JPS627748A - Moistureproof antifungal zeolite composition 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 fluororesin 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., analycime, 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 fluororesin coating agent or its solution followed by separation of the solid phase from the liquid phase, the resultant zeolite phase being heated to >=50 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 moisture-proofing ability and a method for producing the same.

More specifically, the present invention involves treating active natural or synthetic zeolite containing antibacterial metals with a fluororesin coating agent or its solution having moisture-proofing ability to form a film on the surface of the zeolite. An object of the present invention is to provide an antibacterial zeolite composition having moisture-proofing, hydrophobic, or water-repellent properties that minimizes the effects of moisture, and a method for producing the same.

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. be. Taking advantage of the adsorption properties of zeolite, zeolite is widely used in the fields of drying (dehumidification), gas purification, and concentration. When the above-mentioned antibacterial zeolite fine powder or fine particles in which antibacterial metal ions are supported on zeolite are added to various polymers as a filler, they impart antibacterial ability to the polymer and also improve the properties of the polymer. It has been found that it has a significant effect on improving function and function. (Patent application 1973-7361, etc.). For example, antimicrobial zeolite micropowders can be added to paper compositions, natural or synthetic rubber compositions, plastic compositions, and pigment compositions (non-settling and matte pigments) to provide resistance to mold when uniformly dispersed. It has been confirmed that it has the effect of increasing the sterilization and antibacterial ability of various types of bacteria. As the polymer pair, polyethylene,
Polypropylene, polystyrene polyvinyl chloride, polyvinylidene chloride, polyamide, polyester, polyvinyl alcohol, polycarbonate, polyacetal, AB
Thermoplastic synthetic polymers such as S resin, acrylic resin, fluorocarbon resin, polyurethane, phenolic resin, Urya resin,
Thermosetting synthetic polymers such as melamine resin, unsaturated polyester resin, epoxy resin, urethane resin, rayon,
Examples include recycled or semi-synthetic polymers such as cupro, acetate, and triacetate. However, the above-mentioned polymers, organic polymers for the purpose of fiber formation (for example, nylon 6, nylon 66, polyvinyl chloride, polyethylene terephthalate, polyethylene, etc.) and rubber compositions,
When fine particles of antibacterial zeolite are added to a pigment composition and dispersed uniformly, the moisture contained in the antibacterial zeolite may interfere with uniform dispersion or may cause foaming, causing adverse effects. becomes. Furthermore, when the above-mentioned organic polymer is formed into a thin film, or when it is spun, a swelling phenomenon occurs in the reservoir of water adsorbed on the zeolite, which causes non-uniformity of the film or fiber breakage during the spinning process. It causes 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 object of the present invention is to provide economical moisture-proofing, hydrophobicization, or water-repellency to suppress the moisture absorption ability of various activated antibacterial zeolite fine powders or compacts used for adding the above-mentioned polymers. The aim is to establish the technology of nodame. For the above purpose, the present inventor conducted a series of tests on moisture-proofing of antibacterial zeolite and carefully studied the obtained results. The inventors have discovered an antibacterial zeolite composition that solves the above problems, and have arrived at the present invention.

(Means for Solving the Problems) That is, the present invention provides an antibacterial zeolite composition having moisture-proofing ability, which is composed of an activated natural or synthetic zeolite having an antibacterial metal and a fluororesin coated on the surface of the activated natural or synthetic zeolite. I will provide a.

The present invention also provides a method for producing an antibacterial zeolite composition having moisture-proofing ability as described above, in which an activated natural or synthetic zeolite containing an antibacterial metal is impregnated with a fluororesin coating agent or a solution thereof, and then hardened. A method is provided for making antimicrobial zeolite compositions with moisture barrier capabilities 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 an antibacterial theolide composition having moisture-proofing ability obtained by treating an activated natural or synthetic zeolite containing an antibacterial metal with a hydrophobic fluororesin or a solution thereof. In the present invention, in order to make the activated natural or synthetic zeolite moisture-proof or water-repellent, the activated zeolite containing an antibacterial metal can be added to a fluororesin or its solution heated at room temperature or heated, for example. . Instead of the above coating method, a fluororesin or its solution is sprayed onto activated antibacterial zeolite at room temperature or under heating to be moisture-proof or water-repellent to achieve the moisture-proof ability of the present invention. It is also possible to obtain antibacterial zeolite compositions economically.

As mentioned above, it is preferable to obtain the antibacterial zeolite composition having moisture-proofing ability of the present invention by treatment under heating. That is, activated natural or synthetic zeolite containing antibacterial metals is treated in a hydrophobic fluororesin or its solution at a temperature of 60°C or higher, the solid phase and liquid phase are separated, and then the treated When the zeolite phase is heat-treated in a temperature range of 50°C or higher, a film with low surface tension is formed on the zeolite phase and wetting becomes more uniform, resulting in the antibacterial zeolite with high moisture-proofing or water-repellent ability, which is the object of the present invention. The composition is easily obtained. In addition to the above-mentioned coating method, the antibacterial agent having moisture-proofing ability of the present invention can be obtained by adding an appropriate amount of a fluororesin or its solution to the activated antibacterial zeolite and mixing it using a mixer or the like. It is also possible to prepare synthetic zeolite compositions.

In the present invention, activated products of natural and synthetic zeolites containing antibacterial metals are used, and these antibacterial zeolites can be activated by performing normal heat treatment under normal pressure or reduced pressure. This is done by removing the moisture in the zeolite to the required extent. Although the activation temperature varies depending on the type and structure of the antibacterial zeolite, activation is usually carried out in a temperature range of 200 to 600°C. Most of the natural or synthetic zeolites containing antibacterial metals used in the present invention have a moisture content of less than 1% dust when activated in a temperature range of 220 to 500°C.

The natural or synthetic zeolite with activated antibacterial properties used in the present invention may be in the form of powder, particles, pellets, tablets, beads, plates, cylinders, or other special molded bodies (for example) or nicum molded bodies. The present invention can also be applied to antibacterial zeolites in the above-mentioned forms. Therefore, an activated product of antibacterial zeolite in any shape suitable for the purpose of use may be appropriately selected, and the present moisture-proofing method suitable for this product may be implemented.

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 S i 02
/Al2Oφ: at least 1.5, porous natural or synthetic zeolites are preferred, and even if they contain some impurity 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 based on AA203.
It is expressed as o2.2J20. M represents an ion-exchangeable metal ion, 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 crystal water. Many types of zeolite with different compositions, pore diameters, specific surface areas, etc. are known, but as a carrier for antibacterial metal ions used in the present invention, 5i02/
A203 is 1.5 or more, pores are developed,
Moreover, a material having a large specific surface area is preferable.

In the present invention, antibacterial metals include silver (I), copper (metals and ■), zinc (II), mercury (II), tin (■ and ■),
Lead (n), bismuth (II), cadmium (II), chromium (III), cobalt (II), nickel (II)
(7) One or more selected metals are used, and these antibacterial metals are supported on zeolite by ionization with the zeolite using a solution containing the above-mentioned antibacterial metal ions. By performing the exchange at room temperature or high temperature, the required amount of antibacterial metal may be replaced with M in the above general formula. The antibacterial zeolite prepared to a predetermined composition by the ion exchange method 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, as described above. , 200-600
Heat activated at ℃. Next, based on the present invention, for the active antibacterial zeolite obtained by the above method,
Coating with fluororesin may be performed.

As the antibacterial metal in the antibacterial zeolite used as a coating material in the present invention, one or more selected from the above-mentioned antibacterial metal group is 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 supporting it) and the purpose of use.

For example, the amount of metal in the metal-zeolide (anhydrous basis) is suitably 26% by weight or less for silver,9 with a preferred range of 0.001 to 10% by weight. Still referring to copper 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.
It is in. Of course, it is also possible in the present invention to use the above-mentioned silver, copper and zinc in combination. In addition, in the zeolite combination of silver, copper, zinc, mercury, tin, lead, bismuth, cadmium, chromium, cobalt and nickel used in the present invention, for example, sodium, potassium, calcium, magnesium, iron or other metals coexist. Since the antibacterial effect is not hindered even if these metals are present, there is no problem with the coexistence or residual presence of these metals.

As mentioned above, any natural or synthetic zeolite can be used as the Q zeolite material with a S io2/A# 03 molar ratio of 1.5 or more used to support the antibacterial metal in the present invention. For example, natural zeolite is analcine (Analcime: 5i02/A# 03).
= 8.6-5.6), Chabaz
ite: S io2/AA2 o,, = 3.2
~6-0 and 6.4-7.6) clinoptilolite (
C11noptilolite: S i 02 /
AA203=8.5~10.5), erionite (Er
ionite:5i02/Al2O3=5.8~7.4
), Faujasite (SiO2
/AA203=4.2~4.6), mordenite (Mo
rdenite: S io2/A# 03 = 8
．． 3-10.0), Phillip site
site: 5i02/Al2O3=2.6~4.
4) etc. are listed as 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, typical synthetic zeolides include A-type zeolide (SiO2/AA?203=1.5-2.4), X-
type zeolide (Sf02/Al1203 = 2~3
), Y-type zeolide (SiO2/A# 03 = 8
~6), mordenite (S i02/AA203 =
9-10), high silica zeolite (SiOz/Al2
O5>20), and these synthetic zeolites are suitable as a material for preparing the antibacterial zeolite composition having moisture-proofing ability of the present invention. Among the above, particularly preferred are synthetic A-type zeolides, X-type zeolides,
Y-type zeolites, high silica zeolites and synthetic or natural mordenites.

Next, the fluororesin 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 fluororesin is suitable for obtaining the antibacterial zeolite composition having moisture-proofing ability of the present invention. These fluororesins are used as they are or as a solution in a suitable solvent.

As a specific example of a hydrophobic fluorine-based coating agent suitable for the present invention, a fluorine acrylate ester commercially available from Sumitomo 3M Co., Ltd. is still stable even at ℃, so antibacterial zeolite coating is used in the present invention. It is also suitable for subsequent heat treatment. When diluting the former and using it for coating, chlorine-based and petroleum-based solvents, such as 1,1.1-) IJ dichlorotane (boiling point 40°C), are suitable, and the latter (trademark)
FC-77 (boiling point: 97°C, commercially available from Sumitomo 3M Ltd.) is exemplified as a suitable solvent. The coating agent liquid described above forms a preferable film exhibiting low surface tension on the antibacterial zeolite composition of the present invention, and is therefore effective in making it hydrophobic, water repellent, or moisture-proof.

In the present invention, moisture-proofing is carried out by coating activated antibacterial zeolite by the above-mentioned dipping method, spraying method, or mixing method using the above-mentioned coating agent solution or its diluted solution. Then, the treated antibacterial zeolite is heat-treated at room temperature (air drying) or in a temperature range of 50°C or higher under normal pressure or reduced pressure for a predetermined period of time, and as a result, the antibacterial zeolite composition is formed on the surface. The coating is well-uniformed, and a zeolite composition with excellent moisture-proofing properties, hydrophobicity, and water repellency is finally obtained.

Next, embodiments of the present invention will be described with reference to Examples, but the present invention is not limited to these Examples unless the gist thereof is exceeded.

Examples 1 to 5 In this example, JX-900 and ll'1uorad (trademark) FC-721, which are commercially available from Sumitomo 3M Co., Ltd. as a fluororesin coating liquid, were used.
Or, a specific example is described in which the antibacterial zeolite composition having moisture-proofing ability of the present invention is produced by a dipping method using diluted solutions of these coating agents (see Table 1).

In this example, the fluorinated solvent FC-77 was used as the diluent for FC-721, while 1.1.1-trichloroethane was used as the diluent for JX-900.

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

NaAgCuZ: Average particle diameter Day = 4.6 μm
; Ag = 2.39%; Cu = 8.41% (1
(10°C dry basis); Z=A-type synthetic zeolide matrix NaAgCuY: Dav = 1.16 μm;
Ag = 2.45%; Cu = 8.14% (110°C dry basis); Y = base of Y-type synthetic zeolide The fine powders of the above two types of antibacterial zeolites were placed under reduced pressure prior to the coating test. It was activated by firing (under reduced pressure) at 320° C. for 1.5 hours.

Next, 80 ml of the coating liquid shown in Table 1 was added to 30 g of activated antimicrobial zeolite fine powder, and the resulting mixture was gently stirred for about 30 minutes. Next, after separating the two phases, the zeolite phase was heat-treated under the conditions listed in Table 1 to finally obtain an antibacterial zeolite composition having moisture-proofing ability. Examples 1 and 2 used FC-721 as the coating agent, while Example 4 used JX-900. In Example 3, FC-721/FC-77 was used as the coating liquid.
A mixed diluted solution (FC-721=40%) was used, and in Example 5, a JX-900/1.1.1-trichloroethane mixed diluted solution (JX-900=20 vlo) was used.

On the other hand, the water absorption rates of the compositions of Examples 4 and 5 after 24 hours are 55.6% to 67.5% of that of Comparative Example 2. It was confirmed that the antibacterial zeolite compositions obtained in all Examples had sufficient moisture-proofing ability and also sufficient hydrophobicity and water repellency.

Next, in order to examine the antibacterial ability and bactericidal ability of the antibacterial zeolite composition having moisture-proofing ability obtained according to the present invention, evaluation of antibacterial ability and measurement of fungal killing rate were performed. The antibacterial activity was evaluated by the following method.

100mg/rr+A of the test substance! suspended at a concentration of
I let it soak into the disc. The medium is Mueller Hinton for bacteria.
As for the culture medium and fungus, Sabouraud agar medium was used. The test bacteria were suspended in physiological saline at 10/rr+l, and cultured in medium K.
O, 1 ml was dispersed with a Conrage rod, and the test disk was stuck on top. When determining effectiveness, bacteria should be
The presence or absence of inhibition zone formation was observed at 7°C for 18 hours. Furthermore, fungi were determined after one week at 30°C. Next, the fungal mortality rate was measured as follows. Aspergillus flavus and Aspergillus nig
er) spore suspension (104/mA) was injected and mixed into a test substance suspension (50 mg/ml) 9 rr+l, and allowed to act at 30°C for 24 hours. Part 0.1
mA! were dispersed on a Sabouraud agar medium, and after 48 hours at 30°C, the number of surviving individuals was measured to determine the mortality rate.

Tables 3 and 4 show test results for typical antibacterial zeolite compositions having moisture-proofing ability of the present invention. Table 3 shows the antibacterial properties of the antibacterial zeolite composition of the present invention obtained in Example 1 (NaAgCuY).
It turns out that the antibacterial effect against the bacteria Hylococcus aureus and Pseudomonas aeruginosa is good. Next, Table 4 shows Aspergillus fl as the test bacteria.
avus and Aspergillus niger
Example 1 (NaAgCuY),
Example 4 (NaAgCuZ), and Example 5 (m
This figure shows the results of measurements using the antibacterial composition of the present invention having moisture-proofing ability obtained with aAgcuZ.

(194% 467% 96% 5 98% 100%) The measurement results shown in Tables 3 and 4 show that the moisture-proof antibacterial zeolite composition of the present invention has an antibacterial effect. It shows that it is excellent.

Claims (1)

[Scope of Claims] 1. An antibacterial zeolite composition having moisture-proofing ability, comprising an activated natural or synthetic zeolite having an antibacterial metal and a fluororesin coated on the surface thereof. 2. Zeolite is at least 1.5 SiO_2/Al_
A composition according to claim 1 having a molar ratio of 2O_3. 3. Claim 1, 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. Or the composition according to item 2. 4. The composition according to any one of claims 1 to 3, wherein the antibacterial metal is retained in the ion-exchangeable portion of the zeolite. 5. After impregnating the activated natural or synthetic zeolite with antibacterial metals with a fluororesin coating agent or its solution, separating the solid and liquid phases, and then removing the remaining solvent from the treated zeolite phase. A method for producing an antibacterial zeolite composition having moisture-proofing ability by: 6. The method according to claim 5, wherein the impregnation treatment is performed at a temperature of 60°C or higher, and the solvent removal is performed by heating at 50°C or higher. 7. The method according to claim 5 or 6, wherein the zeolite is a powder, granule, or pre-molded compact. 8. Claims 5 to 7, wherein the activated natural or synthetic zeolite having 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. 9. The method according to any one of claims 5 to 8, which uses an impregnation treatment using a solution consisting of a fluororesin and a flame-retardant solvent. 10. SiO_2/Al with zeolite at least 1.5
A method according to any one of claims 5 to 9, having a molar ratio of _2O_3. 11. Claims 5 to 5, 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. 10. The method according to any one of paragraphs 10.