JPH062570B2 - Antibacterial agent - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is a novel amorphous aluminosilicate (hereinafter sometimes referred to as AMAS) having a bactericidal effect against various bacteria and fungi.
Said).

It is known that silver and copper have a bactericidal action. For example, silver has been widely used as a disinfectant in the form of an aqueous solution (Ag ⁺ ) such as silver nitrate. However, such a solution is inconvenient to handle, and thus has a drawback that it is limited in terms of application. Further, it is also known that silver or a compound thereof is adsorbed on an adsorbing material such as activated carbon, alumina or silica gel and used for sterilization purpose. Just by physically adsorbing the antibacterial metal or its compound to the adsorbent as described above, the sterilization in the activated state and the sustainability of the antibacterial effect, the stable retention of the required amount of the antibacterial agent, and the ionization ability It is hard to say that it is enough in terms of etc. Therefore, the inventors of the present invention have conducted extensive studies to improve the drawbacks of the conventional inorganic antibacterial agents, and as a result, the antibacterial metal in the ionic state has a specific surface area of at least 5 m ² / g or more. If fixed and stabilized in salt, the more economical amount of antibacterial metal ion can be used to ideally perform antibacterial and sterilization in the excited state. The present invention has been accomplished by finding that it has many advantages in terms of stability, stability, heat resistance, etc., and is expected to be effective and widely used.

The present invention is a 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 1.8, and y is 1.3 to 15, Preferably 1.3 to 7, more preferably
1.3-3.6) and having an antibacterial and / or bactericidal activity, comprising an amorphous aluminosilicate.

The present invention is also a 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 1.8, and y is 1.3 to 15, Preferably 1.3 to 7, more preferably
Amorphous aluminosilicate represented by (In the formula, M is an ion-exchangeable sodium, potassium, lithium, iron (II), magnesium (II), calcium, cobalt (II), nickel (II) monovalent or divalent)
A valent metal (excluding silver, copper, zinc, mercury, tin, lead, bismuth, cadmium and chromium) or ammonium ion, n is a valence of M, x is 0.6 to 1.8, and y is 1.3 to 15, preferably 1.3 to 7, more preferably
1.3 to 3.6) and an amorphous aluminosilicate represented by the formula (3).

In producing the amorphous aluminosilicate of the present invention, xNa ₂ O · Al ₂ O ₃ · ySiO ₂ is first produced as follows.

An alkali solution (Solution-C) having an alkalinity in the range of 1.2-3.5N is kept under stirring, while a sodium aluminate solution (Solution-A) containing free alkali and a silicic acid containing free alkali. Amorphous aluminum) silicate (main component: Na ₂ O—Al ₂ O ₃ —SiO ₂ ) composed of fine particles that are difficult to dissolve by individually adding predetermined amounts of sodium liquid or colloidal silica liquid (solution -B) In the method for producing an amorphous aluminosilicate by producing a slurry liquid containing a), the addition of Solution-A and Solution-B to Solution-C is carried out in the resulting mixture. Si / A
The ratio of l is in the range of 0.7 to 7.6 during and after the addition, and the mixing is carried out below 55 ° C., and the alkalinity of any aqueous phase during the slurry formation and aging is Solution-A and solution-B so that the alkalinity of pre-prepared solution-C is ± 0.30N
Of the aluminosilicate represented by the formula xN ₂ O · Al ₂ O ₃ · ySiO ₂ (where x and y are as described above) by adjusting the To be done.

Compounds having other ion-exchangeable metals can be derivatized by ion exchange of the above-mentioned sodium-substituted compound.

In the usual synthesis of AMAS, it is extremely easy to prepare porous particles having a specific surface area (SSA) of at least 5 m ² / g and having an average particle diameter (Dav) of 6 μm or less. The above M has the property of ion exchange, and by subjecting this to the necessary amount of one or more antibacterial or bactericidal metal ions described later, the matrix of SSA ⁵ m ² / g AMAS, that is, the solid phase. If it is stably retained in A, the active A having the antibacterial and bactericidal action of the present invention
A MAS composition is obtained.

The AMAS used as a matrix for holding antibacterial metal ions in the present invention is poorly soluble in water, has high heat resistance, and is structurally stable even at high temperatures. As mentioned above, this is In the composition formula, M is an ion-exchangeable monovalent cation such as Na, K or NH _4, or Mg or C.
It represents divalent cations such as a and Fe. Of course, the above A
There is no difference in the presence of monovalent or divalent metals alone or in combination in MAS. Furthermore, the presence of multivalent ions having a valence of 3 or more in AMAS as a minor component does not interfere. AMAS
The exchange capacity of is governed by its composition. Molar ratio SiO ₂
/ MA ₂ O ₃ increases, that is, AMA increases as y increases.
The ion exchange capacity of S gradually decreases, while it tends to increase in proportion to the coefficient x of M _{2 / n} O. For example xN
The exchange capacity of AMAS having a composition of a ₂ O · Al ₂ O ₃ · ySiO ₂ (in this case, exchange ions are Na ⁺ ) is 7.01 and 5.81 for y = 2 and 3, respectively, assuming that x = 1 (constant). me
q / g. Further, when y = 7 and 10,
3.42 and 1.48 meq / g. When y = 30, the exchange capacity is 1.01 meq / g, and when y = 50, it is
Only 0.63 meq / g. In terms of such replacement capacity,
In order to retain an effective amount of antibacterial metal ions in AMAS, y is preferably 30 or less, and the most preferable upper limit value of y is 7. AMA used as a material in the present invention
_{S (xM 2 / n O ·} Al 2 O 3 · ySiO 2) is synthesized on the x obtain those 0.6-1.8 range and the coefficient y is obtained usually more than 1.3. It is of course possible to prepare the antibacterial composition of the present invention by using AMAS having y of 30 or more as a material,
Based on the above reason, the range of y in the present invention is 1.3.
-15, preferably 1.3-7. Therefore, in the present invention, A having a preferable antibacterial and bactericidal action
As MAS compositions, metal oxides - alumina - the main component of silicon dioxide, the general formula of which is represented by _{xM 2 / n O · Al 2} O 3 · ySiO 2, wherein M has ion exchangeability Further, there is an AMAS in which the coefficient x of metal oxide is 0.6 to 1.8 and the coefficient y of silicon dioxide is 1.3 to 7 based on alumina. The present invention further provides an antibacterial agent comprising an antibacterial and bactericidal AMAS composition, wherein a part or all of M constituting the AMAS is replaced with a bactericidal metal ion. Is.
There is no problem even if a polyvalent cation having a valence of 3 or more coexists as a minor component in the above composition.

The metal having an antibacterial action (hereinafter referred to as B) used for the preparation of the AMAS composition having an antibacterial and bactericidal action of the present invention includes silver, copper (monovalent or divalent), zinc, mercury (monovalent or monovalent). Divalent), tin (monovalent or tetravalent), lead (2
Valence), bismuth; (divalent), cadmium (divalent), chromium (divalent or trivalent), and one or more metals selected from the group. Ion exchange between the above-specified salt solution containing one or more antibacterial B ions and the (metal in the solid phase) in the specified AMAS at room temperature or high temperature may be performed under appropriate conditions. If The antibacterial metal ion is retained in the solid phase () by the reaction of and the AMAS having the antibacterial and bactericidal action of the present invention
A composition is obtained. Ion exchange for imparting antibacterial activity to AMAS is preferably performed by either a batch method or a carcum method.

The antibacterial AMAS composition of the present invention obtained by the above-mentioned method has extremely high resistance to various bacteria and molds, and it was confirmed by the test described below that it exhibits excellent bactericidal activity. That is, using this product, Staphylococcus aureus, E
scherichia Coli, Pseudomonas aeruginosa, Candida a
Antibacterial evaluation test against bacteria such as lbicans, Trichophyton mentagrophytes, Aspergillus flavus, Aspergil
By measuring the death rate against fungi such as lus niger,
It was confirmed that this product has strong antibacterial activity and bactericidal activity. Furthermore, Aspergillus niger (ATCC9642), Penicillum
funiculosum (ATCC9644), Chaetomium globosum (ATCC620
5), Trichoderma SP (ATCC9654) and Aureobasidium Pu
The spores were inoculated using 5 kinds of test strains of llulans (ATCC9348), and a mold resistance test by ASTM-G21 was conducted. The polymer molded body containing the antibacterial AMAS of the present invention showed mold resistance. Therefore, it was found that the antibacterial effect is extremely effective and the antibacterial effect lasts for a long period of time, which is extremely effective (Example-11).

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

Dav = 0.2 μm Ag-AMAS powder containing 1.03% silver [Example-1-A; Ag = 1.03% (dry product); SSA = 2
2m ² / g; Starting material AMAS, 1.10Na ₂ O ・ Al ₂ O ₃・ 2.51S
iO ₂ · xH ₂ O] using Stapylococcus aureus, Pseudomonas
An antibacterial evaluation test against aeruginosa and Escherichia cali (observation of presence or absence of inhibition zone by culturing at 37 ° C. for 18 hours) was conducted, and it was found to be extremely effective against any of the above bacteria. The Ag-AMAS is Tri
The effect was also confirmed for chophyton mentagrophytes. Dav = 0.23μm Ag-AM containing 0.22% silver
AS powder [Ag = 0.22% (dry product; SSA = 23 m ² / g; starting material AMAS, 1.10Na ₂ O ・ Al ₂ O ₃・ 2.51SiO ₂・ xH ₂ O) was also subjected to the same evaluation test as above. It was confirmed that the bacteria were still effective against all bacteria, and that the above-mentioned Ag-AMAS was completely trichophyton menta grophyte.
It was found to kill s (see Tables 5-6). Next, the above-mentioned Ag-AMAS containing 0.22% of silver at 500 ° C (2
Hours) For the baked product, the same bacterial evaluation test as described above was performed. As a result, it was confirmed that the heated product also had a sufficient effect on bacteria. The heat resistance of Ag-AMAS of the present invention having antibacterial and bactericidal action is also excellent,
It is clear that the antibacterial activity of this heated product does not deteriorate and the activity is maintained. Next, instead of the above-mentioned Ag-AMAS powder, Ag-AMAS powder [Ag = Dav = 0.2 μm with low silver content [Ag =
0.047% (dry product)] of Aspergil for the measurement of fungal killing rate (measurement of the number of living solids after 48 hours at 30 ° C)
The test was carried out on two species, lus flavus and aspergillus niger, and the mortality rate was 100% in each case.
Furthermore, from the above, Ag-AMAS powder with a lower silver content [Ag
= 0.02% (dry product)], the mortality of Aspergillus flavus and Aspergillus niger was measured to obtain mortality of 99% and 100%, respectively (see Table 6). Further, the effect was still recognized even at a low content of Ag-AMAS. From these results, it is clear that the silver content in the Ag-AMAS of the present invention exerts a sufficient bactericidal effect when it is adjusted to 0.001-1% in normal use. AMAS having antibacterial and bactericidal action of the present invention
In order to maximize the effect of the above, the optimum content of the antibacterial metal (B) naturally varies depending on the type of target bacteria or fungi and the use conditions. If necessary, the concentration of AMAS may be increased by utilizing the aforementioned ion exchange. For example, it is easily possible to prepare Ag-AMAS by utilizing ion exchange and keep the silver content in the Ag-AMAS at 10% or more. (See Example-1-C).

The antibacterial composition Cu-AMAS of the present invention containing copper will be described. Cu-AMAS with Dav = 0.2μm containing 0.27% copper
[Cu = 0.27% (dry product); SSA = 56 m ² / g; Starting material AMAS, 1.03Na ₂ O.Al ₂ O ₃ 3.24SiO ₂ .xH ₂ O] was used to determine the fungal killing rate using Aspergilles flavus. And Aspergillu
s niger, 95% for the former. A value of 67% was obtained for the latter. Furthermore, a lower content of copper synthesized using the same starting material as above, Dav = 0.24 μm C
u-AMAS powder [however, Cu = 0.064% (dry product); SSA
= 54 m ² / g] and the fungal killing rate is measured,
90% for Aspergillus flavus and Aspergillus
We got 57% for niger. As can be seen from these antibacterial tests, it is recognized that the Cu-AMAS of the present invention does not lose its activity even at a low concentration such as a copper content of 0.06% and still exerts its effect on fungi (see Table 7). .

Zn-AMAS [Zn containing 7.26% zinc and having Dav = 0.6 μm
= 7.26% (dry product); SSA = 141 m ² / g; starting material AMAS, 1.42Na ₂ O · Al ₂ O ₃ · 6.04SiO ₂ · xH ₂ O]
The mortality rate against Aspergillus flavus was measured to obtain 39%, and it was confirmed to be effective. Furthermore, AMAS containing Pb ²⁺ , Bi ²⁺ , Cd ²⁺ , Cr ³⁺ , Sn ²⁺ and Hg ²⁺ as antibacterial metal ions was prepared, and the antibacterial properties of these were evaluated and the mortality was measured. In this case, Escherichia col
i, Staphyococcus aureus, pseudomonas aeruginosa, Aspe
rgillus flavus, Aspergillus niger and Trichophyton
mentagrophytes were used with good results (8th
-9 Table).

In the present invention, as described above, any one or two selected from the group consisting of silver, copper, zinc, mercury, tin, lead, bismuth, cadmium and chromium as the metal having a bactericidal action. A strong antibacterial agent having long-lasting activity can be obtained by combining two or more species and retaining them in the AMAS specified in the present invention. Further, there is an advantage that a synergistic effect is exerted by the combined action of two or more kinds of the above-mentioned metals and the antibacterial activity and bactericidal activity against various bacteria and fungi are exerted in a more preferable state.

As described above, the AMAS used as a raw material for the production of the antibacterial AMAS composition of the present invention is amorphous (amorphous). Here, a manufacturing example thereof will be described.

This Example Preparation -1 (AMAS) is a manufacturing example of AMAS having a molar ratio _{SiO 2 / Al 2 O 3 2.5} .

Solution-A: Aluminum hydroxide [Al (OH) ₃ · xH ₂ O; x
0] 1.06 kg, a mixture obtained by adding 49% sodium hydroxide solution (specific gravity = 1.51) 1.73 kg and water was dissolved by heating. Next, water was further added to the solution, and the total volume was finally kept at 4.5. A clear suspension was prepared by passing a microsuspension in the above solution (Solution-A).

Solution-B: Sodium silicate (JIS-3; specific gravity = 1.
4; Na ₂ O = 9.5%; SiO ₂ = 29%) 49% against 4.4 kg
0.13 kg of sodium hydroxide solution (specific gravity = 1.51) and water were added to keep the total volume at 4.5. A clear liquid was prepared by passing a trace amount of the suspension in the solution (solution-B).

Solution-C: 49% sodium hydroxide solution (specific gravity = 1.51)
Water was added to 1.6 kg and the total volume was maintained at 7.8 (solution-
C).

Solution-C was placed in a reaction vessel and kept under stirring at 350 rpm while warming to 38 ° ± 2 ° C. On the other hand, after keeping the above solution-A and solution-C at around 40 ° C., these solutions were simultaneously and individually injected, and both injections were completed in 55 minutes. After the completion of mixing the raw material liquids, the slurry-containing liquid was kept at about 40 ° C. under stirring at 270 rpm for 4 hours to age the generated AMAS. After aging, AM
AS was passed by centrifugation. Next, the above AMA
Hot water washing was performed on S. Excessive pH of washing with water is 1
It was carried out until it reached 0.6. After the completion of washing with water, the AMAS was dried at 100 ° C. to 110 ° C., then pulverized to obtain about 1.99 kg of finally dried AMAS fine powder.

Results of Preparation Example-1: Yield of dry fine powder of AMAS: Approximately 1.99 kg Scientific composition: 1.10 Na ₂ O · Al ₂ O ₃ · 2.51SiO ₂ · xH ₂ O Dav: 0.2 μm SSA: 22 m ² / g Preparation example -2 (AMAS) this example relates to preparation examples of AMAS having a molar ratio _{SiO 2 / Al 2 O 3 3.2} .

Solution-A: Aluminum hydroxide [Al (OH) ₃ · xH ₂ O; x
0] To 2.53 kg, 2.9 kg of 49% 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, and the total volume was finally kept at 6.5. A slight amount of the suspension in the above liquid was passed through to obtain a transparent liquid (Solution-A).

Solution-B: Sodium silicate solution (JIS-3; specific gravity 1.
4; Na ₂ O = 9.5%; SiO ₂ = 29%) 5.5 kg of water was added to keep the total volume at 7.3. A slight amount of the suspension in the above solution was passed to give a clear solution (Solution-B).

Solution-C: 49% sodium hydroxide solution (specific gravity = 1.51)
0.54 kg was diluted with water to keep the total volume at 3.2 (solution-
C).

Solution-C was placed in a reaction vessel, which was then heated to about 35 ° C. and kept under stirring at 500 rpm. On the other hand, the solution-A and the solution-B were heated at about 35 ° C., and were separately and simultaneously injected, and both injections were completed in 1 hour. After mixing the raw material liquid, the slurry-containing liquid is 350 rp at about 35 ° C.
The AMAS produced after being kept under m stirring for 4 hours was filtered off by centrifugation. Next, the above AMAS was subjected to hot water washing in the same manner as in the above-mentioned example. Next, the washed AMAS is dried at 100 ° to 110 ° C. and then finely pulverized to finally obtain about 3.7 kg of finely divided AMAS powder.
was gotten.

Result of Production Example-2: Yield of dry fine powder of AMAS: Approximately 3.7 kg Chemical composition: 1.03Na ₂ O ・ Al ₂ O ₃・ 3.24SiO ₂・ xH ₂ O Dav: 0.2 μm SSA: 56m ² / g Production example -3 (AMAS) This example relates to a production example of an AMAS material required for preparing an amorphous alumino composition having an antibacterial and bactericidal action of the present invention having a molar ratio of SiO ₂ / Al ₂ O ₃ 6.

Solution-A: Aluminum hydroxide [Al (OH) ₃ · xH ₂ O; x
0] 1.37 kg, 49% sodium hydroxide solution (specific gravity = 1.51) 3.6 kg and water were added and the resulting mixture was heated to dissolve. Next, water was further added to the solution to keep the total volume at 3.6. A slight amount of the suspension in the above liquid was passed through to obtain a transparent liquid (Solution-A).

Solution-B: Colloidal silica (trade name Snowtex-
30) Water was added to 12.5 kg to keep the total volume at 10.8. A clear suspension was prepared by passing a slight suspension in the above solution (Solution-B).

Solution-C: 49% sodium hydroxide solution (specific gravity = 1.51)
Water was added to 14.9 kg to keep the total volume at 7.2 (solution-
C).

Put Solution-C into the reaction tank and keep the liquid temperature at 30 ℃
It was kept under m stirring. On the other hand, the solution-A and the solution-B held at about 30 ° C. were simultaneously and individually injected, and both injections were completed in 45 minutes. After the mixing of the raw material liquids was completed, the slurry-containing liquid was aged after being aged at about 30 ° C. for 2 hours and 50 minutes under stirring at 400 rpm.
MAS was passed by centrifugation. The solid phase was washed with warm water (until the excess pH reached 10.8) as in the case of the above-mentioned production example, and then the washed AMAS was 100 °.
Drying at ˜110 ° C. and subsequent crushing finally gave 4.08 kg of fine powder in the dried AMAS.

Yield of dry fine powder of AMAS: 4.08kg Chemical composition: 1.42Na ₂ O · Al ₂ O ₃ · 6.04SiO ₂ · xH ₂ O Dav: 0.2 μm or less SSA: 139 m ² / g Obtained by the above-mentioned production examples 1 to 3 The AMAS used as the material of the present invention is amorphous and porous, the SSA has reached 20 m ² / g or more, and the Dav has fine powder of 1 μm or less in any case. Production Examples 1 to 3
The chemical composition of the AMAS obtained in 1. is as described above, but each has a sufficient exchange capacity preferable for preparing the antibacterial composition of the present invention, and the exchange ion (Na ^The rate of exchange between ⁺ ) and the antibacterial metal ion is extremely rapid, and the binding force between the matrix AMAS and the antibacterial metal ion is extremely large.

Production Example-4 This example relates to the production of amorphous aluminosilicate. In this example, the following solutions were prepared as raw material liquids.

The solution -A: aluminum hydroxide _{[Al (OH) 3 · xH} 2 O; x3]
To 2.12 kg, 3.45 kg of 49% 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, and the total volume was finally maintained at 8.9. A slight amount of the suspension in the above liquid was passed to obtain a transparent liquid.

Solution-B: Sodium silicate (JIS-3, specific gravity = 1.
4; Na ₂ O = 9.5%: SiO ₂ = 29%) 8.7 kg, 49% sodium hydroxide solution (specific gravity = 1.51),
The total volume was maintained at 8.9 by adding 25 kg and water. A slight amount of the suspension in the above liquid was passed to obtain a transparent liquid.

Solution-C: 49% sodium hydroxide solution (specific gravity = 1.5
1) Water was added to 3.1 kg to keep the total volume at 15.6. (Solubility-C alkalinity = 2.42N) Solution-C
(15.6) was placed in a reaction vessel, heated to about 40 ° C., and kept under stirring at 350 rpm. On the other hand, Solution-A
(About 40 ° C; 8.9) and Solution-B (about 40 ° C; 8.9)
) Is injected individually, and both are injected for 1 hour 4
It finished in 0 minutes. When injecting the above solution-A and solution-B into the solution-C, the molar ratio of SiO ₂ / Al ₂ O _{3 in} the obtained mixture was 3.
It was held at 38 (Si / Al = 6.76). In this embodiment,
The Na ₂ O / Al ₂ O ₃ molar ratio at the end of mixing the raw material liquids is 4.43 or N
The molar ratio of a ₂ O / SiO ₂ was 1.31. After the completion of mixing the raw material liquids, the slurry-containing liquid was aged at 250 rpm under agitation at 250 rpm for 5 hours to age the amorphous aluminosilicate formed. After the aging was completed, the amorphous aluminosilicate was filtered by centrifugation. Next, the above silicate was washed with warm water. Washing with water was carried out until the pH of the liquid reached 10.5. The silicate that had been washed with water was dried at around 100 ° C. and then crushed with a Brown crusher to finally obtain 4.1 kg of dried fine powder of amorphous aluminosilicate.

In the synthesis of this example, as shown in Tables 1 and 2, an aqueous solution and a solid phase were sampled during the synthesis and subjected to various tests.

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 Ag-AMAS compositions of the present invention containing a silver (SiO ₂
/ Al ₂ O ₃ = 2.51). Dry powder AMAS produced in the above Production Example _{-1 (1.10Na 2 O · Al 2} O
About _2.5 g of ₃・ 2.51SiO ₂・ xH ₂ O)
gNO ₃ (Example 1-A), 0.3MAgNO ₃ (Example 1-
B) or 0.6 MAgNO ₃ (Example-1-C) solution 500 m
The mixture obtained by the addition was kept at room temperature under stirring at 350 rpm for 5 hours to exchange a part of the ion-exchangeable Na ⁺ of AMAS with Ag ⁺ . After passing through the above ion exchange reaction, the solid phase obtained was washed with water to remove excess Ag ⁺ present in the solid phase. Then, the Ag-AMAS which had been washed with water was dried at 100 ° to 110 ° C. and then made into a fine powder. The results of this example are shown in Table 1.

EXAMPLE -2 This example Cu-AMAS composition of the present invention containing copper (SiO ₂ / Al ₂ O ₃
= 3.24). Production Example-2 above
Dry powder of AMAS (1.03Na ₂ O ・ Al ₂ O ₃・ 3.24)
SiO ₂ · xH ₂ O) About 100 g (Example 2-A) or about 250
gr (Example-2-B) was sampled and the former was 0.02
500 ml of MCu (NO ₃ ) ₂ solution and 500 ml of 0.6 M Cu (NO ₃ ) ₂ solution were added to the latter, and the mixture was diluted with water to keep the whole volume as shown in Table 2. Next, the obtained mixed liquid was kept under stirring at 360 rpm for 6 hours to partially replace Cu ²⁺ with ion-exchangeable Na ⁺ of AMAS (room temperature ion-exchange). After the completion of the ion exchange, the solid phase obtained was washed with water to remove excess Cu ²⁺ existing in the solid phase. Then, the Cu-AMAS that had been washed with water was dried at 100 ° to 110 ° C and made into fine powder.

The results of this example are shown in Table 2. Cu obtained in this example
-Dam of AMAS is 0.2 μm, while SSA is 56 m ² / g in Example-2-A and Example-2-B, respectively.
And 59 m ² / g.

EXAMPLE -3 This example Zn-AMAS compositions of the present invention containing zinc (SiO ₂ / Al ₂
O ₃ = 6.04). Production example described above-
Dry powder of AMAS prepared in 3 (1.42Na ₂ O.Al ₂ O ₃ .6.
04SiO ₂ · xH ₂ O) about 250g was sampled and 0.1M Zn
(NO ₃ ) ₂ (Example-3-A) or 1.0M Zn (NO ₃ ) ₂ (Example-3-B) solution (500 ml) was added and the resulting mixture was added to 40%.
It was kept under stirring at 0 rpm for 7 hours to exchange a part of ion-exchangeable Na ⁺ of AMAS with Zn ²⁺ (ion exchange at room temperature). The product was then passed over and the resulting solid phase was washed with water to remove excess Zn ²⁺ present in the solid phase. The Zn-AMAS that had been washed with water was dried at 100 ° to 110 ° C and then made into a fine powder.

The results of this example are shown in Table 3. Zn obtained in this example
-AMASDav was 0.6 μm, while SSA was almost the same, and values of 140 m ² / g and 141 m ² / g were obtained in Example-3-A and Example-3-B, respectively.

Examples-4-9 Examples-4-9 are antimicrobial AMAS compositions of the present invention.
Bi-AMAS (Dav = 0.1μm), Cr-AMAS (Dav = 0.1μm), Sn-A
MAS (Dav = 0.2μm), Hg-AMAS (Dav = 0.2μm), Pb-AMAS (Da
It shows an example of preparation of v = 0.4 μm) and Cd-AMAS (Dav = 0.2 μm) (Table 4).

As starting material, a dry product of AMAS having a composition of Table 4 with SSA 29 m ² / g was used. Examples 4-7 used about 50 g of AMAS and, as indicated, 150 ml of 0.05M saline solution, these mixtures being 360
It was kept under stirring at rpm for 20 minutes and a part of Na ⁺ of AMAS was replaced with the antibacterial metal ion as shown (ion exchange at room temperature) to obtain an AMAS composition having antibacterial and bactericidal effects. Washing and drying of the notation M-AMAS were carried out according to the above-mentioned examples.

Any antibacterial M-AMA obtained in this example (4 to 9)
Also in the S composition, Dav is composed of fine particles as described above, and SSA reaches 30 m ² / g or more in each case.
The antibacterial AMAS composition of this example is porous and hardly soluble in water. Antibacterial metal ion (M) Bi ²⁺ , Cr ³⁺ , S
n ²⁺ , Hg ²⁺ , Pb ²⁺ , and Cd ²⁺ are AM specified in the present invention.
Since the metal ions are stably bound and present in the matrix of AS, elution of these metal ions from the solid phase is slight, and therefore the stability is extremely high. Since the dissociation of the M-AMAS composition also proceeds in a favorable state, the bactericidal action against bacteria and fungi on the basis of this is strongly performed centering on the active site of the M-AMAS matrix, and as a result, the bactericidal action found in the known bactericides is not found. A favorable effect was confirmed (see the evaluation test for antibacterial activity described later).

Next, in order to evaluate the antibacterial activity against bacteria and fungi of a typical amorphous aluminosilicate composition having antibacterial and bactericidal activity of the present invention, an evaluation test of antibacterial activity, measurement of mortality,
And a mold resistance test was performed. The evaluation method of antibacterial activity was as follows.

Method: The test substance was suspended at a concentration of 100 mg / ml and soaked in a disc.

Mueller Hinton medium was used for bacteria and Sabouraud agar medium was used for fungi.

The test bacteria were suspended in physiological saline at 10 ⁸ cells / ml and added to the medium.
Dispersed with a 0.1 ml conradi stick.

The test disc was mounted on it.

Judgment: For bacteria, presence / absence of inhibition zone formation was observed at 37 ° C. for 18 hours.

The fungus was evaluated after 1 week at 30 ° C. The mortality was measured as follows.

1 ml of the spore suspension (10 ⁴ cells / ml) of the test bacterium was poured into 9 ml of the test substance suspension (500 mg / ml), and the mixture was allowed to act at 30 ° C. for 24 hours. 0.1 ml thereof was dispersed in Sabouraud agar medium, and after 48 hours at 30 ° C., the number of surviving individuals was measured to determine the mortality rate.

Table 5 shows the results of the antibacterial property evaluation test on the Ag-AMAS composition containing silver of the present invention. The Ag-AMAS [Ag = 1.03% (dry basis)] obtained in Example-1-A showed good inhibition zone formation against any of the test organisms shown, and it has excellent antibacterial activity. It has been found. In addition, two Ag-AMASs with lower silver contents (Ag = 0.22% and Ag = 0.02% (dry basis)) prepared using the same kind of AMAS material as the above example were also excellent as shown. It was confirmed to retain antibacterial activity. An antibacterial property evaluation test was conducted under the same test conditions for the purpose of comparing the antibacterial activity of the Ag-AMAS composition of the present invention and a known silver (metal) (Table 5, Comparative Example-1).
In Comparative Example-1, a fine powder of 325 mesh (commercial item) was used as the metallic silver in an extremely large amount compared with the amount of silver in Ag-AMAS. Was not observed at all. Therefore, it is clear that this effect is far beyond the antibacterial composition of the present invention.

Next, Aspergillus flavus, Aspergillus ni
Mortality measurements were performed on the Ag-AMAS compositions of the present invention using ger and Trichophyton mentagrophytes with excellent results. (See Table 6). 0.02% as Ag,
Mortality measurements were performed on Ag-AMAS compositions containing 0.047% and 0.22% (the raw AMAS material is the same as that of Example-1-A), but as for any Ag-AMAS, Aspergillus Mortality to niger was 100%. The mortality rate against Aspergillus flavus is Ag
At 0.02% Ag-AMAS, it is 99%, while Ag is 0.047%
And 0.2-0.2% Ag-AMAS, both were 100%.
Furthermore, Ag-AMAS (Ag = 0.22%) is Trichophyton mentagro
It was confirmed that phytes also had an excellent bactericidal activity with a mortality rate of 100%. In order to compare the bactericidal activity of the antibacterial composition of the present invention and known silver (metal), the mortality against Aspergillus flavus was measured under the same test conditions (Table 6, Comparative Example-2). ). In Comparative Example-2, the mortality is 0% regardless of the fact that 325-mesh silver powder (commercially available) is used in an extremely large amount as compared with the amount of silver in Ag-AMAS. It is clear that the antibacterial composition of the present invention exerts an antibacterial activity superior to that of known antibacterial agents, as compared with Comparative Example-2 and this product.

Next, Cu-AMAS containing Cu [Cu = 0.27% (dry basis);
Example-2-A] using Aspergillus flavus and
Mortality of Aspergillus niger was measured and the former was 95% and the latter 67% (see Table 7). Furthermore, Cu-AMAS [Cu = 0.064% (dry standard) ); AMAS material is the same as that used in the preparation of Example-2-A], and Aspergillus flavus and Aspergil
The mortality of lus niger was measured, and the former value was 90%, and the latter value was 57%. From these results, the effect of Cu-AMAS having a low copper content of the present invention is still recognized.

For Zn-AMAS of the present invention containing zinc, the killing rate against the fungus Aspergillus niger was also measured in the same manner as described above, and Zn-AMAS [Zn = 1.64% (dry basis); Example-3-A] Killed 17%, while Zn-AMAS [Zn = 7.26% (dry basis) containing a higher concentration of zinc; A
MAS material is the same as that used in the preparation of Example-3-A]
A mortality rate of 39% was confirmed using.

Example-10 (Table 7) relates to the composite antibacterial composition of the present invention. In this example, Ag-C containing copper and silver
u-AMAS [Ag = 0.59%; Cu = 3.47% (dry basis); Raw material is 1.03Na ₂ O ・ Al ₂ O ₃・ 3.24SiO obtained in Production Example-2
Aspergillu using AMAS with composition of ₂ · xH ₂ O]
Mortality was measured for fungi of S. flavus and Aspergillus niger, and values of 100% were obtained for all the fungi. When two kinds of antibacterial metals are compounded and stably retained in the AMAS specified in the present invention as in this example, there is an advantage that the bactericidal action is exhibited in a more preferable state based on the synergistic effect.

The results of the antibacterial activity test for the antibacterial AMAS composition of the present invention prepared in Example-4-9 (Table 4) are shown in Tables 8 and 9. As shown in Table 8, cd-A
When using MAS (Example-9), Escherichia coli and Pse
A good zone of inhibition was observed for the other four species except udomonas aeruginosa, while a good zone of inhibition for all six species when using Hg-AMAS (Example-7). It was found that they had excellent antibacterial activity. Further, the antibacterial composition obtained in Example-4-9 was used to measure the mortality of the three kinds of bacteria shown in Table 9 (Table 9). From these results, Bi-AMAS, Cu-AMAS, Su
-It is clear that AMAS, Hg-AMAS, Pb-AMAS, and Cd-AMAS have antibacterial activity. The antibacterial metal in the antibacterial composition and the specified AMAS of the matrix are chemically chemically stable, and these compositions are hardly soluble in water. The elution of the antibacterial metal from the matrix is in units of ppb, which is preferable in terms of stability.

Fine AMAS having antibacterial and bactericidal action of the present invention
By heating the composition in a temperature range of, for example, 200 ° to 500 ° C, the water content therein is easily removed to 1% or less or almost 0%. Since fine particles (Dav 5 μm or less) activated in such a state are well dispersed in a polymer, they are suitable as an antibacterial filler. The activated fine particles having an antibacterial activity of the present invention can be used in the fields of paper, fiber, plastic, rubber, pigment, paint and the like.

Example-11 This example relates to a specific application example as an antibacterial filler. The antibacterial Ag-Cu-AMAS composition described in Example-10 (see Table 7) [Ag = 0.59%; Cu = 3.47
% (Dry basis)] was activated by heating to 300 ° C. for 1 hour and 25 minutes. Next, this was pulverized to obtain fine particles having Dav = 0.3 μm. Polyethylene chips (L.
After adding 2% to DPE), the mixture is about 20 ° C at 185 ° C.
Mixed for minutes. The mixture was then pressed at the same temperature with a load of 45 kg / cm ² and molded into a plate having a thickness of 0.8 mm.

The above plate was cut to prepare a test piece (70 × 70 mm), and the mold resistance test was performed using the ASTM-
Performed by G21. Aspergillu as the test bacteria
s niger (ATCC9642), Penicillium Funiculosum (ATCC964
4), Chaetomium globosum C ATCC6205), Trichoderma S
p (ATCC9645) and Aurebasidium Pullulans (ATCC9348)
5 species were used and inoculated with these spores. The following composition was used as the medium.

_{Medium: K 2 HPO 4 (0.7g)} ; KH 2 PO 4 (0.7g); MgSO 4 · 7H 2 O (0.7g); N
H ₄ NO ₃ (1.0 g); NaCl (0.005 g); FeSO ₄・ 7H ₂ O (0.002 g): ZnSO ₄・
7H ₂ O (0.002g); MnSO ₄ · 7H ₂ O (0.001g); Agar (15g); Pure water (1
000 ml).

The medium was run at 25 ° ± 2 ° C. and 90 ± 5% humidity (RH) for 40 days. The test results are shown in Table 10.

In Comparative Example-3, a 0.8 mm-thick plate (70 × 70 mm; Ag-Cu-AMAS is not added) was prepared using the same polyethylene chip (LDPE) as used in Example-11 and subjected to a blank test. It was It is clear that the amorphous aluminosilicate composition having an antibacterial effect of the present invention has much more excellent resistance to mold than the comparison between Example-11 and Comparative Example-3.

The aluminosilicate having the antibacterial and bactericidal action of the present invention is amorphous as described above. As a typical example, this product X
The line diffraction pattern is shown in FIG. 1-5. Example 1 in FIG.
X of Ag-AMAS [Ag = 1.03% (dry basis)] obtained in A
Although line diffraction was shown, the symbols 1, 2, 3 and 4 in the figure were dry powder, 350 ° C., 450 ° C., and 550, respectively.
The present invention relates to an X-ray diffraction diagram of a product baked at ℃. From this, it can be seen that this product is amorphous (amorphous) and has high heat resistance. FIG. 2 shows an X-ray diffraction pattern of Ag-AMAS [Ag = 11.35% (dry basis)] having a relatively high silver content obtained in Example-1-C. The symbols 4 and 4 refer to dry powder, 350 ° C., 450 ° C. and 550 ° C. calcined products, respectively. Dried or baked Ag-A
MAS is also amorphous. FIG. 3 shows the X-ray diffraction of Cu-AMAS [Cu = 0.27% (dry basis)] obtained in Example-2-A. In the figure, 1, 2, 3 and 4 are dry products. ,
It relates to 350 ° C., 450 ° C. and 550 ° C. fired products. Both the dried products and the Cu-AMAS that were to be fired turned out to be indeterminate. FIGS. 4 and 5 show Zn-AMAS [Zn = 1.64% (dry basis)] obtained in Example-3-A and Zn-AMAS [Zn = obtained in Example-3-B, respectively.
4.51% (dry basis)] shows the X-ray diffraction pattern of the dry powder, but all the antibacterial compositions are completely amorphous.

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

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

The solution -A: Aluminum hydroxide _{(Al (OH) 3 · xH} 2 O; x0 ]
49% sodium hydroxide solution for 5.05 kg (specific gravity = 1.
51) 5.8 kg and water were added, and the resulting mixture was heated and dissolved. Next, water was further added to the solution, and the total volume was finally maintained at 12.9. A slight amount of the suspension in the above liquid was passed to obtain a transparent liquid.

Solution-B: Sodium silicate solution (JIS-3; specific gravity =
1.4; NO ₂ O = 9.5%; SiO ₂ = 29% Water was added to 11 kg to keep the total volume at 14.5. A slight amount of the suspension in the above liquid was passed to obtain a transparent liquid.

Solution-C: 49% sodium hydroxide solution (specific gravity = 1.51)
Water was added to 1.08 kg and the total volume was kept at 6.3 (solution-
Alkalinity of C = 2.16 N). Solution-C (6.3) was placed in the reaction vessel, heated to about 35 ° C. and kept under stirring at 450 rpm. On the other hand, Solution-A (about 35 ° C .; 12.9) and Solution-B · (about 35 ° C .; 14.5) were individually injected, and both injections were completed in 70 minutes. Solution-A
When injecting Solution-B into Solution-C, the Si in the resulting mixture was consistently applied from the beginning to the end of injecting both solutions.
The O ₂ / Al ₂ O ₃ molar ratio was kept at 1.79 (Si / Al = 0.9). In this example, the Na ₂ O / Al ₂ O ₃ molar ratio was 1.99 and the Na ₂ O / SiO ₂ molar ratio was 1.11. After the mixing of the raw material liquids was completed, the slurry-containing liquid was kept at about 35 ° C. under stirring at 350 rpm for 3 hours, and then the produced amorphous aluminosilicate was filtered by centrifugation. Next, the above silicate was washed with warm water. In this case, wash with water
It was carried out until the pH reached 10.6. After the completion of washing with water, the amorphous silicate was dried at around 100 ° C., then crushed with a Brown crusher to finally obtain 7.35 kg of a fine powder of the dried amorphous aluminosilicate.

The X-ray diffraction pattern of the amorphous aluminosilicate obtained in this reference example 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. It exhibits an excellent antibacterial action against mold and bacteria even when used in a relatively small amount.

2. Compared to conventional organic antibacterial agents, the antibacterial composition of the present invention is composed of an inorganic type, so that it is structurally stable, has a very low vapor pressure (nonvolatile), and has high heat resistance. There is.

3. This composition is poorly soluble in water, and its elution into water is negligible at room temperature to high temperature, so it is highly safe.

4. The antibacterial ion, which is one of the constituents of this antibacterial composition, is stably bound to the matrix of amorphous aluminosilicate, and sterilization based on the antibacterial ion located at the active site of the porous matrix is known. It has the advantage that it is more powerful than the liquid antibacterial agents.

5. This product has excellent dispersibility and is expected to be used as an additive (filler) for various polymer materials.

6. This product is odorless, chemically stable, does not cause structural changes, and has the advantage that the antibacterial effect lasts for a long time.

7. The present antibacterial composition exhibits a preferable antibacterial action even in an aqueous phase or a solid phase.

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

[Brief description of drawings]

Figures 1-5 relate to X-ray diffractograms. FIG. 1 shows Ag-AMAS obtained in Example 1-A, and FIG. 2 shows Example 1
Ag-AMAS obtained in 1-C, FIG. 3 is Cu-AMAS obtained in Example-2-A, and FIG. 4 is Z obtained in Example-3-A.
n-AMAS, and FIG. 5 shows Zn-A obtained in Example-3-B.
It is about MAS. 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 the X-ray diffraction of the dry powder of the amorphous aluminosilicate obtained in Reference Example 1. FIGS. 8 and 9 show X-ray diffraction of amorphous aluminosilicate partially converted to calcium and potassium, respectively. The vertical axis of the X-ray diffraction diagram shows relative intensity, and the horizontal axis shows 2θ. Next, FIG. 10 is an electron micrograph of the amorphous aluminosilicate obtained in Production Example-4. The length of the white part in FIG. 10 is 1 μm.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI Technical display location A61K 33/34 8314-4C 33/38 8314-4C C08K 3/34 KAH 7242-4J C08L 101/00 // C09D 5/14 PQM 6904-4J (72) Inventor Saburo Nohara 13-10 Takaza-cho, Nishinomiya-shi, Hyogo (56) Reference JP-A-49-87588 (JP, A)

Claims (4)

[Claims] 1. A 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 1.8, and y is An antibacterial agent comprising an amorphous aluminosilicate having antibacterial and bactericidal properties of 1.3 to 15). 2. The antibacterial agent according to claim 1, which is composed of porous fine particles having a specific surface area of at least 5 m ² / g. 3. A 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 1.8, and y is 1.3 to 15) and an amorphous aluminosilicate represented by the formula (In the formula, M is a monovalent or divalent metal (excluding silver, copper, zinc, mercury, tin, lead, bismuth, cadmium, and chromium) having an ion exchange property) or an ammonium ion, and n is M An amorphous aluminosilicate represented by the formula: x is 0.6 to 1.8 and y is 1.3 to 15). 4. The antibacterial agent according to claim 3, which is composed of porous fine particles having a specific surface area of at least 5 m ² / g.