitrate solution was added, and the p of the resulting mixture-containing liquid was
After adjusting +-1 to 6.5, the mixture was stirred at room temperature for 9 hours and 30 minutes. After the ion exchange reaction was completed, the zeolite phase was filtered and subsequently washed with water. Water washing in this case was carried out until excess silver ions were removed from the zeolite phase by a silver chloride test. Next, the water-washed zeolite was wet-pulverized using water as a medium, and the pulverized product was finally classified using a sieve to collect fine particles. In this example, 135 kg of a silver-containing antibacterial composition having an average particle diameter of 1.111 m was obtained (100°C to 100°C on a dry basis).

・Example 2 below: This example relates to a method for preparing an antibacterial composition of the present invention in which silver is retained in natural zeolite. Domestic natural mordenite (main ingredient: S+02-7215%: k
t20. , 1375%; Fe2O3゜0.20%; C
aO, 3,26%, : K2O, t, 66%-Na
20, t, 86%) 6 t of 0.1M silver nitrate solution was added to 3 kg of 100-250 mesh fine powder,
The H of the obtained mixture-containing liquid was adjusted to 67. Next, raise the temperature and maintain it at 70° to 75°C for 4 hours.
Minute stirring was performed. After the above ion exchange reaction was completed, the zeolite phase was filtered and subsequently washed with water. Water washing in this case was carried out until excess silver ions were removed from the zeolite phase by a silver chloride test. Next, the washed zeolite was wet-pulverized using water as a medium.

Finally, the pulverized product was classified using a sieve to collect fine particles. In this example, a silver-containing antibacterial composition having an average particle diameter of 09 μm and a specific surface area of 369 m2/9 was used.
49 to 9 (I OC!0-110°C (dry basis)) was obtained.

Example 3 This example relates to a method for preparing an antibacterial composition of the present invention in which silver is retained in an octa-type synthetic zeolite. Synthetic A-type zeolide (0,99Na2O・At203"
1.935in2' x H2O; average particle size 1.31
After adding 4 tons of OLJM silver nitrate aqueous solution to 2 kg of dry fine powder of 1 m ) and stirring, dilute acid and water were further added to adjust the pH to maintain the total volume at about 7.11.

In this case, the pH of the aqueous phase was adjusted to 5.6. Next, the mixture containing the slurry was stirred at room temperature for 4 hours.

After the ion exchange was completed, the ion phase in the zeolite phase was washed with water. In this case, washing with water was carried out until there was no excess silver ion in the zeolite phase of the silver chloride test. Next, the silver zeolite that had been washed with water was dried under reduced pressure, and then pulverized using an ultrafine pulverizer. After classification, the fine particles were collected. In this example, 1.58 kg of a silver-containing antibacterial composition having an average particle diameter of 089 μm and a specific surface area of 659 m2/l was used (1000-110°C
(dry standard) similar.

Example 4 This example relates to a method for preparing an antibacterial composition of the present invention in which silver is retained in a Y-type synthetic zeolite. Synthetic Y-type zeolide (1,, o9Na20- At20
．． '3.998402' xH2O: Average particle size 0.
63/1 m) for 2.5 kg of dry fine powder
After adding 5 tons of 08M silver nitrate aqueous solution and stirring, dilute acid and water were further added to adjust the ++ to maintain the total volume at about 91 tons. In this case, the pH of the aqueous solution phase is 52
It was adjusted to Next, the mixed solution containing the slurry was stirred at 29° C. for 3 hours and 10 minutes. After the above ion exchange,
The zeolite phase was filtered and subsequently washed with water.

In this case, washing with water was carried out until excess silver ions in the zeolite phase were eliminated by a silver chloride test. Next, the silver zeolite that had been washed with water was dried under reduced pressure, and then ground and classified using an ultrafine grinder to collect only the fine particles. In this example, a silver-containing antibacterial composition having an average particle diameter of 0.61 Lm and a specific surface area of 894 m2/I was used.
3 kg (100° to 110° C. dry basis) was obtained.

Example 5 This example relates to a method for preparing an antibacterial composition of the present invention in which silver is retained in X-type zeolide. Synthetic X~
type zeolite (1,03Na2O'At203-2.3
38r02' xJ (20; average particle size 2.3 μm
0.12M silver nitrate aqueous solution was added to 4 kg of the dry powder and stirred, and then dilute acid and water were added to adjust the pH to maintain the total pH at about 141.

The pH of the aqueous phase in this case was maintained at 6.8. next.

The mixed solution containing the slurry was stirred at around 25° C. for 3 hours and 30 minutes. After the ion exchange was completed, the zeolite phase was filtered through E and subsequently washed with water. In this case, washing with water was carried out until excess silver ions in the triolide phase were removed by a silver chloride test. Next, the silver zeolite that had been washed with water was wet-pulverized using water as a medium. Finally, the pulverized product was classified using a sieve and only the fine particles were collected.

In this example, the average particle diameter was 1.2 μm1 and the specific surface area was 869.
m 1g of silver-containing antibacterial composition is 3.0'4kf
(1090-110°C dry basis) was obtained.

Average particle size: 12 μm Yield: 3.04 kg True specific gravity: 2.24 Water content: 16.73% Silver content: 3.32% (anhydrous basis) Example 6゜This example uses A-type zeolide. The present invention relates to a method for preparing the antibacterial composition of the present invention retaining zinc. Synthetic 8-type zeolite F (1,03Na20At205,1
．． 0.99M zinc chloride solution for 1.6 kg of dry powder of 915io2'xH2O; average particle size 16 μm)
．． 11 and water to maintain the total volume at 5.81.

The ptl of the aqueous phase in this case was adjusted to 4.7. Next, the obtained slurry-containing mixture was heated to 600-70°C.
Stirring was performed for 6 hours while maintaining the temperature. After ion exchange,
The zeolite phase was filtered and subsequently washed with water. In this case, washing with water was carried out until excess chloride ions in the schizeolite phase were removed by a silver chloride test. Next, after drying the zinc zeolite that has been washed with water at 1,000 to 110°C, it is dried using a centrifugal method. The particles were crushed and classified using a mill, and only the fine particles were collected.

In this example, the average particle diameter was 1.08 m1 and the specific surface area was 733 F.
1.10 kg of zinc-containing antibacterial composition having +1/I
(1000-110°C dry basis) was obtained.

Average particle diameter: 1.0 μm Yield Density: 1.10 kg True specific gravity = 253 Water content: 15.47% Zinc content: 11.14% (dry basis) Example 7゜This example uses 8-type zeolide. The present invention relates to the preparation of antibacterial compositions of the present invention that retain copper.

Synthetic A-type zeo; i'j) (0,99Na20-A/
1.203・1.938102・XH2O: average particle size 1.3 ttm) of dry powder i, s kg, add 3.61 liters of 0.48 M cupric sulfate aqueous solution and water to bring up the total volume. I kept it at about 6.51. The pH of the aqueous phase in this case was adjusted to 4.2.

Next, the obtained slurry-containing liquid was heated and kept at around 70°C, and stirring was continued for 4 hours. After the ion exchange was completed, the zeolite phase was filtered and subsequently washed with water. In this case, water washing was carried out until excess sulfate ions were removed from the schizeolite phase by barium sulfate test. The copper zeolite surface that had been washed with water was dried at 100° to 110°C. Next, the obtained dried product was ground using an ultrafine grinder and classified, and only the fine particles were collected.

In this example, the average particle diameter was 0.9 μm, and the specific surface area was 57'.
9 m2/j; l of the copper-containing antibacterial composition is 1.3
9 ky (1noO~110°C dry basis) was obtained.

Average particle diameter = 09 μm Cap: 1.39 kg True specific gravity: 233 Moisture content: 16.94% Copper content: 6.36 cm (dry basis) Example 8 In this example, A-type zeolide was mixed with silver. The present invention relates to the preparation of a zinc-retained composite antibacterial composition. Synthetic A-type zeolide with an average particle size of 1.6 μm (
1,03Na2O-At2o3゜1.91SIO2・x
AAlNO3 for 0.91 kg of dry powder of H2O)
-Z n (No 3) 2 mixed liquid, [0, i 1 M
AgNO3; 0.98 M Z n (No 3) 2
] about 1.8A? and water to bring the total volume to about 3.2
'/ was kept. In this case, +i of the aqueous solution phase was adjusted to 41. The resulting slurry-containing liquid was then kept at around 25°C under stirring for 6 hours. After the ion exchange was completed, the zeolite phase was filtered and subsequently washed with water to remove excess silver ions and copper ions present in the zeolite phase. Next, after drying the silver and zinc zeolite that has been washed with water under reduced pressure, the dried product is pulverized using an ultrafine pulverizer and then classified.
A portion of fine particles was collected.

In this example, the average particle diameter was 1.1 μm, and the specific surface area was 718.
The silver-zinc-containing antimicrobial composition with m/, 9 is 0.7
8 kg (1000-110°C dry basis) was obtained.

Silver-zinc content using A-type zeolide as a carrier Anti-average particle diameter: 11 μm Yield: Q, 78 kg True specific gravity: 2.45 Moisture content: 529% Antibacterial all-class content liquid: Ag-1,42 %:Zn=6.
82% (dry basis) Example 9 This example relates to the preparation of a composite antibacterial composition of the present invention in which antibacterial silver and zinc are retained in natural zeolite.

1 kl of natural chabasite dry powder weighing 100-200 7 yu of rice weight? against 0.041M silver nitrate-0
, 98M zinc nitrate was added, and the pH was adjusted to maintain the pH at 46. The mixture was stirred at room temperature for 5 hours. After the ion exchange reaction is completed, the zeolite phase is filtered,
Subsequently, it was washed with water. Water washing in this case was carried out until there was no excess silver ion in the zeolite phase according to the silver chloride test. Next, the water-washed zeolite was subjected to wet pulverization using water as a medium, and finally the pulverized product was classified using a sieve to collect only the fine particles. In this example, the average particle diameter was 183μ.
0.74-kg (too~110<0>C dry basis) of a silver-zinc-containing antibacterial composition having a m1 specific surface area of 463 m2/9 was obtained.

Average particle size: 13 μm Yield: 0.74 kg True specific gravity: 2.33 Moisture content: 12.95% Antibacterial Kinmaki content ii: Ag = 0.91%, Zn
=2.85% (anhydrous basis) Example io.

This example relates to the preparation of a composite antibacterial composition in which three types of antibacterial metals, silver, zinc and copper, are retained in synthetic zeolite. Synthetic A- with an average particle size of 24 μm
Type zeolite F (1,02Na2O・At203・1.
96 S 102.XH2O) dry powder 1,55 k
0.048M silver nitrate - 0.59M zinc nitrate - for y
3.1 l of a mixture of 0.61 M cupric nitrate and water were added to maintain the total volume at approximately 5.6 l. In this case, the - of the aqueous solution phase was adjusted to 4.3. The resulting slurry-containing liquid was then kept under stirring at room temperature for 7 hours.

After the ion exchange reaction was completed, the zeolite phase was thoroughly filtered and subsequently washed with water to remove excess silver ions, copper ions, and zinc ions present in the zeolite phase. Next, the washed silver-copper-zinc zeolite was dried under reduced pressure, and the dried product was ground using an ultrafine grinder and then classified to collect only the fine particles.

In this example, the average particle diameter was 1.1 μm, and the specific surface area was 558.
The silver-zinc-copper-containing antibacterial composition having m279 is 1.
23ky (1000-110°C dry basis) was obtained.

Silver-zinc copper content using A-type zeolide as a carrier Average particle diameter: 1.1 μm Yield = 1.23 kg True specific gravity: 2.45 Moisture content: 15.52 Antibacterial metal content: Ag=i , 29%; Zn=6.
36%; Cu = 7.84% (anhydrous basis) Examples 1 to 7 relate to a method for preparing an antibacterial composition of the present invention in which a single antibacterial metal is retained in a natural or synthetic zeolite material. On the other hand, Examples 8 to 10 relate to a method for preparing an antibacterial composition of the present invention in which a plurality of antibacterial metals are held in the same type of zeolite material as in the above-mentioned examples. In all Examples, antibacterial compositions consisting of porous fine particles having an average particle size of 16 μm or less and a large specific surface area were obtained. The dry moisture content of these antibacterial compositions is as described above. An anhydrous antibacterial composition can be easily obtained by heating the dry product. For example, the anhydride can be obtained by heating the dry antibacterial composition under reduced pressure to 270° to 350°C, or by firing it at a temperature in the range of 390° to 550°C.

Table i-2 shows examples regarding the method for molding the antibacterial composition of the present invention. The first table is actually 1il! i Examples 11-18
Table 2 summarizes the molding conditions, while Table 2 shows the molding results. The antibacterial zeolite NaAg Furthermore, the antibacterial zeolite NaAgZn Z powder used in Example 13 was prepared with reference to Example 8. Antibacterial NaC of implementation L1014
u Y powder is a combination of Y-type zeolite (Na'Y) and di-sulfuric acid.
It was prepared by an ion exchange reaction near P114 of a copper aqueous solution. Antibacterial zeolite of Example 15) Na
The Ag Y powder was prepared with reference to Example 4, and the silver-natural mordenite powder of Example 16 was prepared with reference to Example 2, and further with reference to Example 17.
NaCu 2 powder was prepared with reference to Example 7. Moreover, NaZn Z powder 1 of Example 18 was prepared with reference to Example 6.

As described in Table 1, in wet molding, Example 12
．． Examples 16 and 18 use a combination of inorganic and organic binders, and other examples use only an inorganic bentonite binder. In Example 2, bentonite and an organic methyl cellulose (OB-1) binder were used, and in Example 16, bentonite and an organic carboxymethyl cellulose (OB-1) were used as a binder.
OB-2) binder, and in Example 18, bentonite and organic hydroxyethylcellulose (OB-3).
) using a binder. The average particle diameter of the molding materials listed in Table 1 was 18 μm or less in any of the examples.
Moreover, the amounts of materials used are all values on a dry basis. In addition, the amount of binder used in the description is slightly - based on the molding material (dry product).
Showing cents. Next, the moisture required for wet mixing was supplied by simply adding water (denoted as a in the table) or by adding a trithiurea aqueous solution (denoted as b in the table). As for the firing conditions for the dried bead-shaped or islet-shaped molded bodies, as shown in Table 1, two methods were carried out: firing under normal pressure and firing under reduced pressure. The physical property values of the fired molded bodies obtained in the above examples are listed in Table 2. In Example 11, bead-like molding of 1 to 2 shades and 3 to 5 shades was carried out.

The average strength (C) of these two types of molded bodies is 1.8 each.
It was found that antibacterial beads with high strength could be obtained at 9 and 3.76 kg/bead. In Examples 12 to 18, C of the 1/16" antibacterial ret molded body was 4.3 kg or more, while I
A "C of antibacterial gelat is C of Example 14 = 469 kg"
/ Except for Zelet, all of them are 8.9 ky /! It has reached more than Rett. These results show that the molding method of the present invention can produce molded bodies with extremely high hardness. Table 2 also includes the measured values of apparent density.
All of these values are large, indicating that a desirable high-density molded article of the antibacterial composition can be obtained.

Next, an antibacterial test of the antibacterial composition of the present invention will be explained. The antibacterial activity was evaluated using the following method. The test substance was suspended at a concentration of 100 ml and poured into a disk. Mueller IH for bacteria in culture medium
r+ton medium was used, and for fungi, Sabouraud agar medium. The test bacteria were suspended in physiological saline at 108/rne and dispersed in the medium using a 0.1 ml Conlage rod. The disc to be tested was placed in the soil.

For judgment, the presence or absence of an inhibition zone was observed for bacteria after 18 hours had passed at 37°C. Fungi were determined after J weeks at 30°C.

On the other hand, the fungal mortality rate was measured by the following method.

Aspergillus frag
lavus) spore suspension (], O'/ml)
1. me as test substance suspension (500 nQ/ml)
The mixture was poured into 9 mg and allowed to react at 30°C for 24 hours. That 0.1m11! were dispersed on a Zabro agar medium, and after 48 hours at 38°C, the number of living cloth individuals was measured to determine the mortality rate.

Table 4 in the margin below Fungal kill rate measurement using antibacterial composition paV
, =Average particle size The results of the evaluation test for the antibacterial composition of the present invention are listed in Table 3. During the test, both the dry fine powder and the calcined fine powder (anhydrous state) of the antibacterial composition were evaluated against four types of bacteria. It was found that all the antibacterial compositions obtained in Examples 1 to 10 had good antibacterial activity. Furthermore, the fungal mortality rate was measured using Aspergillus flavu according to the method described above.
s), and good results as shown in Table 4 were obtained in all Examples. Comparative Examples A and B in Table 4 are basic zinc carbonate (5ZnO-2CO2・4H2
0) Basic copper carbonate [Cl1003・Cu(OH)2・H
20] in exactly the same manner as in this example.
flavus), the mortality rate was measured. Neither carbonate salt was found to be effective. −
The antibacterial activity is good in strength tree row 6 (zinc-A type zeolite composition) and Example 7 (copper-A type iolite composition*). A comparison of these shows that zeolite He is porous.
It is clear that the antibacterial effect of the antibacterial composition of the present invention retained in the body is significant.

Next, an evaluation test was conducted on the molded product of the antibacterial composition prepared by the method of the present invention against four types of bacteria, and the test results are listed in Table 5. The test was conducted on both the ret molded product and its crushed product, and good results were obtained as shown. In addition, Aspergillus e flavus (Aspe
The mortality rate was measured for both the molded body and its pulverized product using the molded body and its crushed product. Do it according to the law. Aspergillus flaps (Aspergillus flaps)
The antibacterial molded body was immersed in a spore suspension Q (io' spores/ml) of S. flavus), and the killing rate was measured according to the method described above. The evaluation test for the antibacterial activity of the crushed molded product and the measurement of the mortality rate were performed in exactly the same manner as described above.

Table 6 Example of measuring the killing rate against fungi using a molded product of an antibacterial composition Example 19゜This example relates to a test of the water resistance and ability to retain antibacterial activity of a molded product of the antibacterial composition of the present invention. It is. Example 1
Antibacterial molded body obtained according to 1 (3-5III11
Beads; NaAgX; C=3.76kg/bead;
A small column made of glass with an inner diameter of 22fi was uniformly filled with Ag'=1.62cm, and the volume of the packed bed was maintained at 10ml. On the other hand, desalinated water obtained by ion exchange method or city tap water (ca2+ == 1 sppm;
Mg = 5.6 ppm; Ct = 31 ppm
) was passed through water at a flow rate of 25 to 30 me/min to test the water resistance and antibacterial ability of the molded article of the present invention.

Table 7-A Water flow test (desalinated water) Table 7-B Water flow test (tap water) Table 7 shows the relationship between the amount of water flow and the silver concentration in the effluent of the curlew. Table 7-A and Table 7-B show the results obtained using demineralized water and tap water, respectively. It was found that the indicated value shows that the molded product of the present invention has less silver eluted in ppb amount, and the antibacterial molded product is maintained in a preferable state. Furthermore, the molded product was found to have excellent water resistance as no damage was observed during the water flow test. Tap water 15'4/! In order to confirm the antibacterial ability of the used molded body after completing the water flow test, the fungal kill rate was measured using Aspergillus flavus.
) (see Table 8). From this perspective, it is clear that the molded article of the present invention has a high antibacterial retention ability.

Table 8: Example 20 of measuring fungal mortality rate This example relates to testing the water resistance and antibacterial activity of molded bodies of the antibacterial composition of the present invention. Antibacterial IA″ pellets obtained according to Example 18 (NaZnZ:C=13
．． 68kg/pellet: Zn=:5.29%
) was evenly packed into a small column made of glass with an inner diameter of 22 mm, and the bed volume was maintained at 11 ml. In contrast, Example 1
The same tap water as in No. 9 was passed through at a flow rate of 20 to 25 m1/'min, and the relationship between the water flow rate and the concentration of zinc flowing out from the column was examined. The test results are shown in Table 9. Table 9 Water flow test (tap water) The values shown indicate that the elution of zinc from the zinc-zeolide antibacterial pellets of the present invention is carried out under conditions with a favorable amount of PPb. On the other hand, through a water flow test, it was confirmed that the antibacterial property (ret was not damaged and its water resistance was sufficient). In order to confirm the ability to retain force, the mortality rate against fungi was measured using 7 Svergillus flatus (Aspe
rgillus flavug). As a result, it was found that the antibacterial activity of the used pellets was still maintained (see Table 10).

Table 10: Example 21 of Measurement of Fungal Killing Rate This example is an example in which antibacterial treatment was applied to the second item.

Material: / ester / cotton (50150) blend, mesh N 2
00 II/m2 (,) Antibacterial zeolite powder [Example 3: Ag-A type zeolite powder, Ag = 3
．． 78 (anhydrous standard)]: 109/1 l (b) Acrylic resin emulsion (solid content 50%): 201/13 (,) and (b) were dispersed in water. At this time, a dispersant was added equal to the weight of the zeolite. A polyester/cotton blended knit was treated with the above conditioning solution. The pickup was 100% with Mangle. After pre-drying the shredded material in a mangle at 100℃ for 5 minutes, it was dried at 160℃ for 3 minutes.
Heat treatment was performed for 1 minute.

Escherichia coli (Escherichia coli)
When antibacterial tests were conducted on the bacteria Richia colt and Aspergillus flavus, it was confirmed that the antibacterial effect was effective against both bacteria.

The antibacterial composition of the present invention not only has a bactericidal effect, but also has excellent adsorption ability against trace amounts of moisture and carbon dioxide present in the air, as well as harmful carbon monoxide, sulfur dioxide gas, ammonia gas, etc. ing. The antibacterial compositions obtained in Examples 9 and 10 were tested for crosstalk such as gas adsorption (25°C
) is shown in Figure 1-4. In both figures, curve-1 relates to the anti-dental composition obtained in Example 9, and curve-2 relates to the anti-bacterial composition obtained in Example 10. Figure 1 shows sulfur dioxide gas, Figure 2 shows carbon dioxide gas, Figure 3 shows ammonia gas, and Figure 4 shows water adsorption isotherms.

If the molded product of the antibacterial composition of the present invention is used, for example, as an air filter, there is an advantage that air dehumidification and removal of harmful gases can be performed simultaneously with sterilization.

Example 22 This example relates to a method for preparing an antibacterial composition of the present invention in which silver is retained in natural zeolite. Domestic natural mordenite 100-250, the same as used in Example 2
O,] for 3.1 ky of fine powder of Mesosyu, 61 M silver nitrate solution was added, and the Pll of the resulting mixture-containing liquid was 5
Adjusted to 9. Next, this was heated and stirred for 4 hours while maintaining the temperature at 70° to 75°C. After the above ion exchange reaction was completed, the zematode phase was filtered and subsequently washed with water. In this case, washing with water was carried out until there was no excess silver ion in the schizeolite phase according to the silver chloride test. Next, the obtained zeolite was dried under reduced pressure at around 90°C, and then dry pulverized using a Noenotomil. Finally, the pulverized product was classified and the fine particles were collected.

In this example, the average particle diameter was 25 μm and the specific surface area was 371 m2.
/g of silver-containing antimicrobial composition with 2.52 kll
(90°C dry basis) was obtained.

Silver-containing antibacterial composition using natural mordenite as a carrier (
Dry product) Average particle diameter: 25 μm Yield: 2.52 kg True specific gravity, 237 Water content: 660 Silver content: 223% (anhydrous basis) Example 23 This example is based on the antibacterial composition obtained in Example 22. This relates to an example of molding a product. During the main molding, an organic binder [methyl cellulose (0, B, -1): 2%
Specific viscosity of solution at 20°C = 7.000 to 10.00
(1) Only (cps) was used.

The molding conditions for the antibacterial coating (1/8°') are as follows.

Molding conditions of Example-23 Amount of binder used: Methyl cellulose (0, B, -1) 7
．． 5% Moisture during wet mixing: 336% Mixing time: 2 hours 30 trays 1/8" drying temperature: 100° to 105°C Baking time of molded body: 2550° to 560°C (2 hrs) Above molding conditions 178” antibacterial test sample obtained by
The average strength of [Ag=2.21% (anhydrous standard)] is 8.2
7 kg/pellet, the apparent density of the pellet was 1352. In this molding example, as described above, only an organic binder is used, and the methylcellulose used is completely decomposed at the above firing temperature. Therefore, almost no methylcellulose remains in the baked antibacterial 4lets.

The powdered antibacterial composition obtained in Example 22 according to the above-mentioned antibacterial composition evaluation test and its molded product (
178''-lett (Example 23)] was conducted to evaluate its antibacterial properties, and the results shown in Table 11 were obtained.

As shown, the fine powder and antibacterial pellets obtained in Examples 22 and 23 were both found to exhibit good antibacterial activity. Next, using the antibacterial compositions (powder and molded body) obtained in both Examples, Aspergillus flavus ('Aspergill) was prepared by the method described above.
Us flavus) was used to measure the fungal mortality rate. A good mortality rate of 100% was obtained for all samples.

The micronized antibacterial composition of the present invention most preferably has an average diameter of 18 μm or less; however, an antibacterial composition prepared in the same manner as in Example 22 with an average diameter of about 26 μm may also be used.
When used in the form of emulsions, slurries, suspensions, etc., or sprayed using water or other media, and when used on natural fibers, non-woven fabrics, pigments, sheets, paper, plastics, etc. Suitable for imparting antibacterial properties by adding it to paint coating compositions, filter media, air filters, underlay sheets, polymeric materials, etc., or by attaching it to the surfaces of the above materials via adhesives, etc. It was confirmed that it can withstand practical use.

Note that the particle diameters described in this specification were measured by a light transmission method.

[Brief explanation of the drawing]

Figures 1 to 4 relate to crosstalk such as adsorption. - Figure 1 shows sulfur dioxide gas, Figure 2 shows carbon dioxide gas, Figure 3 shows ammonia gas, and Figure 4 shows water adsorption isotherms. In both figures, curve-1 relates to the antibacterial composition obtained in Example 9, and curve-2 relates to the antibacterial composition obtained in Example 1.
This relates to the antibacterial composition obtained in No. 0. All results are shown at 25°C. Full-page engraving (No change from 1 to volume) Fig. 1 SO2 adsorption pressure (mmHg) Fig. 3 NH, adsorption pressure (mmHg) Fig. 4 0 5 10 15 20 )-12Q adsorption pressure (mmHg) Procedure correction port ( Spontaneous) April 1, 1980 Kazuo Wakasugi, Commissioner of the Patent Office1, Indication of the case Patent Application No. 36142 of 19822, Title of the invention Antibacterial composition using zeolite as a carrier and method for producing the same3, Relationship with the case of the person making the amendment Name of patent applicant (095)! ! Boku Co., Ltd. name: Kanto Kagaku Co., Ltd. 4, agent address: 8-10-5 Toranomon-chome, Minato-ku, Tokyo 105
Subject of amendment (1) Drawing (2) Power of attorney 6, contents of amendment il+ Complete the engraving drawing as shown in the attached sheet. (No change in content) (2) Complete the power of attorney as shown in the attached document. 7. List of attached documents (1) 1 copy of engraving drawings (2) 2 copies of power of attorney

Claims (1)

[Claims] 1. Natural zeolite, synthetic zeolite, or both are used as a carrier, and some or substantially all of the ion-exchangeable metals contained in the zeolite are made from silver, copper, and zinc. A particulate antibacterial composition in a water-of-crystal-containing state or in an anhydrous state, which is substituted with at least one metal selected from the group consisting of: 2 Average particle size is 2. &ttm or less, the composition according to claim 1. 3. 0.0006-4% silver, 0.03-10% copper, or 0.004-14% zinc [all heavy! , H (anhydrous basis)] according to claim 1. 4 Multiple metals selected from the group consisting of silver, copper, and zinc are uniformly distributed in the zeolite support, and if silver is present, it is present in a smaller proportion than any other metal. The composition according to claim 1. 5. Using natural zeolite or Taninari zeolite, or both as a carrier, a part or all of the metals capable of ion exchange contained in the zeolite are selected from the group consisting of silver, copper and zinc. product. 6. In a solution with a pH of 7 or less containing ions of at least one metal selected from the group consisting of silver, copper and zinc, the ions and natural, natural zeolite or synthetic zeolite,
A zeolite substituted with the metal is obtained by reacting both or and with, and an inorganic binder and/or an organic binder is added to the metal-substituted zeolite, and wet mixing is performed with water or an aqueous urea solution, A special natural zeolite characterized by molding the obtained mixture into a predetermined shape, then drying this wet molded product, and calcining it under normal pressure or reduced pressure in a temperature range below the onset of thermal decomposition of zeolite. or a synthetic zeolite, or a method for producing at least one in which both of these are used as a carrier, and a portion or substantially all of the ion-exchangeable metal contained in the zeolite is selected from the group consisting of silver, copper, and zinc.