JP2002104909A - Composite germicide and germicidal treatment method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composite germicide enabling simple and safe germicidal treatment, and to provide a germicidal treatment method. SOLUTION: This composite germicide is characterized by consisting of an inorganic/inorganic composite with extremely high germicidal capability obtained by bearing a silver phosphate compound shown by Ag3PO4 or Ag4P2O7 in the pores of a porous inorganic carrier. The 2nd objective method for producing such a composite germicide is characterized by comprising synthesizing the silver phosphate compound in the pores of the porous inorganic carrier by applying multistage-fashion an impregnating crystallization method and bearing the silver phosphate compound in the pores, and the 3rd objective a germicidal treatment method for to-be-treated water or moisture-containing gases using such a composite germicide. This composite germicide has such germicidal characteristics that on contact of the bacteria in water or a moisture- containing gas with the composite germicide, the bacteria are completely exterminated within a short time by the surface characteristics thereof, namely, by the germicidal effect of the silver phosphate compound dispersed and borne in the form of microparticles therein, therefore enables the germicidal treatment of (to-be-treated) water or moisture-containing gases easily and safely.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a disinfectant used for disinfecting water such as drinking water and domestic water and for disinfecting water-containing gas in which bacteria such as breath and sick rooms are present. Inorganic carrier-silver phosphate (Ag ₃ PO
₄ / Ag ₄ P ₂ O ₇ ) complex as an active ingredient of a fungicide,
The present invention relates to a disinfectant capable of easily and safely disinfecting bacteria in water and a disinfecting method using the same. In the present specification, “or” may be represented by “/”.

[0002]

2. Description of the Related Art Water disinfection has long been an indispensable technique for securing drinking water and domestic water. Recently, highly sterilized water is required from the production of foods and pharmaceuticals to the production of LSIs, and is becoming one of the important technologies in the production process even in a wide range of industrial fields. At present, chemical disinfection methods such as chlorine disinfection of drinking water are the mainstream for securing domestic water, etc.In the industrial field, physical disinfection methods using heating or ultraviolet rays are the mainstream. It has become. Similarly, a physical sterilization method is mainly used for a gas containing water such as a patient's breath or a sick room where bacteria exist. The reason why the chemical sterilization method became popular as a sterilization method for drinking water and domestic water is that the basic operation of the sterilization treatment is only mixing of chemicals, the operation is simple and the cost is low, and large quantities of drinking water and domestic water are required. This was because it was suitable as a sterilization method.

However, in recent years, not only chlorine used for disinfection of waterworks but also recurrent contamination of waterworks sources by chlorine used for achieving BOD value of sewage and industrial wastewater and for sterilization is a carcinogen. It has been clarified that they are promoting the growth of trihalomethanes, and there is an urgent need to develop new epidemiologically safe sterilization methods that can replace chemical sterilization methods using such agents (Sawai et al., Inorganic Materials, 4). ,
156-162 (1997)). For this reason, the development of inorganic antibacterial / bactericides prepared by supporting various antibacterial metals on a highly heat-resistant inorganic carrier such as zeolite and their application to daily life and industrial fields have attracted attention. Among various antibacterial metals, silver has a broad antibacterial spectrum (Iwata, zeolite, 13 (2), 8-15 (1996)) and relatively high safety (Otani, antibacterial and antifungal, 24 (6) ), 4
29-432 (1996)), and development of antibacterial and bactericidal agents in which silver is supported on various inorganic carriers has been actively conducted (for example, "Antibacterial and antifungal ceramics (I)", issued by TAIC Corporation). (II), 1995; 199
8). As the inorganic carrier, zeolite, various phosphates, titanium oxide, various layered compounds, glass and the like are used (for example, “Antibacterial and antifungal ceramics (I); (II) , 1995; 19
98).

However, in the case of directly supporting silver ions on an inorganic carrier, the affinity between the carrier and silver ions is often not so large that the supported silver ions are easily eluted and the sterilization life is short. There were drawbacks. For this reason, an attempt has been made to prepare a reagent in which silver is eluted at a controlled rate by using an organic treatment method in the process of carrying silver (Otani, Bactericidal and Fungicide, 20
(8), 413-418 (1992)). However, in general, the combined use of such an organic treatment method causes problems such as a complicated treatment step and an increase in production cost, and a decrease in heat resistance of the reagent due to introduction of an organic substance. Therefore, development of a simple and low-cost preparation method of a silver-carrying inorganic bactericide having a long bactericidal life and excellent bactericidal power and heat resistance has been desired.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has as its object to provide a new disinfectant capable of simple and safe disinfection. Also,
An object of the present invention is to provide a new sterilization treatment method for water to be treated and water-containing gas by the above-mentioned sterilizing agent.

The present inventors have conducted intensive studies to achieve the above object. As a result, the porous inorganic carrier was impregnated with an orthophosphate solution or a hydrogen phosphate solution / diphosphate solution and then dried. The precursor complex obtained by precipitating orthophosphate or hydrogen phosphate / diphosphate in the pores of the carrier is further impregnated with a silver solution, and the orthophosphate or hydrogen phosphate in the precursor complex is impregnated. / 1 of diphosphate
Using a complex disinfectant carrying poorly soluble silver phosphate (Ag ₃ PO ₄ / Ag ₄ P ₂ O ₇ ) obtained by substituting valent cations with silver ions and bringing them into contact with water or a gas containing water. Have found that rapid and complete disinfection of bacteria in water is possible by utilizing their surface properties, and have completed the present invention.

[0007]

Means for Solving the Problems That is, the above objects can be achieved.
The present invention includes the following technical means. (1) Ag in the pores of the porous inorganic carrier_Three PO_FourOr
Ag_Four P_Two O₇ Synthesizes and supports a silver phosphate compound represented by
From a highly bactericidal inorganic-inorganic composite
A composite disinfectant characterized by comprising: (2) A method for producing the composite germicide according to (1).
What is Ag_Three PO_Four Or Ag_Four P_TwoO₇ Phosphorus represented by
By applying impregnated crystallization method in multiple stages
Characterized by being synthesized and supported in the pores of a porous inorganic carrier
A method for producing a disinfectant. (3) The above Ag_Three PO_Four The silver phosphate compound represented by
When synthesizing, the general formula M_Three PO_Four Metaphosphoric acid represented by
Salt (M in the formula represents a monovalent cation, Na⁺ , NH_Four 
⁺ , K⁺ Etc.) or M_n H_3-nPO_Four 
(M in the formula represents a monovalent cation.)
And Na⁺ , NH_Four ⁺ , K⁺ And the like. Also,
n is 1, 2, or 3) as a precursor compound
The method according to (2) above, wherein
Law. (4) The above Ag_Four P_Two O₇ Silver phosphate compound represented by
When synthesizing the general formula M^I _Four P_TwoO₇ The two represented by
Phosphate (wherein M represents a monovalent cation and Na⁺ , H
⁺ , K⁺ Is used as a precursor compound
The manufacturing method according to the above (2), wherein (5) The precursor inorganic compound metaphosphate is added to the porous inorganic carrier.
Or precursor composite obtained by synthesizing and supporting hydrogen phosphate
The body is further impregnated with a silver salt solution,
The monovalent cation of acid salt or hydrogen phosphate with silver ion
By substitution, a silver phosphate compound (Ag_Three PO_Four )
The manufacturing method according to the above (2), which comprises converting. (6) The diphosphate of the precursor compound is added to the porous inorganic carrier.
A silver salt solution is further added to the precursor complex obtained by forming and supporting
The monovalent cation of the diphosphate in the impregnated precursor complex is replaced with silver ion.
By substitution with on, a silver phosphate compound (Ag_Four P_Two 
O₇ )).
Construction method. (7) The composite germicide according to (1) is treated with water to be treated or contains water.
The body is brought into contact and the water to be treated is
Sterilization method characterized by sterilizing water and gas containing water
Law.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail.
You. The composite germicide of the present invention comprises, as a first step, silica or the like.
In the pores of the porous inorganic carrier of the general formula M_Three PO_Four In table
A metaphosphate (wherein M represents a monovalent cation;
Na⁺ , NH_Four ⁺ , K⁺ Etc.) or M
_n H_3-n PO_Four (Wherein M is 1
Represents a cation, usually Na⁺ , NH_Four ⁺ , K⁺ Etc.
It is an ion. N is one of 1, 2, and 3
Take) / general formula M^I _FourP_Two O₇ Diphosphate represented by
(M in the formula represents a monovalent cation, usually Na⁺ , H
⁺ , K⁺ Is impregnated with a solution of
After drying, add the above metaphosphate or hydrogen phosphate
Crystallize the precursor compounds of phosphate
A precursor composite comprising a porous inorganic carrier is prepared. Next
Then, as a second step, the precursor complex is dissolved in water, such as silver nitrate.
Impregnated with a solution of a neutral silver compound to form
After replacing on with silver ions, dry and dry the silver phosphate compound
(Ag_Three PO_Four / Ag_Four P_Two O₇ Combined sterilization carrying)
The preparation of the agent.

Examples of the porous inorganic carrier include, in addition to the above-mentioned silica, alumina, silica-alumina, glass, zeolite, clay, activated carbon, carbon black, various porous ceramics, etc., but are not limited thereto. Commercially available products and natural products can be used as long as they are porous and have a certain level of mechanical strength.

[0010] The above-mentioned composite bactericide can be formed into various shapes such as granules, films, and fine powders depending on the shape of the carrier. It is also possible to use a fine powder in a state of being dispersed in fibers, paper or the like.

[0011] To sterilize water using the composite disinfectant of the present invention, water can be brought into contact with the composite disinfectant. It is possible. Further, as a method for continuously sterilizing the flowing water, a method in which the water to be treated permeates through a water-permeable layer made of a composite sterilizing agent is preferable. Thus, the sterilization treatment of water using the complex disinfectant can be carried out by an extremely simple operation, and can be used as an alternative to the chlorine sterilization method for tap water and sewage, as well as household water purifiers, water supply equipment and It can be applied to prevent bacteria from adhering to baths, prevent the growth of bacteria in air purifiers and humidifiers, and be used as a portable water treatment device.

Although the above has described sterilization of water, the present invention is not limited to this and can sterilize a gas containing water, for example, human breath or even the atmosphere. In this case, when the disinfectant of the present invention is stored in a gas-permeable wrapper and placed on a mask and used by a sick person, the bacteria in the exhaled air are sterilized by contact with the sick person's exhaled gas, and the air is removed. In addition, by disposing the disinfectant of the present invention in a ventilation or cooling / heating device of a hospital room or the like in a hospital, it is possible to perform a disinfection treatment in a room, which is effective in epidemics prevention.

[0013]

The composite germicide of the present invention is used as a precursor composite obtained by supporting orthophosphate or hydrogen phosphate / diphosphate in the pores of a porous inorganic carrier by using an impregnation crystallization method. And a silver phosphate (Ag ₃ PO) obtained by impregnating a silver solution and substituting monovalent cations in the precursor complex with silver ions.
₄ / Ag ₄ P ₂ O ₇ ) -porous inorganic carrier composite,
Since bacteria in water or water-containing gas are sterilized by contacting silver phosphate dispersed and supported in fine particles in these disinfectants, the disinfectant according to the present invention has a high disinfecting effect on underwater bacteria. Have. Therefore, by using the complex disinfectant according to the present invention, it is possible to easily and safely perform the disinfection treatment of water and water-containing gas.

[0014]

EXAMPLES Hereinafter, the bactericidal effect of the composite bactericide according to the present invention will be described in detail with reference to examples of the production method and water treatment, but the present invention is not limited by the following examples. is not. (1) Preparation of used strain and sample solution The strain used in the experiment was Escherichia coli (Escherichia).
a coli: E. a. coli (JCM 1649)) and Staphylococcus a.
ureus: S. aureus (FDA209P)). Each of these strains was subcultured once a month on a normal agar slant medium. In the experiment, at 37 ° C., 20 ± 2 in an L-shaped tube into which 10 ml of a common broth was dispensed.
After culturing with shaking for an hour, the culture was further transferred to an Erlenmeyer flask containing 150 ml of the same medium and cultured with shaking at 37 ° C. for 18 hours.
Centrifugal harvest (4 ° C., 6000 rpm, 10
The washed cells were washed twice with sterile physiological saline and once with sterile purified water, and then uniformly suspended in 300 ml of sterile purified water so as to have a bacterial concentration of 10 ⁶ to 10 ⁷ cells / ml. ,
It was used as a sample suspension (hereinafter referred to as a sample solution).

(2) Samples Used in Sterilization Experiments Table 1 shows the properties of the composite germicidal samples and carrier samples used in the sterilization experiments. Hereinafter, the production method and characteristics of the composite disinfectant sample will be described.

[0016]

[Table 1]

Silver phosphate (Ag ₃ PO ₄ / Ag ₄ P ₂ O)
₇ ) The method for producing the composite fungicide-containing sample is as follows: a natural or synthetic porous inorganic carrier is brought into contact with an orthophosphate solution or a hydrogen phosphate solution / diphosphate solution; After impregnating the precursor complex, the precursor complex obtained by drying and precipitating orthophosphate or hydrogen phosphate / diphosphate is further impregnated with a silver solution to form orthophosphate or orthophosphate in the precursor complex. It is prepared by replacing monovalent cations of hydrogen phosphate / diphosphate with silver ions. For example, preparation examples using three types of commercially available granular silica carriers (100 to 300 μm) having different pore characteristics shown in Table 1 as carrier samples will be described in detail.

1) Silver phosphate (Ag)_Three PO_Four ) Contained compound killing
Preparation of microbial agent sample Dry at 110 ° C for 24 hours, dehydrate and store in a sealed container
Carrier sample 400LS, 075LS or 005LS
Was placed in a 20 mL Erlenmeyer flask, and 0.2 g
M (M = mole / L) ammonium dihydrogen phosphate (N
H_Four H_Two PO_Four ) Add 10 ml of aqueous solution,
Hold for 30 minutes under an aqueous solution of ammonium dihydrogen phosphate
Was impregnated into the pores of the carrier. Surplus dihydrogen phosphate ammo
After removing the aqueous solution by suction, freeze the impregnated sample for 12 hours.
Precursor that has been dried and supported with ammonium dihydrogen phosphate
A united sample was obtained. Next, 0.2M was added to this precursor composite sample.
An aqueous solution of silver nitrate (10 ml) was added, and the mixture was stirred at room temperature under reduced pressure for 30 minutes.
After holding for a while, further ripening of the formed silver phosphate compound
For 2 hours under the same conditions. Excess silver nitrate solution
After removal by suction, the impregnated sample was lyophilized for 12 hours. Profit
Elutriation of the dried sample using a 100 mesh sieve
After removing fine granules, dry at 80 ° C for 24 hours.
Ming silver phosphate (Ag_Three PO_Four )-Particles composed of silica carrier
A composite fungicide sample was obtained.

The silver phosphate (A) obtained by subjecting the carrier 400LS, 075LS or 005LS to the above treatment is described below.
g ₃ PO ₄ ) -supported composite germicide samples were each subjected to S3P-400.
LS, S3P-075LS and S3P-005LS. Here, the production of the target composite germicide sample by the above treatment can be easily confirmed by measuring the powder X-ray diffraction patterns (using CuKα rays) of S3P-400LS, S3P-075LS and S3P-005LS. That is, as shown in Table 1, in each of the carrier samples, only a halo centered at about 2θ = 22 °, which is characteristic of amorphous silica, was observed. In contrast, S3P-400LS, S3P
In -075LS and S3P-005LS, in addition to the specific halo Both the amorphous silica of the, Ag ₃ PO ₄
Some diffraction peaks (d-value of plane distance (ｄ) =
2.69, 2.46, 3.01) (1998 JCPD
S file No. 06-0505) was confirmed.
Note that the amount of silver phosphate (Ag ₃ PO ₄ ) supported increases as the concentration of the impregnating solution and the number of times of impregnation increase, and can be easily adjusted by controlling the processing conditions. When the carrying amount of Ag ₃ PO ₄ is small, the strongest diffraction line of Ag ₃ PO ₄ (d value (Å)) is shown on the X-ray diffraction pattern.
= 2.69) only.

2) Preparation of a composite fungicide sample containing silver phosphate (Ag ₄ P ₂ O ₇ ) A carrier sample 400 LS, 075 LS or 005 LS dried at 110 ° C. for 24 hours, dehydrated and stored in a sealed container.
In a 20 mL Erlenmeyer flask, and add 0.1 g
M (M = mole / L) sodium diphosphate (Na ₄ P
₂ O ₇ ) 10 ml of aqueous solution was added,
The solution was kept for 1 minute, and an aqueous solution of sodium diphosphate was impregnated into the pores of the carrier. After the excess sodium diphosphate aqueous solution was removed by suction, the impregnated sample was freeze-dried for 12 hours to obtain a precursor composite sample carrying sodium diphosphate. Next, 10 ml of a 0.1 M aqueous solution of silver nitrate was added to the precursor composite sample, and the mixture was kept at room temperature and under reduced pressure for 30 minutes, and further kept under the same conditions for 2 hours for ripening of the formed silver phosphate compound. After the excess silver nitrate aqueous solution was removed by suction, the impregnated sample was freeze-dried for 12 hours. The obtained dried sample was elutriated using a 100-mesh sieve to remove fine particles.
For 24 hours, and the silver phosphate of the present invention (Ag ₄ P ₂ O)
₇ ) -A granular composite bactericide sample comprising a silica carrier was obtained.

The carrier 400LS, 075LS or 005LS is then treated with silver phosphate (A)
g ₄ P ₂ O ₇ ) -supported complex germicide samples were each S4P2-4.
00LS, S4P2-075LS and S4P2-005
Abbreviated as LS. Here, the production of the target composite germicide sample by the above-described processing is performed in S4P2-400LS, S4P2-
It can be easily confirmed by measuring the powder X-ray diffraction patterns of 075LS and S4P2-005LS (using CuKα rays). That is, as shown in Table 1, in each of the carrier samples, only a halo centered at about 2θ = 22 °, which is characteristic of amorphous silica, was observed. In contrast, S4P2-400
LS, S4P2-075LS and S4P2-005LS
In each case, in addition to the halo characteristic of the above-mentioned amorphous silica, several diffraction peaks belonging to Ag ₄ P ₂ O ₇ (plane spacing d value (Å) = 2.76, 3.11, 3.28)
(1998 JCPDS File No. 37-01
87) was confirmed. In addition, silver phosphate (Ag ₄ P ₂ O)
₇ ) The amount of loading increases with an increase in the concentration of the impregnating solution and the number of times of impregnation, and thus can be easily adjusted by controlling the processing conditions. When the carrying amount of Ag ₄ P ₂ O ₇ is small, the Ag ₄ P ₂ O
Only the ₇ strongest diffraction lines (d value (Å) = 2.76) are seen.

(3) Sterilization Experiment The sterilization ability of the six complex fungicides was measured in comparison with that of the carrier sample. All measurements of the bactericidal effect were performed by the batch method.
FIG. 1 shows the outline. 150 mL of the aforementioned sample solution 1 is placed in a 300 mL Erlenmeyer flask 2, and 10 mg of one of the above-mentioned granular composite disinfectant sample or carrier sample is added thereto.
The mixture was added and stirred at a constant speed with a shaker (20 ° C., 130 rpm) to such an extent that sedimentation did not occur. In addition, a control solution was prepared by simply stirring the bacterial sample solution under the same conditions. To determine the bactericidal effect, a portion of the sample solution before sample addition is taken in advance, and at the same time as the treatment solution is collected over time, a portion is also collected from this sampled solution, and 1 mL of each is sterilized. Dilute 10-fold with physiological saline at an appropriate stage, and spread 0.1 ml of the diluted solution on a normal agar plate medium.
After culturing at 7 ° C. for 24 hours, the number of colonies in each was measured, and the percentage of the number of colonies of the treatment solution to the number of colonies of the sample solution was calculated and determined as the viable bacterial ratio. In addition, 1 mL of each treatment solution and control solution before and after the sterilization test were collected, and the pH of each filtrate after filtration with a membrane filter was measured with a pH meter.

Example 1 Samples of a granular composite disinfectant (S3P-400LS, S3P-
075LS, S3P-005LS) and carrier sample (40
0LS, 075LS, and 005LS) were added for 30 minutes, 60 minutes, 90 minutes, and 12 minutes in a system to which 10 mg of each was added.
The pH and E.C. Table 2 shows the results of measuring the viability of E. coli.

[0024]

[Table 2]

First, the carrier systems of 005LS, 075LS and 400LS were added. The viable cell ratio after 120 minutes of addition was 79.0%, 18.3% and 11.4%, respectively. Is declining. This means that 1) the E. coli E. It is known that E. coli is resistant to purified water for 3 hours and shows neither growth nor death in 60 minutes, and 2) a carrier having a larger specific surface area (Table 1) has a lower viability. , E .; It is considered that as a result of E. coli being physically adsorbed to the carrier sample, the viable cell count in the aqueous phase apparently decreased. On the other hand, the composite disinfectant samples S3P-005LS and S3P-075LS
And S3P-400LS addition system, but S3P-00
In both 5LS and S3P-075LS-added systems, the viable cell rate became 0% 30 minutes after the addition, and a remarkable bactericidal effect was observed. In the S3P-400LS addition system, the viability rate 30 minutes after addition is 0.001%, but the viability rate 60 minutes after addition is 0%.
The contact time was longer than that of the S3P-005LS and S3P-075LS addition systems, but a remarkable bactericidal effect was observed.

Example 2 Complex bactericide samples (S3P-400LS, S3P-07)
5LS, S3P-005LS) and carrier sample (400L
S, 075 LS, and 005 LS) were added at 30 minutes, 60 minutes, 90 minutes, and 120 minutes after the addition to the system to which 10 mg of the treatment solution was added. Table 3 shows the results of measuring the viable cell ratio of Aureus.

[0027]

[Table 3]

First, the carriers 005 LS, 075 LS and 400 LS were added, and the viability after 120 minutes of addition was 43.6%, 43.8% and 21.8%, respectively. Digit has dropped. This is E.I. coli
Similarly, S.I. Aureus also has a carrier of 005LS, 0
This is probably because the viable cell count in the aqueous phase was physically reduced by the physical adsorption at 75 LS and 400 LS. In contrast,
Composite disinfectant sample S3P-005LS, S3P-075L
S and S3P-400LS were added, and the viable cell rate after 30 minutes of addition was 0.005%, 0.001%, and 0.001%, respectively. Was 0%, and a remarkable bactericidal effect was recognized. S3
In order for the viable cell ratio to be 0% in both the P-005LS and S3P-075LS addition systems, E. coli. Although a longer contact time is required as compared with E. coli, in the S3P-400LS addition system, E. coli is required. col
i and S.I. 60 minutes after the addition of Aureus, the viable cell rate was 0%, and no difference was observed in the sterilization rate.

Example 3 Samples of complex bactericides (S4P2-400LS, S4P2-
075LS, S4P2-005LS) and carrier sample (4
00LS, 075LS, and 005LS) were added for 30 minutes, 60 minutes, 90 minutes and 1
After 20 minutes, the pH and E.C. Table 4 shows the results of measuring the viable cell ratio of E. coli.

[0030]

[Table 4]

First, the carriers 005 LS, 075 LS and 400 LS were added, and the viability after 120 minutes of addition was 79.0%, 18.3% and 11.4%, respectively. Digit has dropped. This means that 1) the E. coli E. It is known that E. coli is resistant to purified water for 3 hours and does not grow or die in 60 minutes, and 2) a carrier having a larger specific surface area (Table 1) has a lower viable cell rate. E. FIG. It is considered that as a result of E. coli being physically adsorbed to the carrier sample, the viable cell count in the aqueous phase apparently decreased. On the other hand, the composite disinfectant samples S4P2-005LS, S4P2-075
LS and S4P2-400LS addition system, but S4P
30 minutes after the addition, the viable cell rate became 0% and a remarkable bactericidal effect was observed with the system containing 2-005LS and S4P2-075LS. Addition 3 for S4P2-400LS addition system
The viability rate after 0 minutes is 0.009%, but the viability rate 60 minutes after addition is 0%, indicating that S4P2-005LS and S4P
Although a longer contact time was required than the P2-075LS addition system, a remarkable bactericidal effect was observed.

Example 4 Complex bactericide samples (S4P2-400LS, S4P2-
075LS, S4P2-005LS) and carrier sample (4
00LS, 075LS, and 005LS) were added for 30 minutes, 60 minutes, 90 minutes and 1
After 20 minutes, the pH and S.P. aureus
Table 5 shows the measurement results of the viable cell ratio of.

[0033]

[Table 5]

First, the carriers 005 LS, 075 LS and 400 LS were added, and the viability after 120 minutes of addition was 43.6%, 43.8% and 21.8%, respectively. Digit has dropped. This is E.I. coli
As in S. aureus in the case of carrier 005LS,
It is considered that this was physically absorbed by 075 LS and 400 LS, and the viable cell count in the aqueous phase was apparently reduced. On the other hand, the composite disinfectant samples S4P2-005LS, S4P2-
075LS and S4P2-400LS addition system,
The viable cell rates 30 minutes after the addition were 0.029% and 0.029%, respectively.
27% and 0.007%, but 3 minutes after addition 60 minutes.
The viable cell rate was 0% in both systems, and a remarkable bactericidal effect was observed. In order for the viable cell ratio to be 0% for both the S4P2-005LS and the S4P2-075LS-added systems, E. coli. Although a longer contact time is required as compared with E. coli, the S4P2-400LS addition system requires E. coli. coli and S. Aureus showed no difference in sterilization rate.

As shown in Tables 2 to 5, in each system, the pH of the treatment solution was almost neutral in the range of 6.0 to 6.6, and the difference from the control solution was ± 0.1. ０．４0.4, and almost no difference was observed. E. FIG. coli, S.E. aureu
s in the range of pH 5 to 9, there is almost no change in the viable cell rate (Onodera, Y., et al., App.
l. Clay Sci. , To be published (2000)), the above-mentioned bactericidal effect observed in the complex bactericide sample is caused by an increase in the pH of the bacterial solution (Suzuki, T., et a).
l. , DENKI KAGAKU, 52, 272 (19
84)). From the above results, the composite fungicide sample of the present invention was obtained from E. coli. coli and S. coli. a
Obviously, it has a significant bactericidal effect regardless of ureus.

[0036]

As described above, 1) a composite germicide comprising an inorganic-inorganic composite having high bactericidal properties is provided. 2) The granular composite germicide of the present invention can remove water to be treated and water. The surface properties of these disinfectants make it possible to disinfect the treated water or the impregnated gas by contact with the contained hydrous gas. 3) That is, silver phosphate dispersed and supported in fine particles in the disinfectant When bacteria contact the vast surface of the compound, the bacteria kill completely and within a short time due to the bactericidal action of silver. Therefore, sterilization of water to be treated and gas containing water is possible. By using a disinfectant, it is possible to disinfect the water to be treated without leaving secondary contaminants such as chlorine in the treated water as in the chlorine disinfection method, and disinfect the water-containing gas in which bacteria exist. Can be Cormorant special effects can be obtained.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram showing an outline of a sterilization experiment.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C01B 25/37 C01B 25/37 Z 25/42 25/42 C02F 1/50 510 C02F 1/50 510A 520 520B 531 531T 540 540E (72) Inventor Takeo Ebina 2-1-15-1 Nakae, Aoba-ku, Aoba-ku, Sendai-city, Miyagi Prefecture (72) In-rain Ingen 6-77-5, Kunimi, Aoba-ku, Sendai-shi, Miyagi Prefecture 204 F-term (reference) 4C058 AA20 BB07 DD07 JJ05 JJ21 JJ26 4C080 AA05 AA07 BB05 HH05 HH09 JJ04 KK08 LL02 LL10 MM01 NN02 NN03 NN04 NN05 NN06 4H011 AA02 BA01 BB18 BC18 DA02 DC10 DD01

Claims (7)

[Claims] 1. The method according to claim 1, wherein Ag is contained in the pores of the porous inorganic carrier._Three P
O_Four Or Ag_Four P_Two O₇ Silver phosphate compound represented by
Inorganic / inorganic composite with high bactericidal properties obtained by forming and supporting
A composite fungicide characterized by being combined. 2. A method for manufacturing a composite disinfectant according to claim 1, wherein the silver phosphate compound represented by Ag3PO ₄ or Ag ₄ P ₂ O _7, applying the impregnated crystal Deho multistage A method for producing a bactericide, characterized in that the bactericide is synthesized and supported in the pores of a porous inorganic carrier. 3. When synthesizing the silver phosphate compound represented by Ag ₃ PO ₄ , a metaphosphate represented by the general formula M ₃ PO ₄ (where M represents a monovalent cation) , Na ⁺ ,
NH ₄ ⁺ , K ⁺ etc.) or M _n H _3-n
Hydrogen phosphate represented by PO ₄ (M in the formula represents a monovalent cation, and is an ion such as Na ⁺ , NH ₄ ⁺ , and K ⁺ .
3. The method according to claim 2, wherein (n is one of 1, 2, and 3) is used as the precursor compound. In the synthesis of silver phosphate compound represented by wherein the above Ag ₄ P ₂ O _7, the general formula M ^I ₄ P ₂ diphosphate represented by O ₇ (in the formula M is Represents a monovalent cation, Na
⁺ , H ⁺ , K ^+, etc.) as the precursor compound. 5. A precursor composite obtained by synthesizing and supporting a metaphosphate or hydrogen phosphate of a precursor compound on a porous inorganic carrier, and further impregnating a silver salt solution with the metal phosphate or metaphosphate in the precursor composite. By substituting the monovalent cation of the hydrogen phosphate with silver ion, a silver phosphate compound (Ag ₃ P
3. The method according to claim 2, wherein said compound is converted to O ₄ ). 6. The precursor inorganic compound phosphorus on a porous inorganic carrier.
The precursor complex obtained by synthesizing and supporting
Monovalent cation of diphosphate in precursor complex impregnated with salt solution
Silver phosphate compound (A)
g_Four P_Two O₇ 3. The method according to claim 2, wherein
Manufacturing method. 7. A sterilization method comprising contacting water to be treated or a gas containing water with the composite disinfectant according to claim 1, and sterilizing the water to be treated or gas containing water according to the surface characteristics of the disinfectant.