JPH0742207B2 - Antibacterial spray composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to an antibacterial spray, and more specifically to an antibacterial spray containing an antibacterial zeolite.

[Conventional technology]

It has been conventionally known to impart antibacterial property (antibacterial property) to a polymer by using an antibacterial zeolite [JP-A-59-59]
No. 133235]. JP-A-59-133235 discloses a zeolite particle-containing polymer comprising an antibacterial zeolite and an organic polymer. However, the antibacterial property of the polymer is due to the action of the antibacterial zeolite existing in the vicinity of the surface of the polymer, and the antibacterial zeolite present inside the polymer has no antibacterial property. Hardly contributes. Therefore, from the viewpoint of increasing the utilization rate of the antibacterial zeolite, the antibacterial zeolite is preferably present only near the surface of the polymer.

Further, in order to obtain the polymer having antibacterial properties described in JP-A-59-133235, it is necessary to mix antibacterial zeolite into the polymer. However, this method cannot be applied to a polymer body already molded into a film, a plate, a container, a fiber, or the like, and is not limited to the polymer body, and cannot be applied to, for example, mold prevention on walls.

[Problems to be solved by the invention]

Therefore, an object of the present invention is to provide an antibacterial spray composition capable of imparting antibacterial property (bactericidal property) to an article to which antibacterial property is desired to be imparted easily and only to the surface of the article, and a spray using the composition. Especially.

[Means for solving problems]

The present invention is 1-10% by weight of antibacterial zeolite, alcohol
It relates to an antibacterial spray composition containing 29 to 49% by weight and 50 to 70% by weight of a propellant.

The present invention will be described below.

The composition of the present invention contains an "antibacterial zeolite". Here, the antibacterial zeolite is a substance in which a part or all of the ion-exchangeable ions in the zeolite are ion-exchanged with an antibacterial metal ion. Examples of the antibacterial metal ion contained in the antibacterial zeolite include ions of at least one metal selected from the group consisting of silver, copper and zinc. Furthermore, a part of the ion-exchangeable ions in the antibacterial zeolite used in the present invention is
Furthermore, it can be one that has been exchanged with ammonium ions. A composition containing an antibacterial zeolite containing ammonium ions is particularly preferable because the polymer to which it is applied rarely discolors with time.

That is, the antibacterial zeolite used in the present invention is a part or all of the ion-exchangeable ions in the zeolite, such as sodium ion, calcium ion, potassium ion, magnesium ion, iron ion and the like, and the antibacterial metal ion and further necessary. By substitution with ammonium ion. The content of silver ions in zeolite is 0.
From 1 to 15%, preferably from 0.1 to 5% is suitable from the viewpoint of exhibiting excellent antibacterial activity. The content of copper ions and zinc ions is preferably 0.1 to 8%. Further, it is appropriate that the content of ammonium ion in the zeolite is 0.5 to 5%, preferably 0.5 to 2% from the viewpoint of effectively preventing discoloration of the polymer or the like by the zeolite. In this specification,% means weight% on a 110 ° C. dry basis.

As the "zeolite" used for the antibacterial zeolite in the present invention, both natural zeolite and synthetic zeolite can be used. Zeolite is generally an aluminosilicate having a three-dimensional skeleton structure, and is represented by XM2 / n ₂ O ₃ Al ₂ O ₃ YSiO ₂ ZH ₂ O as a general formula.
Here, M represents an ion-exchangeable ion and is usually a monovalent or divalent metal ion. n is the valence of the (metal) ion. X and Y represent the respective metal oxides, silica coefficient, and Z represents the number of crystal waters. Specific examples of zeolites include A-type zeolite, X-type zeolite, Y-type zeolite, mordenite, clinoptilolite, chabazite, and erionite. However, it is not limited to these. The ion exchange capacity of these exemplary zeolites is 7 meq of A-type zeolite.
/ g, X-type zeolite 6.4meq / g, Y-type zeolite 5meq / g,
Mordenite 2.6 meq / g, Clinoptilolite 2.6 meq / g,
Chabazite is 5 meq / g and erionite is 3.8 meq / g, both of which have sufficient capacity for ion exchange with ammonium ions and silver ions.

Further, the synthetic zeolite has an average particle size of 0.2 to 10 μm, preferably 0.6 to 6 μm, and a maximum particle size of 10 μm or less, preferably 6 μm or less. Is preferred.

The method for producing the antibacterial zeolite used in the present invention will be described below.

INDUSTRIAL APPLICABILITY The antibacterial zeolite of the present invention can be ion-exchanged in the zeolite by bringing the zeolite into contact with a (mixed) aqueous solution containing antibacterial ions (silver ion, copper ion, zinc ion) prepared in advance and optionally ammonium ion Ions are replaced with the above ions. Contact is 10 to 70
℃, preferably 40 ~ 60 ℃ 3 ~ 24 hours, preferably 10 ~
It can be carried out by a 24-hour batch system or a continuous system (for example, a column method). The pH of the mixed aqueous solution is adjusted to 3-10, preferably 5-7. By this adjustment, it is possible to prevent precipitation of silver oxide or the like on the zeolite surface or in the pores, which is preferable. Further, each ion in the (mixed) aqueous solution is usually supplied as a salt. For example, silver ions are silver nitrate, silver sulfate, etc., copper ions are copper (II) nitrate, copper sulfate, etc., zinc ions are zinc (II) nitrate, zinc sulfate, etc., ammonium ions are ammonium nitrate, ammonium sulfate, ammonium acetate, etc. Can be used.

The content of antibacterial metal ions and the like in the zeolite can be appropriately controlled by adjusting the concentration of each ion (salt) in the mixed aqueous solution. For example, when the antibacterial zeolite contains silver ions and ammonium ions,
The ammonium ion concentration in the mixed aqueous solution was 0.85 M /
~ 3.1 M /, and the silver ion concentration is 0.002 M / ~ 0.15 M /, so that the ammonium ion content is 0.5 ~.
It is possible to obtain an antibacterial zeolite having 5% and a silver ion content of 0.1 to 5%. In addition, antibacterial zeolite is copper ion,
When containing zinc ions, the copper ion concentration in the mixed aqueous solution is 0.1 M / to 0.85 M /, and the zinc ion concentration is 0.15 M /.
~ 1.2M /, depending on the appropriate copper ion content
An antibacterial zeolite having a content of 0.1 to 8% and a zinc ion content of 0.1 to 8% can be obtained.

In the present invention, it is also possible to perform ion exchange by using an aqueous solution containing each ion alone in addition to the mixed aqueous solution as described above and sequentially bringing each aqueous solution into contact with zeolite. The concentration of each ion in each aqueous solution can be determined according to the concentration of each ion in the mixed aqueous solution.

The zeolite after the ion exchange is thoroughly washed with water and then dried. Drying is preferably carried out at 105 ° C. to 115 ° C. under normal pressure or at 70 ° C. to 90 ° C. under reduced pressure (1 to 30 torr).

The composition of the present invention contains an alcohol and a propellant in addition to the antibacterial zeolite.

Examples of the alcohol include ethanol and the like, and ethanol is particularly preferable from the viewpoint of safety.

Examples of the propellant include freon gas [eg trichlorofluoromethane, dichlorofluoromethane or a mixture thereof, dichlorotetrafluoroethane etc.], liquefied petroleum gas [eg propane, butane etc.] and the like. Butane is particularly preferable.

The composition of the present invention comprises antibacterial zeolite 1-10%, preferably 2-6%, alcohol 29-49%, preferably 35-40.
% And propellant 50-70%, preferably 55-65%.

The antibacterial spray composition of the present invention can be obtained in a conventional manner by sealing it in a can equipped with a sprayer. The spray can be used as a deodorant for shoes, a deodorant for body odor after sports, a deodorant, a deodorant for garbage, and a mildew-proofing spray. In addition, various resins,
It can also be used for the purpose of imparting antibacterial properties to the surface of paper, wood, cement, organic wall materials, inorganic wall materials, metals and the like.
That is, for example, polyethylene, polypropylene, vinyl chloride, ABS resin, nylon, polyester, polyvinylidene chloride, polyamide, polystyrene, polyacetal,
Polyvinyl alcohol, polycarbonate, acrylic resin, fluorine resin, polyurethane elastomer, polyester elastomer, phenol resin, urea resin, melamine resin, unsaturated polyester resin, epoxy resin,
Coating by spraying on thermoplastic or thermosetting resins such as urethane resin, rayon, cupra, acetate, triacetate, vinylidene, natural and synthetic rubber, and adding antibacterial, antifungal and algaeproof functions to these resins Is possible.

In the paint field, oil paints, lacquers, varnishes, alkyl resins, aminoalkyd resins, vinyl resins, acrylic resins, epoxy resins, urethane resins, water-based, powder-based, chlorinated rubber-based, phenol-based, etc. It is possible to add antibacterial, antifungal, and algae-proof functions to the coating film by coating it by spraying on the surface of the coating film.
In the algae building field, it is possible to add antibacterial, antifungal, and algaeproof functions by spraying and coating the surfaces of joint materials, wall materials, tiles, concrete, etc.

Wet tissues, paper packaging materials, cellophane paper,
It is possible to add antibacterial and antifungal functions to these papers by coating them by spraying on cardboard, liner paper, and freshness-keeping paper.

INDUSTRIAL APPLICABILITY The antibacterial spray composition of the present invention is not limited to the above-mentioned various fields, but can be used in all fields in which it is necessary to prevent the generation and growth of microorganisms such as general bacteria / fungi and algae.

Hereinafter, the present invention will be described in more detail with reference to Examples.

Reference Example (Preparation of antibacterial zeolite) Zeolite, A-type zeolite _{(Na 2 O · Al 2 O} 3: 1.9SiO 2
XH ₂ O (X = 3 to 5): average particle size 1.5 μm) was used. NH ₄ NO ₃ as a salt for providing the ions for the ion exchange were used AgNO ₃ and Cu (NO _3).

Water is added to 1 kg of A-type zeolite powder heated and dried at 110 ° C to make a slurry of 1.3, and then degassed by stirring, and an appropriate amount of 0.5N nitric acid solution and water are added to adjust the pH to 5 to 7. Then, the whole volume was made into a slurry of 1.8. Next, for ion exchange, NH ₄ NO ₃ 1.5 mol /, AgNO ₃ 0.10 mol /, Cu (N
O ₃ ) ₂ 0.35 mol / mixed aqueous solution 3 was added to bring the total volume to 4.8.
The slurry liquid was maintained at 40 to 60 ° C. and stirred for 10 to 24 hours while maintaining the equilibrium state. After completion of ion exchange, the zeolite phase was filtered and washed with room temperature water or warm water until excess silver and copper ions in the zeolite phase were eliminated. Next, the obtained zeolite was heated and dried at 110 ° C. to obtain an antibacterial zeolite.

Example (Antibacterial Test) A spray can (120 ml volume) was filled with a spray composition containing 2 g of the antibacterial zeolite prepared in Reference Example, 40 g of Freon gas (Freon 12) and 60 g of ethyl alcohol by a conventional method.

A spray paper composition having a diameter of 3 cm and sterilized by dry heat was sprayed with the above composition for spraying uniformly for 2 seconds and 4 seconds to give a test piece. The spray amount of the composition is about 5 m per piece of filter paper after air drying.
g (2 seconds spray) and 10 mg (4 seconds spray).

Then, the bacterial solution was inoculated so that the number of bacteria per test piece was 10 ^{4 to 5} , and the bacteria were stored at 37 ° C and the fungus at 30 ° C. Bacteria were SCDL at 0 (immediately after inoculation), 24 and 48 hours after storage
P liquid medium, fungus is GPLP liquid medium (both Daigo Nutrition Chemistry)
The bacteria in the test piece were washed out with and the washing solution was used as the test solution. For this test solution, the number of surviving bacteria was measured by the pour plate culture method (bacteria; 37 ° C for 2 days, fungus; 25 ° C for 7 days) using a culture medium for measuring the number of viable cells per test piece. Converted. The same amount of the bacterial solution as that inoculated to the test piece was inoculated to a dry heat sterilized filter paper piece having a diameter of 3 cm, which was similarly stored and the viable cell count was measured to serve as a control. The results are shown in Table 1.

(1) Test strain Escherichia coli IFO 3301 (Escherichia coli) Ataphylococcus aureus ATCC 6538P (Staphylococcus aureus) Pseudomonas aeruginosa IID P-1 (Pseudomonas aeruginosa) Bacillus cereus IFO 13494 (Cereus fungus) Aspergilles niger IFO 4407 (black noodle mold) Candida albicans IFO 1594 (Candida) (2) Medium for measuring the number of bacteria For bacteria… SCDLP agar medium (Daigo nutrition chemistry) For fungi… GPLP agar medium (Daigo nutrition chemistry) (3) Preparation of bacterial count Bacteria; ordinary broth After culturing overnight at 37 ° C. in the medium, the culture was prepared by diluting the culture as it was with sterile phosphate buffered saline ^* .

Black noodle mold; potato dextrose agar slant medium at 25 ° C 7
After culturing for one day, conidia were suspended in sterile 0.005% sodium dioctyl sulfosuccinate to prepare.

Candida; after culturing on YM agar slants for 2 days at 25 ℃,
The cells were prepared by suspending them in sterile physiological saline.

* Dissolve 34 g of monopotassium phosphate in 500 ml of purified water to give 1N
-Add 175 ml of sodium hydroxide to adjust the pH to 7.2, and then add purified water to bring the total volume to 1,000 ml. This solution 1.25m
1,000 ml with physiological saline added to l.

[Effects of the Invention] By using the composition of the present invention, antibacterial properties can be imparted to the surface of an object simply and reliably.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location A61K 33/34 33/38

Claims (10)

[Claims] 1. A composition for antibacterial spray containing 1 to 10% by weight of antibacterial zeolite, 29 to 49% by weight of alcohol and 50 to 70% by weight of propellant. 2. The composition according to claim 1, wherein the antibacterial zeolite is one in which a part or all of the ion-exchangeable ions in the zeolite are ion-exchanged with an antibacterial metal ion. 3. The composition according to claim 2, wherein the antibacterial metal ion is an ion of at least one metal selected from the group consisting of silver, copper and zinc. 4. The composition according to claim 2, wherein a part of the ion-exchangeable ions in the zeolite is further ion-exchanged with ammonium ions. 5. The composition according to claim 2, wherein the zeolite is a natural zeolite or a synthetic zeolite. 6. The average particle diameter of the antibacterial zeolite is 0.2-10.
The composition of claim 1 which is μm. 7. The composition according to claim 1, wherein the alcohol is ethanol. 8. The composition according to claim 1, wherein the propellant is a CFC gas or a liquefied gas. 9. A fluorocarbon is trichlorofluoromethane,
A composition according to claim 1 which is dichlorofluoromethane or a mixture thereof or dichlorotetrafluoroethane. 10. The composition according to claim 8, wherein the liquefied petroleum gas is propane or butane.