JPS6270221A - Amorphous aluminosilicate having antimicrobial and/or germicidal action - Google Patents

Abstract

PURPOSE:To impart improved germicidal effect on various bacteria and molds, by forming a novel amorphous aluminosilicate expressed by a specific composition formula. CONSTITUTION:An amorphous aluminosilicate, expressed by the formula (M is silver, copper, zinc, mercury, tin, lead, bismuth, cadmium or chromium; n is the valence of M; x is 0.6-1.8; y is 1.3-50) and constituted of porous fine particles having at least 5m<2>/g specific surface area.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel amorphous aluminosilicate (hereinafter referred to as AMAS
related to).

It is well known that silver and copper have a bactericidal effect, and for example, silver has been widely used as a disinfectant in the form of an aqueous solution (Ag'') such as silver nitrate.However, in the form of a bath liquid, it is inconvenient to handle. Therefore, it has the drawback of being limited in terms of its uses.Furthermore, it is known that silver and its compounds can be adsorbed onto adsorbent materials such as activated carbon, alumina, and silica gel and used for sterilization purposes.The adsorbent materials described above On the other hand, simply physically adsorbing antibacterial metals and their compounds to Rin is insufficient in terms of sterilization in the activated state, sustainability of antibacterial effects, stable retention of the required amount of antibacterial agents, and ionization ability. However, the present inventors have conducted intensive research to improve the drawbacks of conventional inorganic antibacterial agents, and have developed a specific antibacterial metal with a specific surface area of at least 5tr?/? in an ionic state. If it is fixed and stabilized in porous amorphous silicate,
Using this, we can retain more economical antibacterial metal ions.
Antibacterial and sterilizing properties are ideally performed in an excited state, and there are many advantages in terms of sustainability of antibacterial effects, stability of antibacterial substances, stability, and heat resistance, so effective and widespread use is expected. We have discovered that this is the case, and have arrived at the present invention.

The present invention is based on the formula % (where M is silver, copper, zinc, mercury, tin, lead, bismuth, cadmium, or chromium; n is the valence of M; X is 0.6 to 1. The present invention relates to an amorphous aluminosilicate having antibacterial and/or bactericidal properties, coated with a compound having antibacterial and/or bactericidal properties.

The present invention is based on the Bunmu% formula (where M is silver, copper, zinc, mercury, tin, lead, bismuth, cadmium, or chromium, and n is the valence of M and V
: X is 0.6 to 1.8 and y is 1.6 to 50, preferably 1.3 to 7) and the formula % formula % (formula Medium M refers to monovalent or divalent metals (silver, copper, zinc) that have ion exchange properties such as sodium, potassium, lithium, iron (■), magnesium (II), calcium, cobalt (■), and nickel (II). , excluding mercury, tin, lead, bismuth, cadmium and chromium) or asimonium ion, D is the valence of M, x id O, 6 to 1.8, and y is 6 to 5
0, preferably 1.6 to 7)) The amorphous aluminosilicate of the present invention is as follows: xNa2
0s At203” YS102k Manufactured.

An alkaline solution (bath solution-C) with an alkalinity in the range 1.2-3.5 N is kept under stirring, to which a sodium aluminate solution containing free alkali (bath solution-C) is kept under stirring.
and a predetermined amount of a sodium silicate solution (solution-B) containing free alkali were individually added to prepare an amorphous aluminum silicate (main component: Na) consisting of fine particles that are difficult to bathe.
A slurry containing 2O-At203-8i02)'e is produced, and then it is aged to form amorphous aluminum).
In the method for producing silicate, the addition of the solution-A and solution-B to the bath solution
/AtQ ratio is within the range of 2.4 to Z6 during and after the addition, and the mixing is carried out below 55°C, and any aqueous phase during the slurry formation and ripening is The alkalinity of the bath liquid-C was also prepared in advance.
By adjusting bath solution-A and solution-B so that the alkalinity of An aluminosilicate having the following formula is produced.

Compounds with other ion-exchangeable metals can be derived by ion-exchange of the above-mentioned sodium-substituted compounds.

When synthesizing normal AMAS, is the specific surface area (8SA) at least 5rr? /? Composed of the above porous particles,
It is extremely easy to adjust the average particle diameter (Dav) i to 6 μm or less. The above-mentioned M has the property of ion conversion, and by ion-exchanging the necessary amount of one or more of the antibacterial or bactericidal metal ions described below with it, the matrix of SSA5m'/rAMAs can be obtained. That is, by stably retaining it in a solid phase, the active AMAS composition having antibacterial and bactericidal effects of the present invention can be obtained.

AMA8, which is used as a matrix for holding antibacterial metal ions in the present invention, is difficult to bathe in water, has high heat resistance, and is structurally stable even at high temperatures. As mentioned above, this is xMi
The main component is O'At203-ysio2, and M in the composition formula has ion exchange properties, such as Na,
In addition, monovalent cations such as NH4, Mg, Ca, F
It represents a divalent cation such as e.

Of course, monovalent or divalent metals or both may coexist in the AMAS. Furthermore, there is no problem in the presence of polyvalent ions of 6 or more valences as a minor component in AMAS. The exchange capacity of AMAS is governed by its composition. As the molar ratio 510z/AZ203 increases, i.e. y
The ion exchange capacity of AMAS gradually decreases with increasing , while it tends to increase in proportion to the single column coefficient X of M20.

For example, the exchange capacity of AMAS with the composition xNa20-At2o3・yS102 (in this case, the exchange ion is Na+) is 104 and 5.81 meq/7 when y=2 and 6, assuming x=1 (constant). be. Furthermore, 3.42 for y=7 and 10, respectively.
and 1.43 mec4/? becomes. When y=30, the exchange capacity is 1.01 meq/f, and y
=50, it is only 0.66meq/f. In terms of exchange capacity, antibacterial metal ions'i
In order to retain an effective amount in AMAs, y is desirably 30 or less, and the most preferable upper limit of y is 7. AMAS (xM20-A
t203@ySi○2) can be synthesized with an X in the range of 0.6 to 1.8, and a coefficient y of 1.6 or more is usually obtained.As an AMAS'i material with y of 50 or more. Although it is of course possible to prepare the antibacterial composition of the present invention by using it, based on the above reasons, the preferred range of y in the present invention is 1.6 to 7. Therefore, the present invention
An AMAS composition having preferable antibacterial and bactericidal effects is mainly composed of metal oxide-alumina-silicon dioxide, whose general formula is xM20・At203・yS io
It is represented by □, where M has ion converting properties, and the coefficient X of the metal oxide is 0.6 to 1.
8 Also, the coefficient y of the nicked silicon is A kAA S within the range of 1.3 to 7, and the M
The present invention provides AMAS compositions having antibacterial and bactericidal effects, characterized in that part or all of the sterilizing agent is replaced with metal ions having bactericidal effects. Even if a trivalent or higher polyvalent cation coexists as a minor component in the above composition, there is no problem.

The antibacterial metals (hereinafter referred to as B) used in the preparation of the AMAS composition having antibacterial and bactericidal effects of the present invention include silver, copper (monovalent or divalent), zinc, mercury (monovalent or divalent), tin (monovalent or tetravalent), lead (divalent), tin (monovalent or tetravalent), lead (divalent),
(bivalent), cadmium (bivalent), and chromium (bivalent or hexavalent). Ion exchange between the saline solution containing the single or more antibacterial B ions specified above and the π (metal in the solid phase) in AMAS specified above is carried out under appropriate conditions at normal or high temperatures. When carried out, the antibacterial metal ions are retained in the solid phase (B) by the reaction of π0B B + M, and the AMAS composition having antibacterial and bactericidal effects of the present invention can be obtained.
For ion exchange to impart s, either the patch method or the Kirkham method is suitable.

It was confirmed in the tests described below that the antibacterial AMAS composition of the present invention obtained by the above method has extremely high resistance to various bacteria and molds, and exhibits excellent bactericidal activity. That is, using this product, 5 taphylococci
us aureus, Escherichia Col
i, Pseudomonas aeruginosa
, Candida albicans, Tricho
Antibacterial evaluation tests against bacteria such as phyton mentagrophytes and Asperg-illu
s flavus, Aspergillus nig
All measurements of the mortality rate against fungi such as ER were conducted, and it was confirmed that this product has strong antibacterial and bactericidal abilities. Furthermore, Aspergillus niger (ATCC9
642), Pen1ci -11um funicu
losum (ATCC9644), Chaetom
iumglobosum (ATCC6205), T
richoderma 5P (ATCC9645) and Aureobasidium Pullulans (
When these spores were inoculated using 5 types of test bacteria of ATCC 9 (48) and a complete mold resistance test was conducted according to ASTM-C) 21, the molded polymer containing the antibacterial AMAS of the present invention was found to be It was found that the mold resistance was very high and the antibacterial effect lasted for a long period of time, making it extremely effective (Example 11).

Next, the relationship between the content of the antibacterial metal CB) in the AMAS having antibacterial and bactericidal effects of the present invention and the antibacterial effect will be described. First, as B, AMAS containing silver and gold and having antibacterial and bactericidal effects (hereinafter referred to as Ag-AMAS) of the present invention has antibacterial and bactericidal effects.
).

Dav=0.2t1m Ag-AMAS powder containing 1.06% silver [Example-1-A: Ag=1.03
% (dry product): ss*=22ff1t/V; starting material A M A S r 1.10 Na2O"At203
”2-51SiO2”xH2O) i using 5ta
Pylococcusaureus, Pseudom
onas aeruginosa and Escheri
Antibacterial evaluation test against chia cadi (6
After culturing at 7° C. for 18 hours and observing the presence or absence of inhibition zone formation, it was found to be extremely effective against all of the bacteria mentioned above. Also, the kg-AMAS is Trich
The effect was also confirmed for ophyton mentagrophytes. Furthermore, Dav = 0.23 ttm Ag-AMAS powder containing 0.22% silver (
Ag=0.22% (dry product; SSA=23m”/f
: Starting material AMAS, 1.10 Na2O
・At203@2.51 SiO3.xH2O] The same evaluation test as above was conducted, and it was confirmed that it was still effective against all bacteria. Furthermore, the above A g -AMA S is completely Trichop
hyton mentagrophytes 'c (see Tables 5-6). Next, the Ag-AMAS containing 0.22% silver was heated at 500°C.
(2 hours) The same bacteria evaluation test as described above was also conducted on the baked products. As a result, it was confirmed that heated products were also sufficiently effective against bacteria. From this, it is clear that the heat resistance of the A g -AMAS of the present invention, which has antibacterial and bactericidal effects, is excellent, and that the antibacterial activity of the heated product does not deteriorate and its activity is maintained. Next, the above Ag-A
Instead of MAS powder, Ag-AMAS powder CAg=O1047% with low content of silver with Dav = 0.2 ttm
(Dry product)], measurement of fungal mortality rate (measurement of number of surviving individuals after 48 hours at 30°C) f Aspergi
llusflavus and aspergillus
The experiment was conducted on two species of niger, but in both cases,
The mortality rate was 100. Furthermore, using Ag-AMAS powder with a lower silver content [Ag = 0.02% (dry product)], Aspergillus flav.
The mortality rate was measured against Aspergillus us and Aspergillus niger, and the mortality rate was 99% and 10%, respectively (see Table 6). Even lower content of Ag
-The effect of AMAS was still observed. From these results, it is clear that the silver content in Ag-AMA'l of the present invention exhibits sufficient bactericidal action when adjusted to a range of 0.001 to 1 t during normal use. .

In order to maximize the effects of AMAS, which has antibacterial and bactericidal effects of the present invention, the optimal content of antibacterial metal (B) will naturally vary depending on the target bacteria, the type of medicine, and the conditions of use. B in S is, as necessary,
The concentration of gold may be increased using the ion exchange described above.

For example, it is easily possible to prepare Ag-AMASe using ion exchange and maintain the silver content therein at 10 or more. (See Example-1-c).

The antibacterial composition Cu-AMAS of the present invention containing copper will be explained. Dav = 0.27% copper
Cu-AMAS (Cu = 0.2
7% (dry product): 5SA=56tr? /f: starting material AMAS, 1.03 Na2O"At2
03" 3.248 iO2-xH2O) for Aspergillus flavus and Aspergillus niger and obtained values of 95 h for the former and 67 h for the latter. Furthermore, using the same starting materials as above, Cu-AMA with lower content of copper Dav = 0.24 μm synthesized by
S powder [however, cu = 0.064% (dry product); ssA
= 54 m'/VE The fungal mortality rate was measured using gold, and for Aspergillus flavus it was 9.
0% and 57 chi for Aspergillus niger. As can be seen from these antibacterial tests, the Cu-AMAS of the present invention remains effective against fungi without losing its activity even at a low copper concentration of 0.06 cm (No. 7). (see table).

Dav containing 7.26% zinc'k = 0.6 t
in Zn-AMAS CZn=7.26% (dry product): 5SA=141i/2: Starting material AMAS, 1
．． 42N a 2011A1□03・6.04S10□
Aspergillus fl using
The killing rate against S. avus was measured and was 69%, confirming that it was effective. In addition, P as an antibacterial metal ion
b, Bl, Cd.

AMASi containing Cr, Sn and Hgk was prepared, and their antibacterial properties and mortality rates were measured.

In this case, the test bacterium is Escherichia c.
oli.

5taphylococcus aureus, ps
euclomonasaeruginosa, Asp
ergillus flavus, Asper-g
illus niger and Trichophyto
n menta-grophytes was used with good results (see Tables 8-9).

In the present invention, as mentioned above, any one or two metals selected from the group of silver, copper, zinc, mercury, tin, lead, bismuth, and cadmium chromium have a bactericidal effect. The above-mentioned gold composites were combined with A, which was specified in the present invention.
If retained in MAS, a powerful antibacterial agent with long-term activity can be obtained.

In addition, the combined use of two or more of the above metals has the advantage of exhibiting a synergistic effect and exhibiting antibacterial and sterilizing effects against various bacteria and fungi in a more favorable manner.

As mentioned above, AMAS used as a material in producing the antibacterial zeolite composition of the present invention is amorphous (amorphous). An example of its production will be described here.

Production Example-1 (AMAS) This example has a mo/l/ratio of sio. /At2o3= 2.5k
The present invention relates to an example of manufacturing AMAS having the following properties.

Bath liquid - Human: Aluminum hydroxide [At(OH)3.xH
2O;

Next, water was further added to the solution, and the final temperature was maintained at 4.5t. A small amount of suspension in the above bath solution is
Then, a transparent liquid was prepared (bath liquid-A). Solution-B = sodium silicate (, Tl5-3: specific gravity = 1
．． 4: NaO=9.5%; 5102=29
%) 4.4 to 7 to 49 sodium hydroxide bath solution (
Specific gravity = 1.51) 0.13 Add God and water to make the total 4.
I kept it at 5t. A clear liquid was prepared by filtering a small amount of suspended matter in the above Rakuryo (Solution-○).

Bath liquid - 〇: 49% hydrogen oxide) IJium solution (specific gravity = 1
．． 51) Add water to 1.61w? 7.81
(Solution-C).

Solution-C was placed in a reaction tank and heated to e38Q±2°C while being stirred at 350 rpm. On the other hand, after keeping the bath liquid A and the bath liquid Ce at around 40°C,
These solutions were individually injected at the same time, and both injections were completed in 55 minutes. After the mixing of the raw material liquids was completed, the slurry-containing liquid was kept at about 40° C. for 4 hours under stirring at 27 Orpm to ripen the produced AMAS. After aging, AMAS was purified by centrifugation. Next, the hot water law was implemented for AMA8 above. Water washing is carried out until the pH of the filtration reaches 10.6. After the water washing is completed, the AMAS is dried at 100°C to 110°C, and then pulverized to produce a final dried AMAS fine powder of approximately 1.99 kg.
g was obtained.

Results of Production Example-1: Yield of dry fine AMAS powder: Approximately 1.99 kg Chemical composition: 1.10 Na20-At203-2. ! 51S
iO2-H20 Dav: 0.2ttm SSA: 22-/V Production Example-2 (AMAS) This example relates to a production example of AMAS with a molar ratio of 5io2/At2o3''-3,2k.

Solution i-A: Aluminum hydroxide (At(OH)3.XH
2O: x=6] 49% sodium hydroxide solution (specific gravity = 1.51) for 2-53 kf 2.9 ky and water were added and the resulting mixture was heated and dissolved, and then added to the above solution. Then, add more water to make a final total of 6.5L.
I kept it. A small amount of suspended matter in the above liquid was filtered to obtain a clear liquid (bath liquid - human).

Solution-B = silicate) IJum solution (, Tl5-3;
Specific gravity 1.4: Na2O=95%; 51o2=29%
) Water was added to 5.5 yen to maintain the total temperature at 51. A trace amount of suspension in the above solution was mixed to make a transparent liquid (Solution-B) 0 Solution-〇2 49% sodium hydroxide solution (specific gravity = 1.5
1) 0.54kf was diluted with water to maintain the total volume at 6.26 (bath liquid -○).

After the solution-○ was put into the reaction tank, it was heated to about 65°C and maintained under stirring at 500 rpm. About 65
Solution-A and bath solution-B heated to 0.degree. C. were individually injected at the same time, and both injections were completed in 1 hour.

After mixing the raw material liquid, the slurry-containing liquid is heated to 35°C at approximately 65°C.
AMA produced after keeping under stirring in Orpm for 4 hours
S is filtered by centrifugation and then added to the above AMAS
A hot water wash was carried out in the same manner as in the previous example.

The washed AMAS was then dried at 100 DEG -110 DEG C. and then finely pulverized to finally obtain a dry fine powder of AMAS of about 6.7 mm.

Results of Production Example-2: Yield of dry fine AMAS powder: Approximately 6.7 Chemical composition:
1.03 Na2O-At203 ・3.248 to
2@H20 D a v : 0-2μm 5SA :56m'/? This example relates to the preparation of the AMAS material required for the preparation of the amorphous alumino composition with antibacterial and bactericidal metal of the present invention having a molar ratio of 5102/At203=6.

Solution-A: Aluminum hydroxide (At(OH)3.xH
2O: x ; 3 ] 49 for 1.37 kq
% sodium hydroxide solution (specific gravity=1.51) and water were added and the resulting mixture was heated to dissolve. Next, water was further added to the solution to maintain the total volume at 6.66. A trace amount of suspended matter in the above liquid was filtered to obtain a clear liquid (
Solution-A).

Bath liquid-B: Colloidal Shiriyoku (product name: Snowtex)
30) Add water to 12.5 kg and make the whole 10.
I kept it at 84. A transparent liquid was prepared by filtering a small amount of suspended matter in the above liquid (bath liquid-B).

Bath liquid-C: 49% sodium hydroxide solution (specific gravity = 1.5
1) Water was added to 14.9kf to maintain the total volume at 7.2t (Solution-○).

Put solution-C into the reaction tank and keep the liquid at 30℃ at 300℃.
Keep under stirring at rpm. On the other hand, the solution - B and the bath solution - B gold kept at about 60° C. were simultaneously and individually injected, and the injection of both was completed in 45 minutes. After all the mixing of the raw material liquid is completed, the slurry-containing liquid is heated to about 60℃ and 40O
After aging for 2 hours and 50 minutes under stirring at rpm, the produced AMAS was filtered by centrifugation. The solid phase was washed with hot water (IF: carried out until the pH of the I filtration reached 10.8) in the same manner as in the above production example, and then the water-washed AMAS was dried at 1000 to 110°C, and then pulverized. Finally, fine powder 4.0 was added to the dried AMAS.
I got 9 out of 8.

Yield of dry fine powder of AMAS: 4.08 to 9 Chemical composition:
, 1.42 NazO-*z2o3-6.04 Si
n□-H20 Dav * o, 2 μm or less SSA: 139i/? AMAS, which is conveniently used as the material of the present invention obtained in the above-mentioned Production Examples 1 to 6, is amorphous and porous, and the SSA reaches 20 m"/or more in all cases, and the Dav reaches 1 μm in all cases. The following fine powder has been obtained.Manufacturing Example 1
The chemical composition of the AMAS obtained in steps 6 to 6 is as described above, and all of them have sufficient exchange capacity suitable for preparing the antibacterial composition of the present invention, and the exchange ions of the above materials are The exchange rate between (Na+) and antibacterial metal ions is extremely rapid, and the binding force between AMAS of the mother tree and antibacterial metal ions is extremely large.

Next, examples relating to the method for preparing the AMAS composition having antibacterial and bactericidal effects of the present invention will be described.

Example-1 Example-1 relates to a preparation example of an Ag-AMAS composition (S1o2/At203=2.51) of the present invention containing silver. AMA produced in the above production example-1
Dry powder of S (1,10Na2O@At203@2,
513102 ・xH2O) approx. 250 f'c collection 1
．． To this, 0.05 M AgN03 (Example-1-
A), 0.3M AgNO3 (Example 1-B), or 0.6M AgNO3 (Example-1-C) solution 500
- The resulting mixture was kept at room temperature under stirring at 35 Orpm for 5 hours to remove the ion-exchangeable Na of AMAS.
A part of + was converted into Ag by F). After completing the above-mentioned ion exchange reaction, it was filtered, and the resulting solid phase was washed with water to remove excess Ag'' present in the solid phase.The Ag-AMA S that had been washed with water was then heated at 100° to 110°C. The results of this example, which were dried and then pulverized, are listed in Table 1.

Example 2 This example relates to a preparation example of a Cu-AMAS composition (S 102 /ALz03 =3-24) of the present invention containing steel. Dry powder of AMA8 (1,03NazO=At20
3e3,24 SiO2*XH2O) about 1009 (Example 2-A) or about 250 gr (Example 2-B)
), and in the former case o, 02 M Cu(
NO3) 2a liquid 500-5 In the latter case, 0.6 M Cu(
Add 500 dt of NO3)2 solution, further dilute with water, and maintain the total volume as shown in Table 2. Next, mix the obtained mixture into 3
It was kept under stirring at 6 Orpm for 6 hours and partially exchanged with 1 cu2+ with AMAS ion-exchangeable Na'' (ion exchange at room temperature) 0 After the above ion exchange was completed, it was filtered,
The obtained solid phase is washed with water to remove excess C present in the solid phase.
u has been removed. Next, Cu-AM that has been washed with water
AS was dried at 1000-110°C and then pulverized. The results of this example are listed in Table 2. C obtained in this example
The Dav of u-AMAS is 0.2 μm in both cases, and the -10,000 SSA is 56rr in Example-2-A and Example-2-B, respectively. /f and 59 m'/S'.

Example 6 This example shows the Zn-AMAS composition of the present invention containing zinc (
This relates to a preparation example of S10□/At2o3=6.04). AMAS dry powder (1,42Na2O-At203″6,0481
0□-XH20) Approximately 250ft- was collected and 0.
1 M “CZn(NO3)2 (Example-3-A) or 1.0 M Zn(NO3)2 (*Stream side-3-B
)! Add 500 d' of liquid to the resulting mixture'it 400 d'
The mixture was kept under stirring at rpm for 7 hours to convert a part of the ion-exchangeable Na'' of AMAS with '1Zn2+ (ion exchange at room temperature).

The product was then filtered and the solid phase obtained was subsequently washed with water to remove the excess Zn present in the solid phase. After washing with water, the Zn-AMAS was dried at 10.0° to 110° C. and then pulverized.

The results of this example are all listed in Table 6. Z obtained in this example
n -AMAS Dav is 0.6 μm in both cases, while SSA is the same, 140n!# and 141i in Example-3-A and Example-3-B, respectively.
Examples 4 to 9 in which the value of /r was obtained Examples 4 to 9 are antibacterial AMAS compositions of the present invention, B1-AMAS (Dav = 0.1 am)
rCr-AMAS (Dav = 0.1 μm)
, Sn-AMAS (Dav=0.2 pm
), Hg-AMAS (Dav = 0.2μff
L).

P b -AMAS (Dav = 0.4 μm14)
and a preparation example of Cd-AMAS (Dav=0.2 μm) (Table 4).

As a starting material, a dried product of AMAS having the composition described in the fourth coating having 5SA29i/P was used. In Examples 4 to 7, AMAS is about 5Of and <,0.05 as indicated.
150-M saline solution was used and these mixtures were
It is maintained under stirring at 60 rpm for 4:20 minutes, and part of the Na+ in AMAS is replaced with antibacterial metal ions as shown (ion exchange at room temperature), resulting in an AMAS composition having antibacterial and bactericidal effects. M-AMAS water washing/
Drying was carried out according to the previous example.

Which antibacterial M-AMA obtained in this example (4 to 9)
As for the S composition, the Dav is composed of fine particles as described above, and the SSA is 30 m''/f or more.The antibacterial AMA8 compositions of this example are all porous and do not absorb water. It is garbage. Bl, C of antibacterial metal ions (b)
r, Sn, Hg, Pb.

Since Cd2+ and Cd2+ exist stably bonded to the matrix of AMAS specified in the present invention, the amount of these metal ions released from the solid phase is small, and therefore, there is an advantage of extremely high stability. Since the dissociation of the M-AMAS composition also progresses in a favorable manner, the bactericidal action against bacteria and fungi based on K is strongly carried out centering on the active site of the M-AMAS matrix, and as a result, it is superior to known bactericidal agents. (See the antibacterial activity evaluation test below).

Next, in order to evaluate the antibacterial ability of the typical amorphous aluminosilicate composition having antibacterial and bactericidal effects of the present invention against bacteria and fungi, an evaluation test for antibacterial activity, measurement of mortality rate,
and mold resistance tests were conducted. The antibacterial activity was evaluated according to the following method: The test substance was suspended at a concentration of 100 η/- and soaked into a disk.

The medium is Mueller Hizton for bacteria.
For the culture medium and fungus, Sabouraud agar medium gold was used.

The test bacteria were suspended in physiological saline at 10/-, and in the medium at 0.
．． 1 - Dispersed with a Conlage rod.

The test disk was placed on top of it.

Judgment: Bacteria were observed for the presence or absence of inhibition zone formation at 37°C for 18 hours.

Fungi were determined after 1 week at 60°C.

Furthermore, the mortality rate was measured as follows.

A spore suspension of test bacteria (10 spores/d) was injected into 1 di test substance suspension (500 q/-) and mixed for 24 hours.
The reaction was carried out at 0°C. It was dispersed on a 0.1 dk Sabouraud agar medium, and after 48 hours at 60°C, the number of surviving individuals was measured to determine the death rate. are shown in Table 5. Example-1-A
Ag-AMAS l obtained with: Ag = 1.03
(dry standard)] showed good inhibition zone formation against all of the test bacteria listed, and was found to have excellent antibacterial activity. Furthermore, lower silver content f) 2 so Ag − was prepared using the same AMAS material as the top layer.
AMAS CAg=0.22% and Ag=0
．． 02% (dry basis)] was also found to maintain excellent antibacterial ability as indicated. Ag-AMAS of the present invention
In order to compare the antibacterial ability of the composition and known silver (metal), an antibacterial evaluation test was conducted under the same test conditions (Table 5, Comparative Example-1).

Therefore, it is clear that the effect of this antibacterial composition is far inferior to that of the antibacterial composition of the present invention.

Next, Aspergillus flavu was used as a test bacterium.
s.

Aspergillus niger and Trich
Mortality measurements were performed on the Ag-AMAS compositions of the present invention using Ophytonmentagrophytes K and excellent results were obtained. (See Table 6).

0.02chi, 0.047% and 0.22% as Ag
The mortality rate was measured for Ag-AMAS compositions containing As
The mortality rate for pergillus niger is 10
It was 0chi. Also Aspergillus flav
The mortality rate against us K is Ag-A with Ag of 0.02
In MAS, it is 99chi, while Ag is 0.047
Both 100 and 22% Ag-AMAS
%Met. Furthermore, Ag-AMAS (Ag=Q, 22chi) is Trichophyton mentagroph
Excellent psychic sterilization power with a mortality rate of 100 against ytes K?
It was recognized that the In order to compare the bactericidal activity of the antibacterial composition of the present invention and known silver (metal), the mortality rate against Aspergillus flavus was measured under the same test conditions (Table 6 Comparative Example-2) ).

From the comparison between Comparative Examples to Comparative Example 2 and Honjima, it is clear that the antibacterial composition of the present invention exhibits superior bactericidal efficacy than known antibacterial agents.

Next, Cu-AMAS containing copper (Cu=0.
27% (dry basis): Using Example-2-AE, As
per-gillus flavus and Asper
giLlus niger, values of 90% for the former and 57% for the latter were obtained (see Table 7).Furthermore, cu-AMAS with a lower content of copper (cu=
0.064% (dry standard): AMAS material is Example-2
- Aspe
rgillusf 1avus and Aspergil
lus niger mortality rate was measured and the former had a mortality rate of 9
0%, and 57% for the latter.From these results, even the Cu-AMAS with a low copper content of the present invention is still effective.

Regarding the Zn-AMAS of the present invention containing zinc, the fungi Aspergillus ni, ge
Measurements of the mortality rate against r were carried out and Zn-AMAS [
:Zn=1, 64-% (dry basis): Example-6-A
], a mortality rate of 17% was obtained, while Zn-AMAS containing a higher concentration of zinc [Zn = 7.26% (dry basis)
: The AMAS material was the same as that used in the preparation of Example-3-A], and a mortality rate of 69% was confirmed.

Table 7, Measurement of mortality rate (H) Content of antibacterial metal: H (dry basis) Example-10 (Table 7) relates to the composite antibacterial composition of the present invention. In this example, Ag containing copper and silver
-Cu -AMA'S [Ag = 0.59%; Cu
= 3.47% (dry basis): The raw material is t 03 NazO-At2o3-3.24 obtained in Production Example-2.
Aspergillus flavus and A
The mortality rate of Spergillus niger fungi was measured, and a value of 100% was obtained for all fungi. As in this example, when two types of antibacterial metals are fully composited and stably retained in the AMAS specified in the present invention, there is an advantage that the bactericidal action is exhibited in a more favorable state based on the synergistic effect.

Table 8, Antibacterial evaluation test (Examples 7 & 9) Antibacterial AMA of the present invention prepared in Example 4-9 (Table 4)
The results of the antibacterial activity test for the S composition are listed in Table 8 and Table 8g9. As shown in Table 8, cd-A
MAS (Example-9) During defecation, Eschsrich
ia col'i and pseudomonasaer
Good inhibition zone formation was observed for the other four types of bacteria except for S. uginosa f, and -10,000 Hg -AMA S (
Example 7) During use, formation of a good inhibition zone against all six types of bacteria was observed, indicating that the product had excellent antibacterial activity. Furthermore, using the antimicrobial composition obtained in Example 4-9, the killing rate of the three types of bacteria described was measured (Table 9).

These results are F) Bi-AMAS, Cu-AM
AS, Sn-AMA8, Hg-AMA3, P
b-AMA8 and Cd-AMAS have antibacterial activity t-
It is clear that it has. The antibacterial metal in the above-mentioned antibacterial composition and the specified AMAS matrix have a chemically stable bond, and these compositions are resistant to water. The elution of the antibacterial metal from the matrix is 1) unit (1), which is preferable from the viewpoint of stability.

Fine AMAS having antibacterial and bactericidal effects of the present invention
The composition is made of fine particles activated to such a state that the moisture therein can be easily removed to less than 1 or almost 0 by heating, for example, in the low temperature range of 2000 to 500°C. (Dav 5μ or less) can be well dispersed in a polymer, so it is suitable as an antibacterial filler. The activated microparticles having antibacterial activity of the present invention can be applied to paper, fibers,
Possible applications include plastic rubber, pigments, and paints.

Example 11 This example relates to a specific example of application as an antibacterial filler. The Ag-Cu-AMAS composition having antibacterial properties (Ag=0
．． 59%: Cu = 3.47% (dry standard)] is 300°C
It was activated by heating for 1 hour and 25 minutes.

Next, this was crushed to obtain fine particles with Dav = 0.3μ. The above fine particles were placed on a polyethylene chip (L,
After adding 2% to D, P, E, ), the mixture is approximately 18
Mixed for 20 minutes at 5°C. Next, the mixture was heated to 45°C at the same temperature.
It was pressurized with a load of kf/- and molded into a plate with a thickness of 0.8 .

The above plates were cut to prepare test pieces (70 x 70 m), which were used for mold resistance tests on A3TM-
It was carried out by 021. The test bacterium is Asper
gillus niger (ATCC9642), Pe
nicilium Funiculosum (ATcc
9644), Chaetomium globosu
m CATCC6205), Trichoderma
5p (ATCC9645) and Aurebasidi
um Pu1lulans (ATCC9ro48)
Five species were used and these spores were harvested. The following composition was used as the medium.

Medium: K2HPO4 (0,7f) :KH2PO4
(0,7j') :Mg504a7H20(0,7r
) :NH4No3(1,Of) :NaC1(0
,005f)FIBSO4117H20(0,002
f): ZnSO4” 7H20 (0,002r
) :Mn5o4・7az○(0,001?):Aga
r (15F): Pure water (1000+g).

The culture was carried out for 40 days at 25°±2°C and humidity (R,H,) 90±5°C. The test results are shown in Table 10.

Table 10, Mold Resistance Test Example - 110 Comparative example with no growth of bacteria - 6 Comparative example with 10 to 60 microorganisms growing - The same polyethylene chip (L) as used in Example 11 was used.
, D, P', R,) 'i was used to prepare a plate (7Q x 70 m: Ag-Cu-AMAS) with a thickness of 0.8
(no additives) was prepared and subjected to a blank test. Example-11
From the comparison between Comparative Example 3 and Comparative Example 3, it is clear that the amorphous aluminosilicate composition having antibacterial activity of the present invention has extremely excellent resistance to mold.

The aluminosilicate having antibacterial and bactericidal effects of the present invention is amorphous as described above. Favorite X as a song type example
The line diffraction diagram is shown in Figures 1-5.

Figure xi shows the Ag-AMAS obtained in PJ-1-A (
1.2.6 and 4 in the figure are the X@ diffraction of dry powder, 650°C, 450°C, and 550°C calcined product, respectively. It concerns a line diffraction diagram. From this, it is clear that the favorite is amorphous (non-crystalline) and has high heat resistance. Figure 2 shows Ag-AM with relatively high silver content obtained in Example-1-C.
The X-ray diffraction diagram of A8 (Ag = 11.35% (dry basis)) is shown, and the symbols 1, 2, 6 and 4 in the figure relate to dry powder, 350°C, 450°C and 550°C fired products, respectively. Ag-
AMAS is also amorphous. Figure 3 shows Cu-AMAS (Cu = 0.27% (
1.2.6 and 4 in the figure are dry products, respectively, at 650°C.

This relates to products fired at 450°C and 550°C. It turns out that both dried and calcined Cu-AMAS is amorphous. 4 and 5 show Z n -AMAS [Zn=1.
64 (dry basis)] and the dry powder of Zn-AMAS (Zn = 4.51% (dry basis)) obtained in Example-3-B. The composition is also completely amorphous.

Photo-1 (full scale; 1 μm) is Example-2-
This is an electron micrograph of Cu-AMAS obtained in A, which is clearly amorphous.

Reference Example 1 This reference example relates to the production of an amorphous aluminosilicate. In this example, the following solution was used as the raw material solution.

Solution-A: Aluminum hydroxide (Az(oH)3.xH
2 O: Next, add more water to the solution to make a final solution of 12
．． I kept it at 9t. A trace amount of suspended matter in the above liquid was filtered to obtain a clear liquid.

Solution-B = Sodium silicate solution (JIS-3: specific gravity =
i, 4:N0zO=9. ! M:5102=29111
- Water was added to maintain the total volume at 14.5 tons. A trace amount of suspended matter in the above liquid was filtered to obtain a clear liquid.

Solution ic: 49s sodium hydroxide solution (specific gravity = 1.5
1) Add water to 1.08kF, total volume t-6,3
(alkalinity of solution-C=2.16N) 0 solution-〇(6,3z)1 was placed in a reaction tank, then heated to about 35°C and kept under stirring at 450 rpm.

To this, solution-A (approximately 35°C: 12.9t) and bath solution-B (approximately 65°C: 14.5t) were individually injected, and both injections were completed in 70 minutes. The solution -
When injecting solution-β into solution-〇, the molar ratio of SiO□/At203 in the resulting mixture is t 79 (s1/Az
= 3.58). In this example, the Na2o/At203 molar ratio at the end of mixing the raw material liquid was 1
．． 99, and the NazO/SiO□ molar ratio was 1.11. After the mixing of the raw material liquids was completed, the slurry-containing liquid was kept at about 65° C. and stirred at 35 Q rpm for 6 hours, and the amorphous aluminosilicate produced was purified by centrifugation.

A hot water procedure was then carried out on the above silicates. In this case, washing with water was carried out until the pH of the P solution reached 10.6. After washing with water, the amorphous silicate was dried at around 100°C, and then crushed in a Braun pulverizer to finally obtain 7.391w of dried amorphous aluminosilicate fine powder.

In this example, the X-ray diffraction diagram of the amorphous aluminosilicate is shown in FIG.

The main characteristics and effects of the amorphous aluminosilicate composition having antibacterial and bactericidal effects of the present invention are summarized below.

1. Demonstrates excellent antibacterial effects against mold and bacteria when used in relatively small amounts.

2. Compared to conventional organic antibacterial agents, the antibacterial composition of the present invention is composed of an inorganic system, so it is structurally stable, has an extremely low vapor pressure (nonvolatile), and has high heat resistance. It has characteristics.

3. This composition is tolerant to water, and dissolves into water at room temperature ~
The amount is negligible even at high temperatures, so it is highly safe.

4. The antibacterial ion, which is one of the components of this antibacterial composition, is stably bonded to the amorphous aluminosilicate matrix,
Sterilization based on antibacterial ions located at active sites in a porous matrix has the advantage of being more powerful than known liquid antibacterial agents.

5. This product has excellent dispersibility and is expected to be used as an additive (filler) for various polymeric materials. 6. This product is odorless, chemically stable, and does not cause structural changes. It has the advantage of maintaining its antibacterial effect over a long period of time.

7. This antibacterial composition exhibits a favorable antibacterial effect even in the water bath liquid phase or the same phase.

It is expected that the amorphous aluminosilicate composition having antibacterial action of the present invention having the above-mentioned characteristics and effects will be used as an antibacterial agent in a wide range of fields.

[Brief explanation of drawings]

Figures 1-5 relate to X-ray diffraction diagrams. FIG. 1 shows Ag-AMAS obtained in Example-1-A. Figure 2 shows Ag-AMAS obtained in Example-1-C.
. FIG. 6 shows Cu-AMAS obtained in Example-2-A. Figure 4 shows Z n -AMA obtained in Example-3-A.
S. Furthermore, FIG. 5 shows the Zn-AMA obtained in Example-3-B.
This is related to S. FIG. 6 is an electron micrograph of Cu-AMAS obtained in Example-2-A. In FIG. 6, the length of the white part is 1 μm. FIG. 7 shows X-ray diffraction of the dry powder of amorphous aluminosilicate obtained in Reference Example 1. - Figures 8 and 9 show the X-ray diffraction of an amorphous aluminosilicate partially converted to calcium and potassium, respectively. Next, FIG. 10 is an electron micrograph of an amorphous aluminosilicate. The length of the white part in Figure 10 is 1
There are μm″″c. Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Figure 8 Section 4 10 20
3ri 40Figure 9 4 lO2o 30
4゜Procedural amendment 1, Indication of the case 1985 Patent application #5185635 2, Title of the invention Amorphous aluminosilicate having antibacterial and/or bactericidal activity 3, Person making the amendment Relationship to the case Patent application Person's address: Zenji Hagiwara, outside number 11, number 4, agent number 6, contents of amendment (1) After line 10 of line 23 of the specification, insert the following starting with a new line. [Green-■ [I] This example relates to the production of amorphous aluminosilicate. In this example, the following solution was used as the raw material liquid. !
4 were made. Solution-8: Aluminum hydroxide [Af(OH), xH
49% sodium hydroxide solution (specific gravity = 1.51) 3.45 kit for 2O;
and water, and the resulting mixture was heated to dissolve. Next, more water was added to the solution to maintain a final total volume of 8.91. A small amount of suspended matter in the above liquid was filtered to obtain a transparent liquid. Sodium disilicate CJIS-3; specific gravity =
1.4; Na20=9.5%:5iO2=29%)8.
7 kg and 49% sodium hydroxide solution (specific gravity = 1
．． 51), 0.25Ag and water were added to maintain the total volume at 8.92. A trace amount of suspended matter in the above liquid was filtered to obtain a transparent liquid. m-Q-C: 49% sodium hydroxide solution (specific gravity = 1.
51)3. Add water to IAi+ to make the total volume 15.61
was held at (Alkalinity of solution-0=2.42N) Solution-C (15,61) was placed in a reaction tank, heated to about 40°C and kept under stirring at 350 rpa+. In contrast, solution-A (approximately 40°C; 8.9N) and solution-
B (approximately 40°C; 8, 91) were injected separately, and both injections were completed in 1 hour and 40 minutes. The above solution-
When injecting A and Solution-B into Solution-〇, the molar ratio of Sio2/Al2Oi in the resulting mixture was consistently 3.38 (Si
/Affi=6.76). In this example, Na20/A120 at the end of mixing the raw material liquid
3(7) The molar ratio is 4.43 and Na20/S
The molar ratio of iO2 was 1.31. After mixing the raw material liquids, the combined liquid of Sufu 1 and Fu is heated to 2 at about 40℃.
Aging of the amorphous aluminosilicate produced was carried out by keeping it under stirring at 50 rpm for 5 hours. After aging, the amorphous aluminum/silicate was filtered out by centrifugation. A hot water procedure was then carried out on the above silicates. Washing with water is ffL
The test was carried out until the IIH of 10.5 was reached. The silicate that had been washed with water was dried at around 100°C and then crushed in a Braun pulverizer to finally obtain 4.1 kg of dried amorphous aluminosilicate fine powder. In the synthesis of this example, as shown in Tables 1 and 2, samples of aqueous solution and solid phase were collected during the synthesis and subjected to various tests. (2) Insert "obtained in Production Example-4" before "amorphous" in the third line from the bottom of No. 55 of the specification. that's all

Claims (5)

[Claims] 1. Formula xM_2_/_nO・Al_2O_3・ySiO_2(
where M is silver, copper, zinc, mercury, tin, lead, bismuth, cadmium, or chromium, n is the valence of M, and x is O. 6 to 1.8 and y is 1.3 to 50). 2. The amorphous aluminosilicate having antibacterial and/or bactericidal activity according to claim 1, characterized in that it is composed of porous fine particles having a specific surface area of at least 5 m^2/g. 3. An activity consisting of fine particles with low hygroscopicity suitable for a filler obtained by carrying out a step including heat treatment of an amorphous aluminosilicate having antibacterial and/or bactericidal activity according to claims 1 to 4. material. 4. Formula xM_2_/_nO ・Al_2O_3・ySiO_2
(where M is silver, copper, zinc, mercury, tin, lead, bismuth, cadmium, or chromium; n is the valence of M; x is O.6 to 1.8; and y is 1 .3 to 50) and the formula xM_2_/_nO・Al_2O_3・ySiO_2(
In the formula, M is a monovalent or divalent metal with ion exchange properties (excluding silver, copper, zinc, mercury, tin, lead, bismuth, cadmium and chromium) or an ammonium ion, and n is the valence of M. , x is 0.6 to 1.8, and y is 1.6 to 50). 5. The composition according to claim 4, characterized in that it is composed of porous fine particles having a specific surface area of at least 5 m^2/9.