WO2000038524A1

WO2000038524A1 - Aluminosilicate antibacterial agents

Info

Publication number: WO2000038524A1
Application number: PCT/JP1999/007244
Authority: WO
Inventors: Mikio Sakaguchi; Takanori Kodera
Original assignee: Kao Corporation
Priority date: 1998-12-25
Filing date: 1999-12-24
Publication date: 2000-07-06
Also published as: JP3292726B2; TW592638B

Abstract

Aluminosilicate antibacterial agents having excellent antibacterial and packing properties. These antibacterial agents consist of aluminosilicate particles which have a composition aM2O.bAl2O3.cSiO2.dRmAn.yH2O (wherein M represents Na and/or K:R represents one or more members selected from the group consisting of Na, K, Ca and Mg; A represents one or more members selected from the group consisting of CO3, SO4, NO3, OH and Cl; a is from 1 to 6; b is from 2 to 8; c is from 2 to 12; d is from 0 to 4 (excluding 0); m is from 1 to 2; n is from 1 to 3; and y is from 0 to 32); are in the form of needles, plates or columns, and carry thereon one or more metals selected from the group consisting of Ag, Cu, Fe, Zn, Ca, Mg and Ce.

Description

Description Aluminosilicate antimicrobial agent Technical field

TECHNICAL FIELD The present invention relates to an antibacterial agent comprising aluminosilicate particles having a novel particle form carrying a metal (sometimes referred to as an aluminosilicate antibacterial agent). Conventional technology

Zeolite particles carrying an antibacterial metal are inexpensive and highly stable, so they are widely applied to polymers and fibers as antibacterial agents.For example, the antibacterial agent disclosed in Japanese Patent Publication No. 63-260810 A zeolite composition is disclosed. However, zeolite particles exhibit a smooth, dice-like angular shape with a smooth surface due to the cubic habit of the crystal system, and are therefore kneaded into polymers and fibers, and coated on these surfaces together with a binder. In this case, there is a drawback that the binding to the polymer or the fiber is not sufficient, and the strength of the polymer or the fiber may be deteriorated. Another drawback is that the surface area of the zeolite particles alone or exposed on the surface of polymers, fibers, etc. is small, so that the antibacterial effect is insufficient. Here, the exposed surface area is not a specific surface area due to gas adsorption or the like, but is a surface that is preferably in contact with bacteria, in other words, a geometric surface area. Disclosure of the invention

An object of the present invention is to provide an aluminosilicate antibacterial agent having excellent antibacterial properties and filling properties.

That is, the gist of the present invention is:

_{(1) a M 2 0 ·} b A 1 2 0 3 · c S i 0 2 - d R mA n · y H 2 0 Wherein, M is Na and Z or K, R is Na, K, selection barrel (1) or more from the group consisting of C a and Mg, A is from the group consisting of _{C0 3, S O4, NO3,} OH and C 1 One or more selected, a is 1 to 6, b is 2 to 8, c is 2 to 12, d is 0 to 4 (excluding 0), m is 1 to 2, n is 1 to 3, y indicates 0 to 32)

Aluminosilicate particles having a composition represented by the following formula and having any one of a needle shape, a plate shape, and a columnar shape include at least one selected from the group consisting of Ag, Cu, Fe, Zn, Ca, Mg, and Ce. Antibacterial agent consisting of aluminosilicate particles carrying metal

(2) a! _{_{M 2 0 · a 2 H 2}} 0 · b A 1 2 〇 _{_{3 · c S i 0 2 -}} dRmAn - y H 2 〇

Wherein, M is Na and Z or K, R is Na, K, selection barrel (1) or more from the group consisting of C a and Mg, A is CO _3, S0 _4, NOs, from the group consisting of OH and C 1 One or more selected, a! Is 0 to 1 (except 1), a and + a ₂ are 1 to 6, b is 2 to 8, c is 2 to 12, d is 0 to 4, m is 1 to 2, and n is 1 -3 and y indicate 0-32. Here, a ₂ H ₂₀ indicates structural water present in the crystal, and yH ₂₀ indicates crystal water. ]

Aluminosilicate particles having a composition represented by the following formula and having any one of a needle shape, a plate shape, and a columnar shape include at least one selected from the group consisting of Ag, Cu, Fe, Zn, Ca, Mg, and Ce. An antimicrobial agent comprising aluminosilicate particles carrying a metal, and

_{(3) aM 2 0 · b} A 12 0 3 · c S i 0 2 - d RmAn - y H 2 〇

Wherein, M is Na and Roh or K, R is Na, K, selection barrel (1) or more from the group consisting of C a and Mg, A than C0 _3, S0 _4, NOs, the group consisting of OH and C 1 One or more selected, a is 1 to 6, b is 2 to 8, c is 2 to 12, d is 0 to 4 (excluding 0), m is 1 to 2, n is 1 to 3, y indicates 0 to 32)

Aluminum having a composition represented by the formula: needle-like, plate-like, or columnar Nosilicide particles are protonated, and then antibacterial consisting of metal-supported aluminosilicate particles that carry one or more metals selected from the group consisting of Ag, Cu, Fe, Zn, Ca, Mg and Ce. A method of producing an agent, wherein the antibacterial agent has a crystallinity of 1% or more and less than 100% as compared with the aluminosilicate particles before the protonation treatment, from metal-supported aluminosilicate particles. A method for producing an antibacterial agent. BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a view showing the crystal morphology of the raw material aluminosilicate particles obtained in Example 7.

FIG. 2 shows an X-ray diffraction pattern 5 of the raw material aluminosilicate particles obtained in Example 7.

FIG. 3 is a view showing a crystal form of the antibacterial agent particles obtained in Example 9.

FIG. 4 is an X-ray diffraction pattern of the antibacterial agent particles obtained in Example 9. BEST MODE FOR CARRYING OUT THE INVENTION

Aluminosilicate gate particles used as a raw material in the present invention have the formula _{(1): aM 2 0 ·} b A 12 0 3 · c S i 0 2 - d RmAn ■ y H 2 0

Wherein, M is Na and / or K, R is Na, K, C a and selection barrel (1) or more from the group consisting of Mg, A is C_〇 _{_3,} S0 _4, N0 _3, from 〇_H and C 1 One or more selected from the group consisting of: a is 1 to 6, b is 2 to 8, c is 2 to 12, d is 0 to 4 (excluding 0), m is 1 to 2, and n is 1 ~ 3, y indicates 0 ~ 32)

And has a needle-like, plate-like or columnar form. The antibacterial agent of the present invention has one major feature in using aluminosilicate particles having the above composition and having the above form. By using such aluminosilicate particles, it has excellent antibacterial properties and also has good filling properties for polymers, fibers The effect that an excellent antibacterial agent can be obtained is exhibited.

In the composition of the aluminosilicate particles, M is preferably Na. Incidentally, when M is Na and K, aM ₂ 〇 is, ai 'Naz O' az ' Ks OC However, a + a _2' represented by = a). Also, R is preferably N a, A is preferably C_〇 ₃ or N_〇 _3.

The aluminosilicate particles used in the present invention have a needle-like, plate-like, or columnar shape. Here, the needle-like form refers to a form having a thickness of 50 O nm or less and an aspect ratio of 2.0 or more to the thickness, and the plate-like form refers to a thickness. Is 300 nm or less, and the plate diameter is 2.0 or more in terms of the aspect ratio with respect to the thickness. The columnar shape means that the thickness is 50 nm or more and the length is long. It means that the aspect ratio with respect to the thickness is 1.0 or more and less than 2.0.

Such aluminosilicate particles can be obtained as an aggregate of needle-like crystals, plate-like crystals or columnar crystals depending on the production conditions. The aluminosilicate particles are preferably those in which the above-mentioned crystals are aggregated to form a spherical, tetrapod-like, or massive aggregate, and these secondary aggregates may be used.

When the aluminosilicate particles are a spherical aggregate, those having a main X-ray diffraction peak at d = 0.365 ± 0.015 nm are preferable from the viewpoint of maintaining the spherical particle shape. Here, the “main X-ray diffraction peak” refers to the strongest peak or a peak showing a diffraction intensity of 20% or more of the strongest diffraction peak intensity.

Also, as the aluminosilicate particles, JCPDS (Joint Commiteon Powder Diffraction Standards) No. 20-379, 20-743, 25-776, 25-149, 2 5-1 5 0 0, 3 0-1 1 70, 3 1-1 272, 34-1 76, 3 5-4 79, 35-6 53, 3 8-5 1 3, 3 8-5 1 Those having at least one type of force-clinite-like X-ray diffraction pattern selected from the group consisting of 4, 38—5 15 and 45-1373 are preferred. In particular, the X-ray diffraction pattern JCPDS No. 38—5 13 is shown, and it is preferable that the approximate composition is a = 3, b = 3, c = 6, d = 2, R = Na, m = 1, n = 1 to 3.

The average particle size of the aluminosilicate particles used in the present invention is preferably from 0.1 to 500 m, more preferably from 1 to 100 m.

By the way, when the specified aluminosilicate particles are used as a raw material of an antibacterial agent and the antibacterial agent is kneaded into a plastic, it may react with an antioxidant and change color. Therefore, from the viewpoint of preventing such discoloration, equation (2):

_{_{a 1 M 2 0 · a 2}} H 2 0 · b A 1 2 0 3 - c S i 0 2 - d RmAn · y H 2 0 wherein, M is Na and or K, R is Na, K, C one or more of the Bareru selected from the group consisting of a and Mg, bees (0 _3, 30 _4, 1 ^ 0 _3, one or more Bareru selected from the group consisting of 〇_H and C 1, a, from 0 to 1 (where , 1), a, + a ₂ is 1 to 6, b is 2 to 8, c is 2 to 12, d is 0 to 4, m is 1 to 2, n is 1 to 3, y is 0 To 32.]

It is preferable to use an aluminosilicate particle (hereinafter, sometimes referred to as an aluminosilicate particle (A)) having a composition represented by the following formula and having any one of a needle shape, a plate shape, and a column shape as an antibacterial agent. . Here, a ₂ H ₂ ◦ denotes structural water present in the crystals of the aluminosilicate particles (A), and such water component is a so-called immobile water which is not released by heating. is there. On the other hand, yH ₂₀ indicates crystallization water present in the crystals of the aluminosilicate particles (A), and such water components are released by heating at 600 at 1 hour.

The aluminosilicate particles (A) represented by the formula (2) are the aluminosilicate particles represented by the formula (1) [The aluminosilicate particles represented by the formula (1) are referred to as raw material aluminosilicate particles. May be obtained by performing a protonation treatment described below. In the aluminosilicate particles used as raw materials, d is a value other than 0. In the aluminosilicate particles (A), d may be 0. The antimicrobial agent in which a metal is supported on such aluminosilicate particles (A) is a raw material before protonation treatment. Its crystallinity is lower than that of aluminosilicate particles. This decrease in crystallinity is due to the fact that in the composition of the raw material aluminosilicate particles, M decreases with protonation and is replaced by H. After the protonation treatment, the raw material aluminosilicate particles A M ₂₀ in the composition of (a) is represented as a, M ₂₀ · a ₂ H ₂において in the composition of the aluminosilicate particles (A). From the viewpoint of preventing discoloration of the plastic described above, specifically, the crystallinity of the antibacterial agent is 1% or more and less than 100% as compared with the raw material aluminosilicate particles before the protonation treatment, preferably. Is 1 to 50%, more preferably 1 to 20%. If the crystallinity of the aluminosilicate particles is lower than 1%, it becomes difficult to carry the amount of metal necessary for the expression of antibacterial properties. Therefore, the crystallinity is preferably 1% or more. Here, the crystallinity can be determined by X-ray diffraction, and refers to the ratio of the highest diffraction intensity of the antimicrobial agent at the same peak to the highest diffraction intensity of the aluminosilicate particles as a raw material.

The crystallinity of the antibacterial agent can be adjusted to a desired range by the degree of the protonation treatment.

As a method for producing the raw material aluminosilicate Ichito particles used in the present invention include, but are not limited especially, for example, an alumina raw material and silica raw material C_〇 ₃ ² -, S_〇 ₄ ² -, N 0 ₃ -, C The reaction may be carried out in an alkaline solution in the presence of 1-or the like. Examples of the alumina raw material include aluminum oxide, aluminum hydroxide, and sodium aluminate. Examples of the silica raw material include gay sand, silica stone, water glass, and sodium gayate. Alternatively, as a raw material for both the alumina raw material and the silica raw material, for example, clay minerals such as kaolin, montmorillonite, bentonite, myriki, talc, and aluminosilicate minerals such as mullite may be used. Good.

C_〇 ₃ ² - The raw materials, carbon dioxide, sodium carbonate, potassium carbonate, sodium potassium, calcium carbonate, magnesium carbonate and the like, S_〇 ₄ ² - Examples of the raw material for NO ₃ include sodium sulfate, potassium sulfate, and potassium sodium sulfate. Examples of the NO ₃ − material include nitric acid, sodium nitrate, and potassium nitrate. Examples of the C 1− material include sodium chloride and chloride. Potassium and the like.

Examples of the alkali of the alkaline solution include oxides such as sodium oxide and potassium oxide; hydroxides such as sodium hydroxide and hydroxylated lime; carbonates such as sodium carbonate, carbonated lime and sodium carbonate; Sodium bicarbonate, bicarbonate such as hydrogen bicarbonate, etc. can be used. If necessary, oxides such as calcium oxide and magnesium oxide; hydroxides such as calcium hydroxide and magnesium hydroxide; carbonates such as calcium carbonate, magnesium carbonate and dolomite; calcium hydrogen carbonate and magnesium hydrogen carbonate And the like may be used.

The aluminosilicate particles used in the present invention can be obtained by blending and mixing the above various compounds at a predetermined ratio. The mixing ratio is appropriately determined depending on the desired composition of the obtained aluminosilicate particles. In particular, the mixing ratios of the raw materials are expressed as aM ₂₀ , b A 12 〇 ₃ , c S i 〇 ₂ , dRm An (for example, K〇H is K ₂ 〇, Na OH is Na ₂を, BZc = 0.01 to 10; a / c = 0.01 to 100 and 3 (= 0.01 to 100).

The solid content concentration of the aluminosilicate particles represented by the above composition during the reaction is desirably 0.1 to 50% by weight.

In addition, the reaction temperature when producing aluminosilicate particles increases the degree of crystallinity of the aluminosilicate particles, stabilizes the morphology of the aluminosilicate particles, and reduces the chemical and pressure resistance load on the reaction vessel. From the viewpoint of reduction, the temperature is preferably 15 to 300 ° C, more preferably 60 to 150 ° C, and further preferably 80 to 130 ° C. The reaction time is preferably at least 2 hours, more preferably at least 8 hours, from the viewpoint of completely performing the crystallization reaction. The aluminosilicate particles obtained by such a method are excellent in sorption properties and dispersibility, and have the property of increasing the mechanical strength of the filling material when used as a filler. As for the form of use of the aluminosilicate particles, powders are suitable because of their high dispersibility.

Next, a metal is supported on the aluminosilicate particles. The metal used in the present invention is at least one selected from the group consisting of Ag, Cu, Fe, Zn, Ca, Mg and Ce. Since these are antibacterial metals, they are supported. Aluminosilicate particles are useful as antibacterial agents. The term “antibacterial” refers to fungi and bacteria, and refers to the property of killing or inhibiting the growth of these bacteria.

Examples of a method for supporting a metal include an ion exchange method and a method for depositing fine metal particles. Specific examples of the ion exchange method include a method in which aluminosilicate particles are dispersed in a solution of a metal salt, ion-exchanged, filtered, washed, dried, and, if necessary, heat-treated. As a specific example of the method for depositing fine metal particles, there is a method in which aluminosilicate particles are dispersed in a solution of a metal salt, and fine metal particles are precipitated on the surfaces of the aluminosilicate particles using a precipitant such as an acid or an alkali. The amount of metal carried in the antibacterial agent should be 0.1 to 10% by weight in terms of the total amount of metals such as Ag, Cu, Fe, Zn, Ca, Mg, and Ce from the viewpoint of antibacterial properties and economy. And more preferably 0.5 to 5% by weight. The amount of metal carried in the antibacterial agent is measured by X-ray fluorescence. It is to be noted that the crystallization of the obtained antibacterial agent does not substantially change simply by supporting the metal on the aluminosilicate particles as a raw material.

Specific examples of the proton treatment, proton exchange by reacting in H ₂ S_〇 _{_{4, HC 1, HN0 3,}} NH 4 N 0 gradually acidic aqueous solution containing ₃ or the like aluminosilicate gates particles, or once Then, a method of heating or heating as necessary is used. Further, after the support, heat treatment may be performed at 100 to 800 ° C. if necessary. Such a protonation treatment is performed before or after the metal is supported on the aluminosilicate particles. You can do it when you let it.

There is no particular limitation on the type of acid used for the protonation treatment, and known organic acids and inorganic acids can be used.

A specific protonation method is as follows. The aluminosilicate particles are dispersed in ion-exchanged water so as to have a solid concentration of 1 to 30% by weight. The pH of the slurry at this time is between 8 and 13. The acid is slowly added to the slurry while stirring. At this time, it is preferable to perform the acid treatment so that the pH of the slurry is 2 to 7, preferably 3 to 5. From the viewpoint of maintaining the crystallinity of the aluminosilicate particles and securing the amount of metal required for the development of antibacterial properties, the pH of the slurry during the acid treatment is preferably within this range. .

The antibacterial agent of the present invention obtained by the above-described method is not only excellent in antibacterial properties but also has a complex surface, so that it is also excellent in filling properties and used in powder. It may be used as a mixture with other inorganic powders, organic powders, metal powders and the like, and may be used as a molded product if necessary. Specific applications include additives for various detergents, fillers for paper, plastics, fibers, fabrics, and building materials, pigments for cosmetics, and water treatment agents.

From the viewpoint of preventing discoloration, the antibacterial agent of the present invention and the anti-discoloration agent and stabilizer may be simultaneously added, or may be adhered to and coated on the particle surface. Examples of discoloration inhibitors or stabilizers include metal oxides such as zinc oxide, phosphate, hydrotalcites, magnesium oxide, calcium oxide, titanium oxide, calcium stearate, phenolic, sulfuric, and phosphorus-based materials. Antioxidants, ultraviolet absorbers and the like. Hereinafter, the present invention will be described in more detail with reference to Examples.

Example 1

Sodium hydroxide 9 4 g dissolved in deionized water 1 0 0 0 ml, further nitrate (6 1%) 1 3 0 g and aluminate Natoriu厶溶solution (N a ₂ 〇 = 2 0.3 1 wt% A 1 2 0 ₃ = 2 5.8 2 wt%, mixing the H ₂ 0 = 5 3. 8 7 wt 1 2 4 g The solution, water glass (N a 2 〇 = 9.7 wt%, S i 0 ₂ = 2 9.7 _{wt%, H 2 O = 6 0.} 6 % by weight) were added to and mixed with 1 27 g, 1 The reaction was carried out at 00 ° C for 15 hours. After the reaction, the produced aluminosilicate particles were washed, filtered, and dried to obtain powder of the aluminosilicate particles. The obtained aluminosilicate particles had a form in which needle-like crystals were aggregated. The powder of the obtained aluminosilicate particles was subjected to X-ray diffraction using an X-ray diffractometer (RAD-C, CuK, manufactured by Rigaku Corporation). It had a strong diffraction peak at 69 nm, which corresponded to J CPDS No. 38-513. The composition of the aluminosilicate gates particles, been filed schematically 3Na _₂ 0 · 3 A 1 ₂ 〇 ₃ · 6 S i 0 ₂ · NaN_〇 ₃ · 4 H ₂ 0.

77 g of the obtained powder of aluminosilicate particles was added to a solution of 3.38 g of silver nitrate dissolved in 1000 Om1 of ion-exchanged water, and dispersed at 100 ° C for 1 hour to ion-exchange Ag. After that, the mixture was filtered and washed to obtain Antibacterial Agent 1. The obtained antibacterial agent 1 had a spherical shape in which needle-like crystals were aggregated, and contained 2.38% by weight of Ag. The amount of metal such as Ag in the antibacterial agent was measured by X-ray fluorescence. Example 2

50 g of the aluminosilicate powder used in Example 1 was added to ion-exchanged water to which 75 g of 1N hydrochloric acid had been added, dispersed at 100 ° C. for 1 hour, and subjected to protonation treatment. Ag was ion-exchanged in the same manner as in Example 1 to obtain Antibacterial Agent 2. The obtained antibacterial agent 2 showed a spherical morphology in which needle-like crystals similar to the antibacterial agent 1 were aggregated, had a crystallinity of 76%, and supported 2.48% by weight of Ag.

Example 3

In a solution prepared by dissolving 16 g of the aluminosilicate particles obtained in Example 1 in 63 ml of silver nitrate and 7.279 g of zinc nitrate hexahydrate in 160 ml of deionized water. The mixture was dispersed at 100 ° C. for 2 hours, ion-exchanged Ag and Zn, and then filtered and washed to obtain antibacterial agent 3. The obtained antimicrobial agent 3 is the same needle as antimicrobial agent 1. It exhibited a spherical morphology of aggregates of crystalline crystals, and 2.49% by weight of Ag and 7.7% by weight of Zn were supported.

Example 4

16 g of the aluminosilicate particles obtained in Example 1 was dissolved in a solution obtained by dissolving 2.683 g of silver nitrate 63 and calcium nitrate tetrahydrate in 1.600 ml of ion-exchanged water. The mixture was added and dispersed at 100 ° C. for 2 hours to ion-exchange Ag and Ca, followed by filtration and washing to obtain antibacterial agent 4. The obtained antibacterial agent 4 exhibited a spherical morphology in which needle-like crystals were aggregated like the antibacterial agent 1, and contained 2.38% by weight of Ag and 1.9% by weight of Ca.

Example 5

16 g of the aluminosilicate particles obtained in Example 1 were mixed with 0.63 g of silver nitrate, 2.9 13 g of magnesium nitrate hexahydrate and 14.08 g of ammonium nitrate in deionized water. It was added to a solution dissolved in 160 ml, dispersed at 100 ° C. for 2 hours, ion-exchanged Ag and Mg, and then filtered and washed to obtain antibacterial agent 5. The obtained antibacterial agent 5 exhibited a spherical morphology in which needle-like crystals were aggregated, as in antibacterial agent 1, and contained 2.38% by weight of Ag and 7.7% by weight of ^^.

Example 6

A powder of 77 g of the aluminosilicate particles obtained in Example 1 was dissolved in 3.000 g of ion-exchanged water with 3.38 g of silver nitrate and 3.4.1 g of cerium nitrate hexahydrate. The solution was added to the solution, dispersed at 100 ° C. for 1 hour, ion-exchanged Ag and Ce, and then filtered and washed to obtain antibacterial agent 6. The obtained antibacterial agent 6 exhibited a spherical morphology in which needle-like crystals were aggregated as in antibacterial agent 1, and contained 2.5% by weight of Ag and 2.8% by weight of Ce.

Example 7

Sodium hydroxide 4 7 g was dissolved in deionized water 1 in 0 0 0 m l, further § Rumin sodium solution (N a ₂ 0 two 2 0.3 1 wt%, A 1 ₂ 〇 ₃ = 25.8 2% by weight, H ₂ 0 = 5 3.87 weight 73 g was added to the mixed solution, and water glass (Na ₂₀ = 9.7 weight%, Sio ₂ = 29.7 weight%, H ₂ 0 = 60.6% by weight), and mixed, and reacted at 100 ° C for 2 hours. After the reaction, 15 g of sodium hydroxide was dissolved in 5 Oml of ion-exchanged water, and a solution obtained by mixing nitric acid (615 g) was further added to the obtained reaction solution. The reaction was carried out at 10 ° C. After the reaction, a powder of aluminosilicate particles was obtained in the same manner as in Example 1. The obtained aluminosilicide particles were composed of columnar and needle-like crystals which were aggregated into tetrapods. The powder of the obtained aluminosilicate particles was subjected to X-ray diffraction using an X-ray diffraction apparatus, and as a result, d = 0.368 It had a strong diffraction peak at nm, which corresponded to JCPDS No. 38-51 3. The composition of the aluminosilicate particles was approximately 3Na ₂ 0 '3A l ₂ 0 ₃ · 7Si 0 ₂ -2NaN0 ₃ -. 4 were are H ₂ 〇 the S EM photograph of the obtained aluminosilicate Ichito particles Figure 1 shows the X-ray diffraction pattern in Figure 2.

Except that the obtained aluminosilicate particle powder was used, the same treatment as in Example 1 was carried out to ion-exchange Ag to obtain antibacterial agent 7. The obtained antibacterial agent 7 showed a form in which columnar and needle-like crystals aggregated and developed into a tetrapod-like form, and contained 2.49% by weight of Ag.

Example 8

Antibacterial agent 2 obtained in Example 2 was further heat-treated at 600 ° C. for 5 hours to obtain antibacterial agent 8. The obtained antimicrobial agent 8 had the same particle morphology and Ag carrying amount as antimicrobial agent 1.

Example 9

After 100 g of the raw material aluminosilicate particles obtained in Example 7 were dispersed in 900 g of ion-exchanged water and the temperature was raised to 100 ° C, lmo 1 Z1 aqueous nitric acid solution was added to 1 m 1 / 95 Om 1 was added dropwise at a rate of minutes. The pH of the solution at the end of the dropwise addition was 3.2. The solid content was separated by filtration, washed, and ion-exchanged water containing 58 g of silver nitrate dissolved therein 900 g g, and dispersed at 100 ° C. for 1 hour to carry out Ag ion exchange, followed by filtration and washing to obtain antibacterial agent 9. The crystallinity of the obtained antibacterial agent 9 was 36%, and octane was carried in an amount of 0.91% by weight. Approximate composition of an antimicrobial agent, excluding the A g was _{3Η 2 0 · 3 A 12 0} 3 · 7 S i 0 2 · 0. 2NaN_〇 ₃ · _4Η ₂ 〇. Fig. 3 shows a SEM photograph of the obtained antibacterial agent, and Fig. 4 shows its X-ray diffraction pattern.

The crystallinity of the antibacterial agent was determined by comparing the maximum diffraction intensity in the X-ray diffraction pattern of the raw material aluminosilicate particles obtained in Example 7 shown in FIG. 2 with the antibacterial agent obtained in this example shown in FIG. It was calculated as the ratio of the highest diffraction intensity, which is the same corresponding peak in the X-ray diffraction pattern of the agent. The crystallinity of the antibacterial agent in other examples was calculated in the same manner.

Example 10

After 100 g of the aluminosilicate particles obtained in Example 7 were dispersed in 900 g of ion-exchanged water and heated to 100 ° C, 300 ml of lmo 1/1 nitric acid aqueous solution was added at a rate of lm 1 / min. It was dropped. The pH of the solution at the end of the dropwise addition was 4.9. After the solids were separated by filtration and washed, 1.58 g of silver nitrate was added to 900 g of ion-exchanged water in which they had been dissolved, dispersed at 100 ° C for 1 hour, and subjected to Ag ion exchange, followed by filtration and washing. Thus, an antibacterial agent 10 was obtained. The obtained antimicrobial agent 10 had a crystallinity of 45% and was loaded by 98% by weight of ^ t. Approximate composition of an antimicrobial agent, excluding the A g was _{3H 2 0 · 3 A 12 0} 3 · 7 S i 0 2 · 0. 2NaN_〇 ₃ · _4Η ₂ 〇.

As described above, it can be seen that the antibacterial agents 1 to 10 obtained in Examples 1 to 10 all have a large particle surface area because their particle surfaces have a complicated acicular shape. Test example

The antibacterial properties of the antibacterial agents 1 to 10 obtained in Examples 1 to 10 were evaluated. For the evaluation of antibacterial activity, Staphylococcus aureus (IFO12732) was used. Antibacterial agents were suspended and dispersed in an agar medium, and the respective minimum inhibitory concentrations (MIC) after 24 hours at 37 ° C. Was evaluated. The results are shown in Table 1. As a comparative example, a conventional zeolite carrying an antibacterial metal (Ag, carrying amount: 2.0% by weight) was used. In the table, ◎ indicates that the growth of the fungus was inhibited, and X indicates that the fungus had grown.

table 1

As shown in Table 1, the antimicrobial agents 1 to 10 obtained in Examples 1 to 10 all had a lower MIC than the conventional antimicrobial metal-supported zeolite used in Comparative Examples. It is small and has excellent antibacterial properties. Industrial applicability

The aluminosilicate antibacterial agent of the present invention has excellent antibacterial properties, has an aggregated form such as a sphere, and has a large surface area, and therefore has excellent filling properties. And fillers for paper, plastics, fibers, building materials, etc., pigments for cosmetics, and water treatment agents.

Claims

The scope of the claims

_{1. aM 2 0 ■ b A 12} 0 3 · c S i 0 2 - d RmAn · y H 2 0

Wherein, M is Na and Z or K, R is Na, K, selection barrel (1) or more from the group consisting of C a and Mg, A is C_〇 _3, S0 _4, NOs, the group consisting of OH and C 1 At least 1 kind, a is 1 to 6, b is 2 to 8, c is 2 to 12, d is 0 to 4 (excluding 0), m is 1 to 2, and n is 1 to 3. , Y represents 0 to 32)

Selected from the group consisting of Ag, Cu, Fe, Zn, Ca, Mg, and Ce in the form of needle-like, plate-like, or columnar aluminosilicate particles having a composition represented by Antibacterial agent consisting of aluminosilicate particles carrying more than one kind of metal

_{2. a 1 M 2 0 · a} 2 H 2 0 · b A 1 2 0 3 · c S i 0 2 - d RmAn - y H

2 〇

Wherein, M is Na and or K, R is Na, K, C a and M g consisting selection barrel (1) or more from the group, A is C_〇 _{_3,} S0 _4, N0 _3, from 〇_H and C 1 One or more selected from the group consisting of: a, 0 to 1 (excluding 1), a, + a ₂ is 1 to 6, b is 2 to 8, c is 2 to 12, and d is 0 to 4, m is 1-2, n is 1-3, y is 0-32. Here, a ₂ H ₂₀ indicates structural water present in the crystal, and yH ₂₀ indicates crystal water. ]

Aluminosilicate particles having a composition represented by the following formula and having any of a needle-like, plate-like, or columnar shape are added to at least one selected from the group consisting of Ag, Cu, Fe, Zn, Ca, Mg, and Ce. Antibacterial agent consisting of aluminosilicate particles carrying metal

3. The main X-rays at d = 0.365 ± 0.015 nm for aluminosilicate particles 3. The antibacterial agent according to claim 1, which has a diffraction peak.

4. The aluminosilicate particles are J CPDS No. 20-379, 20-743, 25-776, 25-149, 9, 25-150, 30 1 1 70, 3 1-1 272, 34-1 76, 3 5-4 79, 35-6 5 3, 3 8-5 1 3, 38-5 1 4, 3 8-5 15 and 4 5-1 373 The antibacterial agent according to any one of claims 1 to 3, wherein the antibacterial agent has one or more selected X-ray diffraction patterns.

_{5. aM 2 0 · b A 12} 0 3 · c S i 0 2 - d RmAn · y H 2 0

Wherein, M is Na and Roh or K, R is Na, K, C a and selection barrel (1) or more from the group consisting of M g, A is C0 _3, from S_〇 _4, N0 _3, OH and C 1 One or more selected from the group consisting of: a is 1 to 6, b is 2 to 8, c is 2 to 12, d is 0 to 4 (excluding 0), m is 1 to 2, and n is 1 ~ 3, y indicates 0 ~ 32)

Aluminosilicate particles having a composition represented by the following formula and having any one of a needle shape, a plate shape, and a column shape are subjected to protonation treatment, and then Ag, Cu, Fe, Zn, Ca, Mg, and Ce A method for producing an antimicrobial agent comprising metal-supported aluminosilicate particles, which carries one or more metals selected from the group consisting of: Of antibacterial agents consisting of metal-supported aluminosilicate particles with a crystallinity of 1% or more and less than 100%