JPS627747A - Hydrophobic antifungal zeolite composition coated with silicone film and its production - Google Patents

Abstract

PURPOSE:To obtain the titled composition with hygroscopicity inherent in zeolite suppressed, suitable as additives to polymeric materials, by coating a silicone coating agent on the surface of activated zeolite having antifungal metal. CONSTITUTION:Either natural or synthetic zeolite with a molar ratio: SiO2/Al2 O3>=1.5 (e.g, analcime, A-type zeolite) is immersed in an aqueous solution of antifungal metal (e.g., Ag, Cu, Zn) ion to perform ion exchange to prepare activated zeolite containing the antifungal metal. The resulting zeolite is impregnated at >=60 deg.C with either silicone coating agent with a viscosity <=2,000cps or its solution followed by separation of the solid phase from the liquid phase, the resultant zeolite phase being heated to >=60 deg.C to expel the residual solvent, thus obtaining the objective composition.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to an antibacterial zeolite composition having hydrophobic properties and a method for producing the same. An antibacterial zeolite composition that has moisture-proof, hydrophobic, or water-repellent properties by treating a certain natural or synthetic zeolite with a hydrophobic silicone coating agent or its solution to suppress the zeolite's inherent moisture absorption ability to the required level. It provides products and methods of manufacturing them.

It is a well-known fact that by thermally activating various zeolites and removing the water of crystallization therein, cavities are formed in the zeolite matrix, where water adsorption and selective adsorption of other gases take place. Zeolites are widely used in the fields of drying (dehumidification), gas purification, and concentration by taking advantage of the adsorption properties of certain zeolites. It has been found that when fine powders or particles are added to various polymers as fillers, they impart antibacterial ability to the polymers and have a significant effect on improving the properties and functions of the polymers. (Special application 1975-7561 etc.). For example, antibacterial zeolite fine powder can be added to paper compositions, natural or synthetic rubber compositions, plastic compositions, and pigment compositions (non-settling and matte pigments), etc. to ensure uniform dispersion and to provide resistance against mold. It has been confirmed that it is highly potent and has the effect of sterilizing various bacteria and increasing its antibacterial ability. As the polymer, polyethylene,
Polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyamide, polyester, polyvinyl alcohol, polycarbonate, polyacetal, A
Thermoplastic synthetic polymers such as BEI resin, acrylic resin, fluororesin, polyurethane, thermosetting synthetic polymers such as phenol resin, urea resin, melamine resin, unsaturated polyester resin, epoxy resin, urethane resin, rayon, cupra, Examples include recycled or synthetic polymers such as acetate and triacetate.However, the above-mentioned polymers and organic polymers for the purpose of fiber formation (for example, iron 6, nylon 66, polyvinyl chloride, and
[S1chi v7 te'lid'-to poly1chi v7, etc.)
When fine particles of antibacterial zeolite are added to rubber compositions or pigment compositions and dispersed uniformly, water contained in the antibacterial zeolite may interfere with uniform dispersion or cause foaming. This can cause negative effects. When the above-mentioned organic polymer is formed into a thin film and spun, a swelling phenomenon occurs due to the small amount of water adsorbed on the zeolite, and this can be caused by the non-uniformity of the film or the spinning process. This may cause thread breakage. Normally, various general-purpose zeolites and antibacterial zeolites used for kneading into polymers are usually added in the form of activated fine powder, but zeolite fine powder in a warm state is The present inventor has confirmed through numerous tests that the powder is extremely active and therefore easily adsorbs moisture in the atmospheric gas, which adversely affects the function of the polymer as described above.

The purpose of the present invention is to establish an economical hydrophobization technique for suppressing the hygroscopic ability of the activated antibacterial zeolite fine powders used for the addition of the above-mentioned polymers.
The purpose of this research is to establish a technology to temporarily suppress the moisture absorption ability of molded antibacterial zeolite to make it hydrophobic or water repellent. For the above purpose, the present inventor conducted a series of tests on making antibacterial zeolite hydrophobic and made it water repellent, and after intensively studying the results obtained, the inventors determined that coating with a silicone coating agent system or its solution was carried out. The present invention has been achieved by discovering that the above-mentioned problems are solved and that the antibacterial zeolite obtained is an antibacterial zeolite composition. An antimicrobial zeolite composition having hydrophobic properties is provided, which comprises an activated natural or synthetic zeolite having a hydrophobic property and a silicone-based coating coated on the surface thereof.

In addition, the present invention provides a method for producing an antibacterial zeolite composition having hydrophobic properties, in which activated natural or synthetic zeolite having an antibacterial metal is impregnated with a silicone coating agent or a solution thereof, and then hardened. A method is provided for preparing antimicrobial zeolite compositions having hydrophobic properties by separating the phase and liquid phase and then removing residual solvent from the treated zeolite phase.

The present invention will be explained in detail below. The present invention is a hydrophobic antibacterial zeolite composition obtained by treating an activated natural or synthetic zeolite containing an antibacterial metal with a hydrophobic silicone coating agent or a solution thereof. In the present invention, in order to hydrophobize the natural or synthetic zeolite in an activated state, the activated zeolite containing an antibacterial metal can be added to a silicone coating agent or its solution heated at room temperature or heated, for example. Instead of the above coating method, a silicone-based coating agent or a solution thereof is sprayed onto the activated antibacterial zeolite at room temperature or under heating to be hydrophobized. It is also possible to obtain zeolite compositions economically.

As mentioned above, it is preferable to obtain the hydrophobic antibacterial zeolite composition of the present invention by treatment under heating. That is, an activated natural or synthetic zeolite containing an antibacterial metal is treated in a hydrophobic silicone coating agent or its solution at a temperature of 60°C or higher, and then the solid phase and liquid phase are separated, and then the treatment is carried out. If the finished zeolite phase is heat-treated in a temperature range of 60°C or higher, the formation of a silicone film on the zeolite phase and the wetting will be evenly distributed, and the antibacterial zeolite composition with high hydrophobicity or water repellency, which is the object of the present invention, can be obtained. easily obtained. In addition to the above-mentioned coating method, a suitable amount of a silicone coating agent or its solution is added to the activated antibacterial zeolite and mixed using a mixer or the like to obtain the hydrophobic property of the present invention. It is also possible to prepare antibacterial zeolite compositions.

In the present invention, active substitutes for natural and synthetic zeolites containing antibacterial metals are used. □These antibacterial zeolites are activated by carrying out conventional heat treatment under normal pressure or reduced pressure. This is done by removing the moisture in the antibacterial zeolite to the required extent. The activation temperature varies depending on the type and structure of the antibacterial zeolite, but
Usually, this activation is carried out in a temperature range of 200 to 600°C. Most of the natural or synthetic zeolites with antibacterial metals used in the present invention have a molecular weight of 220 to 500
Activation in the temperature range of 0.degree. C. changes the phase of water to 1 or less.

The forms of natural or synthetic zeolites with activated antibacterial properties used in the present invention include powder-1 particles, pellets,
The present invention can also be applied to antibacterial zeolites in the form of tablets, beads, plates, and the above-mentioned side shapes. Therefore, it is sufficient to appropriately select an activated antibacterial zeolite in any shape suitable for the purpose of sinus use, and to carry out the nine-point hydrophobization method suitable for this.

Next, types of zeolite suitable for supporting antibacterial metal ions used in the present invention will be described.

In the present invention, the silica-alumina molar ratio Sin, /A
4. Synthetic zeolites are preferred as natural zeolites with an O of at least 1.5, and even if they contain some impure components, there is no problem in preparing an antibacterial zeolite composition. Zeolite is generally an aluminosilicate with a three-dimensionally developed skeleton structure, and is generally composed of XMyuO, kl, Ol, y8 based on Al2O2.
10. -ZH,O. Represents a metal ion that can be exchanged, usually a monovalent to divalent metal,
n corresponds to this valence. On the other hand, X and y represent the coefficients of metal oxide and silica, respectively, and 2 represents the number of crystallized water. Many types of zeolites with different compositions, pore sizes, specific surface areas, etc. are known, but as the carrier for the antibacterial metal ions used in the present invention, as mentioned above, Si
It is preferable that O2/'AltOs is 1.5 or more, that pores are developed, and that the specific surface area is large. In the present invention, antibacterial metals include silver (I), copper (■ and ■),
Zinc (II) Mercury (H), Tin (■ and ■), Lead (Ill
, bismuth (II), cadmium (II), chromium (I)
), cobalt (III), and nickel (It), and these antibacterial metals are supported on zeolite using a solution containing the above-mentioned antibacterial metal ions. By performing ion exchange with zeolite at room temperature or high temperature, the required amount of antibacterial metal can be replaced with M in the above general formula. The antibacterial zeolite is washed with water to remove excess metal ions from the antibacterial zeolite solid phase, then dried at around 100 to 110°C, and finally heat activated at 200 to 600°C as described above.

In accordance with the present invention, the active antibacterial zeolite obtained by the method described above may then be coated with liquid paraffin.

The antibacterial metals in the antibacterial zeolite used as a coating material in the present invention are selected from the above-mentioned group of antibacterial metals, and two or more types are used. Furthermore, the amount of antibacterial metal in antibacterial zeolite varies depending on the type of antibacterial metal and the structure of the zeolite matrix that supports it, as well as depending on the purpose of use.

For example, the metal content in the metal-zeolide (anhydrous basis) is suitably 261i% or less for silver, and the preferred range is 0.001 to 10%. Regarding steel and zinc, the amount of copper or zinc in the metal-zeolide (based on anhydrous zeolite) should not exceed 25% by weight, with a preferred range of 0.01 to 15% by weight.
The measurement department. Of course, it is also possible in the present invention to use the above-mentioned silver, copper and zinc in combination. Also, in the zeolite combination of silver, copper, zinc, mercury, lead, bismuth, cadmium, chromium, cobalt and nickel used in the present invention, for example, sodium, potassium, calcium, magnesium, iron or other metals coexist. Even if these metals are present, the antibacterial effect will not be hindered, so there is no problem with the coexistence or residual presence of these metals.

As mentioned above, as the zeolite material with a SiO, /AJ, O, molar ratio of 1.5 or more used to support antibacterial metals in the present invention, any zeolite, natural or synthetic, can be used. It is. For example, analcime (510t/Alt O) is a natural zeolite.
s = 3.6-5.6), Chabasite (Chaba
Zite: SiOt/Al, o, = 12-6. o
and 6.4-7.6), clinoptilolite (C11
nopti-10111,8: SiO,/Al,
O, = 8.5~10.5), erionite (Eri
onite: Sin, /A720g = 5.8
~7.4), Favjasite
: SiO, /A720. ==4.2~4.6), mordenite (mordenite: 5i02/AltO
s = 8.3~10.0), phillipsite (Ph
Flip θ11, θ: 51ot/hl*as
= 2.6 to 4.4) are suitable for use. These typical natural zeolites are suitable as the zeolite material necessary for preparing the antibacterial zeolite of the present invention. On the other hand, a typical synthetic zeolide is 8-type zeolide (S10./A^0.=1.5-2.4
), X-type se, t lie) (5ift/A40g=
2-3), Y-type zeolide (510t/AItOs
= 3 to 6), mordenite (S i 02 /hilt
Os "" 9-10) High silica zeolite (5i
02/AA! tOs>20), and these synthetic zeolites are suitable as a material for preparing the hydrophobic antibacterial zeolite composition of the present invention. Particularly preferred in the upper side are synthetic A-type zeolides, x
- type zeolides, Y-type zeolides, high silica zeolites and synthetic or natural mordenites.

Next, the silicone coating agent used as the coating agent and the coating method will be explained in detail.

As mentioned above, as the coating agent of the present invention, a silicone-based coating agent is suitable for obtaining the hydrophobic antibacterial zeolite composition of the present invention. These silicone coating agents are used as they are or as a solution in a suitable solvent. In order to facilitate the zeolite coating operation, the viscosity (at 25° C.) of the silicone coating agent is preferably 2000 cps or less. These liquids can be used by spraying the necessary amount when coating the activated antibacterial zeolite as described above, or by adding the necessary amount to the activated antibacterial zeolite using a mixing machine and mixing. Ru.

Alternatively, the coating may be carried out by adding activated antimicrobial zeolite to the silicone coating agent or its solution to form two phases (dip processing). As mentioned above, the coating method using a silicone-based coating agent itself or a solution with a viscosity of 20,000 pθ or less facilitates the coating operation of the activated antibacterial zeolite and improves the antibacterial zeolite's moisture resistance, water repellency, and The silicone coating agent suitable for controlling hydrophobicity appropriately is preferably one whose structure is thermally stable at at least 100°C, such as a product manufactured by Shin-Etsu Chemical Co., Ltd. Name K
Dimethylsiloxane-based coating agents such as F-96, methylhydrodiene polysiloxane-based coating agents such as KF-99, methyltrichlorosilane-based coating agents such as KO-88, decyltrimethoxysilane-based KBM- Coating agents such as s1o3c are suitable for the present invention; they are chemically stable, non-corrosive, have a high flash point, are excellent in durability, and have high heat resistance. For KF-96 above, the viscosity is O
A: 5-100G, 000cps (25°C) are commercially available, but in the present invention, these viscosity is 2.
000 cps or less is preferable, and most preferably 1,000 cps or less.

KF-99: I-ting liquid [approx. 15 cps (25°C)]
] can be used in the present invention in combination with a catalyst, and KO
-88 is diluted with a solvent to reduce the silicone content to 9 to 10.
It can also be used in the present invention as a diluted solution with a low viscosity of about 1.5%. Furthermore, the above-mentioned KBM-slasa (: viscosity 3
cps (25° C.)] and its diluted solution with a solvent can also be used in the present invention with good results. The diluent is at least 100%
It is made by diluting it to the required silicone concentration with a thermally stable solvent at ℃. These coating solutions have the function of forming a uniform silicone film or wetting on the activated antibacterial zeolite and making it hydrophobic or water repellent. Hydrocarbon and aromatic solvents are generally known as solvents used to prepare diluted solutions of silicone coating agents, but in the present invention, the coating method as described above is used. If necessary, we recommend a solvent that is flame retardant and structurally stable even at temperatures around 100°C. Examples of solvents having such characteristics include carbon tetrachloride and trichloroethylene. The amount of silicone in the silicone-containing diluted solution mentioned above is controlled by the type and shape of the target activated zeolite, and by the degree of water repellency or hydrophobicity required. In the present invention, the lower limit of silicone coating content in the silicone diluent to obtain a hydrophobically rich antibacterial zeolide composition with satisfactory properties is 0.1% (volume percent). It is. Below the above lower limit, the hydrophobic water repellency of the zeolite obtained decreases significantly as the silicone content decreases. Preferably, the silicone-based coating agent solution is used by spraying onto the activated zeolite or mixed with the straddle zeolite for coating. In the case of the latter mixing method, the necessary amount of coating liquid is added to the activated antibacterial zeolite using a mixer or the like, and mixing is carried out. Alternatively, as described above, coating (dipping) with silicone may be performed in the coexistence of two phases of activated antibacterial zeolite and coating liquid. Then, the treated antibacterial zeolite phase obtained was finally
Heat treatment in the temperature range of 00° C. is carried out under normal pressure or reduced pressure to remove excess solvent in the zeolite phase and to uniformly form and wet the zeolite with a silicone film.

The activated antimicrobial zeolite obtained from this preferred coating method is hydrophobic to water clear.

Next, the main characteristics of the antibacterial zeolite composition that is rich in hydrophobicity and water repellency obtained by the method of the present invention will be described.

The moisture absorption capacity (water absorption capacity) of the highly hydrophobic antibacterial zeolite of the present invention can be adjusted arbitrarily by selecting the coating method of the present invention. The performance can be further adjusted by selecting a coating method using a silicone-based coating agent or a diluted solution thereof, or a coating method using both in some cases, depending on the purpose of use. Silicone-based coating in the diluted solution □This is carried out by appropriately adjusting the agent content, -1 heat treatment conditions, etc. When the silicone-based coating method of the present invention is applied to activated antibacterial zeolite, the obtained The antibacterial zeolite composition having hydrophobicity or water repellency is structurally extremely stable and has a great advantage in heat resistance.Furthermore, the moisture absorption ability of the antibacterial zeolite composition rich in hydrophobicity obtained by the present invention is as described above. It can be adjusted as desired, and the individual crystalline particles constituting the above composition have less agglomeration (see attached photo), and have more favorable properties as a filler for polymers than from a physical standpoint. When the highly hydrophobic antibacterial zeolite composition of the present invention is used as a filler for the purpose of imparting antibacterial properties to a polymer, the amount of zeolite added to the polymer increases. The method of hydrophobizing activated antibacterial zeolite of the present invention can be applied not only to antibacterial zeolite powder but also to hydrophobizing granular products and molded products, which will be described later. As shown in the Examples, the hydrophobic antibacterial zeolite composition of the present invention can then be heated to restore the original hygroscopicity and other functions of the zeolite.

The regeneration temperature in this case varies depending on the type and structure of the highly hydrophobic antibacterial zeolite composition, but is usually 230 to 650°C.
Thermal activation is performed in a temperature range of .

Next, in order to test the antibacterial activity of the hydrophobized zeolite composition obtained according to the present invention, Escherich Acoli (lli:
5cherichia co:Li), Staphylococcus aureus (Staphylococcus aureus)
ureus), Pseudomonas aeruginosa (Pae
udomonas aerg-inosa), Candida albicans
), Aspergillus 7 rapaz (Aspergill-x
a flavua), Aspergillus niger (muspe
rgilla niger), Trichophyton ment
Evaluation of antibacterial activity and Aspθrgi11uaf1 using bacteria such as Agrophytes)
The fungal mortality rate was measured using S. avus, Muspergil: IUA niger, and the like. the result,
It was confirmed that the hydrophobic zeolite composition of the present invention still has excellent antibacterial and bactericidal properties (see Examples below).

Next, embodiments of the present invention will be described with reference to Examples, but the present invention is not limited to these Examples (as long as the present invention does not exceed the gist thereof).
uY: Silicone KBM-31030 [decyltrimethoxysilane-based coating agent;
25° C.] or a diluted solution thereof to produce a highly hydrophobic antibacterial zeolite composition according to the present invention. In this example, a highly hydrophobic antibacterial zeolite composition was produced using a dipping process.

(1) Antibacterial zeolite used The following antibacterial Y-type zeolide fine powder was used.

NaA, )ilouY: average particle diameter Dav+1.57μ
m;A, jil=2.415%;C! u=8.33%
(100°C dry basis); Y = Y-type zeolide matrix The above antibacterial zeolite fine powder was activated by firing at 340'C to 350'C for 3 hours prior to coating.〇(II) Use Coating liquid KBM-31osO (Example 1) KBM-3103010HOJ-, CHOl2 mixed liquid (Example 2) A diluted solution of Trichlene (CHCjl, CHOl, ) was used in the coating test.
) Hydrophobization method 80 m of the coating liquid described in the previous section was added to about 34.9 ml of antibacterial zeolite fine powder NaA, 1 il OuY activated by the above method, and the resulting mixture was subsequently stirred for 25 minutes. . After completing the above coating operation, the antibacterial zeolite phase was separated by suction method, and then heat-treated for 310 minutes under the conditions listed in Table 1.
5C/CHCj1. Although the antibacterial zeolite obtained in the coating method using a silicone diluted solution (using a CHCl2 diluted solution) has a slightly lower moisture-proofing ability compared to Example 1, the water absorption rate is still preferably 2% or less even after 24 hours. value is maintained.

The highly hydrophobic antibacterial zeolite composition obtained by the methods of Examples 1 and 2 shows almost no aggregation of the primary particles constituting it, and this shows that when it is added as a filler to a polymer, This is preferable because uniform dispersion can be achieved. The electron micrograph shown in Figure 1 is the highly hydrophobic antibacterial zeolite obtained in Example 1 (coated and heat-treated N
a/JOuY) (SKM; magnification XIQ, 000). It is clear from this that the formation of the silicone film on the individual particles constituting the antibacterial zeolite is uniformly carried out under favorable conditions9, and that almost no aggregation of the primary particles is observed. This point is one of the features of the present invention and deserves special mention.

Example i This example uses activated antibacterial zeolite fine powder (Na
A commercially available (manufactured by Shin-Etsu Chemical Co., Ltd.) silicone-based coating agent 1-96 (dimethylsiloxane-based: 500 cp (at 25°C)) was used as a coating solution for AgZ (Z = mother body of A-type synthetic zeolite). An antibacterial zeolite composition rich in hydrophobicity (
The present invention relates to a specific example of preparing NaAgZ).

(1) Antibacterial zeolite fine powder used NaAgZ:D
av = 3.1 μm; A, 9 = 1.29% (anhydride group ratio); z = matrix of A-type zeolide.
□ (n) Coating liquid IF'-96 used (viscosity 50ocps at 25°C)
III Hydrophobization method 120g of KF-96 (500cps) was added to 290J of NaAgZ powder activated by the above method,
Mixing was carried out for about 90 minutes using a mixing machine (small kneader: twin shaft) while shutting off outside air. After finishing coating with silicone by mixing method,
The mixture was further heat-treated at a temperature of 90°C for 48 minutes to ensure that the silicone film formed on the NaAgZ phase was evenly distributed. 5 to 7I of the antibacterial zeolite composition (NaA, 9Z) rich in hydrophobicity was accurately weighed, and a moisture absorption test was conducted on it at a constant temperature and humidity of 25° ± 2°C and RH = 73 ± 2%. . The test results are shown in Figure 2. Curve 1 shows the moisture absorption curve obtained using the highly hydrophobic antibacterial zeolite composition (NaA9Z) obtained in this example, while curve 2 (comparative example) is for comparison purposes. This is a moisture absorption curve obtained using an activated product of NaA, 9Z powder (calcined at 450 to 460°C for 2 hours and 10 minutes) used in this example. The hydrophobic antibacterial zeolite (NaAgZ) coated with silicone KF-96 in this example has a water absorption rate of about 3.5% after 10 hours, and it is still about 5% even after 24 hours. As is clear from the one-sided cotton 2, the water absorption rate of the simply activated NaAgZ powder was 13.2 after 10 hours, and reached 2C7% after 24 hours. .

Hydrophobic antibacterial zeolite phase composition of Example 3
The moisture absorption capacity was about 115 that of the comparative example NaA, 9Z (activated product), and it was found that the former had favorable moisture resistance.

Example 4゜This example is a molded body of activated antibacterial zeolite (N
The same coating liquid KBM-310 as in Example 1 was used as a coating liquid for aOuZ 1/16' Beret.
This figure shows a specific example of producing a molded article of an antibacterial zeolite composition with high hydrophobicity using No. 30. In this example, a molded body of an antibacterial zeolite composition rich in hydrophobicity was prepared by a dipping process.An antibacterial zeolite molded body (NaCuZ 1/1 (S' pellet: 0u=4.51% (anhydrous standard) ; Z=A-
Example 1 for 41 g of zeolide type zeolide matrix; average value of compressive strength δ = 6.81 (9/Bellet) was activated by firing at 500°C for 1 hour (this activation 1/16' pellet) Same viscosity as about 5 ape (25℃): KBM-
90 ml of 31030 Coating Solution was added and the resulting mixture was stirred gently for 56 minutes. After separating the two phases,
The zeolite molded body phase was heated to 90°C for 40 minutes.Heat-treated NaC obtained by the above method! uZ1
/16' pellets 8 to 10.9 were accurately weighed, and a moisture absorption test was conducted on them at constant temperature and humidity of 23°±2°C and FLH=70±2%. In addition, the N used in this example is the ninth in the comparison.
A0uZ 1/16' A hygroscopic ability test of an active substitute for Berets (activated by heating at 500°C for 1 hour; hydrophobically treated female) was conducted on the antibacterial agent prepared in the above example and rich in aqueous properties. The test was carried out under the same conditions as the test for the molded product of the zeolite composition.

The water absorption rate of the molded body of the highly hydrophobic antibacterial zeolite composition obtained in this example was 0.75% after 4 hours.
And after 24 hours, it was 3.17. On the other hand, the water absorption rate of the activated NaCuz 1/16' Hellet for comparison was 1'8.84% after 24 hours. From the comparison of these values, the moisture absorption capacity of the former is approximately 1/6 of the latter. It was found that it was suppressed.

Example 5. ~11° This example uses KF-96 (25°C), which is commercially available from Shin-Etsu Chemical Co., Ltd. as a silicone coating liquid.
500 cps) and KF-99 (viscosity about 15 ape at 25°C) diluted in a flame retardant solvent (silicone content = 4-10 vlo; see Table 3). A specific example of producing a highly hydrophobic antibacterial zeolite composition by this method will be described.

In this example, carbon tetrachloride (CC14; boiling point 76.6°C) or trichlorethylene (0HIJ.
cHcl, boiling point 86.9°C) was used.

The following two types of fine powder were used as antibacterial zeolite.

NaA, j7c! uZ: Dav = 2.45 μm
; Ag = 2.30%; Cu = 8.57% (dry basis); Y = matrix of Y-type zeolite The above powder was activated by calcining for 1 hour at approximately 340°C prior to the coating test. . Next, 240 ml of the coating liquid shown in Table 3 was added to the activated antibacterial zeolite powder 609, and the resulting mixture was gently stirred for about 15 minutes. The zeolite phase was heat-treated under the conditions listed in Table 3 to finally obtain an antibacterial zeolite composition rich in hydrophobicity. Examples 1o and 11 (7) KF-99
7CHC1, CHOlv (IP-99 = 9v10) When coating using a diluted solution, a KF-99 curing catalyst 0AT-PC (commercial product of Shin-Etsu Chemical Co., Ltd.) is used (use ratio KF-99:CATPC). =100:
1).

The moisture absorption test of the nine antibacterial zeolites obtained in Examples 5 to 11 was carried out at a constant temperature and humidity of 27°C and RE = 72 ± 2%. The summary of the results is shown in Table 4. ◎ Comparative Example 2 It shows the water absorption rate of activated NaAg0uZ (approximately 340℃, 1 hour), and after 24 hours it was 24
．． On the other hand, the water absorption rate of the hydrophobic zeolite composition of the present invention (NaAJCuZ) of Example 6 was only 6.12 after 24 hours. Therefore, it can be seen that the moisture absorption capacity of the latter is suppressed to about 1/4 of that of the former. Next, Comparative Example 3
shows the water absorption rate of activated Na4!70uY (approximately 340°C, 1 hour). The hygroscopic ability of the hydrophobic zeolite composition (NaAgOuY) of the present invention is lower than that of Comparative Example 3 in Example 5 and Examples 7 to 110, which were processed under the conditions shown in Table 3. It is clear from the table.

Antibacterial property test Next, in order to examine the antibacterial ability of the hydrophobic antibacterial zeolite composition obtained according to the present invention, the antibacterial activity was evaluated and the fungal killing rate was measured. The evaluation was carried out by the following method: The test substance was suspended at a concentration of 1oo119/d,
0 medium infiltrated into the disks is Muelxer Hinton for bacteria.
As for the culture medium and fungus, Sabouraud agar medium was used. The test seeds were suspended in physiological saline 108/y+ and added to the medium with 0
．． 1) Dispersion was carried out using a conlage stick, and the test disk was attached on top of it. To judge the effectiveness, in the case of bacteria, the presence or absence of inhibition zone formation was observed after 18 hours at 37°C. In the case of fungi, the presence or absence of inhibition zone was observed after 18 hours at 30°C. After a week, the fungal mortality rate was determined as follows:
s rlavus and Aapergillus ni
ger spore suspension (10'/rni,) to the test substance suspension (500/d). Inject and mix into the water, 2
It was operated for 4 hours at 50"C.

Disperse 0.1 d of it on Sabouraud agar medium and incubate at 30°C.
After 48 hours, the number of surviving individuals was measured and the mortality rate was determined.

Tables 5 and 6 show test results for typical antibacterial zeolite compositions rich in hydrophobicity of the present invention. Table 5 relates to the evaluation of the antibacterial properties of the highly hydrophobic antibacterial zeolite compositions of the present invention obtained in Example 6 (NaAgOuZ) and Example 9 (NaA, li+ouY). From the table, it can be seen that all the antibacterial samples have good antibacterial ability against the four types of bacteria listed.

Table 5 Evaluation of antibacterial properties (Examples 6 and 9) Next, Table 6 shows Aspergillus f.
lavus and Aspergillus niger
Example 6 (NaAg0uZ)
, Example 9 (NaA, 9CuY) and Example 10
(NaAg0uZ) was measured using a highly hydrophobic antibacterial zeolite composition. These measurement results indicate that the highly hydrophobic antibacterial zeolite composition of the present invention has excellent antibacterial and bactericidal abilities.

Table 6 Example of measuring fungal mortality rate 6 100 to 92% Example 9
98 to 96% Example 10
82% 100%

[Brief explanation of the drawing]

Figure 1 is an electron micrograph (SEM: magnification x 1n) of the antibacterial zeolite composition with hydrophobicity obtained by the present invention.
, ooo). Figure 2 is a moisture absorption curve. Curve 1 in the figure shows the antibacterial zeolite composition rich in hydrophobicity (NaAg
Curve 2 is for comparative purposes and includes an active substitute for the NaAgZ powder used in this example. This is a book showing the moisture absorption curves obtained.

Claims (1)

[Claims] 1. A hydrophobic antibacterial zeolite composition comprising an activated natural or synthetic zeolite having an antibacterial metal and a silicone coating agent coated on the surface thereof. 2. The composition according to claim 1, wherein the silicone coating agent has a viscosity (at 25° C.) of 2000 cps or less. 3. Zeolite is at least 1.5 SiO_2/Al_
A composition according to claim 1 or 2 having a molar ratio of 2O_3. 4. Claims 1 to 4, wherein the antibacterial metal is one or more metals selected from the group of silver, copper, zinc, mercury, tin, lead, bismuth, cadmium, chromium, cobalt, and nickel. The composition according to any one of Item 3. 5. The composition according to any one of claims 1 to 4, wherein the antibacterial metal is retained in the ion-exchangeable part of the zeolite. 6. After impregnating the activated natural or synthetic zeolite with antibacterial metals with a silicone-based coating agent or its solution, separating the solid and liquid phases, and then removing the remaining solvent from the treated zeolite phase. A method of making antimicrobial zeolite compositions having hydrophobic properties. 7. The method according to claim 6, wherein the impregnation treatment is performed at a temperature of 60°C or higher, and the solvent removal is performed by heating at 60°C or higher. 8. The method according to claim 6 or 7, wherein the zeolite is a powder, granules, or a preformed compact. 9. Claims 6 to 8, wherein the activated natural or synthetic zeolite containing antibacterial metals is provided with antibacterial metals by ion exchange by impregnating the zeolite with a solution of antibacterial metal ions. The method described in any one of the paragraphs. 10. The method according to any one of claims 6 to 9, wherein impregnation is performed using a solution consisting of a silicone coating agent and a flame-retardant solvent. 11. The method according to any one of claims 6 to 10, wherein the silicone coating agent has a viscosity (25° C.) of 2000 cps or less. 12. SiO_2/Al with zeolite at least 1.5
Claims 6 to 11 having a _2O_3 molar ratio
The method described in any one of the paragraphs. 13. Claims 6 to 6, wherein the antibacterial metal is one or more metals selected from the group of silver, copper, zinc, mercury, tin, lead, bismuth, cadmium, chromium, cobalt, and nickel. 12. The method according to any one of paragraphs 12.