JPH0525012A - Antimicrobial composition - Google Patents

Abstract

PURPOSE:To obtain an antimicrobial composition having more improved performances by increasing a killing rate of bacteria and fungi by an antimicrobial substance by blending the antimicrobial substance comprising an aluminosilicate as a parent material with antimicrobial silica gel. CONSTITUTION:Crystalline aluminosilicate (zeolite) and/or amorphous aluminosilicate (AMAS) is blended with 0.02-25% antimicrobial metal selected from silver, copper and zinc to give antimicrobial zeolite and/or antimicrobial AMAS, which is incorporated with antimicrobial silica get having an antimicrobial layer containing the antimicrobial metal. A zeolite having a molar ratio of SiO2/Al2O3 of <=14 is preferable as the zeolite and antimicrobial AMAS shown by the formula (M is metal replaceable with ion) wherein x is 0.6-3.0 and y is 1.3-50 is preferable as the AMAS. The antimicrobial silica gel is prepared by treating active silica gel with an alkali solution and a solution of aluminosilicate, forming a non-antimicrobial layer composed of aluminosilicate on the active surface thereof and changing the non-antimicrobial layer to an antimicrobial layer by ion exchange reaction.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel antibacterial composition having an excellent antibacterial action. More specifically, the present invention further enhances the original antibacterial performance of the antibacterial agent against bacteria and fungi without impairing the conventional antibacterial zeolite or antibacterial amorphous aluminosilicate. Therefore, a novel antibacterial composition comprising the above antibacterial substance and another antibacterial substance having silica gel as a matrix is provided.

The antibacterial composition of the present invention exerts its power in fields requiring antibacterial and antifungal properties.

[0003]

2. Description of the Related Art One of the inventors of the present invention is an inorganic antibacterial agent having a highly safe crystalline crystalline aluminosilicate (zeolite) or amorphous aluminosilicate (AMAS) as a matrix. Proposed the use of substances (Japanese Patent Publication Sho 63
-54013, Japanese Patent Publication 1-32254, Japanese Patent Publication 2-
46620).

The above-mentioned inorganic antibacterial agents are highly safe, and because of their broad antibacterial spectrum, they are highly versatile.
In addition, there is an advantage that the antibacterial to bactericidal effect is maintained for a long time. However, the problem of increasing the bactericidal rate of the above-mentioned antibacterial agent against bacteria and fungi to a more preferable degree and further improving the antibacterial performance has not been solved. In particular, Asperg
With respect to the sterilization rate of fungi such as illus niger, the use of the above-mentioned known antibacterial agents did not necessarily give satisfactory results, and there was a drawback that it took a considerably long time to completely kill the above-mentioned bacteria. . Therefore, in order to kill the fungus in a short time, it was necessary to increase the amount of the antibacterial agent used. However, increasing the amount of antibacterial agent is not necessarily the best solution in order to increase the killing rate of bacteria, and it is necessary to introduce new means into the antibacterial zeolite or antibacterial AMAS to improve it. is there.

[0005]

DISCLOSURE OF INVENTION Problems to be Solved by the Invention It is possible to further enhance the performance of antibacterial agents by further increasing the killing rate of the above-mentioned antibacterial zeolite and antibacterial AMAS against bacteria and fungi, and especially against fungi. It is an object of the present invention. For this purpose, in the present invention, a novel antibacterial composition is constructed by combining an antibacterial zeolite or an antibacterial AMAS and an antibacterial gel containing silica gel whose fundamental structure is fundamentally different from each other as a matrix. By doing so, satisfactory results in terms of performance were obtained.

[0006]

DISCLOSURE OF THE INVENTION The present inventors have constructed an antibacterial composition comprising an antibacterial substance having zeolite and / or AMAS as a matrix and an antibacterial silica gel having a silica gel matrix having an antibacterial layer as the former antibacterial composition. Noh was significantly improved, and Escherichia coli, S
taphylococcus aureus, Bati
In addition to general bacteria such as illus subtilis,
It has been found that the antibacterial activity against fungi such as Aspergillus niger is surprisingly improved. The inventors have also completed the present invention by discovering that the killing rate against these bacteria is also increased by incorporating the latter into a known antibacterial substance of the former, and the killing time is significantly shortened. That is, when the contents of the known antibacterial zeolite, antibacterial AMAS and antibacterial metal in the antibacterial composition of the present invention are set to the same amount, the antibacterial activities of these antibacterial agents are compared at the same level. The present inventors have found that the antibacterial composition of the present application has a far higher killing rate (sterilization) than the above-mentioned two known antibacterial agents.

The antibacterial composition of the present invention, as described above,
It improves the antibacterial activity of known antibacterial zeolite and antibacterial AMAS, and further enhances the performance of these antibacterial agents. More specifically, general bacteria and especially fungi (molds)
The sterilization speed of is amazingly increased. In addition, it was confirmed that the present composition has a great anti-algae effect. In addition, the dispersibility of the composition is extremely good, which is an advantage that a homogeneous dispersion can be achieved when the composition is mixed with various polymer or coated with it for antibacterial purpose. Have

The present invention relates to zeolite and / or A
A novel antibacterial composition comprising an antibacterial substance having MAS as a matrix and an antibacterial silica gel having an antibacterial layer stably held on a silica gel matrix is proposed. More specifically, the present invention relates to a crystalline aluminosilicate (antibacterial zeolite) and / or an amorphous aluminosilicate (containing at least one antibacterial metal selected from silver, copper and zinc antibacterial metals). Antibacterial amorphous aluminosilicate; amorphous aluminosilicate is referred to as AMAS) and an antibacterial silica gel having an antibacterial layer in which at least one antibacterial metal selected from the above antibacterial metal group is held by ionic bonding The present invention relates to an antibacterial composition.

In the present application, at least one metal selected from the group of antibacterial metals consisting of silver, copper and zinc is used as the metal having a bactericidal action. Each of the above metals is alone (Ag ⁺ , Cu ²⁺ , Zn ²⁺ ) or composite (Ag ⁺ -C).
u ²⁺ , Ag ⁺ -Zn ²⁺ , Ag ⁺ -Zn ²⁺ ) ion-exchangeable zeolite, AMAS, and aluminosilicate, which have a necessary amount of ion-bonded silica gel having an anti-bacterial layer capable of ion-exchange. And is used for antibacterialization of the mother body.

The materials used for the preparation of the antibacterial zeolite and the antibacterial AMAS, which are constituents of the antibacterial composition of the present application, and the antibacterialization method thereof will be described. Non-antibacterial zeolite and AMAS are aluminosilicates having a three-dimensionally developed skeleton structure, the former is amorphous, which shows a diffraction peak peculiar to the type of zeolite by X-ray diffraction. It is shown. On the other hand, the latter AMA
S is amorphous (amorphous), which shows no diffraction peak. Both based on the _{Al 2 O 3 xM O · Al} 2
It is represented by a general formula of O ₃ · ySiO ₂ · ZH ₂ O.
M represents an ion-exchangeable metal, which is usually a monovalent to divalent metal, and n corresponds to the valence of M. Also x and y
Represent the coefficients of metal oxide and silica, respectively. Naho Z represents the number of water molecules. By the way, non-antibacterial zeolite or AMAS used in the material of the present invention.
Is preferably porous and has a developed specific surface area. More specifically, as the zeolite material of the present application, either natural or synthetic zeolite can be used, but in view of the ion exchange capacity for antibacterial metal ions etc., SiO ² / Al in the above general formula is used. A zeolite material having a molar ratio of ₂ O ₃ of 14 or less is preferable. For example, the site (c
_{habazite: SiO 2 / Al 2 O} 3 = 3.2~
6.0 and 6.4-7.6), clinoptilolite (SiO ₂ / Al ₂ O)
₃ = 8.5-10.5), A type zeolite (SiO ₂ /
Al ₂ O ₃ = 1.4 to 2.4), X-type zeolite (Si
O ₂ / Al ₂ O ₃ = 2 to 3), Y-type zeolite (SiO
₂ / Al ₂ O ₃ = 3 to 6) and mordenite (SiO ₂ /
Al ₂ O ₃ = 9 to 10) has a large porosity and a large specific surface area, and has a sufficient exchange capacity for holding a necessary amount of antibacterial metal by ionic bonding. When an antibacterial zeolite is prepared by partially or completely replacing the ion-exchangeable M in the above formula with an antibacterial metal ion by the ion exchange method using the exemplified zeolite,
The antibacterial metal such as silver, copper or zinc is stably retained in the zeolite matrix, which has the advantage that the antibacterial effect lasts for a long time. By using the above zeolite material, the total amount of antibacterial metal is 0.01 to 35 by the ion exchange method.
% (Anhydrous basis) It is easy to stably support the zeolite matrix. However, the present composition exhibits a sufficient antibacterial effect when the total amount of antibacterial metal in the antibacterial zeolite used as one component of the composition of the antibacterial composition of the present application is 0.02 to 25%. Next, aseptic AMA used for the preparation of antibacterial AMAS, which is a component of the antibacterial composition of the present application.
As described above, the S material is amorphous and has the same general formula as the zeolite material. AM
The AS material is preferably a porous material having a large specific surface area, and a material having a coefficient x = 0.6 to 3.0 and y = 1.3 to 50 in the above formula is the antibacterial material. It is more preferable in terms of the ion exchange capacity with respect to the metal and the rate of ion exchange with the antibacterial metal. To make this antibacterial,
In accordance with the preparation of the antibacterial zeolite described above, the ion exchange of the AMAS material and silver, copper or zinc may be carried out at room temperature or at a high temperature so that a necessary amount of the antibacterial metal is stably held in the matrix by ionic bonding. The antibacterial amorphous aluminosilicate (antibacterial AMAS) used in the present application has a general formula of 0.6 to 3.
0M 'O · Al ₂ O ₃ · 1.3-50 SiO ₂ · ZH
It is represented by ₂ O. Z is the number of water molecules, and M'represents a monovalent or divalent metal (alkali metal, ammonium, alkaline earth metal) and an antibacterial metal (silver copper and zinc). M'includes a monovalent to divalent metal and an antibacterial metal, and they may coexist. By the way, one of the constituents of the antibacterial composition of the present application is the antibacterial AM used.
The total amount of antibacterial metal in AS varies depending on the type and combination of antibacterial metals used, but in the usual case, antibacterial AM
When the total amount of antibacterial metal in AS is 0.02 to 25% (anhydrous basis) is used for the constitution of the present antibacterial composition, the antibacterial composition of the present invention exhibits a sufficient antibacterial effect. .

A method of physically adsorbing a water-soluble antibacterial metal compound onto a silica gel matrix is conceivable as a method for antibacterializing silica gel. However, in this method, the elution of the antibacterial metal is larger than that of the matrix and the purpose of the present application cannot be endured. . The aqueous solution containing silica gel has silanol groups.

[0012]

It is also possible to consider a method in which the antibacterial metal ion is exchanged with an antibacterial metal ion to make it antibacterial. However, its ion exchange capacity is also small, and therefore even if it is replaced with an antibacterial metal ion, the expected antibacterial activity cannot be obtained. For the purpose of further increasing the antibacterial performance of a known inorganic antibacterial agent, an antibacterial silica gel prepared by the following method is used as an essential component for each constituent, and an antibacterial composition is prepared by combining this with a known antibacterial agent. It is considered that it is optimal to have the configuration as in the present application.

Next, the antibacterial silica gel having an antibacterial layer having at least one antibacterial metal selected from the group of antibacterial metals selected from silver, copper and zinc, which is used as an essential component of the composition of the present application, is held by ionic bonding. First, a method for preparing an intermediate composition having an antibacterial layer in its mother body using a silica gel material will be described. By treating active silica gel with alkaline solution and aluminosilicate solution, the active surface of silica gel (pore surface)
A non-antibacterial layer made of aluminosilicate is formed, and the ion-exchangeable metal in the layer is mainly an alkali metal, the amount of which is 4 per 1 g on the anhydrous basis of the reaction product.
A reaction product (intermediate composition) is prepared which is less than millimolar. In this case, the shape of the silica gel material is not particularly limited. For example, it may be powder, particles, crushed products, or molded products such as beads and pellets, but finer ones are more preferable in view of the reaction surface in the chemical treatment. Furthermore, considering the physical properties of silica gel, a network structure is developed with innumerable pores inside, and the pore volume (PV), pore diameter (PD) and specific surface area A porous material having a large (SSA) value is preferable. Specifically, P. V. Is 0.3
It is preferably at least cm ³ / g (anhydrous basis),
Those having 0.4 cm ³ / g or more are more desirable. P. D.
Also, it is desirable that it is as large as possible, preferably 50 Å or more, and more preferably 70 Å or more. The SSA of silica gel is preferably at least 100 m ² / g, and more preferably 200 m ² / g or more (both are anhydrous standards). Next, silica gel is roughly classified into two types, A type and B type, from the chemical structure due to the difference in the connection of silica colloidal particles. Generally, P. V. The latter is larger than the former. Type A has a large hygroscopic force in low humidity, while type B has a weak hygroscopic force in low humidity, but has a characteristic of adsorbing a large amount of moisture of 50% or more at high humidity (see JIS-ZO701). As the silica gel material used in the present application, any of the above-mentioned A type and B type can be used, but the ion exchange capacity of the antibacterial layer formed in the intermediate composition is increased, that is, mainly the ion exchangeable In order to increase the amount of alkali metal present, B-type silica gel is more preferable than A-type silica gel. The alkaline solution may be NaOH, KOH, LiOH.
Alkali metal hydroxide solutions such as The treatment of silica gel involves adjusting the pH of the solution to, for example, 8.4 to 13.
It is usually carried out at room temperature or under heating while keeping the range of 5. When the pH of the aqueous phase is kept around 9 to 9.5, the amount of silica (Si) eluted into the aqueous phase due to the chemical reaction of silica gel is relatively small, and most of the reaction products such as sodium silicate are generated. The substance is stably retained on the surface of the active pores of silica gel. On the other hand, when the alkalinity of the aqueous phase increases, sodium silicate is retained on the active pore surface (solid phase) of silica gel, while S
The elution amount of i also tends to increase. In the preparation of the intermediate composition having the antibacterial layer used in the present invention, it is desirable to keep the pH in the range of 8.4 to 13.5 as described above, but it is more preferable to maintain the pH in the range of 8.7 to 13. It is more preferable to keep Examples of the aluminosilicate solution added to silica gel include NaAlO ₂ and KAlO.
₂ , an alkali metal aluminate solution such as LiAlO ₂ can be used. Further, an aluminate solution obtained by reacting an aluminum compound with an excess of strong alkali instead of the aluminate can be used in the present application.
The antibacterial layer of the intermediate composition is ion-bonded, and the amount of alkali metal that can be ion-exchanged is adjusted by controlling factors such as pH, concentration of aluminate, reaction time and reaction temperature when the silica gel material is reacted. It is carried out by. The chemical reaction as described above is carried out to form an antibacterial layer made of aluminosilicate on the active surface (pore surface) of silica gel, and the amount of ion-exchangeable mainly alkali metal in the layer is adjusted to the above-mentioned value. As described above, it is easy to prepare the intermediate composition in an amount of 4 mmol or less per gram on the anhydrous basis. Next, when the prepared intermediate composition is made to be antibacterial, the ion-exchangeable alkali metal etc. forming the antibacterial layer of the intermediate composition and silver are formed according to the preparation of the antibacterial zeolite or antibacterial AMAS described above. The ion exchange reaction of copper or zinc may be carried out at room temperature or at high temperature to stably hold the required amount of the antibacterial metal in a single or complex state on the silica gel matrix by ionic bonding. By such a method, for example, an antibacterial gel containing the total amount of antibacterial metal in an amount of 0.02 to 15% (anhydrous basis) is prepared and used in the composition of the antibacterial composition of the present invention. The composition has an excellent antibacterial effect.

Evaluation Method of Antibacterial Activity As an evaluation method of the antibacterial activity of the antibacterial composition of the present application and a known antibacterial agent (comparative example), in the present application, the minimum inhibitory concentration (MIC; unit ppm) is measured and the shake flask is used. The time-dependent change in the number of bacteria was measured by the method (SF method; test method of Textile Products Processing Council). The molded product was tested for antibacterial activity by the spray method. These test methods will be described below.

Test Method (i) Preparation of Bacterial Fluid of Bacteria Test bacterial cells cultured in an agar medium at 37 ° C. for 18 hours were suspended in a phosphate buffer (1/15 M, pH = 7.2) and then suspended for 10 minutes.
A suspension of ⁸ cells / ml was prepared, and this was appropriately diluted and used in the test.

(Ii) Preparation of Fungal Bacterial Fluid Conidia of the test bacterium, which had been cultivated in a potato dextrose agar slant medium at 25 ° C. for 7 days, were suspended in sterilized 0.05% polysorbate 80-containing physiological saline to give 10 ⁸ cells. / M
1 of the suspension was prepared, and this was diluted appropriately and used for the test.

(Iii) Method for measuring MIC by method A The substance to be tested is suspended in phosphate buffer to a concentration of 2 × 10 ⁴ ppm, and this is diluted two-fold to form a concentration gradient of 10 steps. Dispense 1 ml into a petri dish and use Mueller H
inton2 medium (bacteria) or Sabouraud
It was poured into 9 ml of Dextrose Agar medium (fungus) and solidified, and the test bacterium was streaked and judged 48 hours later.

(Iv) Method for measuring MIC by method B The substance to be tested is suspended in a phosphate buffer solution at a concentration of 2 × 10 ⁴ ppm, and this is diluted 10-fold to form a concentration gradient of 10 steps. 1 ml was dispensed into a dish, and the mixture was diluted with 9 ml of 2% sodium glutamate agar medium to be solidified, and the test bacteria were streaked and judged 48 hours later.

(V) Method for measuring the time-dependent change in the number of bacteria by the SF method A predetermined amount of sample (antibacterial material) was placed in a 200 ml Erlenmeyer flask containing a fixed amount of phosphate buffer, and then the test bacteria suspension was placed in this. The suspension was added at a predetermined cell / ml. The mixed solution in the Erlenmeyer flask was shaken at 25 ° C., and the number of bacteria was measured over time. The medium described below was used for the bacterial count, and the bacterial count was measured after 48 hours at 37 ° C. for bacteria and after 48 hours at 25 ° C. for fungi.

(Vi) Method for testing molded article by spraying method (spray method) Test object (50 × 50 × 1.5 m) washed with alcohol cotton
A certain amount of the bacterial solution was sprayed on each surface of m) and stored at 35 ° C. for a predetermined time. At the time of measurement, the temperature of the bacteria on the subject was washed out, and the number of bacteria was measured for this washout liquid.

(Vii) Used strain Escherichia coli IFO-1273
4 Staphylococcus aureus IFO
-12732 Pseudomonas aeruginosa IF
O-12689 Aspergillus niger IFO-311
25 Bacillus subtilis IFO-137
19 (viii) Medium used MIC measurement by method A, measurement of change in bacterial count over time by SF method, and test of molded body by spray method Bacterium: Mueller Hinton2 medium (BBL) Fungus: Sabouraud Dextrose Aga
r medium (BBL) MIC measurement by method B: 20% sodium glutamate agar medium antibacterial zeolite (Z symbol), antibacterial AMAS (A symbol) and antibacterial gel used for each component of the antibacterial composition of the present application (G symbol) was prepared by the method described above.
Typical MIC values (minimum inhibitory concentration; unit ppm) of these individual antibacterial agent fine powders are shown in Table 1-A . The indicated MIC value is measured by the above-mentioned two methods, Method A and Method B. Antibacterial composition Considering the type and amount of antibacterial metal, and taking into consideration the measurement error of MIC measurement value, G antibacterial gel (matrix B type silica gel) is a known Z antibacterial material (zeolite matrix is A Type zeolite; molar ratio SiO ₂ / Al ₂ O ₃ = 2.1) and antibacterial agent A (matrix is amorphous aluminosilicate; molar ratio SiO ₂ / Al ₂ O ₃ =
The MIC value is smaller than that of 3.24), and therefore it can be said that the antibacterial activity is excellent.

Next, the compositions of the G, Z and A antibacterial agent samples used in the present application are summarized in Table 1-B . The indicated Z antibacterial zeolite fine powder is a commercially available A type zeolite (molar ratio Si
O ₂ / Al ₂ O ₃ = 2.1; SSA = 598 m ² / g;
Sodium type NaZ; average particle size Dav = 3.6 μm)
Was prepared by ion exchange with an aqueous solution of an antibacterial metal-containing salt. A amorphous antibacterial aluminosilicate fine powder is AMAS
(1.03Na ₂ O ・ Al ₂ O ₃・ 3.24SiO ₂・
xH ₂ O); Dav = 1.2 μm) was ion exchanged with an aqueous solution of silver and zinc antibacterial metal-containing salts. The fine powder of G antibacterial gel is commercially available B type silica gel (true specific gravity 2.2, SSA ≈ 450 m ² / g, PD ≈ 60 Å, PV
It was prepared by chemically treating (.apprxeq.0.75 ml / g) by the method described above to synthesize an intermediate composition having an antibacterial layer and making it antibacterial.

[0024]

[0025]

Also in terms of sterilization rate, the G antibacterial agent is much larger than the Z and A antibacterial agents. In relation to this, changes over time in the number of bacteria are illustrated in Table-2 and Table-3 .

[0027]

[0028]

Table 2 shows Aspergillus nig.
er initial bacterial count 3.4 × 10 ⁵ cells / ml, temperature 25 ° C., and phosphate buffer 100 ml under the conditions of antibacterial zeolite fine powder [Z-4; NaAgZ; Ag = 3.3.
0% (anhydrous basis)] and antibacterial gel fine powder [G-5;
Ag = 3.10% (anhydrous basis); Aspergillus niger was used as the base material]
The measurement results of the change with time of the number of (fungal) bacteria are shown.
1.7 mg of antibacterial metal amount (Ag) in 100 ml of test liquid
If the Z-4 antibacterial agent is used at a fixed value of 3
After the lapse of time, the number of bacteria was 5.2 × 10 ⁴ cells / m
Although a considerable number of bacteria survived in 1, the number of surviving bacteria was 0 at the time of 5 minutes when the G-5 antibacterial agent was used, and the bacteria were completely dead. When the antibacterial metal amount (Ag) in 100 ml of the test liquid is kept at 4.3 mg, the number of remaining bacteria is 1.9 × 10 ⁴ ce after 3 hours when using the Z-4 antibacterial agent.
At 11 / ml, there are still significant fungi remaining. On the other hand, when the amount of antibacterial metal (Ag) in 100 ml of the test liquid was kept at 4.2 mg, which is almost the same as the above test, the fungus was completely killed in 5 minutes after the use of the G-5 antibacterial agent, and was 0. is there. Table-2
The sterilization rate of the latter is surprisingly higher than that of the former, as seen from the change with time of the antibacterial zeolite (Z) and the antibacterial gel (G) with respect to the fungus. Next, Table 3 shows bacteria (Stap).
hylococcus aureus) is displayed. That is, Table 3 shows that Staphylo
Initial number of coccus aureus bacteria 1.5 × 10 ⁶ c
ells / ml, temperature 25 ° C and phosphate buffer 100
antibacterial zeolite fine powder [Z-4; N
aAgZ; Ag = 3.3% (anhydrous basis)] and antibacterial gel fine powder [G-5; Ag = 3.10% (anhydrous basis);
The matrix is Staphyl using the above-mentioned B type silica gel]
The measurement results of the time-dependent change in the number of bacteria of Ococcus aureus (bacteria) are described. When the antibacterial metal amount (Ag) in 100 ml of the test liquid is kept at a constant value of 0.66 mg, the remaining bacterial count is 5.9 × 10 cells / ml when 30 minutes have passed when using the Z-4 antibacterial agent. The bacterium is completely dead after 60 minutes. On the other hand, test liquid 1
When the antibacterial metal amount (Ag) in 00 ml is maintained at 0.65 mg which is almost the same as the above, when the G-5 antibacterial agent is used,
After 10 minutes, the bacteria are completely dead. Furthermore, when the antibacterial metal amount (Ag) in 100 ml of the test liquid is maintained at a constant value of 0.17 mg, it takes 60 minutes for complete killing of the bacterium with the Z-4 antibacterial agent, but with the G-5 antibacterial agent, it takes about 60 minutes. ㆞ When using the same amount of silver, the above bacteria completely die in 20 minutes.
The results of Table-3 show that when the amount of antibacterial metal in the test solution is constant,
It is clear that the antibacterial gel (G-5) exhibits a better killing rate against bacteria than the antibacterial zeolite (Z).

Next, unlike the above-mentioned antibacterial agents, the sterilization rate of bacteria of antibacterial zeolite and antibacterial gel containing copper as an antibacterial metal will be explained. The latter shows extremely superior antibacterial activity as compared with the former, and the sterilization rate of the latter is overwhelmingly higher than that of the former. As a specific example, antibacterial zeolite fine powder [Z-5; NaCuZ; Cu = 7.0
3% (anhydrous basis)] and antibacterial gel fine powder [G-6;
Cu = 1.58% (anhydrous basis); Staphylococcus in the case of using the above-mentioned B-type silica gel as a matrix]
The time course of the number of aureus bacteria is shown in Table-4-A .

[0031]

When G-6 fine powder was used under the test conditions shown, the bacteria Staphylococcus aureu
s is completely dead after 4 hours. On the other hand Z-
When 5 fine powders were used, the reduction rate of bacteria was not small over the above time, and the number of surviving bacteria was high, 3.4 × 10 ⁶ cells / m 2.
It is l. Furthermore, with the latter antibacterial agent, even after 24 hours, the above-mentioned bacteria were not completely killed, and still 2.1.
× 10 ¹ cells / ml are alive. From the test results in Table 4, it is apparent that the antibacterial activity of the antibacterial gel containing copper as an antibacterial metal and the antibacterial activity of the antibacterial zeolite are significantly superior to the latter. It is truly surprising that such a large difference in antibacterial activity is observed between the two, and this is a remarkable matter.

The characteristics of the individual antibacterial agents used as constituents in the present invention and the antibacterial effect of the antibacterial composition of the present invention obtained by combining the agents will be described below. The antibacterial composition (D) of the present application contains a known antibacterial zeolite (Z) having the above antibacterial properties and / or a known antibacterial AMAS (A) and an antibacterial silica gel (G) as essential components. It is configured by combining required amounts. The order of antibacterial activity is D> A ≧ Z. Further, when the amounts of antibacterial metals in the antibacterial agents are compared at the same level, the bactericidal rate of the antibacterial composition (D) of the present application is extremely higher than that of Z or A. There is a feature that sterilization is performed in a shorter time (see Examples). It does not matter if the antibacterial composition (D) of the present application contains an unexpected third component in consideration of its addition to the polymer. For example D
Water, various solvents such as alcohol, various plasticizers, organic or inorganic additives, fillers, compounding agents, lubricants, activators, UV absorbers, stabilizers, antioxidants, reinforcing agents, colorants , A matting agent, a flame retardant, a modifier, a pigment and the like may be contained.

The antibacterial silica gel (G), which is a component of the antibacterial composition (D) of the present application, uses A-type or B-type silica gel as a matrix, which is the same as the known inorganic antibacterial agents Z and A. The chemical composition and the skeletal structure of the matrix are basically different. The antibacterial layer formed in the G antibacterial agent is formed on the large-diameter pore surface of the silica gel matrix, which is very stable. The antibacterial metals such as silver, copper and zinc which are ion-bonded in this antibacterial layer have a uniform distribution,
Further, the above layer exists in a state of being shielded by a large amount of silica in the matrix. The pore size retained by the Z or A antibacterial agent is smaller than that of the G antibacterial agent. For example, when the matrix of the Z antibacterial agent is A type or X type zeolite, the pore size thereof is only 4Å and 10Å, respectively. Therefore, the diffusion rate of antibacterial metal ions (hydrated state) in the pores generated based on the dissociation of the above-mentioned three kinds of bacterial agents is much higher in the pores of the agent G than in the pores of the agents Z and A. Is large. This means that the contact area between general bacteria or fungi and the antibacterial agent is larger in G. Therefore, the agent G is extremely advantageous in sterilization as compared with the agents Z and A. The matrix structure of agents Z and A is G
It is essentially different from that of the agent, and the antibacterial metal ion generated by the dissociation of the two also diffuses through the macropores and pores, but the diffusion is slow because the micropores are extremely small. As a result, there is a drawback that it takes a long time to contact the antibacterial metal ion with the fungus. As a result, antibacterial metals that do not substantially contribute to the antibacterial action due to such a phenomenon also exist in the Z or A matrix. Further, the adsorption of bacteria and fungi (molds) on the active surface of the agent G is significantly larger than that on the surface of the known agents Z and A.

The significant difference in the antibacterial-bactericidal activity of the Z, A and G antibacterial agents as described above is caused by the fundamental difference in the maternal structure. Therefore, compared with the former two kinds of antibacterial agents, the latter is effective. It exhibits a surprisingly excellent antibacterial to bactericidal effect. Therefore, in order to obtain the same antibacterial effect as the former using the latter, there is an advantage that the amount of the latter used can be smaller (see, for example, Table-2, Table-3 and Table-4). The D antibacterial composition of the present application obtained by adding the required amount of G antibacterial agent having such characteristics to Z or A antibacterial agent remarkably improves the original antibacterial performance of the known latter antibacterial agent, and the amount used is It exhibits a small and preferable bactericidal effect.

Z constituting the antibacterial composition (D) of the present application,
Both the A and G antibacterial agents are sparingly soluble in solvents such as water, alcohol, acetone and esters. Solubility (25 ° C) of these antibacterial agents in water is very low at 1 pp
It is of the order of m or less and is negligible. Therefore, when Z and / or A is mixed with G by a wet method to prepare a D antibacterial composition, the amount of metal ions present in the aqueous solution phase or the solvent phase is negligible, so that Ion exchange reactions between the individual constituents are not triggered via the liquid phase. Therefore, the composition of the D composition obtained by the wet method does not change, and the antibacterial activity of the composition is maintained unchanged, and the excellent antibacterial effect is exhibited for a long period of time. Next, when the antibacterial composition (D) of the present invention is prepared by mixing by a dry method, there is no interaction between the constituents, so that there is no problem and it has a preferable antibacterial activity and a bactericidal rate. Excellent compositions are obtained in a dry process. The true specific gravities of the constituents Z, A and G antibacterial agents are all around 2, and G is highly dispersible, so a predetermined amount is mixed by a dry method or a wet method to prepare a homogeneous D composition. It's easy to do. In the preparation of the D composition by the dry method, it is easy to obtain a homogeneous composition by pulverizing and mixing a predetermined amount of powder or granules of Z, A and G in a dried or anhydrous state with a ball mill or other mixer. Is obtained. In the preparation of the D composition by the above-mentioned wet method, water, alcohol, acetone or ester solvent is used as a medium, and a predetermined amount of each component is mixed to obtain a mixture having a constant composition. Should be removed.

The particle size of the antibacterial composition (D) of the present invention is not particularly limited, and mechanical pulverization or mixing may be carried out to adjust the particle size to a desired one according to the application. Further, depending on the use, the composition may be molded into pellets, tablets or other suitable shapes. When the antibacterial composition of the present invention is added to a polymer and mixed to make the latter antibacterial, it is desired to make the particle size of the former smaller.
In such a case, it may be finely pulverized by using a special pulverizer such as a JET pulverizer to obtain a predetermined fine powder (eg Dav = S μm, 7 μm and 10 μm).

As described above, the antibacterial composition (D) of the present invention contains a Z and / or A antibacterial agent containing at least one antibacterial metal selected from the antibacterial metal group of silver, copper and zinc. It is prepared by mixing and homogenizing a G antibacterial agent having an antibacterial layer in which at least one kind of antibacterial metal selected from the above-mentioned antibacterial metal group is held by ionic bonding, by a wet or dry method. The G content occupied in the D composition is at least 5 in order to exert preferable antibacterial to bactericidal activity.
%is necessary. The antibacterial activity of D increases as the G content increases. Therefore, the original antibacterial activity of Z and A is further improved in proportion to the amount of G increase. Next, the preferable content of the antibacterial metal in the D antibacterial composition varies depending on the kind of the antibacterial metal, but in general, the total amount of the antibacterial metal is 0.01 to
It suffices if it is present in an amount of 25%, and a sufficient antibacterial effect is exhibited in the presence of 0.02 to 20% thereof. Antibacterial composition (D) of the present invention is preferably composed by adding a G antibacterial agent containing silver corresponding to at least 5% of the silver content in the Z and / or A antibacterial agent. The one with power is obtained.

The antibacterial composition of the present invention, when added to a polymer as an antibacterial filler, exhibits more excellent antibacterial activity as compared with conventionally known inorganic or antibacterial agents.
When used as an antibacterial filler, the present antibacterial composition is preferably powder-particulate, the particle size of which, depending on the application,
It may be selected appropriately. When applied to thick molded articles such as various containers, pipes, granules or thick denier fiber systems, the antibacterial composition of the present invention has a particle size of several μm.
The number of particles may be up to several + μm or 100 μm or more. On the other hand, it is preferable that the particle diameter is smaller when molding into a fine denier fiber or filter. For example, in the case of clothing fibers, it is preferably 8 μm or less, particularly 5 μm or less. Further, when forming into a film or net, the particle size of the present composition may be quite large.

When the above-mentioned powdery to particulate antibacterial composition of the present invention is incorporated into a polymer, heating is carried out under reduced pressure or normal pressure to obtain the water content in the composition. It is necessary to remove it as needed. The degree of water removal is governed by the type and properties of the polymer of interest. The dispersibility of the antibacterial composition in the polymer is good. The dispersion is usually carried out with heating using various mixers. In this case, of course, it does not matter if the target polymer contains various third components. For example, various plasticizers, additives, fillers, compounding agents,
Even if the lubricant, the activator, the ultraviolet absorber, the stabilizer, the antioxidant, the reinforcing agent, the colorant, the gloss agent, the flame retardant, the modifier, the pigment and the like are contained, the antibacterial property is not hindered.

The polymer containing the antibacterial composition of the present invention can be prepared by injection molding, compression molding, laminating molding, extrusion molding,
It can be processed into various molding methods by an inflation molding method, a blow molding method, and other molding methods.

The polymer used in the present invention is a synthetic or semi-synthetic organic polymer and is not particularly limited. For example, thermoplastic synthetic polymers such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyamide, polyester, polyvinyl alcohol, polycarbonate, polyacetal, ABS resin, acrylic resin, fluorine resin, polyurethane elastomer, polyester elastomer, phenol resin. , Thermosetting synthetic polymers such as urea resin, melamine resin, unsaturated polyester resin, epoxy resin and urethane resin, and regenerated or semi-synthetic polymers such as rayon, cupra, acetate and triacetate. When high sterilization to antibacterial curing is required, it is more preferable that the surface area of the molded body is large. As one of the methods, it is possible to form it into a fiber shape. From this point of view, the preferred organic polymer is a fiber-forming polymer such as nylon 6, nylon 66, polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, polyethylene terephthalate, polybutylene terephthalate, polyacrylonitrile, polyethylene, polypropylene. , And synthetic polymers such as copolymers thereof, and regenerated or semi-synthetic polymers such as rayon, cupra, acetate and triacetate. Further, as a method of keeping the surface area of the molded body larger, it is conceivable to mold it into a foam. Preferred polymer materials from the viewpoint of trial production of the foam include, for example, polyethylene, polyethylene styrene, polypropylene, ethylene-vinyl acetate copolymer (EXA), polyvinyl chloride, acrylonitrile-butadiene-styrene resin (ABS), acrylic resin, phenol. Examples of the resin include nylon, polyvinyl alcohol, viscose, and rubber. Even if a plasticizer, a stabilizer, a filler, an antioxidant, a lubricant, a coloring agent, a modifier, etc. are hardened in these foaming materials, there is no problem in antibacterial activity.

The proportion of the antibacterial composition of the present invention in the polymer is governed by the type and characteristics of the polymer.
Usually, if it is contained in an amount of 0.005 to 40% by weight, a preferable antibacterial effect is exhibited. When the amount is less than the above lower limit, it is insufficient in view of sterilization-antibacterial effect and durability of effect. On the other hand, the bactericidal effect is almost unchanged even if the above upper limit is exceeded,
On the other hand, the influence on the physical properties of the polymer tends to increase depending on the amount of the antibacterial composition added. From this viewpoint, the addition of the antibacterial composition of the present invention to the polymer is 0.01 to 3
0% by weight is preferable, and when the antibacterial composition of the present invention is added to fibers, addition of 0.05 to 15% by weight usually provides sufficient antibacterial activity.

[0044]

The following is a description of embodiments of the present invention by way of examples, but these are merely examples and the present invention is not limited thereto. Antibacterial composition (D) of the present invention
Also, the measurement of the time course of the bacterial count when the antibacterial agents (Z and A) described in Comparative Examples are used is carried out by the above-mentioned evaluation method of the antibacterial activity (method of measuring the time course of the bacterial count by the SF method). Moreover, the antibacterial activity of the molded product was measured by a spray method.

Examples 1-14 Table 5 shows the specific constitution and preparation method of the antibacterial D composition of the present invention.

[0047]

Table 5 lists examples of combinations of Z or A antibacterial agents and G antibacterial agents and preparation methods for preparing D compositions. In addition, the detailed composition and mixing ratio of each antibacterial agent are shown in the table.
4-B and related examples are listed in the table. The D compositions of Examples-1,2,3,4,7,8,9,10,12,13 and 14 were prepared by the dry method. That is, a predetermined amount of powder of the dried Z and G agents was mixed in a ball mill and homogenized. The D compositions of Examples-5 and 6 were prepared wet using water. That is, in this example, about 30% is added to the powder of the Z and G agents in a predetermined amount.
Water was added and mixed by a wet method. The obtained mixture was dried at 100 ° to 110 ° C to remove water, and then made into a fine powder. Next, in preparing the D composition of Example-11, about 35% of an ethyl alcohol solvent was added to a mixture of agents A and G at a constant ratio, and wet mixing was performed. The resulting mixture was heated to remove the solvent and then pulverized.

For the purpose of evaluating the antibacterial performance of the D composition of the present invention prepared by the above-mentioned method, Escherichia coli was used as a bacterium.
ichia coli, Staphylococcus
aureus and Bacillus subtil
using is and Aspergillus as a fungus
Using a niger (black mold), the time-dependent change in the number of bacteria (mortality) was measured. In Tables 5-12 of the examples, the related comparative examples are described for the purpose of comparison with the examples. The mixing ratio of the antibacterial agents a and b in the table is% by weight (anhydrous basis). a is a Z or A antibacterial agent, and b is G
Represents an antibacterial agent. Further, in the table, the collected amount of the antibacterial composition and the amount of the antibacterial metal contained in the test liquid in relation to this are described. By carrying out the antibacterial activity test while keeping the antibacterial metal in the test liquid substantially constant, it is possible to easily compare the performances of the antibacterial agents of both Examples and Comparative Examples. In some Naho tables, reference values for bacteria (changes in the number of bacteria during a blank test over time) are described for reference.

The antibacterial compositions of the present invention shown in Examples 1 and 2 are composed of a combination of Z and G antibacterial agents containing a relatively low content of silver as an antibacterial metal.

[0051]

As shown in Table 6, when the amount of antibacterial metal (Ag) in the antibacterial composition was kept substantially constant, as the amount of G agent added to Z agent increased, Staphyloc
It can be seen that occus aureus dies in a shorter time. Comparative Example-1 is a antibacterial agent (Z) only, Example-
1 is a) 70-b) 30% and Example-2 is a) 50.
-B) 50% antibacterial composition is used. Comparative example-
1, the viable cell count of Staphylococcus aureus was 2.2 × 10 ² cells / ml at the time point of 60 minutes.
Although a considerable amount of bacteria remain, it is 1.7 × 10 ¹ cells / ml in Example-1 after 25 minutes. In addition, in Example-2, the above-mentioned bacteria are completely killed at the same time point of 25 minutes as described above. More than these tests, Staphylococcus au of the antimicrobial composition of the present invention
It is clear that the killing rate against reus is high, and that the antibacterial activity of the obtained D antibacterial composition of the present invention is remarkably improved and becomes stronger as the amount of the agent G is increased relative to the agent a. is there.

Next, the D composition of the present invention used for the tests of the antibacterial activity of Examples 3 and 4 is of the same series as the antibacterial composition used in Examples 1 and 2 above. Yes,
It is composed of Z and G agents. In Comparative Example-2, a
Antibacterial agent (Z) only, a) 80-b) 20 in Example-3
% And in Example-4 a) 50-b) 50% of the antibacterial composition was used to produce Aspergillus nig.
The chronological change in the number of er bacteria was measured.

[0054]

Under the test conditions shown in Table 7, A
The sterilization rates for spergillus niger are in the order of sample number 1-4>1-2> 1-1. That is, in the test in which the antibacterial metal (Ag) in the test liquid was kept constant at about 2 mg, as the content of the G agent in the D antibacterial composition (composed of Z and G agents) increased. , The antibacterial rate is significantly increased. For example, As at 60 minutes in Table-6
The number of viable bacteria of pergillus niger is a comparative example.
In the test of No. 2, a remarkable decrease in the number of bacteria is seen, at 9.2 × 10 ³ cells / ml and in the test of Example-3, 6.7 × 10 ² cells / ml. In Example-4, the above-mentioned fungus was completely killed at the time of the above-mentioned 60 minutes, and was 0. From this, the effect of the antibacterial composition of the present application on fungi (molds) is surprising.

The D antibacterial composition of the present invention used in Examples 5 and 6 has a constitution different from that described in the above-mentioned Examples, which is an antibacterial metal containing silver and zinc as an antibacterial metal. Agent (Z) and antibacterial agent (G).

[0057]

As shown in Table 8, the antibacterial composition of the present invention containing silver and zinc as the antibacterial metal was prepared from the general bacteria E.
It is also effective against Scherichia clli as compared with known inorganic antibacterial agents. Under the indicated test conditions, 30% of the D antibacterial composition a) 70-b) of the present invention was faster than the antibacterial agent (NaAg ZnZ) of Comparative Example-3 in a shorter time.
ichia clli is killed, and when the D antibacterial composition a) 50-b) 50% of the present invention is used, the killing rate of the above-mentioned bacterium is very high, and the bacterium completely disappears after 10 minutes. Is dying.

The antibacterial composition D of the present invention used in Examples 7 and 8 comprises a antibacterial agent (Z) containing silver and copper as antibacterial metals and a b antibacterial agent containing silver and zinc as antibacterial metals. (G).

[0060]

As can be seen in these examples, the D antibacterial composition of the present invention comprises Staphylococcus a
It exhibits a favorable antibacterial activity against Ureus (Table 9), and the bactericidal rate of the above-mentioned bacteria is that when the antibacterial metal in the antibacterial composition is kept almost constant, the antibacterial raw gel in the D composition ( It is accelerated with an increase in the addition amount of G). Comparative Example-4
Using Known Antibacterial Zeolite of Example and Example-7
Comparing the results of 8 and 8, the remarkable bactericidal effect of the antibacterial composition D of the present invention against bacteria is clear.

[0062]

In Examples 9 and 10, the D antibacterial composition was composed of a antibacterial agent (Z) and b antibacterial agent (G) containing silver as an antibacterial metal. Under the test conditions as shown in Table 10, the D antibacterial composition of the present invention exerts an excellent effect on the bacterium Bacillus subtilis, and the antibacterial metal (A
g) When the amount is almost constant, the killing rate becomes higher as the addition amount of the G agent in the D composition increases. From the comparison of Examples-9 and 10 and Comparative example-5, it is clear that the D composition of the present application exhibits an excellent bactericidal effect.

Next, the D antibacterial composition used in Example-11 is composed of a antibacterial agent (A: antibacterial AMAS) and b antibacterial agent (G) containing silver and zinc as antibacterial metals. .

[0065]

Under the test conditions as shown in Table 11,
The present antibacterial composition is Aspergillus niger
It shows a preferable bactericidal activity against. That is, the D antibacterial composition obtained by adding the antibacterial gel to the known antibacterial AMAS has a higher bactericidal rate against fungi than the former (the number of bacteria in Comparative Example 6 and Example-11). Comparison of changes over time).

In Examples 12 and 13, the antibacterial composition of the present invention composed of a antibacterial agent (Z) and b antibacterial agent (G) having a relatively high silver content (Ag≈11%) was used. hand,
The change in the number of bacteria with respect to Aspergillus niger was measured over time. As shown in Table-11,
Compared with the known antibacterial agents (Ag = 11.30%; NaAgZ), the antibacterial composition of the invention shows a surprising bactericidal activity against the abovementioned fungi. As seen in Examples-12 and 13, in the antibacterial test in which the amount of antibacterial metal (Ag) in the test liquid was kept almost constant, the bactericidal activity of the D composition was remarkably increased as the amount of the antibacterial gel added increased. It was confirmed that the fungus was completely killed in a very short time.

In Example-14, a antibacterial agent (NaAgC
The antibacterial composition of the present application comprising uZ; Z) and b antibacterial agent (antibacterial gel containing silver and zinc; G) is used to maintain a constant amount of silver in a test solution, Staphyl
The change in the number of bacteria with respect to Ococcus aureus was measured over time. Compared with the known antibacterial agent of Comparative Example-8, the antibacterial composition of Example-14 killed the bacteria in a shorter time.

[0069]

[0070]

[0071]

The sterilization rate of the inorganic antibacterial agent against bacteria is governed by the type, composition, content of antibacterial metal, conditions at the time of testing (temperature, number of bacteria, concentration of antibacterial agent) and the like. In the bacterial test described in the above-mentioned Examples, the antibacterial activity test of the antibacterial composition of the present invention was carried out by changing the type, composition, amount of antibacterial metal, number of bacteria, etc. of the inorganic antibacterial agent. In the bacterial test when the antibacterial metal content in the antibacterial composition of the present invention or the known inorganic antibacterial agent is kept substantially constant, the former shows a surprisingly excellent effect as compared with the latter, And the killing rate of fungi
It was confirmed that it would be amazingly large.

Example-15 Example-15 relates to a trial production of a low density polyethylene (LDPE) molded article having an antibacterial function and an antibacterial activity test thereof.

The antibacterial zeolite (Z-4; Ag = 3.30%) and the antibacterial gel (G-5; shown in Table 1-B).
An antibacterial composition of the present invention was prepared by homogenizing an equal mixture (Ag = 3.10%) (dry basis) by a dry method. The antibacterial composition was further refined using a JET pulverized material to obtain a fine powder having an average particle diameter Dav = 2.5 μm. The above fine powder is heat treated at 250 ° C. for 2 hours,
A trace amount of water in it was removed. Then, a predetermined amount of the above-mentioned antibacterial composition was LDPE (Asahi Kasei Co., Ltd. Suntech F-
1920), the content in the former mixture is 3%
(Anhydrous basis). The mixture is 220
After being heated to 20 to 230 ° C., melt-mixed (N ₂ -gas atmosphere) at the same temperature and homogenized, pressure-molded to 10
It was molded into a plate shape of 0 × 100 × 1.5 mm. The molded body is cut into 50 × 50 × 1.5 mm test pieces (P
E-2), and the antibacterial activity test was conducted by the spraying method using this.

According to the molding method described above, a test piece of 50 × 50 × 1.5 mm (PE-B) for blank test containing no antibacterial agent was used.
L) was prepared. Further, for comparison purposes, LDPE sample PE-1 (50 × 50 × 1.5 mm) containing 3% of fine antibacterial zeolite (Z-4; Dav = 2.9 μm) was prepared according to the above.

Table 14 shows the test results of the antibacterial activity obtained using these samples.

[0077]

Comparing the test results of the PE-1 and PE-2 specimens, the LDPE specimen containing 3% of the antibacterial composition of the present application is better against Staphylococcus aureus than the specimen containing 3% of the known antibacterial zeolite. It is clear that the antibacterial activity is better. The sterilization rate of the former specimen is much higher than that of the latter specimen.

The effects of the present invention are summarized below (1) By using the antibacterial composition of the present invention,
It has a feature that sterilization of general bacteria and fungi (mold) can be performed in a shorter time as compared with known inorganic antibacterial agents.

(2) The bactericidal rate of bacteria of the antibacterial composition of the present invention is surprisingly high as compared with known inorganic antibacterial agents.

(3) The composition of the antibacterial composition as described in the present application remarkably improves the action of known inorganic antibacterial agents against bacteria.

(4) In order to obtain the same antibacterial effect as that of known inorganic antibacterial agents, the antibacterial composition of the present invention can be used in a smaller amount and is economical.

(5) The antibacterial gel used as an essential component of the constitution of the antibacterial composition of the present invention is excellent in dispersibility, and therefore a homogeneous antibacterial composition can be prepared by a dry method or a wet method. , Easily possible.

(6) The antibacterial composition of the present invention can be used in various fields in which antibacterial / mold prevention is essential. In particular, the present composition is excellent not only in antibacterial activity but also in dispersibility, and therefore, when it is added to a polymer as an antibacterial filler, excellent effects are exhibited.

(7) The safety of the antibacterial composition of the present invention is great. Almost no toxicity of this is observed.

(8) The antibacterial composition is expected to be used not only in the fields of antibacterial and antifungal, but also in the field of antialgae.

(9) The antibacterial composition not only exerts an effect in the fields of antibacterial and antifungal, but also possesses a deodorizing effect based on the characteristics of the matrix constituting the composition. Therefore, the composition is expected to be used in a wide range of fields requiring antibacterial to antifungal and deodorant.

(10) When the antibacterial composition is added to other organic or inorganic antibacterial agents (antibacterial apatite, antibacterial glass, etc.), it is expected that the latter antibacterial performance is further enhanced.

The embodiment of the present invention is as follows.

1. Amorphous aluminosilicate (antibacterial zeolite) and / or amorphous aluminosilicate (antibacterial amorphous) containing at least one antibacterial metal selected from silver, copper and zinc antibacterial metals Aluminosilicate)
And an antibacterial composition containing an antibacterial silica gel having an antibacterial layer containing at least one antibacterial metal selected from the above-mentioned antibacterial metal group.

2. The matrix of the antibacterial zeolite is A,
2. The antibacterial composition according to 1 above, which comprises at least one zeolite selected from the group consisting of X, Y, mordenite, chabazite and clinoptilolite.

3. The antibacterial amorphous aluminosilicate has the general formula xM'O. Al ₂ O ₃ . ySiO ₂ . ZH ₂ O [where n is the valence of the metal M ′ and the coefficient x = 0.6 to
3.0 and y = 1.3 to 50. Z is the number of water molecules. The antibacterial composition according to the above 1, wherein M'is represented by a monovalent or divalent metal (alkali metal, ammonium, alkaline earth metal) and antibacterial metal (silver, copper and zinc).

4. 2. The antibacterial composition according to the above 1, wherein the matrix of the antibacterial silica gel is B-type silica gel.

5. The total amount of antibacterial metal in the antibacterial composition comprising the antibacterial zeolite and / or the antibacterial amorphous aluminosilicate and the antibacterial silica gel is at least 0.02.
% Or more, the antibacterial composition according to 1 above.

6. The antibacterial composition according to the above 1, which is obtained by adding an antibacterial silica gel containing silver corresponding to at least 5% of the silver content in the antibacterial zeolite and / or the antibacterial amorphous aluminosilicate. .

7. An antibacterial polymer composition comprising the above antibacterial composition 1.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] September 9, 1991

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be amended] Detailed explanation of the invention

[Correction method] Change

[Correction content]

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel antibacterial composition having an excellent antibacterial action. More specifically, the present invention is intended to further enhance the original antibacterial performance of the antibacterial agent against bacteria and fungi without impairing the physical properties and characteristics of known antibacterial zeolite or antibacterial amorphous aluminosilicate. Further, there is provided a novel antibacterial composition comprising the above antibacterial substance containing another antibacterial substance having silica gel as a matrix.

The antibacterial composition of the present invention exerts its power in fields requiring antibacterial and antifungal properties.

[0003]

2. Description of the Related Art One of the inventors of the present invention is a crystalline aluminosilicate (zeolite) or an amorphous aluminosilicate (hereinafter referred to as "AMA", which is highly safe and has a wide antibacterial spectrum width.
It has been proposed to use an inorganic antibacterial substance based on "S" (Japanese Patent Publication No. 63-54013, Japanese Patent Publication No. 1-322).
54, Japanese Examined Patent Publication No. 2-46620).

The above-mentioned inorganic antibacterial agents are highly safe, and because of their broad antibacterial spectrum, they are highly versatile.
In addition, there is an advantage that the antibacterial to bactericidal effect is maintained for a long time. However, the problem of increasing the bactericidal rate of the above-mentioned antibacterial agent against bacteria and fungi to a more preferable degree and further improving the antibacterial performance has not been solved. In particular, Aspergi
With respect to the sterilization rate of fungi such as illus niger, the use of the above-mentioned known antibacterial agents did not necessarily give satisfactory results, and there was a drawback that it took a considerably long time to completely kill the above-mentioned bacteria. . Therefore, in order to kill the fungus in a short time, it was necessary to increase the amount of the antibacterial agent used. However, increasing the amount of antibacterial agent is not necessarily the best solution in order to increase the killing rate of bacteria, and it is necessary to introduce new means into the antibacterial zeolite or antibacterial AMAS to improve it. is there.

[0005]

DISCLOSURE OF INVENTION Problems to be Solved by the Invention It is possible to further enhance the performance of antibacterial agents by further increasing the killing rate of the above-mentioned antibacterial zeolite and antibacterial AMAS against bacteria and fungi, and especially against fungi. It is an object of the present invention. For this purpose, in the present invention, a novel antibacterial composition is constructed by combining an antibacterial zeolite or an antibacterial AMAS and an antibacterial gel containing silica gel whose fundamental structure is fundamentally different from each other as a matrix. By doing so, satisfactory results in terms of performance were obtained.

[0006]

DISCLOSURE OF THE INVENTION The present inventors have constructed an antibacterial composition comprising an antibacterial substance having zeolite and / or AMAS as a matrix and an antibacterial silica gel having a silica gel matrix having an antibacterial layer as the former antibacterial composition. Noh was significantly improved, and Escherichia coli, S
taphylococcus aureus, Bati
In addition to general bacteria such as illus subtilis,
It has been found that the antibacterial activity against fungi such as Aspergillus niger is surprisingly improved. The inventors have also completed the present invention by discovering that the killing rate against these bacteria is also increased by incorporating the latter into a known antibacterial substance of the former, and the killing time is significantly shortened. That is, when the contents of the known antibacterial zeolite, antibacterial AMAS and antibacterial metal in the antibacterial composition of the present invention are set to the same amount, the antibacterial activities of these antibacterial agents are compared at the same level. The present inventors have found that the antibacterial composition of the present application has a far higher killing rate (sterilization) than the above-mentioned two known antibacterial agents.

The antibacterial composition of the present invention, as described above,
It improves the antibacterial activity of known antibacterial zeolite and antibacterial AMAS, and further enhances the performance of these antibacterial agents. More specifically, general bacteria and especially fungi (molds)
The sterilization speed of is amazingly increased. In addition, it was confirmed that the present composition has a great anti-algae effect. In addition, the dispersibility of the composition is extremely good, which is an advantage that a homogeneous dispersion can be achieved when the composition is mixed with various polymer or coated with it for antibacterial purpose. Have

The present invention relates to zeolite and / or A
A novel antibacterial composition comprising an antibacterial substance having MAS as a matrix and an antibacterial silica gel having an antibacterial layer stably held on a silica gel matrix is proposed. More specifically, the present invention relates to a crystalline aluminosilicate (antibacterial zeolite) and / or an amorphous aluminosilicate (containing at least one antibacterial metal selected from silver, copper and zinc antibacterial metals). Antibacterial amorphous aluminosilicate; amorphous aluminosilicate is referred to as AMAS) and an antibacterial silica gel having an antibacterial layer in which at least one antibacterial metal selected from the above antibacterial metal group is held by ionic bonding The present invention relates to an antibacterial composition.

In the present application, at least one metal selected from the group of antibacterial metals consisting of silver, copper and zinc is used as the metal having a bactericidal action. Each of the above metals is alone (Ag ⁺ , Cu ²⁺ , Zn ²⁺ ) or composite (Ag ⁺ -C).
u ²⁺ , Ag ⁺ -Zn ²⁺ , Ag ⁺ -Zn ²⁺ ) ion-exchangeable zeolite, AMAS, and a silica gel having an ion-exchangeable antibacterial layer composed of aluminosilicate. , Used for antibacterialization of the mother body.

The materials used for the preparation of the antibacterial zeolite and the antibacterial AMAS, which are constituents of the antibacterial composition of the present application, and the antibacterialization method thereof will be described. Antibacterial zeolite and AMAS are aluminosilicates having a three-dimensionally developed skeleton structure, the former is crystalline, and this shows a diffraction peak peculiar to the type of zeolite by X-ray diffraction. It is a thing. On the other hand, the latter AMA
S is amorphous (amorphous), which shows no diffraction peak. Both based on the _{Al 2 O 3 xM 2 / n} O · Al 2
It is represented by a general formula of O ₃ · ySiO ₂ · ZH ₂ O. M represents an ion-exchangeable metal, which is usually a monovalent to divalent metal, and n corresponds to the valence of M. Further, x and y represent the coefficients of metal oxide and silica, respectively. Incidentally, Z represents the number of molecules of water, by the way, non-antibacterial zeolite or AM used as the material of the present invention.
AS is preferably porous and has a developed specific surface area. More specifically, as the zeolite material of the present application, either a natural or synthetic zeolite can be used,
From the viewpoint of ion exchange capacity for antibacterial metal ions and the like, a zeolite material having a SiO ₂ / Al ₂ O ₃ molar ratio in the above general formula of 14 or less is preferable.

For example, a chabazite
e: SiO ₂ / Al ₂ O ₃ = 3.2 to 6.0 and 6.
4-7.6), clinoptilolite (clinopti)
_{lolite: SiO 2 / Al 2 O} 3 = 8.5~10.
5), A-type zeolite (SiO ₂ / Al ₂ O ₃ = 1.4
To 2.4), X-type zeolite _{(SiO 2 / Al 2 O 3} =
2 to 3), Y-type zeolite _{(SiO 2 / Al 2 O 3} = 3
6) and mordenite _{(SiO 2 / Al 2 O 3} = 9~1
0) is porous and has a large specific surface area, and has a sufficient exchange capacity for holding a necessary amount of antibacterial metal by ionic bonding. Using the exemplified zeolite,
When the antibacterial zeolite is prepared by partially or completely substituting the ion-exchangeable M in the above formula with the antibacterial metal ion by the ion exchange method, the antibacterial metal of silver, copper or zinc is stably retained in the zeolite matrix. Therefore, there is an advantage that the antibacterial effect lasts for a long time. By using the above zeolite material, it is easy to stably support the total amount of the antibacterial metal on the zeolite matrix of 0.01 to 35% (anhydrous basis) by the ion exchange method. However, the total amount of antibacterial metal in the antibacterial zeolite used as one component of the composition of the antibacterial composition of the present application is 0.02 to 25%.
The present composition exerts a sufficient antibacterial effect in the presence of.

Next, an antibacterial AMAS used for the preparation of an antibacterial AMAS, which is a component of the antibacterial composition of the present application.
The material is amorphous as described above, and it has the same general formula as the zeolite material. AMAS
It is preferable that the material is porous and has a large specific surface area, and that the coefficient x = 0.6 to 3.0 in the above formula and y = 1.3 to 50 is the material of the antibacterial metal. It is more preferable in terms of the ion exchange capacity and the rate of ion exchange with the antibacterial metal. If this is to be antibacterial, according to the preparation of the antibacterial zeolite described above, ion exchange of the AMAS material with silver, copper or zinc is carried out at room temperature or high temperature to stably ion bond the required amount of antibacterial metal to the base material. It can be held by.

The antibacterial amorphous aluminosilicate (antibacterial AMAS) used in the present invention has a general formula of 0.6 to 3.0 M '.
_{2 / n} O · Al ₂ O ₃ · 1.3 to 50 SiO ₂ · ZH ₂ O
It is represented by. Z is the number of water molecules, M'represents monovalent or divalent metals (alkali metals, ammonium, alkaline earth metals) and antibacterial metals (silver, copper and zinc). M'includes a monovalent to divalent metal and an antibacterial metal, and they may coexist. By the way, one of the constituents of the antibacterial composition of the present application is the antibacterial AMA used.
The total amount of antibacterial metal in S depends on the type of antibacterial metal used,
If the total amount of antibacterial metal in the antibacterial AMAS is usually 0.02 to 25% (anhydrous basis), the antibacterial properties of the present invention can be varied depending on the combination. The composition exerts a sufficient antibacterial effect.

A method of physically adsorbing a water-soluble antibacterial metal compound onto a silica gel matrix is conceivable as a method for antibacterializing silica gel, but this method causes a large elution of the antibacterial metal from the matrix and cannot withstand the purpose of use of the present application. . The aqueous solution containing silica gel has silanol groups.

[0015]

Since it has, the method of ion-exchange it with antibacterial metal ions to make it antibacterial is also conceivable. However, its ion exchange capacity is also small, and therefore even if it is replaced with an antibacterial metal ion, the expected antibacterial capacity cannot be obtained. For the purpose of further increasing the antibacterial performance of a known inorganic antibacterial agent, an antibacterial silica gel prepared by the following method is used as an essential component for each constituent, and an antibacterial composition is prepared by combining this with a known antibacterial agent. It is considered that it is optimal to have the configuration as in the present application.

Next, the antibacterial silica gel having an antibacterial layer which holds at least one antibacterial metal selected from the group of antibacterial metals of silver, copper and zinc, which is used as an essential component of the composition of the present application, by an ionic bond will be described. First, a method for preparing an intermediate composition having a non-antibacterial layer in its mother body using a silica gel material will be described. By treating active silica gel with an alkali solution and an aluminosilicate solution, an antibacterial layer of aluminosilicate is formed on the active surface (pore surface) of silica gel, and the ion-exchangeable metal in the layer is formed. Is mainly an alkali metal, and the amount of the reaction product (intermediate composition) is 4 mol / g or less based on the anhydrous basis of the reaction product (intermediate composition). In this case, the shape of the silica gel material is not particularly limited. For example, it may be powder, particles, crushed products, or molded products such as beads and pellets, but finer ones are more preferable in view of the reaction surface in the chemical treatment.

Further, taking into consideration the physical properties of silica gel, a network structure is developed with numerous pores inside, and pore volume (PV) and pore diameter (PD). A porous material having a large specific surface area (SSA) and a large specific surface area (SSA) is preferable. Specifically, P. V. Is 0.3c
It is preferably at least m ³ / g (anhydrous basis), and
Those having a density of 4 cm ³ / g or more are more desirable. P. D. As for, it is desirable that it is as large as possible, preferably 5
It is 0 Å or more, more preferably 70 Å or more. The SSA of the silica gel at least 100m is desirable that the ² / g, that of 200 meters ² / g or more (both anhydrous basis)
Are more preferred.

Next, silica gel is roughly classified into two types, A type and B type, from the chemical structure, depending on the difference in the series of colloidal particles of silica. Generally, P. V. The latter is larger than the former. Type A has a large hygroscopic power at low humidity, while type B has a weak hygroscopic power at low humidity but 50 at high humidity.
%, It has the property of adsorbing a large amount of moisture (JIS-Z
O701). As the silica gel material used in the present application, any of the above-mentioned A type and B type can be used, but the ion exchange capacity of the antibacterial layer formed in the intermediate composition, that is, mainly the alkali metal which is ion exchangeable B-type silica gel is more preferable than A-type silica gel in order to increase the amount of a.

As the above-mentioned alkaline solution, NaOH, K
An alkali metal hydroxide solution such as OH or LiOH is used. The treatment of silica gel is usually carried out at room temperature or under heating while keeping the pH of the solution in the range of 8.4 to 13.5. When the pH of the aqueous phase is kept around 9 to 9.5, the amount of silica (Si) eluted into the aqueous phase due to the chemical reaction of silica gel is relatively small, and most of the reaction products such as sodium silicate are generated. The substance is stably retained on the surface of the active pores of silica gel. On the other hand, when the alkalinity of the aqueous solution phase increases, sodium silicate is retained on the active pore surface (solid phase) of silica gel, but on the other hand, the amount of Si eluted into the aqueous solution phase tends to increase.

In the preparation of the intermediate composition having an antibacterial layer used in the present invention, the pH is adjusted to 8.4 to pH as described above.
It is desirable to keep it in the range of 13.5, but it is more preferable to keep it in the range of 8.7 to 13. Also,
As the aluminosilicate solution added to silica gel,
For example, an alkali metal aluminate solution such as NaAlO ₂ , KAlO ₂ , or LiAlO ₂ can be used. Further, an aluminate solution obtained by reacting an aluminum compound with an excess of strong alkali instead of the aluminate can be used in the present application. The amount of ion-exchangeable alkali metal ion-bonded to the antibacterial layer of the intermediate composition should be adjusted by controlling factors such as pH, concentration of aluminate, reaction time and reaction temperature when the silica gel material is reacted. Adjusted by. The chemical reaction as described above is carried out to form an antibacterial layer made of aluminosilicate on the active surface (pore surface) of silica gel, and the amount of ion-exchangeable mainly alkali metal in the layer is adjusted to the above-mentioned value. As described above, it is easy to prepare the intermediate composition in an amount of 4 mmol or less per gram on the anhydrous basis.

Next, when the prepared intermediate composition is made to be antibacterial, the above-mentioned antibacterial zeolite or antibacterial AMAS is used.
In accordance with the preparation of the intermediate composition, the ion-exchange reaction of alkali-exchangeable alkali metal etc. forming the antibacterial layer of the intermediate composition with silver, copper or zinc is carried out at room temperature or high temperature to obtain the required amount of antibacterial metal alone. Alternatively, the silica gel matrix may be stably held by ionic bonding in a composite state. By such a method, for example, an antibacterial gel containing the total amount of antibacterial metal in an amount of 0.02 to 15% (anhydrous basis) is prepared and used in the composition of the antibacterial composition of the present invention. The composition has an excellent antibacterial effect.

The characteristics of the individual antibacterial agents used as constituents in the present invention and the antibacterial effect of the antibacterial composition of the present invention obtained by combining the antibacterial agents will be described below. The antibacterial composition (D) of the present application contains a known antibacterial zeolite (Z) having the above antibacterial properties and / or a known antibacterial AMAS (A) and an antibacterial silica gel (G) as essential components. It is configured by combining required amounts. The order of antibacterial activity is D> A ≧ Z. Further, when the amounts of antibacterial metals in the antibacterial agents are compared at the same level, the bactericidal rate of the antibacterial composition (D) of the present application is extremely higher than that of Z or A. There is a feature that sterilization is performed in a shorter time. The antibacterial composition (D) of the present application may contain a third component in advance in consideration of its addition to the polymer. For example, in D, various solvents such as water and alcohol, various plasticizers, organic or inorganic additives, fillers, compounding agents, lubricants, activators, ultraviolet absorbers, stabilizers, antioxidants, reinforcing agents, Colorants, matting agents, flame retardants, modifiers, pigments and the like may be contained.

The antibacterial silica gel (G), which is a component of the antibacterial composition (D) of the present application, uses A-type or B-type silica gel as a matrix, which is the same as the known inorganic antibacterial agents Z and A. The chemical composition and the skeletal structure of the matrix are basically different. The antibacterial layer formed in the G antibacterial agent is formed on the large-diameter pore surface of the silica gel matrix, which is very stable. The antibacterial metals such as silver, copper and zinc which are ion-bonded in this antibacterial layer have a uniform distribution,
Further, the above layer exists in a state of being shielded by a large amount of silica in the matrix. As compared with the G antibacterial agent, the pore sizes of the Z and A antibacterial agents are smaller. For example, when the matrix of the Z antibacterial agent is A type or X type zeolite, the pore size thereof is only 4Å and 10Å, respectively. Therefore, the diffusion rate in the pores of antibacterial metal ions (hydrated state) generated based on the dissociation of the above three kinds of antibacterial agents is much higher in the pores of the agent G than in the pores of the agents Z and A. Is. This means that the contact area between general bacteria or fungi and the antibacterial agent is larger in G. Therefore, the agent G is extremely advantageous in sterilization as compared with the agents Z and A. The matrix structure of agents Z and A is G
It is essentially different from that of the agent, and the antibacterial metal ion generated by the dissociation of the two also diffuses through the macropores and pores, but the diffusion is slow because the micropores are extremely small. As a result, there is a drawback that it takes a long time to contact the antibacterial metal ion with the fungus. As a result, antibacterial metals that do not substantially contribute to the antibacterial action due to such a phenomenon also exist in the Z or A matrix. Further, the adsorption of bacteria and fungi (molds) on the active surface of the agent G is significantly larger than that on the surface of the known agents Z and A.

The significant difference in the antibacterial-bactericidal activity of the Z, A and G antibacterial agents as described above is caused by a fundamental difference in the structure of the mother body. Therefore, compared with the former two antibacterial agents, the latter is effective. It exhibits a surprisingly excellent antibacterial to bactericidal effect. Therefore, in order to obtain the same antibacterial effect as the former using the latter, there is an advantage that the amount of the latter used can be smaller (see, for example, Table-2, Table-3 and Table-4). The D antibacterial composition of the present application obtained by adding the required amount of G antibacterial agent having such characteristics to Z or A antibacterial agent remarkably improves the original antibacterial performance of the known latter antibacterial agent, and the amount used is It exhibits a small and preferable bactericidal effect.

Z constituting the antibacterial composition (D) of the present application,
Both the A and G antibacterial agents are sparingly soluble in solvents such as water, alcohol, acetone and esters. Solubility (25 ° C) of these antibacterial agents in water is very low at 1 pp
It is of the order of m or less and is negligible. Therefore, when Z and / or A is mixed with G by a wet method to prepare a D antibacterial composition, the amount of metal ions present in the aqueous solution phase or the solvent phase is negligible, so that Ion exchange reactions between the individual constituents are not triggered via the liquid phase. Therefore, the composition of the D composition obtained by the wet method does not change, and the antibacterial activity of the composition is maintained unchanged, and the excellent antibacterial effect is exhibited for a long period of time. Next, when the antibacterial composition (D) of the present invention is prepared by mixing by a dry method, there is no interaction between the constituents, so that there is no problem and it has a preferable antibacterial activity and a bactericidal rate. Excellent compositions are obtained in a dry process. The true specific gravities of the constituents Z, A and G antibacterial agents are all around 2, and G is highly dispersible, so a predetermined amount is mixed by a dry method or a wet method to prepare a homogeneous D composition. It's easy to do. In preparing the D composition by the dry method, a homogeneous composition can be easily obtained by pulverizing and mixing a predetermined amount of powder or granules of Z, A and G in a dry or anhydrous state with a ball mill or other mixer. Is obtained. In the preparation of the D composition by the above-mentioned wet method, water, alcohol, acetone or ester solvent is used as a medium, and a predetermined amount of each component is mixed to obtain a mixture having a constant composition. Should be removed.

The particle size of the antibacterial composition (D) of the present invention is not particularly limited and may be adjusted to a desired particle size by mechanical pulverization or mixing depending on the application. Further, depending on the use, the composition may be molded into pellets, tablets or other suitable shapes. When the antibacterial composition of the present invention is added to a polymer and mixed to make the latter antibacterial, it is desired to make the particle size of the former smaller.
In such a case, it may be finely pulverized using a special pulverizer such as a JET pulverizer to obtain a predetermined fine powder (eg Dav = 5 μm, 7 μm and 10 μm).

As described above, the antibacterial composition (D) of the present invention contains a Z and / or A antibacterial agent containing at least one antibacterial metal selected from the antibacterial metal group of silver, copper and zinc. It is prepared by mixing and homogenizing a G antibacterial agent having an antibacterial layer in which at least one kind of antibacterial metal selected from the above-mentioned antibacterial metal group is held by ionic bonding, by a wet or dry method. The G content occupied in the D composition is at least 5 in order to exert preferable antibacterial to bactericidal activity.
%is necessary. The antibacterial activity of D increases as the G content increases. Therefore, the original antibacterial activity of Z and A is further improved in proportion to the amount of G increase. Next, the preferable content of the antibacterial metal in the D antibacterial composition varies depending on the kind of the antibacterial metal, but in general, the total amount of the antibacterial metal is 0.01 to
It suffices if it is present in an amount of 25%, and a sufficient antibacterial effect is exhibited in the presence of 0.02 to 20% thereof. Antibacterial composition (D) of the present invention is preferably composed by adding a G antibacterial agent containing silver corresponding to at least 5% of the silver content in the Z and / or A antibacterial agent. The one with power is obtained.

The antibacterial composition of the present invention, when added to a polymer as an antibacterial filler, exhibits more excellent antibacterial activity as compared with conventionally known inorganic antibacterial agents. When used as an antibacterial filler, the present antibacterial composition is preferably in the form of powder to particles, and the particle size thereof may be appropriately selected according to the application. When applied to a thick molded product such as various containers, pipes, granules or thick denier fiber system, the particle size of the antibacterial composition of the present invention is from several μm to
It may be several + μm or 100 μm or more. On the other hand, in the case of molding into fine denier fibers or filters, the particle size is preferably smaller. For example, in the case of clothing fibers, it is preferably 8 μm or less, particularly 5 μm or less. Further, when forming into a film or net, the particle size of the present composition may be quite large.

When the above-mentioned powdery to particulate antibacterial composition of the present invention is incorporated into a polymer, heating is performed under reduced pressure or normal pressure to obtain the water content in the composition. It is necessary to remove it as needed. The degree of water removal is governed by the type and properties of the polymer of interest. The dispersibility of the antibacterial composition in the polymer is good. The dispersion is usually carried out with heating using various mixers. In this case, of course, it does not matter if the target polymer contains various third components. For example, various plasticizers, additives, fillers, compounding agents,
Even if the lubricant, the activator, the ultraviolet absorber, the stabilizer, the antioxidant, the reinforcing agent, the colorant, the gloss agent, the flame retardant, the modifier, the pigment and the like are contained, the antibacterial property is not hindered.

The polymer containing the antibacterial composition of the present invention is prepared by injection molding, compression molding, laminating molding, extrusion molding,
It can be processed into various molding methods by an inflation molding method, a blow molding method, and other molding methods.

The polymer used in the present invention is a synthetic or semi-synthetic organic polymer and is not particularly limited. For example, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyamide, polyester, polyvinyl alcohol, polycarbonate, polyacetal, ABS resin, acrylic resin, fluororesin, polyurethane elastomer, thermoplastic synthetic polymer such as polyester elastomer, phenol resin , Thermosetting synthetic polymers such as urea resin, melamine resin, unsaturated polyester resin, epoxy resin and urethane resin, and regenerated or semi-synthetic polymers such as rayon, cupra, acetate and triacetate. When a high sterilization to antibacterial effect is required, it is more preferable that the surface area of the molded product is large. As one of the methods, it is possible to form it into a fiber shape. From this point of view, the preferred organic polymer is a fiber-forming polymer such as nylon 6, nylon 66, polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, polyethylene terephthalate, polybutylene terephthalate, polyacrylonitrile, polyethylene, polypropylene. , And synthetic polymers such as copolymers thereof, and regenerated or semi-synthetic polymers such as rayon, cupra, acetate and triacetate. Further, as a method of keeping the surface area of the molded body larger, it is conceivable to mold it into a foam. Preferred polymer materials from the viewpoint of such foam trial production include, for example, polyethylene, polystyrene, polypropylene, ethylene-vinyl acetate copolymer (EVA), polyvinyl chloride, acrylonitrile-butadiene-styrene resin (ABS), acrylic resin, phenol. Examples of the resin include nylon, polyvinyl alcohol, viscose, and rubber. Even if a plasticizer, a stabilizer, a filler, an antioxidant, a lubricant, a colorant, a modifier and the like are mixed in these foaming materials, there is no problem in antibacterial activity.

The proportion of the antibacterial composition of the present invention in the polymer depends on the type and characteristics of the polymer,
Usually, if it is contained in an amount of 0.005 to 40% by weight, a preferable antibacterial effect is exhibited. When the amount is less than the above lower limit, it is insufficient in view of sterilization-antibacterial effect and durability of effect. On the other hand, the bactericidal effect is almost unchanged even if the above upper limit is exceeded,
On the other hand, the influence on the physical properties of the polymer tends to increase depending on the amount of the antibacterial composition added. From this viewpoint, the addition of the antibacterial composition of the present invention to the polymer is 0.01 to 3
0% by weight is preferable, and when the antibacterial composition of the present invention is added to fibers, addition of 0.05 to 15% by weight usually provides sufficient antibacterial activity.

The following is a description of embodiments of the present invention by way of examples, but these are merely examples, and the present invention is not limited thereto. Antibacterial composition (D) of the present invention
Also, the measurement of the time course of the number of bacteria when using the antibacterial agents (Z and A) described in Comparative Examples is carried out by the evaluation method of the antibacterial activity described below (the method of measuring the time course of the number of bacteria by the SF method). Moreover, the antibacterial activity of the molded product was measured by a spray method.

Evaluation Method of Antibacterial Activity As an evaluation method of the antibacterial activity of the antibacterial composition of the present application and known antibacterial agents shown as comparative examples, in the present application, the minimum inhibitory concentration (MIC; unit ppm) is measured and shaken. The time-dependent change in the number of bacteria was measured by the flask method (SF method; test method of Textile Products Processing Council). The molded product was tested for antibacterial activity by the spray method. These test methods will be described below.

Test Method (i) Preparation of Bacterial Bacterial Solution Test bacterial cells cultured in an agar medium at 37 ° C. for 18 hours were suspended in a phosphate buffer (1/15 M, pH = 7.2) for 10 minutes.
A suspension of ⁸ cells / ml was prepared, and this was appropriately diluted and used for the test.

(Ii) Preparation of Fungal Bacterial Fluid Conidia of the test bacterium, which had been cultivated in a potato dextrose agar slant medium at 25 ° C. for 7 days, were suspended in sterile 0.05% polysorbate 80-added physiological saline to give 10 ⁸ cells. / M
1 of the suspension was prepared, and this was diluted appropriately and used for the test.

(Iii) Method for measuring MIC by Method A The substance to be tested was suspended in phosphate buffer at a concentration of 2 × 10 ⁴ ppm, and this was 2-fold diluted to form a 10-step concentration gradient. Dispense 1 ml into a petri dish and use Mueller H
inton2 medium (bacteria) or Sabouraud
It was poured into 9 ml of Dextrose Agar medium (fungus) and solidified, and the test bacterium was streaked and judged 48 hours later.

(Iv) Method for measuring MIC by method B The substance to be tested was suspended in phosphate buffer at a concentration of 2 × 10 ⁴ ppm, and this was diluted 10-fold to form a 10-step concentration gradient. 1 ml was dispensed into a dish, and the mixture was diluted with 9 ml of 2% sodium glutamate agar medium to be solidified, and the test bacteria were streaked and judged 48 hours later.

(V) Method for measuring changes in the number of bacteria over time by SF method A predetermined amount of sample (antibacterial material) was placed in a 200 ml Erlenmeyer flask containing a fixed amount of phosphate buffer, and then the suspension of test bacteria was placed in this. The suspension was added at a predetermined cell / ml. The mixed solution in the Erlenmeyer flask was shaken at 25 ° C., and the number of bacteria was measured over time. The medium described below was used for the bacterial count, and the bacterial count was measured after 48 hours at 37 ° C. for bacteria and after 48 hours at 25 ° C. for fungi.

(Vi) Method for testing molded article by spraying method (spray method) Test object (50 × 50 × 1.5 m) washed with alcohol cotton
A certain amount of the bacterial solution was sprayed on each surface of m) and stored at 35 ° C. for a predetermined time. At the time of measurement, the bacterial solution on the subject was washed out, and the number of bacteria was measured for this washed solution.

(Vii) Used strain Escherichia coli IFO-1273
4 Staphylococcus aureus IFO
-12732 Pseudomonas aeruginosa IF
O-12689 Aspergillus niger IFO-311
25 Bacillus subtilis IFO-137
19 (viii) Medium used MIC measurement by method A, measurement of change in bacterial number over time by SF method and test of molded body by spray method: Bacteria: Mueller Hinton 2 medium (BBL) Fungus: Sabouraud Dextrose Aga
r medium (BBL) MIC measurement by method B: 2.0% sodium glutamate agar medium antibacterial zeolite (Z symbol), antibacterial AMAS (A symbol) and antibacterial agent used for each component of the antibacterial composition of the present application The sex gel (G symbol) was prepared by the method described above.
Typical MIC (minimum inhibitory concentration; unit: ppm) values of these individual antibacterial agent fine powders are shown in Table 1-B. The indicated MIC value is measured by the above-mentioned two methods, Method A and Method B. Antibacterial composition Considering the kind and amount of antibacterial metal, and taking into account the measurement error of MIC measurement value, G antibacterial agent (matrix B type silica gel) is a known Z antibacterial agent (zeolite matrix is A type). Zeolite; Molar ratio SiO
₂ / Al ₂ O ₃ = 2.1) and A antibacterial agent (base is amorphous aluminosilicate; molar ratio SiO ₂ / Al ₂ O ₃ = 3.2)
It can be said that the MIC value is smaller than that of 4) and therefore the antibacterial activity is superior.

Next, the compositions of the G, Z and A antibacterial agent samples used in the examples of the present application are summarized in Table 1-A. The indicated Z antibacterial agent fine powder is a commercially available A type zeolite (molar ratio SiO
₂ / Al ₂ O ₃ = 2.1; SSA = 598 m ² / g; sodium NaZ; average particle size Dav = 3.6 μm) was prepared by ion exchange with an aqueous solution of antibacterial metal-containing salts. A antibacterial agent fine powder is AMAS (1.03Na ₂ O ・ A
l ₂ O ₃ .3.24 SiO ₂ .xH ₂ O; Dav = 1.
2 μm) was ion-exchanged with an aqueous solution of silver and zinc antibacterial metal-containing salts. G antibacterial agent fine powder is commercially available B
Type silica gel (true specific gravity 2.2, SSA ≈ 450 m ² /
g, PD≈60Å, PV≈0.75 ml / g) was chemically treated by the above-mentioned method to synthesize an intermediate composition having an antibacterial layer and prepared by antibacterialization.

[0044]

[0045]

Reference Example First, Tables 2 and 3 show the results of comparing the antibacterial effects when the Z, A and G antibacterial agents were used alone.

Table 2 shows Aspergillus ni.
Ger's initial bacterial count of 3.4 × 10 ⁵ cells / ml, temperature of 25 ° C. and phosphate buffer of 100 ml under the conditions of antibacterial zeolite fine powder [Z-4; NaAgZ; Ag = 3.
30% (anhydrous basis)] and antibacterial gel fine powder [G-
5; Ag = 3.10% (anhydrous basis); Aspergillus nig using the above-mentioned B-type silica gel as a matrix]
The measurement result of the time-dependent change of the bacterial count of er (fungus) is shown. The amount of antibacterial metal (Ag) in 100 ml of the test liquid was 1.7.
When kept at a constant value of mg, when the Z-4 antibacterial agent was used, the number of bacteria was 5.2 × 10 ⁴ cells after 3 hours.
Although a considerable amount of bacteria survived at s / ml, when the G-5 antibacterial agent was used, the number of surviving bacteria was 0 at 5 minutes, and the bacteria were completely dead. When the antibacterial metal amount (Ag) in 100 ml of the test liquid was kept at 4.3 mg, the number of remaining bacteria was 1.9 × 10 ⁴ after 3 hours when using the Z-4 antibacterial agent.
At cells / ml, there are still significant fungi remaining.
On the other hand, when the amount of antibacterial metal (Ag) in 100 ml of the test liquid was kept at 4.2 mg, which is almost the same as the above test, the fungus was completely killed in 5 minutes after the use of the G-5 antibacterial agent, and was 0. is there.
From the time-dependent changes of the antibacterial zeolite (Z) and the antibacterial gel (G) with respect to fungi in Table 2, it can be seen that the latter has a higher bactericidal rate than the former.

[0048]

Next, Table 3 shows the bacteria (Stapyloc).
Occurrence of occus aureus) is displayed. That is, Table 3 shows that Staphylococcu
Initial number of Saureus 1.5 × 10 ⁶ cells /
ml, a temperature of 25 ° C., and a phosphate buffer of 100 ml, under the conditions of antibacterial zeolite fine powder [Z-4; NaAgZ;
Staphylococc using Ag = 3.3% (anhydrous basis)] and antibacterial gel fine powder [G-5; Ag = 3.10% (anhydrous basis); the matrix is B-type silica gel described above].
The measurement results of the time-dependent change in the number of bacteria of us aureus (bacteria) are described. When the antibacterial metal amount (Ag) in 100 ml of the test liquid is kept at a constant value of 0.66 mg, Z-
When 4 antibacterial agents were used, the number of remaining bacteria was 5.9 × 10 cells / ml at the time of 30 minutes, and the bacteria were completely dead after 60 minutes.

On the other hand, if the amount of antibacterial metal (Ag) in 100 ml of the test liquid is kept at 0.65 mg, which is almost the same as the above, when the G-5 antibacterial agent is used, the bacteria are completely removed in 10 minutes. Is dying. Furthermore, when the antibacterial metal amount (Ag) in 100 ml of the test liquid is kept at a constant value of 0.17 mg, Z-
4 antibacterial agents require 60 minutes to completely kill the bacteria, but G-5
As for the antibacterial agent, when approximately the same amount of silver is used,
It is completely dead over the course of minutes. The results of Table 3 show that, when the amount of antibacterial metal in the test solution is constant, the antibacterial gel (G-5) exhibits a superior sterilization rate against bacteria than the antibacterial zeolite (Z). Is shown.

[0051]

Next, different from the above-mentioned antibacterial agent, the sterilization rate of antibacterial zeolite and antibacterial gel containing copper as an antibacterial metal against bacteria will be described. The latter shows extremely superior antibacterial activity as compared with the former, and the sterilization rate of the latter is overwhelmingly higher than that of the former. As a specific example, antibacterial zeolite fine powder [Z-5; NaCuZ; Cu = 7.0
3% (anhydrous basis)] and antibacterial gel fine powder [G-6;
Cu = 1.58% (anhydrous basis); Staphylococcus in the case of using the above-mentioned B-type silica gel as a matrix]
Table 4 shows the changes over time in the number of aureus bacteria.

[0053]

When G-6 fine powder was used under the test conditions shown, the bacteria Staphylococcus aureu
s is completely dead after 4 hours. On the other hand Z-
When 5 fine powders were used, the reduction rate of bacteria was small and the number of surviving bacteria was high over the above-mentioned time, and 3.4 × 10 ⁶ cells / m 2 was used.
It is l. Furthermore, with the latter antibacterial agent, even after 24 hours, the above-mentioned bacteria were not completely killed, and still 2.1.
× 10 cells / ml are alive. From the test results in Table 4, it is apparent that the antibacterial activity of the antibacterial gel containing copper as an antibacterial metal and the antibacterial activity of the antibacterial zeolite are significantly superior to the latter. It is truly surprising that such a large difference in antibacterial activity is observed between the two, and this is a remarkable matter.

Next, examples of the antibacterial composition according to the present invention will be shown.

Table 5 collectively shows the specific constitution and preparation method of the antibacterial composition of the present invention used in Examples 1-14.

[0057]

Table 5 lists examples of combinations of Z or A antibacterial agents and G antibacterial agents and preparation methods for preparing the composition (D symbol) according to the present invention. The detailed composition and mixing ratio of each antibacterial agent are also described in Table 5 and the table of the related examples. Examples-1,2,3,4,7,8,
The D compositions of 9, 10, 12, 13 and 14 were prepared by the dry method. That is, a predetermined amount of powder of the dried Z and G agents was mixed in a ball mill and homogenized. The D compositions of Examples-5 and 6 were prepared wet using water. That is, in this example, about 30% of water was added to a predetermined amount of powder of the Z and G agents, and mixing by a wet method was performed. The resulting mixture is 100 ° -110 ° C
After being dried in water to remove water, a fine powder was obtained. Next, in preparing the D composition of Example-11, A
And about 35% of ethyl alcohol solvent was added to a constant ratio mixture of agent G and wet mixing was performed. The resulting mixture was heated to remove the solvent and then pulverized.

For the purpose of evaluating the antibacterial performance of the D composition of the present invention prepared by the above-mentioned method, Escherichia coli was used as a bacterium.
ichia coli, Staphylococcus
aureus and Bacillus subtil
using is and Aspergillus as a fungus
Using a niger (black mold), the time-dependent change in the number of bacteria (mortality) was measured. The results of the comparative examples are also shown in Tables 6 to 13 of the examples. The mixing ratio of the antibacterial agents a and b in the table is% by weight (anhydrous basis).
a represents a Z or A antibacterial agent, and b represents a G antibacterial agent. Further, in the table, the collected amount of the antibacterial composition and the amount of the antibacterial metal contained in the test liquid in relation to this are described. By carrying out the antibacterial activity test while keeping the antibacterial metal in the test liquid substantially constant, it is possible to easily compare the performances of the antibacterial agents of both Examples and Comparative Examples. In some Naho tables, reference values for bacteria (changes in the number of bacteria during a blank test over time) are described for reference.

Examples 1-2 The antibacterial compositions of the present invention shown in Examples-1 and 2 contain Z and G containing a relatively low content of silver as an antibacterial metal.
It is composed of a combination of antibacterial agents.

[0061]

As shown in Table 6, when the amount of antibacterial metal (Ag) in the antibacterial composition was kept substantially constant, as the amount of G agent added to Z agent increased, Staphyloc
It can be seen that occus aureus dies in a shorter time. Comparative Example-1 is a antibacterial agent (Z) only, Example-
1 is a) 70-b) 30% and Example-2 is a) 50.
-B) 50% antibacterial composition is used. Comparative example-
1, the viable cell count of Staphylococcus aureus was 2.2 × 10 ² cells / ml at the time point of 60 minutes.
And a considerable amount of bacteria remain, but in Example-1, it is 1.7 × 10 5 cells / ml after 25 minutes. In addition, in Example-2, the above-mentioned bacteria are completely killed at the same time point of 25 minutes as described above. From these tests, the Staphylococcus aur of the antibacterial composition of the present invention
The death rate for eus is high, and G
D of the present invention obtained as the amount of the agent added is increased.
It is clear that the antibacterial activity of the antibacterial composition is surprisingly improved and becomes stronger.

Examples 3-4 Next, the D compositions of the present invention used in the tests of the antibacterial activity of Examples 3 and 4 were the same as the antibacterial compositions used in Examples 1 and 2 above. It belongs to the same system and is composed of Z and G agents. In Comparative Example-2, a antibacterial agent (Z)
Only, the antimicrobial composition of a) 80-b) 20% in Example-3 and a) 50-b) 50% in Example-4 was used to measure the time course of the number of Aspergillus niger. It was implemented.

[0064]

Under the test conditions shown in Table 7, A
The sterilization rates for spergillus niger are in the order of sample number 1-4>1-2> 1-1. That is, in the test in which the antibacterial metal (Ag) in the test liquid was kept constant at about 2 mg, as the content of the G agent in the D antibacterial composition (composed of Z and G agents) increased. , The antibacterial rate is significantly increased. For example, As at 60 minutes in Table-7
The number of viable bacteria of pergillus niger is a comparative example.
In the test of No. 2, a remarkable decrease in the number of bacteria is seen, at 9.2 × 10 ³ cells / ml and in the test of Example-3, 6.7 × 10 ² cells / ml. In Example-4, the above-mentioned fungus was completely killed at 0 in the above-mentioned 60 minutes. From this, the effect of the antibacterial composition of the present application on fungi (molds) is surprising.

Examples 5-6 The D antibacterial composition of the present invention used in Examples 5 and 6 has a composition different from that described in the above-mentioned Examples, which is silver as an antibacterial metal. And a containing zinc
It is composed of an antibacterial agent (Z) and an antibacterial agent (G).

As shown in Table 8, the antibacterial composition of the present invention containing silver and zinc as the antibacterial metal is a general bacterium, E
It is also effective against Scherichia coli as compared with known inorganic antibacterial agents. Under the indicated test conditions, 30% of the D antibacterial composition a) 70-b) of the present invention was faster than the antibacterial agent (NaAg ZnZ) of Comparative Example-3 in a shorter time.
Killing ichia coli. Furthermore, the antibacterial composition D) a) 50-b) 50% of the present invention has a very high killing rate of the above-mentioned bacteria, and the bacteria are completely dead after 10 minutes.

[0068]

[0069] The silver and zinc as Example 7-2 8 D antimicrobial composition of the present invention used in Examples -7 and 8 a antibacterial agent containing silver and copper as an antibacterial metal (Z) and antibacterial metal Contains b
It is composed of an antibacterial agent (G).

As shown in Table 9, the D antibacterial composition of the present invention comprises Staphylococcus aureus.
The antibacterial activity of the antibacterial gel is excellent, and the bactericidal rate of the above-mentioned bacteria is such that when the antibacterial metal in the antibacterial composition is kept almost constant, the amount of antibacterial gel (G) added in the D composition Accelerated with the increase of. When the test using the known antibacterial zeolite of Comparative Example-4 and the results of Examples-7 and 8 are compared, the remarkable antibacterial effect of the antibacterial composition D of the present invention against bacteria is clear.

[0071]

[0072] At a Example 9-1 10 Example 9 and 10, D antimicrobial composition is composed of a antibacterial agent containing silver as an antimicrobial metal (Z) and b antimicrobials (G) . Under the test conditions as shown in Table 10, the D antibacterial composition of the present invention was treated with the bacteria Bac.
It exhibits an excellent effect against illus subtilis, and when the amount of antibacterial metal (Ag) in the D composition is almost constant, the killing rate becomes higher as the addition amount of the G agent in the D composition increases. It is getting bigger. Examples-9 and 1
From the comparison between 0 and Comparative Example-5, it is clear that the D composition of the present application exhibits an excellent bactericidal effect.

[0073]

Example 11 Next, the D antibacterial composition used in Example-11 is composed of a antibacterial agent (A) and b antibacterial agent (G) containing silver and zinc as antibacterial metals.

Under the test conditions as shown in Table 11,
The present antibacterial composition is Aspergillus niger
It shows a preferable bactericidal activity against. That is, the D antibacterial composition obtained by adding the antibacterial gel to the known antibacterial AMAS has a higher bactericidal rate against fungi than the former (the number of bacteria in Comparative Example 6 and Example-11). Comparison of changes over time).

[0076]

Examples 12 to 13 In Examples 12 and 13, the antibacterial properties of the present invention composed of an antibacterial agent (Z) and an antibacterial agent (G) having a relatively high silver content (Ag≈11%) The composition is utilized in an Asper
The change in the number of bacteria with respect to gills niger was measured. As shown in Table-12, the antibacterial composition of the present invention shows a surprising bactericidal activity against the above fungi as compared with known antibacterial agents (Ag = 11.30%; NaAgZ). . From the results of Examples-12 and 13,
In the antibacterial test in which the amount of antibacterial metal (Ag) in the test liquid was kept almost constant, the bactericidal power of the D composition increased remarkably as the amount of the antibacterial gel added increased, and the fungus was completely killed in an extremely short time. It was confirmed to do.

[0078]

Example 14 In Example-14, the antibacterial composition of the present invention composed of an antibacterial agent (NaAgCuZ; Z) and an antibacterial agent (antibacterial gel containing silver and zinc; G) is used. Then, the amount of silver in the test solution is kept constant, and Staphylococcu
The change with time of the number of bacteria for S. aureus was measured. As shown in Table 13, the antibacterial composition of Example-14 kills the bacteria in a shorter time as compared with the known antibacterial agent of Comparative Example-8.

[0080]

The sterilization rate of the inorganic antibacterial agent against bacteria is governed by the type, composition, content of antibacterial metal, conditions at the time of testing (temperature, number of bacteria, concentration of antibacterial agent) and the like. In the bacterial test described in the above-mentioned Examples, the antibacterial activity test of the antibacterial composition of the present invention was carried out by changing the type, composition, amount of antibacterial metal, number of bacteria, etc. of the inorganic antibacterial agent. In the bacterial test when the antibacterial metal content in the antibacterial composition of the present invention or the known inorganic antibacterial agent is kept substantially constant, the former shows a surprisingly excellent effect as compared with the latter, And the killing rate of fungi
It was confirmed that it would be amazingly large.

Example-15 Example-15 relates to a trial production of a low density polyethylene (LDPE) molded product having an antibacterial function and an antibacterial activity test thereof.

The antibacterial zeolite (Z-4; Ag = 3.30%) and the antibacterial gel (G-5; shown in Table 1-A).
An antibacterial composition of the present invention was prepared by homogenizing an equal mixture (Ag = 3.10%) (dry basis) by a dry method. The antibacterial composition was further refined using a JET pulverized material to obtain a fine powder having an average particle diameter Dav = 2.5 μm. The above fine powder is heat treated at 250 ° C. for 2 hours,
A trace amount of water in it was removed. Then, a predetermined amount of the above-mentioned antibacterial composition was LDPE (Asahi Kasei Co., Ltd. Suntech F-
1920), the content in the former mixture is 3%
(Anhydrous basis). The mixture is 220
After being heated to 20 to 230 ° C., melt-mixed (N ₂ -gas atmosphere) at the same temperature and homogenized, pressure-molded to 10
It was molded into a plate shape of 0 × 100 × 1.5 mm. The molded body is cut into 50 × 50 × 1.5 mm test pieces (P
E-2), and the antibacterial activity test was conducted by the spraying method using this.

According to the above-mentioned molding method, a 50 × 50 × 1.5 mm blank test piece (PE-B) containing no antibacterial agent was used.
L) was prepared. Further, for comparison purposes, LDPE sample PE-1 (50 × 50 × 1.5 mm) containing 3% of fine antibacterial zeolite (Z-4; Dav = 2.9 μm) was prepared according to the above.

Table 14 shows the test results of antibacterial activity obtained using these samples.

[0086]

Comparing the test results of the PE-1 and PE-2 specimens, the LDPE specimen containing 3% of the antibacterial composition of the present application is better against Staphylococcus aureus than the specimen containing 3% of the known antibacterial zeolite. It is clear that the antibacterial activity is better. The sterilization rate of the former specimen is much higher than that of the latter specimen.

Finally, the effects obtained by the composition according to the present invention are summarized below.

(1) The use of the antibacterial composition of the present invention is characterized in that it is possible to sterilize general bacteria and fungi (mold) in a shorter time than known inorganic antibacterial agents.

(2) The bactericidal rate of bacteria of the antibacterial composition of the present application is surprisingly high as compared with known inorganic antibacterial agents.

(3) By taking the composition of the antibacterial composition as in the present application, the action of known inorganic antibacterial agents against bacteria is remarkably improved.

(4) In order to obtain the same antibacterial effect as that of known inorganic antibacterial agents, the antibacterial composition of the present invention can be used in a smaller amount and is economical.

(5) The antibacterial gel used as an essential component of the composition of the antibacterial composition of the present invention is excellent in dispersibility, and therefore a homogeneous antibacterial composition can be prepared by a dry method or a wet method. Can be easy.

(6) The antibacterial composition of the present invention can be used in various fields in which antibacterial / mold prevention is essential. In particular, the present composition is excellent not only in antibacterial activity but also in dispersibility, and therefore, when it is added to a polymer as an antibacterial filler, excellent effects are exhibited.

(7) The antibacterial composition of the present invention is very safe. Almost no toxicity of this is observed.

(8) The antibacterial composition is expected to be used not only in the fields of antibacterial and antifungal, but also in the field of antialgal agents.

(9) The antibacterial composition not only exerts an effect in the fields of antibacterial and antifungal, but also possesses a deodorizing effect based on the characteristics of the matrix constituting the composition. Therefore, the composition is expected to be used in a wide range of fields requiring antibacterial to antifungal and deodorant.

(10) When the antibacterial composition is added to other organic or inorganic antibacterial agents (antibacterial apatite, antibacterial glass, etc.), it is expected that the latter antibacterial performance will be further enhanced.

The embodiment of the present invention is as follows.

1. Crystalline aluminosilicate (antibacterial zeolite) and / or amorphous aluminosilicate (antibacterial amorphous alumino) containing at least one antibacterial metal selected from silver, copper and zinc antibacterial metals. Silicate)
And an antibacterial composition containing an antibacterial silica gel having an antibacterial layer containing at least one antibacterial metal selected from the above-mentioned antibacterial metal group.

2. The matrix of the antibacterial zeolite is A,
2. The antibacterial composition according to 1 above, which comprises at least one zeolite selected from the group consisting of X, Y, mordenite, chabazite and clinoptilolite.

3. The antibacterial amorphous aluminosilicate general formula _{xM '2 / n O · Al} 2 O 3 · ySiO 2 · ZH 2 O
[In the formula, n is the valence of the metal M ′, and the coefficient x = 0.
6 to 3.0 and y = 1.3 to 50. Z is the number of water molecules. M'is a monovalent or divalent metal (alkali metal,
Ammonium, alkaline earth metal) and antibacterial metal (silver, copper and zinc)].

4. 2. The antibacterial composition according to the above 1, wherein the matrix of the antibacterial silica gel is B-type silica gel.

5. The total amount of antibacterial metal in the antibacterial composition comprising the antibacterial zeolite and / or the antibacterial amorphous aluminosilicate and the antibacterial silica gel is at least 0.02.
% Or more, the antibacterial composition according to 1 above.

6. The antibacterial composition according to the above 1, which is obtained by adding an antibacterial silica gel containing silver corresponding to at least 5% of the silver content in the antibacterial zeolite and / or the antibacterial amorphous aluminosilicate. .

7. An antibacterial polymer composition comprising the above antibacterial composition 1.

Claims (2)

[Claims] 1. A crystalline aluminosilicate (antibacterial zeolite) and / or amorphous aluminosilicate (antibacterial) containing at least one antibacterial metal selected from the group of antibacterial metals of silver, copper and zinc. Antibacterial silica gel having an antibacterial silica gel containing an antibacterial amorphous aluminosilicate) and an antibacterial layer containing at least one antibacterial metal selected from the above antibacterial metal group. 2. An antibacterial polymer composition containing the antibacterial composition of claim 1.