JP3503125B2 - Method for producing antibacterial / antifungal agent and antibacterial / antifungal agent - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an antibacterial / antifungal property-imparting material and an antibacterial / antifungal property-imparting material for imparting antibacterial and antifungal properties to plastic stationery and wall materials used in hospitals The present invention relates to a moldability imparting material.

[0002]

2. Description of the Related Art In recent years, stationery, daily sundries, bathroom products, etc. have been treated with antibacterial and antifungal treatments in consideration of health and hygiene so that various microorganisms such as molds and bacteria do not propagate. There is. In particular, in hospitals where antibiotics are heavily used, there is a great demand for plastic stationery and wall materials with antibacterial / antifungal properties because of the need to prevent nosocomial infections.

Conventionally, this kind of antibacterial / antifungal treatment has been carried out by kneading an antibacterial / antifungal agent into a resin used as a base material. Since such kneading is performed at high temperature,
When an organic antibacterial / antifungal agent is used, it scatters and the antibacterial / antifungal effect is weakened. For this reason,
Inorganic antibacterial and antifungal agents are used for kneading. Usually, microorganisms such as bacteria propagate on the surface of the base material, so that the antibacterial / antifungal agent exerts a sufficient antibacterial / antifungal effect if it is present on the surface of the base material or near the surface layer. However, in the method of kneading, since the amount of the antibacterial / antifungal agent exposed on the surface is extremely small, a sufficient antibacterial / antifungal effect cannot be obtained unless a large amount of the antibacterial / antifungal agent is kneaded. In that case, most of the antibacterial and antifungal agents are wasted. In addition, when a large amount of antibacterial / antifungal agent is added, there is a problem that the color is changed by light or the like.

Therefore, in order to solve the above drawbacks, a method for producing an antibacterial / antifungal property-imparting material is disclosed in JP-A-2-145.
As shown in 625, a radiation-polymerizable monomer and / or oligomer (radiation-curable resin) containing a metal-containing antibacterial / antifungal agent is applied to the surface of a substrate, and then the applied film is applied. A method has been proposed in which the coating film is cured by irradiating with an electron beam to impart antibacterial and antifungal properties to the surface of the base material. In this method, as the metal-containing antibacterial / antifungal agent, for example, a material in which a metal having antibacterial / antifungal properties such as silver is supported on zeolite is used. The metal-containing antibacterial / antifungal agent is added to the radiation-polymerizable monomer and / or oligomer in an amount of 1.5 wt% or more in order to obtain a sufficient antibacterial / antifungal effect.

[0005]

However, in the method for producing such an antibacterial / antifungal property-imparting material, since an inorganic metal antibacterial / antifungal agent is used, the coating film is cured by irradiation with an electron beam. However, depending on the content of the antibacterial / antifungal agent, the transparency may deteriorate. Further, since the antibacterial / antifungal agent contains a metal, when exposed to the air, a substance that easily reacts with the metal, such as silver, may react with halogen or sulfide, and when such a reaction occurs, Antibacterial and antifungal properties are lost, and light resistance is poor. Further, when a product provided with antibacterial and antifungal properties is burned and discarded by this method, there is a problem that a residue remains. Therefore, in order to eliminate such problems, it is not necessary to use an inorganic metal-based antibacterial / antifungal agent, and the antibacterial / antifungal agent can be effectively used without waste. Is desired to be realized.

Further, Japanese Patent Laid-Open No. 7-33892 describes the use of an organic tin compound, a chlorhexidine compound or the like as an organic antibacterial agent. However, since organotin compounds have strong toxicity and odor, while chlorhexidine is easily decomposed by light, it is not desirable to use these compounds as antibacterial agents.

The present invention has been made based on the above circumstances, and it is not necessary to use an inorganic metal-based antibacterial / antifungal agent, and the antibacterial / antifungal agent can be effectively used without waste. Further, it is intended to provide a method for producing an antibacterial / antifungal property-imparting material and an antibacterial / antifungal property-imparting material using an antibacterial / antifungal agent having less toxicity and odor and being hard to decompose by light. .

[0008]

A method for producing an antibacterial / antifungal property-imparting material according to the invention of claim 1 for achieving the above object is a 3-iodo-2-propynylbutylcarbamate and N, N. -Dimethyl-N'-phenyl-N'-
A coating agent containing a radiation-curable resin containing an antibacterial / antifungal agent containing at least one of (fluorodichloromethylthio) -sulfamide is applied on a substrate, and then the surface of the coating agent is irradiated with radiation to perform the coating. It is characterized by imparting antibacterial and antifungal properties to the substrate by forming a cured film of the agent.

A method for producing an antibacterial / antifungal property-imparting material according to a second aspect of the present invention is the method according to the first aspect, wherein the antibacterial / antifungal agent is added to the radiation curable resin in an amount of 100 to 2000.
It is characterized by the addition of ppm.

The method for producing an antibacterial / antifungal property-imparting material according to the third aspect of the present invention is 3-iodo-2-propynylbutylcarbamate and N, N-dimethyl-N'-phenyl-.
An antibacterial / antifungal agent containing at least one of N '-(fluorodichloromethylthio) -sulfamide, and a photopolymerization initiator are coated on a base material, and then the coating agent is applied. The surface of the substrate is irradiated with ultraviolet rays to form a cured coating film of the coating agent, thereby imparting antibacterial and antifungal properties to the substrate.

The antibacterial / antifungal property-imparting material according to the invention of claim 4 is 3-iodo-2-propynylbutylcarbamate and N, N-dimethyl-N'-phenyl-N '-(fluorodichloromethylthio)-. A coating agent containing an antibacterial / antifungal agent containing at least one of sulfamides in a radiation curable resin is applied on a substrate, and then the surface of the coating agent is irradiated with radiation to form a cured coating film of the coating agent. It is characterized by having done.

An antibacterial / antifungal property-imparting material according to the invention of claim 5 is characterized in that, in the invention of claim 4, 100 to 2000 ppm of the antibacterial / antifungal agent is added to the radiation curable resin. It is a thing.

The antibacterial / antifungal property-imparting material according to the invention of claim 6 is 3-iodo-2-propynylbutylcarbamate and N, N-dimethyl-N'-phenyl-N '-(fluorodichloromethylthio)-. An antibacterial / antifungal agent containing at least one of sulfamides, and a coating agent containing a photopolymerization initiator in an ultraviolet curable resin are applied on a substrate, and then the surface of the coating agent is irradiated with ultraviolet rays to form a coating solution. It is characterized in that a cured film of a coating agent is formed.

[0014]

The invention according to claim 1 has the above-mentioned constitution and serves as an antibacterial and antifungal agent, 3-iodo-2-propynylbutylcarbamate and N, N-dimethyl-N'-phenyl-.
A coating agent containing N '-(fluorodichloromethylthio) -sulfamide containing at least one of N'-(fluorodichloromethylthio) -sulfamide is used. By irradiating the surface of the coating agent with the coating agent to form a cured coating film of the coating agent, the base film can have sufficient antibacterial and antifungal properties. In particular, the present inventors have confirmed that the base material film treated by such a method has a bactericidal / mold-killing power rather than an antibacterial / mold-proof property. Further, since the addition amount of the antibacterial / antifungal agent may be very small, it can be used without waste, the cost can be reduced, and the transparency of the coating agent does not decrease so much. Furthermore, since the antibacterial / antifungal agent contains no metal, it is less susceptible to the substances in the air when exposed to the air, and when burned for disposal, almost no residue remains. There is an advantage that the burning process becomes easy.

According to the third aspect of the present invention, by the above-mentioned constitution, 3-iodo-2-propynylbutylcarbamate and N, N-dimethyl-N'-phenyl-N '-(fluorodichloromethylthio) are used as antibacterial and antifungal agents. -Use sulfamide containing at least one of
A coating agent containing an antifungal agent and a photopolymerization initiator in an ultraviolet curable resin is applied to, for example, the surface of a base film, and then the surface of the coating agent is irradiated with ultraviolet rays to form a cured coating film of the coating agent. As a result, the base film can have sufficient antibacterial and antifungal properties. In particular, the present inventors have confirmed that the base material film treated by such a method has a bactericidal / mold-killing power rather than an antibacterial / mold-proof property. Further, since the addition amount of the antibacterial / antifungal agent may be very small, it can be used without waste, the cost can be reduced, and the transparency of the coating agent does not decrease so much. Furthermore, since the antibacterial / antifungal agent contains no metal, it is less susceptible to the substances in the air when exposed to the air, and when burned for disposal, almost no residue remains. There is an advantage that the burning process becomes easy.

[0016]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS A first embodiment of the present invention will be described below with reference to the drawings. FIG. 1 is a diagram for explaining a method for producing an antibacterial / antifungal property-imparting material according to the first embodiment of the present invention, FIG.
Is a schematic configuration diagram of an electron beam irradiation apparatus used in the method for producing the antibacterial / antifungal property-imparting material, and FIG. 3 is a schematic circuit diagram of an electron beam generation unit of the electron beam irradiation apparatus.

In the first embodiment, the case where the base material imparting antibacterial / antifungal properties is a polymer film (hereinafter also referred to as a base material film) will be considered. For such a polymer film, for example, polymethylmethacrylate, polycarbonate, polystyrene, polypropylene, polyvinyl chloride, polyethylene, polyester, etc. are used. The thickness of the polymer film of the base material can be appropriately selected according to the product to be used, but is preferably in the range of 5 μm to 300 μm, and particularly soft such as polyethylene and polyvinyl chloride. 50 μm when using
It is desirable to be in the range of up to 200 μm.

In the method of manufacturing the antibacterial / antifungal property-imparting material of the first embodiment, the organic halogen-based antibacterial / antibacterial
A material containing an antifungal agent is used as a coating agent applied to the surface of the base film. The main components of the radiation curable resin are an acrylic oligomer and an acrylic monomer. Representative oligomers include epoxy acrylate, urethane acrylate, polyester acrylate and the like. Because of the high viscosity of oligomers, it is important to select a suitable diluent for its use. The monomer plays the role of this diluent. The types of monomers include monofunctional monomers and polyfunctional monomers. The purpose of the former is to reduce the viscosity and improve the adhesiveness, while the latter is used to improve the curability and obtain properties such as hardness.

The organic halogen-based antibacterial / antifungal agents include organic iodine-based or organic chlorine-based agents,
Those having extremely good compatibility with the radiation curable resin are used. A material that can maintain antibacterial properties and antifungal properties even when irradiated with radiation is used. Specifically, 3-iodo-2-propynylbutylcarbamate (IC≡CCH ₂ OCONHC ₄ H ₉ ) is used as an antibacterial / antifungal agent. This antibacterial / antifungal agent has a radiation curing resin content of 500pp
m is added. As described above, in the first embodiment, the added amount of the antibacterial / antifungal agent is 1/30 or less as compared with the conventional method using the metal-containing antibacterial / antifungal agent. There is. Generally, the amount of antibacterial / antifungal agent added is
The range of 100 ppm to 2000 ppm is preferable, and the range of 300 ppm to 1000 ppm is particularly desirable. The organic halogen-based antibacterial / antifungal agent contains no metal.

In the method for producing the antibacterial / antifungal property-imparting material of the first embodiment, first, as shown in FIG. 1 (a), a radiation curable resin 12 and an organic halogen antibacterial / antifungal agent 16 are mixed. The coating agent 10 is applied to the surface of the base film 2. Here, in FIG. 1, the antibacterial / antifungal agent 16 is illustrated as being present as a solid in the radiation curable resin 12, but in reality, the antibacterial / antifungal agent 16 is a radiation curable resin. It blends well in 12. As a method of applying the coating agent 10, for example, a gravure coating method, a Meyer rod method, a curtain coating method, or the like can be used.

Next, as shown in FIG. 1B, the surface of the coating agent 10 applied to the base film 2 is irradiated with an electron beam. Then, radicals are generated, which causes
Polymerization or crosslinking reaction of the monomers and / or oligomers occurs to form a polymer. As a result, a cured film of the coating agent 10 is obtained. Here, the thickness of the cured coating film of the coating agent 10 applied is preferably in the range of 1 μm to 50 μm. In particular, the lower limit of the film thickness of the cured film is preferably 2 μm in order to ensure the surface durability and the like, while the upper limit of the cured film thickness is a large warp of the base film 2 due to the cured film. It is desirable that the thickness be 20 μm in order to prevent the occurrence of The dose of the electron beam with which the surface of the coating agent 10 is irradiated is preferably in the range of 10 kGy to 150 kGy, and particularly preferably in the range of 20 kGy to 100 kGy. As described above, the method for producing the antibacterial / antifungal property-imparting material of the first example is completed, and the base film 2 is provided with antibacterial property and antifungal property.

Now, the electron beam irradiation apparatus used in the method of the first embodiment will be described. Such an electron beam irradiation apparatus is used for polymerization or crosslinking treatment on the surface of the object to be treated, and as shown in FIG.
The irradiation chamber 60 and the irradiation window 70 are provided.

The electron beam generator 50 has a terminal 52 for generating an electron beam and an accelerating tube 54 for accelerating the electron beam generated at the terminal 52 in a vacuum space (acceleration space). In order to prevent the electrons from colliding with the gas molecules to lose energy and to prevent the filament 52a from being oxidized, the inside of the electron beam generating unit 50 is 1.3 × 10 ⁻⁴ by a pump or the like not shown. 1.3 x 10 ^-5 Pa
Maintained in a vacuum. The terminal 52 includes a linear filament 52a that emits thermoelectrons and a filament 52a.
gun structure 52b supporting a and filament 52a
And a grid 52c for controlling the thermoelectrons generated in.

Further, as shown in FIG. 3, the electron beam generator 5
0 is a heating power source 56a for heating the filament 52a to generate thermoelectrons, a control DC power source 56b for applying a voltage between the filament 52a and the grid 52c, a grid 52c and an irradiation window portion 70. A DC power source 56c for acceleration that applies a voltage (acceleration voltage) is provided between the window foil 72 and the window foil 72.

The irradiation chamber 60 includes an irradiation space 62 for irradiating the object to be processed with an electron beam. Further, the object to be processed is moved in the irradiation chamber 60 from the left side to the right side in FIG. 2 by a conveying means (not shown) using rollers or the like. The periphery of the electron beam generator 50 and the irradiation chamber 60 is lead-shielded so that X-rays that are secondarily generated during electron beam irradiation do not leak outside.

The irradiation window portion 70 is a window foil 72 made of metal foil.
And a window frame structure 74 that supports the window foil 72 while cooling the window foil 72. The window foil 72 separates the vacuum atmosphere in the electron beam generating unit 50 from the irradiation atmosphere in the irradiation chamber 60, and the irradiation chamber 6 is separated by the window foil 72.
The electron beam is taken out within 0. As the metal used for the window foil 72, Ti foil having a thickness of about 10 μm is most often used.

The filament 52 is heated by the heating power source 56a.
When the filament 52a is heated by applying a current to a, the filament 52a emits thermoelectrons, and the thermoelectrons are attracted in all directions by the control voltage of the control DC power supply 56b applied between the filament 52a and the grid 52c. this house,
Only those that have passed through the grid 52c are effectively taken out as electron beams. The electron beam extracted from the grid 52c is accelerated in the acceleration space in the accelerating tube 54 by the acceleration voltage of the accelerating DC power supply 56c applied between the grid 52c and the window foil 72, and then the window foil. The object to be irradiated is irradiated through the irradiation chamber 60 below the irradiation window 70 through the irradiation chamber 72. The beam current is usually adjusted by setting the heating power supply 56a and the acceleration DC power supply 56c to predetermined values and making the control DC power supply 56b variable. Generally, in the electron beam irradiation apparatus, the dose absorbed by the object to be processed is proportional to the beam current. For this reason,
The absorbed dose of the electron beam can be adjusted by changing the beam current.

When such an electron beam irradiation apparatus is used in the method for producing the antibacterial / antifungal property-imparting material of the first embodiment, generally, the acceleration voltage is set to a value within the range of 100 kV to 500 kV. Is preferred. In particular, when the polymer film used as the base film 2 is one that is easily deteriorated by an electron beam such as polycarbonate or polypropylene, it is desirable to set the acceleration voltage to a value within the range of 100 kV to 250 kV. . Further, as in the first embodiment, when a surface treatment is performed, if a large amount of oxygen exists around the object to be treated, the radicals generated by irradiating the electron beam react with oxygen, The radical polymerization reaction is hindered. Therefore, the irradiation atmosphere in the irradiation chamber 60 is a nitrogen atmosphere. Specifically, the oxygen concentration in the irradiation atmosphere is preferably 1000 ppm or less, and particularly 500
It is desirable to set it to ppm or less.

Next, the inventors of the present invention carried out the antibacterial
A test for confirming the antibacterial effect and a test for confirming the antifungal effect were performed on the base film treated by the method for producing the antifungal property-imparting material.

In these tests, as the base film,
Lumira (registered trademark) (polyester film (PET)) manufactured by Toray Industries, Inc. was used. The base film has a thickness of 100 μm. The following three types of coating agents were mixed and used. That is, epoxy diacrylate (PEDA) as an oligomer,
Hydroxyethyl acrylate as monomer (HE
A) and 3-iodo-2-propynylbutyl carbamate (IC≡CCH ₂ OCONHC) as an antibacterial / antifungal agent
₄ H ₉ ) was used as a mixture. Here, the antibacterial / antifungal agent is composed of 30 mol% of oligomer and 70 mol of monomer.
% Mixture (radiation curable resin) to a concentration of 500 ppm. Next, this coating agent is applied to a base film with a Mayer bar coater to a thickness of 5 μm.
Was applied. After that, the acceleration voltage of the electron beam irradiation device is set to 165 kV, the irradiation atmosphere in the irradiation chamber 20 is set so that the oxygen concentration is 300 ppm or less, and the surface of the applied coating agent is irradiated with an electron beam at a dose of 50 kGy. By this, a cured coating film of the coating agent was formed. As an electron beam irradiation device, CB manufactured by Iwasaki Electric Co., Ltd.
250/15 / 180L was used.

First, the base film thus obtained is
Then, a test was conducted to confirm the antifungal effect. This mildew test
Is a test of the former Soviet Union national standard GOST-9049-75.
It was done according to. Here, as the test mold, ・ Aspergillus niger ・ Penicillium citrinum ・ Alternaria sp. ・ Chaetomium globosum ・ Cladosporium cladosporioides 5 kinds of bacterial strains were used. First, the above processing was performed
Film test with base film cut into 5 cm x 5 cm square
Piece A₁And the base film that has not been subjected to such treatment
cm × 5 cm square film test piece B₁And make
It was And the film test piece A₁, B₁GO respectively
Placed on ST agar. Next, add the above 5 test strains
The mixed spore suspension obtained by mixing is used as a medium and film sample.
Specimen A₁, B₁Sprinkle 1 ml on the side of and cover the container with a lid.
Culture was performed at a temperature of 27 ° C. And each film test piece
A₁, B₁The film test piece A₁, B
₁The state of the above mold was observed. The test results are shown in Figure 4.
You Here, each film test piece A ₁, B₁Against that
Three samples were prepared and tested, but all were the same.
One result was obtained. From FIG. 4, according to the method of the first embodiment,
Film test piece B not treated₁Then, after leaving
On the 7th day, mold development was not observed yet, but on the 14th day
Mold grows on the eyes and covers less than one third of the total area.
wait. And on the 21st day, the growth of mold is 3% of the total area.
Over one-third, less than two-thirds, and on the 28th day
Growth has exceeded two-thirds of the total area. On the other hand, the
Film test piece A treated by the method of one embodiment₁
Then, mold growth was not recognized even on the 28th day after leaving it.
It was Therefore, the substrate substrate treated by the method of the first embodiment is
It was confirmed that the film has a sufficient antifungal effect.

The present inventors also used a substrate film treated in the same manner as above, using silver ion-containing zeolite as an antibacterial / antifungal agent instead of 3-iodo-2-propynylbutyl carbamate. An antifungal test was conducted on. The test results are shown in the lower part of FIG. Here, three types of film test pieces C were produced. That is, the amount of the silver ion-containing zeolite added to the radiation curable resin was 1.
There are three types, one is 0 wt%, the addition amount of silver ion-containing zeolite is 1.5 wt%, and the addition amount of silver ion-containing zeolite is 2.0 wt%.
As shown in FIG.
Even after addition of wt%, mold growth was observed after 2 weeks of standing. Therefore, in the method of the first example, the amount of the antibacterial / antifungal agent added is very small compared to the method using the conventional silver ion-containing zeolite, but the substrate treated by the method of the first example It can be seen that the film is superior in antifungal property as compared with the film treated by the method using the conventional silver ion-containing zeolite.

Next, a test for confirming the antibacterial effect was conducted on the substrate film treated by the above method. Here, three kinds of test bacteria were used: Staphylococcus aureus (Staphylococcus aureus), Pseudomonas aeruginosa (Pseudomonas aeruginosa), and Escherichia coli (Escherichia coli). First, a film test piece A ₂ produced using a substrate film treated by the above method and a film test piece B ₂ produced using a substrate film not subjected to such treatment were prepared. next,
The culture solution of each bacterial species was diluted with sterilized physiological saline, and 0.1 ml of the diluted culture solution of each bacterial species was put into two Petri dishes. Then, the film test pieces A ₂ and B ₂ were placed on the culture solutions of the respective bacterial species and left overnight. Then add 2 ml of sterilized saline to each dish,
After shaking well, the viable cell count (X) in the solution was measured, and the viable cell count under the film was determined from this. This test result is shown in FIG.
Shown in. From FIG. 5, in the film test piece B _{2 which} was not treated by the method of the first example, the viable cell count under the film was 9.2 × 10 ⁴ cells / m for Staphylococcus aureus.
l, Pseudomonas aeruginosa, the number of viable bacteria under the film is 1.6 ×
As for 10 ⁵ cells / ml, the viable cell count under the film was 1.5 × 10 ⁵ cells / ml for E. coli. On the other hand, in the film test piece A ₂ treated by the method of the first embodiment,
The viable cell count (X) in the liquid was not detected for each bacterial species. Therefore, the viable cell count under the film is below the measurement limit (20
It is considered to be less than or equal to. Therefore, it was confirmed that the substrate film treated by the method of the first example has a sufficient antibacterial effect.

In the method for producing the antibacterial / antifungal property-imparting material of the first embodiment, 3-iodo-2-propynylbutylcarbamate is used as the antibacterial / antifungal agent, and the antibacterial / antifungal agent is contained in the radiation curable resin. For example, after applying the coating agent thus applied to the surface of the base material film, the surface of the coating material is irradiated with an electron beam to form a cured coating film of the coating material, so that the base material film has sufficient antibacterial and antibacterial properties. It can have moldiness. In particular, according to the tests conducted by the present inventors, it was confirmed that the base material film treated by such a method has a bactericidal activity and a fungicidal activity rather than an antibacterial activity and an antifungal activity.

Further, since the addition amount of the antibacterial / antifungal agent may be very small, the antibacterial / antifungal agent can be effectively used without waste, the cost can be reduced, and the transparency of the coating agent is so high. Does not fall. Furthermore, since the antibacterial / antifungal agent contains no metal, it is less susceptible to the substances in the air when exposed to the air, and when burned for disposal, almost no residue remains. There is an advantage that the burning process becomes easy. In addition, 3-iodo-2-propynyl butyl carbamate used as an antibacterial / antifungal agent has the characteristics that it has little toxicity and odor and is hardly decomposed by light.

Next, a second embodiment of the present invention will be described with reference to the drawings. FIG. 6 is a diagram for explaining a method for producing an antibacterial / antifungal property-imparting material according to the second embodiment of the present invention.

In the second embodiment, as in the first embodiment, the case where the base material imparting antibacterial / antifungal properties is a polymer film will be considered. In the method for producing an antibacterial / antifungal property-imparting material according to the second embodiment, an ultraviolet-curable resin containing an organic halogen-based antibacterial / antifungal agent and a photopolymerization initiator is added to the surface of the base material. Used as a coating agent to be applied. Here, the main components of the ultraviolet curable resin are an acrylic oligomer and an acrylic monomer. As the organic halogen-based antibacterial / antifungal agent, an organic iodine-based or organic chlorine-based agent having extremely good compatibility with the ultraviolet curable resin is used. Specifically, 3-iodo-2-propynylbutyl carbamate is used as an antibacterial / antifungal agent. This antibacterial / antifungal agent is added to the UV curable resin in an amount of about 500 ppm. Generally, the amount of the antibacterial / antifungal agent added is preferably in the range of 100 ppm to 2000 ppm, particularly 300 ppm to 1000 pp.
It is desirable to set it in the range of m. Further, as the type of the photopolymerization initiator, there are benzophenone which is a hydrogen abstraction type initiator and orthobenzoylbenzoic acid other than the above, and benzoin ether which is an intramolecular cleavage type initiator. This photopolymerization initiator is 2
About wt% is added.

In the method of manufacturing the antibacterial / antifungal property-imparting material of the second embodiment, first, as shown in FIG. 6A, the ultraviolet curable resin 14, the organic halogen-based antibacterial / antifungal agent 16a and the photopolymerization are used. The coating agent 10 a mixed with the initiator 18 is applied to the surface of the base film 2. Here, in FIG. 6, the antibacterial / antifungal agent 16a and the photopolymerization initiator 18 are illustrated as being present as solids in the ultraviolet curable resin 14, but in reality, the antibacterial / antifungal agent is actually used. The agent 16a and the photopolymerization initiator 18 are well dissolved in the ultraviolet curable resin 14.

Next, as shown in FIG. 6 (b), the coating agent 10a applied to the base film 2 is irradiated with ultraviolet rays. Then, a radical is easily generated by the photopolymerization initiator 18, whereby a polymerization reaction or a cross-linking reaction of the monomer and / or oligomer occurs in a chain to form a polymer. As a result, a cured film of the coating agent 10a is obtained. Here, the thickness of the cured coating film of the applied coating agent 10a is preferably in the range of 1 μm to 50 μm. In particular, the lower limit of the film thickness of the cured film is preferably 2 μm in order to ensure the surface durability and the like, while the upper limit of the cured film thickness is a large warp of the base film 2 due to the cured film. It is desirable that the thickness be 20 μm in order to prevent the occurrence of In an apparatus that irradiates ultraviolet rays, for example, the lamp load (tube input per unit arc length) is 80 W / cm to 320 W / cm.
A high pressure mercury lamp is used. Then, the high-pressure mercury lamp is used to irradiate ultraviolet rays for several seconds to several tens of seconds. Thus, the method for producing the antibacterial / antifungal property-imparting material of the second embodiment is completed, and the base film 2 is provided with antibacterial property and antifungal property.

Next, the inventors of the present invention carried out the antibacterial treatment of the second embodiment.
A test for confirming the antibacterial effect and a test for confirming the antifungal effect were performed on the base film treated by the method for producing the antifungal property-imparting material.

In these tests, as the base film,
Lumira (registered trademark) (polyester film (PET)) manufactured by Toray Industries, Inc. was used. The base film has a thickness of 100 μm. In addition, as a coating agent, benzoin isopropyl ether as a photopolymerization initiator was added to the coating agent used in the test in the first example.
The thing added wt% was used. Next, apply this coating agent to the base film with a Mayer bar coater to a thickness of 5μ.
It was applied so that it would be m. After that, by using a high pressure mercury lamp (lamp load 80 W / cm) manufactured by Iwasaki Electric Co., Ltd., the surface of the applied coating agent is irradiated with ultraviolet rays from a position of 10 cm in height for 10 seconds, whereby a cured coating film of the coating agent is obtained. Was formed.

Then, the base film thus obtained was subjected to a mildew proof test and an antibacterial test. Here, the antifungal test and the antibacterial test were performed in the same manner as the antifungal test and the antibacterial test in the first example. Therefore, detailed description of the procedure and the like will be omitted. As a result of the mildew proof test, in the substrate film treated by the method of the second example, similar to the experiment in the first example, no mold growth was observed even after 28 days of standing. Further, as a result of the antibacterial test, in the base film treated by the method of the second example,
Similar to the experiment in the above-mentioned first example, the viable cell count in the liquid was not detected, and therefore it is considered that the viable cell count is below the measurement limit (20) under the film. Thus, it was confirmed that the base film treated by the method of the second example had a sufficient antibacterial effect and antifungal effect.

In the method for producing the antibacterial / antifungal agent of the second embodiment, 3-iodo-2-propynylbutylcarbamate is used as the antibacterial / antifungal agent, and the antibacterial / antifungal agent and the photopolymerization initiator are used. The coating agent contained in the ultraviolet curable resin is applied to the surface of the base material film, for example, and then the surface of the coating material is irradiated with ultraviolet rays to form a cured coating film of the coating material. It can have antibacterial and antifungal properties. In particular, according to the tests conducted by the present inventors, the base film treated by such a method has a bactericidal power, rather than an antibacterial power / antifungal power.
It has been confirmed that it has a sterilizing effect. Other effects are similar to those of the first embodiment.

The present invention is not limited to the above embodiments, but various modifications can be made within the scope of the invention. In each of the above examples, the case where 3-iodo-2-propynylbutylcarbamate is used as the antibacterial / antifungal agent has been described. For example, the antibacterial / antifungal agent is an organic halogen-based one, and is decomposed. Temperature is 12
N, N-dimethyl-N'-phenyl-N '-(fluorodichloromethylthio) -sulfamide, which has a very good thermal stability at 0 ° C. and is used for antifungal paints, may be used. The present inventors conducted the above-mentioned antifungal test / antibacterial test when N, N-dimethyl-N′-phenyl-N ′-(fluorodichloromethylthio) -sulfamide was used as the antibacterial / antifungal agent. However, similar results were obtained. As antibacterial / antifungal agents, 3-iodo-2-propynylbutyl carbamate and N, N-dimethyl-
A mixture of N'-phenyl-N '-(fluorodichloromethylthio) -sulfamide may be used.

In the first embodiment described above, the case where the acrylic resin is used as the radiation curable resin has been described, but the methacrylic resin may be used as the radiation curable resin. Generally, any resin can be used as long as it is cured by the energy of radiation. Also in the second embodiment, as the ultraviolet curable resin, for example, a methacrylic resin may be used.

Further, in the above-mentioned first embodiment, the case where the surface of the coating agent is irradiated with the electron beam to form the cured coating film of the coating agent has been described. However, instead of the electron beam, for example, γ ray or the like is used. May be. By irradiating various kinds of radiation other than the electron beam to form a cured coating film of the coating agent, it is possible to give the substrate sufficient antibacterial and antifungal properties. However, since the dose rate of γ-rays is much smaller than that of electron beams,
To obtain a dose of 0 kGy, gamma rays have to be irradiated for several hours. For this reason, when the process according to the present invention is performed using γ-rays, it is difficult to perform in-line processing. Therefore, at present, it seems desirable to use electron beams.

[0047]

As described above, according to the invention of claim 1, 3-iodo-2-propynylbutyl carbamate and N, N-dimethyl-N'- are used as antibacterial and antifungal agents.
A compound containing at least one of phenyl-N '-(fluorodichloromethylthio) -sulfamide is used,
A coating agent containing an antibacterial / antifungal agent contained in a radiation curable resin, for example, after being applied to the surface of a base film, the surface of the coating agent is irradiated with radiation to form a cured coating film of the coating agent. The base film can have sufficient antibacterial and antifungal properties, and since the addition amount of the antibacterial and antifungal agent can be very small, it can be used without waste and the cost can be reduced. With
It does not significantly reduce the transparency of the coating agent, and since the antibacterial and antifungal agent does not contain any metal, it becomes less susceptible to the substances in the air when exposed to the air and burns. Antibacterial that can be easily burnt with almost no residue when discarded
It is possible to provide a method for producing an antifungal agent.

According to the invention of claim 3, 3-iodo-2-propynylbutylcarbamate and N, N-dimethyl-N'-phenyl-N '-(fluorodichloromethylthio) -sulfamide are used as antibacterial and antifungal agents. Using a coating containing at least one of the above, a coating agent containing an antibacterial / antifungal agent and a photopolymerization initiator in an ultraviolet curable resin, for example, is applied to the surface of the base film, and then ultraviolet rays are applied to the surface of the coating agent By irradiating the substrate with the composition to form a cured coating film of the coating agent, the base film can have sufficient antibacterial and antifungal properties.
Since the addition amount of the antifungal agent may be very small, the antifungal agent can be used without waste, the cost can be reduced, and the transparency of the coating agent is not so deteriorated. Since it contains no metal, it is less susceptible to the substances in the air when exposed to the air, and when burned for disposal, almost no residue remains, and combustion treatment can be performed easily. It is possible to provide a method for producing an antifungal material.

[Brief description of drawings]

FIG. 1 is a diagram for explaining a method for producing an antibacterial / antifungal property-imparting material according to the first embodiment of the present invention.

FIG. 2 is a schematic configuration diagram of an electron beam irradiation apparatus used in the method for producing the antibacterial / antifungal property-imparting material.

FIG. 3 is a schematic circuit diagram of an electron beam generator of the electron beam irradiation device.

FIG. 4 is a diagram showing the results of antifungal tests conducted on the film treated by the method of the first embodiment of the present invention and the film treated using silver ion-containing zeolite as an antibacterial / antifungal agent. .

FIG. 5 is a diagram showing the results of an antibacterial test performed on the film treated by the method of the first embodiment of the present invention.

FIG. 6 is a diagram for explaining a method for producing an antibacterial / mildewproofing material, which is a second embodiment of the present invention.

[Explanation of symbols]

2 Base film 10,10a coating agent 12 Radiation curable resin 14 UV curable resin 16,16a Antibacterial and antifungal agents 18 Photopolymerization initiator 50 electron beam generator 52 terminal 52a filament 52b Gun structure 52c grid 54 Accelerator 56a Heating power supply 56b Control DC power supply 56c DC power supply for acceleration 60 irradiation room 62 irradiation space 70 Irradiation window 72 Window foil 74 Window frame structure

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yoichi Sano 2-10-15 Higashi-Awaji, Higashiyodogawa-ku, Osaka City Katayama Chemical Research Institute Co., Ltd. (56) Reference JP-A-1-316265 (JP, A) ( 58) Fields surveyed (Int.Cl. ⁷ , DB name) C08J 7/00 C08J 7/04

Claims (6)

(57) [Claims] 1. 3-Iodo-2-propynylbutyl carbamate and N, N-dimethyl-N'-phenyl-N '.
A coating agent containing an antibacterial / antifungal agent containing at least one of-(fluorodichloromethylthio) -sulfamide in a radiation curable resin is applied on a substrate, and then the surface of the coating agent is irradiated with radiation to obtain A method for producing an antibacterial / antifungal property-imparting material, which comprises imparting antibacterial property and antifungal property to the substrate by forming a cured film of a coating agent. 2. The method for producing an antibacterial / antifungal property-imparting material according to claim 1, wherein 100 to 2000 ppm of the antibacterial / antifungal agent is added to the radiation curable resin. 3. 3-Iodo-2-propynylbutyl carbamate and N, N-dimethyl-N'-phenyl-N '.
-(Fluorodichloromethylthio) -sulfamide antibacterial and antifungal agent containing at least one, and a photopolymerization initiator after coating a coating agent containing ultraviolet curing resin on a substrate, the surface of the coating agent A method for producing an antibacterial / antifungal property-imparting material, which comprises imparting antibacterial properties and antifungal properties to the substrate by irradiating the substrate with ultraviolet rays to form a cured coating film of the coating agent. 4. 3-Iodo-2-propynylbutyl carbamate and N, N-dimethyl-N'-phenyl-N '.
A coating agent containing an antibacterial / antifungal agent containing at least one of-(fluorodichloromethylthio) -sulfamide in a radiation curable resin is applied on a substrate, and then the surface of the coating agent is irradiated with radiation to obtain Antibacterial characterized by the formation of a cured film of the coating agent
Antifungal material. 5. The antibacterial / antifungal agent according to claim 4, wherein the antibacterial / antifungal agent is added to the radiation curable resin in an amount of 100 to 2000 ppm. 6. 3-Iodo-2-propynylbutyl carbamate and N, N-dimethyl-N'-phenyl-N '
-(Fluorodichloromethylthio) -sulfamide antibacterial and antifungal agent containing at least one, and a photopolymerization initiator after coating a coating agent containing ultraviolet curing resin on a substrate, the surface of the coating agent An antibacterial / antifungal property-imparting material, characterized in that a cured coating film of the above-mentioned coating agent is formed by irradiating the surface with ultraviolet rays.