JPH0680528A - Antimicrobial phosphate double salt, its propellant and its use - Google Patents

Abstract

PURPOSE:To obtain an antimicrobial plastic product having a long life by firmly bonding an antimicrobial agent having a long life only to the surface of the plastic product. CONSTITUTION:When a mold, a roller, etc., is sprayed with a propellant comprising 0.1-40wt.% antimicrobial phosphate double salt having <=10mum diameter prepared by supporting 0.1-5.0wt.% silver on a slightly soluble orthophosphate double salt consisting essentially of calcium and zinc, 0.01-2wt.% coupling agent and 58-99.98wt.% dispersion medium as liquid drops having 10-300mum diameter by a double liquid nozzle and a plastic product is produced by using the mold or roller, the antimicrobial phosphate double salt is transferred and firmly bonded to the surface.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an improved antibacterial / antifungal phosphate double salt, which is highly safe and durable, an antibacterial plastic spray containing the same, and a novel composition utilizing the same. The present invention relates to a method for producing a molded product having various antibacterial / antifungal plastics.

[0002]

2. Description of the Related Art Conventionally, it has been known that a trace amount of silver ion has antibacterial and antifungal properties. For example, Japanese Patent Publication Sho 52
Japanese Patent Publication No. 38666 discloses a method in which a silver nitrate solution is added to activated carbon to support silver, and the activated carbon for a water purifier has antibacterial / antifungal properties by a small amount of dissolved silver ions. Various inventions have also been made on a base material for supporting silver. For example, Japanese Patent Laid-Open No. 62-210098
JP-A No. 63-54013 discloses a bactericidal zeolite composition in which a silver ion is supported on a zeolite having a large specific surface area by an ion exchange method. Japanese Patent Laid-Open No. 63-265809 discloses a method of substituting a part of silver ions with ammonium ions in order to prevent discoloration of the bactericidal zeolite composition. No. 111709 discloses a method of supporting an ammine complex salt and an amine complex salt of silver in order to improve the alkali resistance of the bactericidal zeolite. Further, JP-A-1-221304 discloses an antibacterial agent in which a part of interlayer alkali metal of an inorganic layered compound such as montmorillonite is replaced with ammine silver, amine silver or the like, and further JP-A-2-221304. Japanese Patent No. 96508 discloses an antibacterial agent in which silver is supported on a sparingly soluble phosphate or condensed phosphate.

On the other hand, in Japanese Patent Publication No. 63-54013 mentioned above, a bactericidal zeolite composition in which silver ions are supported on a zeolite by an ion exchange method is mixed with nylon, polyester, and an acrylic polymer and spun, and then antibacterial. A method for producing a functional fiber is disclosed, and further, JP-A-63-63
JP-A-250325 discloses an antibacterial spray containing an antibacterial zeolite carrying an antibacterial metal such as silver by an ion exchange method, an alcohol, and a propellant.

[0004]

[Problems to be Solved by the Invention] Japanese Patent Publication No. 52-3866
The activated carbon supporting silver disclosed in Japanese Patent No. 6 has a drawback that when admixed with resin, the gas adsorbed by the activated carbon is released and the resin foams.
The silver-added glass disclosed in Japanese Patent Publication No. 98 has the drawbacks that it is difficult to make it into powder and that the elution of silver is fast. Similarly, the silver-loaded inorganic material disclosed in Japanese Patent Application Laid-Open No. 1-221304 has been disclosed. The layered compound also has a problem that it is difficult to form a powder. Further, JP-B-63-54013, JP-A-63-265809, and JP-A-2
Since the silver-supported zeolite composition disclosed in JP-A-1111109 has a strong adsorptivity, it has a drawback that when it is kneaded into a resin, it is foamed by vaporization of the adsorbed solvent and the like, and the kneaded resin is discolored. there were. In addition, JP-A-2-96
The sparingly soluble phosphate and condensed phosphate disclosed in Japanese Patent No. 508 have problems in terms of the amount of silver supported, the holding power, and the baking treatment. The first problem to be solved by the present invention is
An object is to provide a long-life silver-supported antibacterial agent by producing a base material capable of holding silver at a high concentration for a long time.

As disclosed in Japanese Examined Patent Publication No. 63-54013, a bactericidal zeolite composition carrying silver ions is mixed with nylon, polyester and acrylic polymer and spun to produce an antibacterial fiber. In such a method, since the antibacterial agent is distributed throughout the fiber-forming polymer, the antibacterial agent dispersed inside may not function effectively as an antibacterial agent and may adversely affect the physical properties of the fiber. There is also. In particular, unlike the case of fine fibers, the amount of such wasted antibacterial agents also increases in the case of ordinary thick plastic products. In order to solve such a problem, even if an antibacterial agent is applied to the surface of a plastic product, it will run off in a short period of time, making it difficult to impart antibacterial properties to the plastic product for a long period of time. A second problem to be solved by the present invention is to solve such a problem.

As disclosed in JP-A-63-250325, an antibacterial spray composition containing an antibacterial zeolite carrying an antibacterial metal such as silver by an ion exchange method, an alcohol, and a propellant, When using in a closed can with a sprayer, the spray pressure becomes low and the droplets become large immediately after the start of use and immediately before the end of use. Because of the small capacity of the small spray can that can be held in, it will be replaced immediately, and it is troublesome to use it for injection molding, and the treatment of the remaining empty can also became a problem. A third problem to be solved by the present invention is to solve such a problem,
The aim is to ensure uniform spray application.

[0007]

Means for Solving the Problems In order to solve the first problem, the present inventors have proposed a sparingly soluble orthophosphoric acid double salt of calcium and zinc, or calcium, zinc, magnesium, strontium and the like. 0.1 to 5.0% by weight of silver is supported on a sparingly soluble orthophosphoric acid double salt with one or more metals selected from the group consisting of alkaline earth metals other than calcium, aluminum, copper and zirconium. Provided is an antibacterial phosphate double salt.

Some of the inventors of the present invention have already proposed Japanese Patent Application No. 2-41827 as one method for solving the first problem.
In No. 7, magnesium, calcium, strontium, aluminum, manganese, nickel, copper,
And an antibacterial and antibacterial property, characterized in that 0.1 to 5.0% by weight of silver is supported on a sparingly soluble orthophosphoric acid double salt of two or more metals selected from the group consisting of zinc. A moldy phosphoric acid double salt was provided. Furthermore, in Japanese Patent Application No. 3-315618, zinc phosphate contains 0.1 to 5.0% by weight of silver or copper, or 0.1 to 5.0% by weight of silver and copper in total. Provided is an antibacterial / antifungal zinc phosphate compound characterized by being carried. The antibacterial phosphoric acid double salt according to the present invention is a further development of these inventions,
As a result of examining these inventions again in detail, it was found that the sparingly soluble orthophosphoric acid double salt of calcium and zinc has the most excellent characteristics and plays a central role in the antibacterial phosphorus according to the present invention. It has reached the acid double salt.

In the antibacterial phosphoric acid double salt according to the present invention, the sparingly soluble orthophosphoric acid double salt of calcium and zinc, which is the core thereof, tends to increase the specific surface area of the double salt when the ratio of calcium increases. Also, when a certain amount of silver is supported, the concentration of eluted silver tends to be low. This tendency is substantially maintained even for the sparingly soluble orthophosphoric acid double salt containing not only calcium and zinc but also metals such as magnesium, strontium, aluminum, copper and zirconium. Furthermore, when immersed in water for a long period of time, calcium phosphate gradually dissolves, but zinc and other phosphates do not dissolve and remain semi-permanently as a matrix. do not do. Therefore, by utilizing such a mechanism, it becomes possible to release a trace amount of silver ions over a long period of time.

If the amount of silver supported on the sparingly soluble orthophosphoric acid double salt is less than 0.1%, sufficient antibacterial property cannot be obtained, and if it exceeds 5.0%, discoloration or the like may occur. There is a fear. In addition, in order to produce a fine antibacterial phosphoric acid double salt that strongly binds and supports silver, enhances dispersibility when kneaded into resin, and can be used as a spray, mechanochemical reaction is used. It is preferable to manufacture it.

In order to solve the second problem, the present inventors have further solved the above-mentioned sparingly soluble orthophosphoric acid double salt of calcium and zinc, or calcium, zinc and magnesium.
0.1 to 5.0% by weight of a poorly soluble orthophosphoric acid double salt with one or more metals selected from the group consisting of alkaline earth metals other than calcium such as strontium, aluminum, copper and zirconium. Diameter 10μm supporting silver
The following antibacterial phosphoric acid double salt 0.1-40% by weight, coupling agent 0.01-5% by weight, and dispersion medium 55-99.
A spray agent for antibacterial plastics comprising 89% by weight is provided.

The present inventors have already filed Japanese Patent Application No. 3-3574.
No. 91, magnesium, calcium, strontium, aluminum, manganese, nickel,
0.1 to 5.0% by weight of a slightly soluble orthophosphoric acid double salt of two or more metals selected from the group consisting of copper and zinc
An antibacterial / antifungal phosphoric acid double salt having a particle size of 30 μm or less, which carries silver, 0.1 to 20% by weight, a dispersion 4.9 to 60% by weight, and a propellant 20 to 95% by weight. We provided a spray for fungi and fungi. The spray for antibacterial plastics according to the present invention is a further development of this spray for antibacterial / mold prevention.

In a general antibacterial propellant, the size of the particles of the antibacterial phosphoric acid double salt may be 30 μm or less, and even if the diameter exceeds 10 μm, the propellant The dispersibility and stability of the composition are somewhat low, and the injection nozzle is only slightly clogged, but like the spray agent for antibacterial plastics according to the present invention, the surface of an object spray-coated with a particularly low concentration is homogeneous. In the case of the problem of the nature, it is necessary to reduce the size of the sprayed droplets,
Accordingly, the particle size of the antibacterial phosphoric acid double salt is 1 mm in diameter.
It should be 0 μm or less. In order to produce such fine antibacterial phosphoric acid double salt, it is preferable to utilize a mechanochemical reaction.

As the coupling agent in the present invention,
Isopropyl triisostearoyl titanate, isopropyl tri (dioctyl pyrophosphate) titanate, isopropyl tri (n-aminoethyl) titanate, tetraoctyl bis (di-tridecyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-) Butyl) bis (di-tridecyl) phosphite titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyrophosphate) ethylene titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumylphenyl titanate, tetraisopropyl bis (dioctyl) Titanate coupling agents such as phosphite) titanate or acetoalkoxyaluminum diisopropylate Preferred aluminum-based coupling agent. These coupling agents have a hydrolyzable hydrophilic group portion that binds well to the antibacterial phosphate double salt having a hydrophilic surface, and a large-molecular-weight hydrophobic group portion that adheres well to the resin. By the action, the antibacterial phosphoric acid double salt spray-coated on the mold or roll is well adapted to the resin, so that it is almost 100% transferred to the resin, adheres well to the resin and does not easily fall off. Therefore, it is more preferable to select a coupling agent having a hydrophobic group portion that has a higher affinity for the resin to be transferred.

As the dispersion medium in the present invention, n-pentane, n-hexane, isohexane, n-peptane, n
Hydrocarbons such as octane, isooctane, n-decane, petroleum benzine, cyclohexane, benzene, methylene chloride, carbon tetrachloride, 1,1,1-trichloroethane,
Trichloroethylene, Freon 113, Freon 141b,
Halogenated hydrocarbons such as fluorobenzene and benzotrifluoride, alcohols such as ethanol, methanol, n-propanol, isopropanol and secondary butanol, ketones such as acetone, methylacetone and methylethylketone, and silicone such as dimethyl silicone oil. One or more kinds of oils and water are selected and used.

In addition to the antibacterial phosphoric acid double salt, the coupling agent and the dispersion medium, a releasing agent may be added to the spray agent for antibacterial plastics according to the present invention, or ethers and esters. A stabilizer such as polyhydric alcohol may be added. Further, a dispersant or a surfactant may be added.

In the antibacterial plastic spray agent according to the present invention, if the amount of the antibacterial phosphate double salt is less than 0.1%, a sufficient antibacterial property cannot be obtained unless a large amount of spray is used, so that gold It adversely affects the mold, roll, sheet, etc., and if it exceeds 40% by weight, spraying becomes difficult. A particularly preferred range is 0.5 to 10% by weight. The coupling agent is
When it is less than 0.01% by weight, it is difficult to adhere to a mold, roll, sheet or the like, and when it is transferred to a plastic molded product, it tends to fall off. If it exceeds 5% by weight, the surface of the antibacterial phosphoric acid double salt is covered with the coupling agent and the antibacterial property is lost.

In order to solve the second and third problems, the present inventors further used the above-mentioned spray agent for antibacterial plastics according to the present invention and having a diameter of 10 by using a two-fluid nozzle.
Fine droplets of ~ 300 μm are sprayed on the inner surface of the plastic molding die, and then the plastic is molded to transfer the antibacterial phosphoric acid double salt to the surface of the molded plastic, thereby to form the antibacterial plastic. A method for using an antibacterial spray for antibacterial plastics, which is characterized in that it is produced, and a plastic sheet is prepared by using the two-fluid nozzle to form an antibacterial spray for antibacterial plastics into fine droplets having a diameter of 10 to 300 μm Alternatively, the antibacterial property is characterized in that an antibacterial phosphoric acid double salt is transferred and pressure-bonded from the roller to the surface of the sheet or the film by spray coating on the roller when the film is molded or processed to produce an antibacterial plastic sheet or film. Using a two-fluid nozzle, the method of using the spray agent for plastics and the spray agent for antibacterial plastics according to the present invention Use of a spray agent for antibacterial plastic, characterized in that it is sprayed directly onto a plastic sheet or film as fine droplets having a diameter of 10 to 300 μm and then heat-processed to produce an antibacterial plastic product. Suggest a method.

The present inventors have already filed Japanese Patent Application No. 3-3574.
According to the specification of No. 91, not only the antibacterial and antifungal spray agent according to the invention is directly spray-coated on the wall surface of a bathroom, bath, etc., but also spray-coated on the inner surface of a mold of a plastic injection molding machine to obtain a plastic product. Disclosed is a method of transferring an antibacterial / antifungal agent onto the surface of the. The present invention is a further development of this method.

In the method of using the spray agent for antibacterial plastics according to the present invention, the two-fluid nozzle is a nozzle provided in the center for injecting gas such as compressed air, and a concentric slit provided around the nozzle. A nozzle that ejects a liquid such as the sprayed atomized atomized into a mist, and the liquid that flows out from the nozzles around it is blown off by the high-speed gas flow ejected from the nozzle in the center. The particles are ejected as fine particles. If the viscosity, surface tension, density, and gas type of the propellant are the same, the average diameter of the droplets ejected from this two-fluid nozzle is approximately
Since it is inversely proportional to the linear velocity of the injected gas, the diameter of the droplet of the propellant can be adjusted within a range of 10 to 300 μm with relative ease.

It is necessary to frequently replace the spray can, and immediately after the start of use and immediately before the end of use, the injection pressure becomes low, the injection speed becomes slow, and the droplets become too large. Is not preferred. Further, even with the other one-fluid nozzle, fine droplets cannot be formed, and the coating concentration on the surface of the object becomes high, which is not preferable. The antibacterial plastic spray agent according to the present invention has an application area of 1 m.
^Since 10 ml or less per ² is sufficient, it is preferable to use a two-fluid nozzle that can spray a small amount. If the diameter of the sprayed droplets is less than 10 μm, they will float in the air and become difficult to adhere to the mold, and if they exceed 300 μm, adjacent droplets will easily coalesce, resulting in uneven distribution. Therefore, it is not preferable.

The first method of using the spray agent for antibacterial plastics according to the present invention is a method of spray coating the inner surface of a molding die and transferring it to the surface of the molded plastic, which is injection molding. Method, vacuum molding method, pressure molding method, pressure molding method, vacuum casting method, blow molding method, foam molding method and the like. A second method of use is a method of continuously spray-coating on a molding or processing roller and continuously transferring it to a plastic sheet or a plastic film, which can be applied to a calendar molding method, a melt extrusion laminating method, or the like. The third method is a method in which a plastic sheet or film is directly spray-coated, and then pressed by a die from above and below to be molded, or heat-treated with a heating roller.

These methods of use according to the present invention include thermoplastic resins such as polyethylene, polypropylene, polyacryl, polyamide, polyester, vinyl chloride and polystyrene, phenol resins, epoxy resins, urea resins,
It can also be applied to thermosetting resins such as unsaturated polyester resins, and elastic bodies such as urethane rubber.

[0025]

The function of the antibacterial phosphoric acid double salt according to the present invention is not known in detail, but it is considered as follows. The poorly soluble orthophosphoric acid double salt of calcium and zinc tends to increase the specific surface area of the double salt as the ratio of calcium increases, and the concentration of eluted silver tends to decrease when a certain amount of silver is supported. It is in. This tendency is maintained even for a double salt containing not only calcium and zinc but also a metal such as magnesium, strontium, aluminum, copper and zirconium. Therefore, the phosphate double salt according to the present invention has a It is considered that the surface area is large and silver is strongly supported, so that it is possible to elute a trace amount of silver ions for an extremely long period of time. Furthermore, when immersed in water for a long period of time, only the calcium phosphate gradually dissolves, and zinc and other phosphates do not dissolve but remain as a matrix semipermanently. The elution of silver ions due to the dissolution of salts compensates for the attenuation of the silver ion concentration eluted from other parts, so that a minute amount of silver ions can be released gradually without attenuating the concentration. Will be possible.

It is not clear in detail how the antibacterial phosphoric acid double salt according to the present invention is transferred from the mold or roller to the plastic and firmly adhered by the antibacterial plastic spray agent according to the present invention. However, the following can be considered as the following. The antibacterial phosphate double salt adhering to the mold or roller forms fine protrusions, which penetrate into the melted or softened plastic and are firmly fixed to the plastic by a coupling agent, and Since the surface is smoothed, it is considered that the antibacterial phosphoric acid double salt according to the present invention is firmly adhered to the plastic and does not peel off thereafter.

[0027]

【Example】

A. Production of Antibacterial Phosphoric Acid Double Salt [Example A1] 750 ml of 25% phosphoric acid aqueous solution was added at 50 ° C.
Zirconium oxide (ZnO) 194.7 with heating and stirring
g to make it react, and further calcium hydroxide (Ca
(OH) ₂ ) 35.4 g was added and reacted. The reaction slurry was cooled to room temperature, transferred to a 2 l ball mill, kneaded for 6 hours, then 8.4 g of silver nitrate (AgNO ₃ ) was added, and further kneaded for 4 hours. The obtained slurry was washed with water, filtered, dried at 250 ° C., and pulverized to obtain a powder (hereinafter referred to as “powder 1”). The content of silver supported on this powder 1 was 1.0% by weight, and the average diameter was 2.3 mμ.

[Example A2] Zinc oxide (ZnO) 132.0 was added to 600 g of a 40% phosphoric acid aqueous solution heated to 80 ° C.
g, calcium carbonate (CaCO ₃ ) 163.2 g, and
Aluminum hydroxide (gibbsite _Al 2 _O 3 · 3H
₂ O) 42.4 g was gradually added and reacted, and the mixture was kept at 80 ° C. for 3 hours, then left to stand at room temperature and transferred to a 2 l alumina ball mill at the time when it reached 40 ° C., and silver nitrate (AgNO
₃ ) 7.9 g was added and kneaded for 10 hours. The obtained slurry was treated in the same manner as in Example A1 to obtain a powder (hereinafter referred to as "powder 2"). The content of silver supported on this powder 2 was 1.2% by weight, and the average diameter was 2.1 mμ.

[Comparative Example A1] 1/20 M silver nitrate aqueous solution 5
To 00 ml, 250 g of a dried product of sodium type A zeolite (Toyo Builder manufactured by Tosoh Corporation) was added, and the mixture was stirred at room temperature for 3 hours, then filtered and washed with water to remove excess silver ions. This was dried at 110 ° C. and pulverized to obtain a powder (hereinafter referred to as “powder 3”). The content of silver supported on this powder 3 was 1.1% by weight, and the average diameter was 3.0 mμ.

[Comparative Example A2] Calcium hydrogen phosphate (C
aHPO ₄ 2H ₂ O) 516 g and calcium carbonate (Ca
The powder obtained by mixing 200 g of CO ₃ ) was placed in a 2 l ball mill, 1000 g of pure water was added and kneaded for 16 hours, then 8 g of silver nitrate (AgNO ₃ ) was added and kneaded for another 4 hours. The obtained slurry was washed with water, filtered, dried at 250 ° C. and pulverized to obtain a powder (hereinafter referred to as “powder 4”).
The content of silver supported on this powder 4 was 1.1% by weight, and the average diameter was 3.3 mμ.

B. Production of Antibacterial Plastic Spray Agent [Example B] 16 g of each of Powder 1 and Powder 2 obtained in Examples A1 and A2, and a titanate coupling agent (manufactured by Ajinomoto Co., Inc., product number KR TTS) ) 0.16
g and 1000 ml of ethanol were added and dispersed and mixed with a homogenizer for 10 minutes to obtain a spray agent (hereinafter referred to as "spray agent 1" and "spray material 2").

[Comparative Example B] 1000 ml of ethanol was added to 16 g of the powder 3 obtained in Comparative Example A1, and the mixture was dispersed and mixed for 10 minutes with a homogenizer (hereinafter referred to as "Spray Agent 3").
I got). Further, the powder 4 obtained in Comparative Example A2 was treated in the same manner to obtain a propellant (hereinafter referred to as "spray agent 4").

C. Comparison of spraying conditions (1) Spraying / transfer of spraying agent Using a mold with completely cleaned inner surface, using an injection molding machine, at a molding processing temperature of 230 ° C, polypropylene (Noblene JHG manufactured by Mitsui Toatsu Co., Ltd.) ) Was molded, and a test piece of 25 × 50 × 2.5 mm (hereinafter referred to as “test piece 1”) was obtained from the obtained molded product. Further, the propellant 1 obtained in Example B was put into a tank (SCU-PA type spray cart unit manufactured by Spraying System Japan Co., Ltd.) equipped with a stirrer, and sprayed onto the inner surface of the mold using a one-fluid nozzle. After that, manufacture a molded product in the same way, and measure 25 x 50 x 2.5 m.
A test piece of m (hereinafter referred to as "test piece 2") was obtained. Furthermore,
Using a two-fluid nozzle from the same tank, diameter 10-3
After being ejected as a droplet of 00 μm onto the inner surface of the mold, a molded product was manufactured in the same manner to obtain a 25 × 50 × 2.5 mm test piece (hereinafter referred to as “test piece 3”).

(2) Observation of Transferring State by Microscope The surface of the test pieces 2 and 3 thus obtained was magnified at a magnification of 2 using a metallographic microscope (model PMG3 manufactured by Olympus Corp.).
As a result of observing at 00 times, the test piece 2 has a spotted pattern of the spray, and the test piece 3 has a uniform vaporization trace of spray droplets with a diameter of 50 to 100 μm. Was distributed in. Based on these results, the following test was carried out by spraying as droplets having a diameter of 10 to 300 μm using a two-fluid nozzle.

D. Adhesion state test (1) Spraying / transfer of spray agent The spray agent 2 obtained in Example B was put in a tank (SCU-PA type spray cart unit manufactured by Spraying System Japan Co., Ltd.) with a stirrer, and After ejecting the liquid droplets having a diameter of 10 to 300 μm on the inner surface of the mold using a fluid nozzle, a molded product is manufactured in the same manner as the test piece 1 and 25 ×
50 x 2.5 mm test piece (hereinafter referred to as "test piece 4")
Got Moreover, after spraying the spraying agent 3 and the spraying agent 4 obtained in Comparative Example B respectively on the inner surface of the mold in the same manner, a molded product was manufactured in the same manner, and each of them was 25 × 50 × 2.5 m.
m test pieces (hereinafter referred to as “test piece 5” and “test piece 6”) were obtained.

(2) Adhesion state test C. The test piece 3 obtained at the time of comparison of the spraying conditions and the above-mentioned test pieces 4, 5 and 6 manufactured under the same conditions as the test piece 3.
Each of them was placed in an ultrasonic cleaner (Model UT-204 high frequency output 200W manufactured by Sharp System Products Co., Ltd.) containing distilled water for 10 minutes, and then the water adhering to the surface was wiped 10 times with gauze. After that, it was observed again with a microscope. As a result, as shown in Table 1,
No drop of the antibacterial agent was observed in the spray agent for antibacterial plastics according to the present invention.

[Table 1]

E. Light resistance test For the test pieces 1, 3, 4, 5, and 6, a light resistance test was performed at 63 ° C. for 100 hours using a fade odometer.
The degree of discoloration of each test piece was observed. As a result, as shown in Table 2, discoloration was not observed at all in the products using the antibacterial phosphoric acid double salt according to the present invention.

[Table 2]

F. Moisture and Heat Resistance Test Specimens 1, 3, 4, 5, and 6 were put into an autoclave and kept at 121 ° C. for 15 minutes, and then the degree of discoloration of each specimen was observed. As a result, as shown in Table 3, discoloration was not observed at all in the products using the antibacterial phosphoric acid double salt according to the present invention.

[Table 3]

G. Antibacterial property test pieces 1, 3, 4, 5, and 6 were put in a bag made by heat-sealing a polyethylene film, and Escherichia coli (IPO 3301) and Staphylococcus aureus (IFO 3060) were placed therein. After dropping 0.1 ml of the bacterial solution consisting of the above, the bacterial solution was thoroughly spread over both sides of the test piece, and then the air inside the bag was discharged and sealed. These were pressed with a weight and placed in an incubator and kept for 24 hours. Thereafter, the surviving bacteria in the bag were washed out with 10 ml of phosphate buffer, and the number of surviving bacteria was measured for 1 ml of the washed-out liquid by the pour plate culture method using SCDLP agar medium. As a result, as shown in Table 4, it was found that the antibacterial phosphoric acid double salt according to the present invention was effectively transferred to plastic and had excellent antibacterial properties.

[Table 4]

H. Antifungal test Test pieces 1, 3, 4, 5, and 6 were prepared by putting sterilized potato dextrose agar medium in several dishes to solidify.
Placed on top of it, and separately cultivated Aspergillus niger (IPO 4414) was dispersed in 10 ml of 0.005% aqueous solution of dioctyl sodium sulfosuccinate in 10 ml of platinum and the spores were separated by centrifugation and the spores were separated by GPL.
The spore fluid dispersed in 10 ml of P medium was sprayed on each test piece and cultured in an incubator at 25 ° C. for 14 days. As a result, as shown in Table 5, it was found that the antibacterial phosphoric acid double salt according to the present invention was effectively transferred to plastic and had excellent antifungal properties.

[Table 5]

I. Transfer from Roller When using an extrusion laminating machine, using a nylon film (15 μm thickness) as a base film and polyethylene as a laminating resin, when producing a laminating film, non-contact of the primary cooling roll on the laminating resin side On the side surface, the spray agent for antibacterial plastics according to the present invention (spray agent 1) was applied with a two-fluid nozzle to a diameter of 10 to 3
An antibacterial laminate film was produced while spraying as 00 μm droplets. At this time, the film winding speed was 80 m / min, and the transfer amount of the antibacterial agent was about 200 mg / m ^2.
Met. As a result of observing the obtained film with a microscope,
It was confirmed that the antibacterial phosphoric acid double salt according to the present invention was transferred onto the film.

H. Direct spraying onto a sheet A polystyrene sheet was sprayed with the spray agent for antibacterial plastics according to the present invention (spray agent 1) with a two-fluid nozzle to a diameter of 10
As droplets of ˜300 μm, they were directly applied by spraying, sandwiched between molds from above and below, heated under pressure, and molded into a tray having a pattern on the bottom. As a result of observing the obtained tray with a microscope, it was confirmed that the antibacterial phosphoric acid double salt according to the present invention was transferred onto the film.

[0043]

Since the antibacterial phosphoric acid double salt according to the present invention has the above-mentioned constitution and action, it exhibits excellent antibacterial and antifungal properties for a long period of time, and is a spray for antibacterial plastic according to the present invention. Since the agent has the above-mentioned structure and action, it is applied uniformly or directly to the plastic surface indirectly or directly through a mold, roller, etc., and is extremely strongly adhered, so that the plastic product can be used for a very long time. The antibacterial and antifungal properties of can be maintained. Further, the method of using the antibacterial plastic spray agent according to the present invention has clarified means for effectively utilizing such a spray agent for the first time. From the above, it is considered that these present inventions make a great contribution in maintaining a healthy national life.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Satomi Manabe 866-25, Fuukainaka-cho, Sakai City, Osaka Prefecture (72) Inventor Yoshishi Yamada, Aichi Prefecture 3-21-4 Midorigaoka, Okazaki City (72) Inventor, Satoshi Takeuchi Aichi Prefecture 3-72, Suwa, Toyokawa City (72) Inventor Shin Minowa 151 Yakushiyama, Narumi-cho, Midori-ku, Nagoya-shi, Aichi

Claims (5)

[Claims] 1. A sparingly soluble orthophosphoric acid double salt of calcium and zinc, or calcium, zinc and magnesium,
0.1 to 5.0% by weight of a poorly soluble orthophosphoric acid double salt with one or more metals selected from the group consisting of alkaline earth metals other than calcium such as strontium, aluminum, copper and zirconium. Antibacterial phosphate double salt loaded with silver 2. The antibacterial phosphoric acid double salt according to claim 1, having a diameter of 10 μm or less, 0.1 to 40% by weight, and a coupling agent of 0.1.
01-5% by weight and dispersion medium 55-99.89% by weight
Spray agent for antibacterial plastics 3. The spray agent for antibacterial plastic according to claim 2, which has a diameter of 10 to 300 by using a two-fluid nozzle.
After spraying as fine droplets of μm on the inner surface of the plastic molding die, the plastic is molded, and the antibacterial phosphoric acid double salt is transferred to the surface of the molded plastic to produce the antibacterial plastic. Method of using spray agent for antibacterial plastic characterized by 4. The spray agent for antibacterial plastic according to claim 2, which has a diameter of 10 to 300 by using a two-fluid nozzle.
Fine droplets of μm are spray-applied to a roller when molding or processing a plastic sheet or film, and the antibacterial phosphoric acid double salt is transferred and pressure-bonded from the roller to the surface of the sheet or film to form an antibacterial plastic sheet or film. Of using a spray for antibacterial plastics, characterized in that 5. The spray agent for antibacterial plastic according to claim 2, which has a diameter of 10 to 300 by using a two-fluid nozzle.
A method for using a spray agent for antibacterial plastics, which comprises spraying a microscopic droplet of μm directly onto a plastic sheet or film and then heat-processing to produce an antibacterial plastic product.