JPS63250325A - Antimicrobial composition for spray - Google Patents

Abstract

PURPOSE:To obtain the titled composition containing an antimicrobial zeolite, alcohol and propellant. CONSTITUTION:An antimicrobial zeolite [zeolite in which an ion capable of carrying out ion exchange is partially or wholly substituted by an antimicrobial metal ion (ion of silver, copper or zinc)] and propellant (e.g. flon gas such as trichlorofluoromethane or liquefied petroleum gas such as propane or butane) are incorporated to provide the aimed antimicrobial composition for spray. The composition contains suitably 1-10%, preferably 2-6% antimicrobial zeolite, 29-49%, preferably 35-40% alcohol and 50-70%, preferably 55-65% propellant. The spray is used as spray for deordorizing of shoes, deordorizing of body smell after sport, deodorant, deordorizing of garbage and antimicroorganism. Further, the spray can also be used for purpose providing antimicrobial properties on the surface of various kinds of resins, papers, woods, metals, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an antibacterial spray, and more particularly to an antibacterial spray containing an antibacterial zeolite.

[Conventional technology]

It has been known for some time that antibacterial zeolites can be used to impart bactericidal properties (antibacterial properties) to polymers [Japanese Patent Application Laid-Open No. 59-19902]
-133235 Publication]. JP-A-59-133235 discloses a polymer containing zeolite particles consisting of antibacterial zeolite and an organic polymer. However, the antibacterial properties of the polymer are due to the action of antibacterial zeolite present near the surface of the polymer, and the antibacterial zeolite present inside the polymer has no effect on the antibacterial properties of the polymer. contributes little. Therefore, from the viewpoint of increasing the utilization rate of the antibacterial zeolite, it is preferable that the antibacterial zeolite exists only near the surface of the polymer.

Furthermore, in order to obtain the antibacterial polymer described in JP-A-59-133235, it is necessary to mix antibacterial zeolite into the polymer.

However, this method cannot be applied to polymers that have already been molded into films, plates, containers, fibers, etc., and it cannot be applied not only to polymers but also to mold-proofing walls, etc. at all.

[Problem that the invention seeks to solve]

Therefore, an object of the present invention is to provide an antibacterial spray composition that can easily impart antibacterial properties (sterilizing properties) only to the surface of an article to which it is desired to impart antibacterial properties, and a spray using the composition. There is a particular thing.

[Means for solving problems]

The present invention relates to an antimicrobial spray composition comprising an antimicrobial zeolite, an alcohol and a propellant.

The present invention will be explained below.

The composition of the present invention contains "antibacterial zeolite". Here, the antibacterial zeolite is one in which some or all of the ion-exchangeable ions in the zeolite have been ion-exchanged with antibacterial metal ions. 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, some of the ion-exchangeable ions in the antibacterial zeolite used in the present invention are
Furthermore, it can be ion-exchanged with ammonium or nium ions. Compositions containing antibacterial zeolites containing ammonium ions are particularly preferred because the polymers to which they are applied are less likely to discolor over time.

That is, the antibacterial zeolite used in the present invention replaces some or all of the ion-exchangeable ions in the zeolite, such as sodium ions, calcium ions, potassium ions, magnesium ions, iron ions, etc. with the antibacterial metal ions and further necessary 1 for ammonium ion by
It has been replaced. The content of silver ions in the zeolite is suitably from 0.1 to 15%, preferably from 0.1 to 5%, from the viewpoint of exhibiting excellent antibacterial activity. In addition, the content of copper ions and zinc ions is both 0.1 to 8%.
It is preferable that Furthermore, the ammonium ion content in the zeolite is 0.5 to 5%, preferably 0.5%.
From the viewpoint of effectively preventing discoloration of polymers and the like caused by the zeolite, it is appropriate to set the content to 2%. still,
In this specification, % refers to % by weight on a dry basis at 110°C.

As the "zeolite" used for the antibacterial zeolite in the present invention, both natural zeolite and synthetic zeolite can be used. Zeolites are generally aluminosilicates with a three-dimensional skeleton structure, and have a general formula of XM2/nO.・YS102・2H,
Displayed as O. Here, M represents an ion exchangeable ion, and is usually a monovalent or divalent metal ion. n is (
(metal) ion valence. X and Y represent the respective metal oxide and silica coefficients, and Z represents the number of water of crystallization. Specific examples of zeolites include A-type zeolite, X-type zeolite, Y-type zeolite, mordenite, clinoptilolite, chabasite, and eri-onite. However, it is not limited to these. The ion exchange capacity of these exemplary zeolites is A
type zeolite? meq/g % X-type zeolite 6, 4
meq/g, Y-type zeolite 5 meq/g.

mordenite 2.6 meq/g, clinoptilolite 2.13 meq/g, chabasite 5 meq/g
, Erionai) 3.3 meq/g, and both have sufficient capacity for ion exchange with ammonium ions and silver ions.

In addition, the synthetic zeolite should have 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, to ensure good atomization when sprayed. This is preferable.

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

The antibacterial zeolite of the present invention is produced by contacting the zeolite with an aqueous solution containing (mixed) antibacterial ions (silver ions, copper ions, zinc ions) and, if necessary, ammonium ions, prepared in advance, so that the ions in the zeolite can be exchanged. The ion is replaced with the above ion. Contact is 10-7
It can be carried out at 0°C, preferably 40 to 60°C, for 3 to 24 hours, preferably 10 to 24 hours, by a batch method or a continuous method (for example, a column method). In addition, p of the above mixed aqueous solution
) I is adjusted to 3-10, preferably 5-7. This adjustment is preferable because it can prevent silver oxides and the like from being deposited on the zeolite surface or into the pores.

Further, each ion in the (mixed) aqueous solution is usually supplied as a salt. For example, silver ions include silver nitrate, silver sulfate, etc., copper ions include copper nitrate (■), copper sulfate, etc., zinc ions include zinc nitrate (■), zinc sulfate, etc., and ammonium ions include ammonium nitrate, ammonium sulfate, ammonium acetate, etc. Can be used.

The content of antibacterial metal ions, etc. in the zeolite can be appropriately controlled by adjusting the a degree 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 is 0.85M.
/l~3.1M/β, silver ion concentration 0. (10) 2M
/42~0.15M/! By doing so, an antibacterial zeolite having an ammonium ion content of 0.5 to 5% and a silver ion content of 0.1 to 5% can be obtained as appropriate.

In addition, when the antibacterial zeolite contains copper ions and zinc ions, the copper ion concentration in the mixed aqueous solution is 0.1M/
1 to 0.85M/β, zinc ion concentration is 0.15M/β
~1. ．． By adjusting the ratio to 2M/Il, an antibacterial zeolite having an appropriate copper ion content of 0.1 to 8% and a zinc ion content of 0.1 to 8% can be obtained.

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

After ion exchange, the zeolite 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 3 Qtorr).

In addition to the antimicrobial zeolite, the composition of the invention contains alcohol and a propellant.

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

Examples of the propellant include chlorofluorocarbon gas (for example, trichlorofluoromethane, dichlorofluoromethane, or a mixture thereof, or dichlorotetrafluoroethane) or liquefied petroleum gas (for example, propane, butane, etc.). Particularly preferred is butane.

The composition of the invention comprises 1-10% antibacterial zeolite, preferably 2-6%, alcohol 29-49%, preferably 35-40% and propellant 50-70%, preferably 55%.
It is suitable that the content is 65%.

An antibacterial spray can be obtained from the antibacterial spray composition of the present invention by sealing it in a can with an atomizer according to a conventional method. The spray can be used for deodorizing shoes, body odor after sports, deodorant, garbage deodorizing, and anti-mold spray. Also, various resins,
It can also be used to impart antibacterial properties to the surfaces of paper, wood, cement, organic wall materials, inorganic wall materials, metals, etc.

That is, for example, polyethylene, polypropylene, vinyl chloride, ABSI resin, nylon, polyester, polyvinylidene chloride, polyamide, polystyrene, polyacetal, polyvinyl alcohol, polycarbonate, acrylic resin, fluororesin, polyurethane elastomer, polyester elastomer, phenol resin, urea resin. ,
Antibacterial properties can be applied to thermoplastic or thermosetting resins such as melamine resins, unsaturated polyester resins, epoxy resins, urethane resins, rayon, Kinipla, acetate, triacetate, vinylidene, natural and synthetic rubbers by spraying the coating on them.・It is possible to add anti-mold and anti-algae functions.

In the paint field, there are a variety of oil-based paints, lacquers, paints, alkyl resins, amino alkyd 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, anti-mold, and anti-algae functions to the paint film by spraying it on the surface of the paint film.

In the construction field, it can be sprayed to coat the surfaces of joints, wall materials, tiles, concrete, etc. to add antibacterial, anti-mold, and anti-algae properties.

In the paper manufacturing field, wet tissues, paper packaging materials, cellophane paper,
It is possible to add antibacterial and anti-mildew properties to cardboard, paperboards, and freshness-preserving papers by spraying them to coat them.

The antibacterial spray composition of the present invention can be used not only in the above-mentioned fields but also in any field that requires prevention of the generation and proliferation of microorganisms such as general bacteria, fungi, and algae.

The present invention will be explained in more detail below with reference to Examples.

Reference example (preparation method of antibacterial zeolite)
120. :1,9SiO,"XH2O (X = 3~
5): Average particle size 1.5 μra) was used.

Salt to provide each ion for ion exchange
H4N 03, A g N Os and CLI (NO
3) z was used.

Add water to 1 kg of type A zeolite powder heated and dried at 110°C to make a slurry of 1.31, then stir and degas, and then add an appropriate amount of 0.5N nitric acid solution and water to make a slurry of 1.31.
H was adjusted to 5 to 7, and the entire slurry was made into a 1.81 slurry. Next, for ion exchange, Nl (, NO.

1.5-E-ru/β, AgN0. A mixed aqueous solution 31 of Q, l Q mol/1 and CLI (NO3) 20.35 mol/1 was added to make the total volume 4.81, and this slurry liquid was maintained at 40 to 60°C and stirred for 10 to 24 hours. An equilibrium state was reached and maintained. After the ion exchange was completed, the zeolite phase was passed through the mouth and washed with room temperature water or warm water until excess silver ions and copper ions in the zeolite phase were removed. Next, the obtained zeolite was heated and dried at 110°C,
Antibacterial zeolite was obtained.

Example (antibacterial test) 2 g of antibacterial zeolite prepared in the reference example, fluorocarbon gas (
A spray composition consisting of 40 g of Freon 12) and 60 g of ethyl alcohol was poured into a spray can (120 m
! , packed).

The above spray composition was uniformly sprayed on a dry heat sterilized filter paper piece having a diameter of 3 cm for 2 seconds and 4 seconds to prepare a test piece. The spray amount of the composition is approximately 5 mg (sprayed for 2 seconds) and 10 mg (sprayed for 4 seconds?!) per filter paper piece after air drying.
>.

Next, a bacterial solution was inoculated so that the number of bacteria per test piece was 104 to S, and the bacteria were stored at 37°C and the fungi at 30°C. At 0 (immediately after inoculation), 24 and 48 hours after the start of storage, the bacteria in the test pieces were washed out using 5CDLP liquid medium for bacteria and GPLP liquid medium for fungi (both manufactured by Daigo Nutritional Chemical Co., Ltd.), and the washing liquid was used as the test liquid.

For this test solution, the number of viable bacteria was measured by the pour plate culture method (bacteria: 2 days at 37°C, fungi: 7 days at 25°C) using a culture medium for bacterial count measurement, and the number of viable bacteria per test piece was determined. The same amount of bacterial solution as that inoculated on the test piece was
A control paper was inoculated onto a piece of dry heat sterilized filter paper, stored in the same manner, and the number of viable bacteria was measured. The results are shown in Table 1.

(1) Test strain cherichia coli IFO3301 (
Escherichia coli) Ataphylococcus aureus
ATCC6538P (Staphylococcus aureus) Pseudomonas aeruginosa II
D P-1 (Pseudomonas aeruginosa) Bacillus cereus
IFO13494 (Bacillus cereus) Aspergill
us niger rFo 4407 (black noodle mold) C
andida albicans IFO1594 (Candida> (2) m number measurement medium for bacteria 5CDLP agar medium (Carpenter Nutritional Chemistry) for fungi
GPLP agar medium (Daiko Nutrient Chemistry) (3) Preparation of bacterial solution Bacteria: After culturing in ordinary bouillon medium at 37°C overnight,
The culture was prepared directly by diluting it with 0 sterile phosphate buffered saline.

Steamed noodle mold; potato dextrose agar slant medium at 25℃
After culturing for 7 days, sterilize 0. (10) Prepared by suspending conidia in 5% sodium dioctyl sulfosuccinate.

After culturing the cells on a YM agar slant medium at 25° C. for 2 days, the cells were suspended in sterile physiological saline and prepared.

*Dissolve 34 g of potassium phosphate in 5 (10) d of purified water, add 175 ml of IN-sodium hydroxide, and adjust the pH.
After preparing 7.2, purified water was further added to bring the total amount to 1. (
10) 0m1! shall be.

This solution 1.25rnI! Add physiological saline to 1. (1
0)0m1! Something that is bound.

Table 1 Changes over time in test bacteria inoculated onto test pieces* Test sample: unsprayed filter paper; This means that no bacteria were detected.

〔Effect of the invention〕

By using the composition of the present invention, antibacterial properties can be easily and reliably imparted to the surface of objects.

Claims (12)

[Claims] (1) An antibacterial spray composition containing an antibacterial zeolite, alcohol, and a propellant. (2) Antibacterial zeolite 1-10%, alcohol 29-29%
49% and 50-70% propellant. (3) The composition according to claim (1), wherein the antibacterial zeolite is obtained by ion-exchanging some or all of the ion-exchangeable ions in the zeolite with antibacterial metal ions. (4) The composition according to claim (3), wherein the antibacterial metal ion is an ion of at least one metal selected from the group consisting of silver, copper, and zinc. (5) The composition according to claim (3), wherein a part of the ion-exchangeable ions in the zeolite are further ion-exchanged with ammonium ions. (6) The composition according to claim (3), wherein the zeolite is a natural zeolite or a synthetic zeolite. (7) Zeolite is A-type zeolite, X-type zeolite,
Y-type zeolite, mordenite, clinoptilolite,
The composition according to claim (3), which is chabasite or erionite. (8) The average particle size of antibacterial zeolite is 0.2 to 10μ
The composition according to claim (1), which is m. (9) The composition according to claim (1), wherein the alcohol is ethanol. (10) The composition according to claim (1), wherein the propellant is fluorocarbon gas or liquefied petroleum gas. (11) Claim No. 10, wherein the fluorocarbon gas is trichlorofluoromethane, dichlorofluoromethane, or a mixture thereof, or dichlorotetrafluoroethane.
Compositions as described in Section. (12) The composition according to claim (10), wherein the liquefied petroleum gas is propane or butane.