JP3108522B2 - Antibacterial composite - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antibacterial transparent resin, an antibacterial adhesive and an antibacterial resin molded product used for household goods or building materials.

[0002]

2. Description of the Related Art In recent years, most household products are made of resin, and the use of transparent resin is expanding because the inside can be seen through. On the other hand, the surface of most resins is a place where microorganisms live, and there is a demand for improved cleanliness.

[0003] In addition, paints mainly composed of resin are used on the surfaces of many household articles and building materials. Above all, a coating mainly composed of a transparent resin can protect and polish the surface without impairing the texture of the base.

[0004] However, most of the painted surface is a place where microorganisms live, and there is a demand for prevention of contamination such as darkening of the painted surface and improvement of cleanliness. Therefore, an organic antibacterial agent such as phenol is used by being mixed in a paint.

Further, transparent resin films for food packaging are:
Widely used for home and business use. On the other hand, almost all transparent resin films for food packaging are habitats of bacteria, and there is a demand for improved cleanliness.

[0006] Adhesives are used in many household articles and building materials. The main component of the adhesive is a natural or artificial polymer, and in most cases, bacterial propagation is observed at these sites of use, causing problems such as darkening and unsanitation. Therefore, an organic antibacterial agent such as phenol is used by being mixed with an adhesive.

[0007] Mixing of antibacterial particles into a resin molded product such as a thermoplastic resin to exert an antibacterial effect has been used for containers, wash tubs, trays and the like used in kitchens and bathrooms. . These are mainly obtained by kneading antibacterial particles into thermoplastic resin pellets in advance and molding them by injection molding or the like. Conventionally, the particle size of the antibacterial particles mixed into the resin has been about 0.5 to 10 μm.

[0008]

In general, microbial contamination on the resin surface starts when the microorganisms come into contact with water containing nutrients on the resin surface, and further adheres dust and the like, and finally generates slime. , Leading to bacterial growth. In particular,
In the case of a transparent resin, the occurrence of discoloration such as darkening on the surface significantly deteriorates characteristics of the resin. or,
In a transparent resin film for food packaging, safety for the human body is extremely important.

[0009] However, organic antibacterial agents conventionally used for suppressing the growth of microorganisms have a problem in safety to the human body and the environment.

Conventionally, antibacterial particles in the vicinity of the surface of a molded resin product after molding are easily buried in the resin. Particularly, the smaller the particle size, the more remarkable this tendency is. There were problems such as difficult control. On the other hand, when an attempt is made to apply the antibacterial particles to a thermosetting resin, the conventional antibacterial particles are easily subjected to a chemical change due to a sulfide added to cure the thermosetting resin, and the resin is converted into a resin. It was colored.
In addition, the thermosetting resin molded by compression molding generally has a low viscosity immediately after mixing with the sulphidating agent, so the surface of the finished antibacterial resin molded product is completely covered with the resin. There is a problem that the antibacterial particles are not in a form that shows outcrops.

[0011] The present invention has been made in consideration of the above-mentioned conventional problems, and a transparent resin which can prevent microbial contamination and has high safety to the human body and the environment, a paint containing the transparent resin as a main component,
Another object is to provide an antibacterial transparent resin such as a transparent resin film.

It is another object of the present invention to provide an antibacterial adhesive having high safety to the human body and the environment.

It is another object of the present invention to provide an antibacterial resin molded article which can be imparted with antibacterial properties and can enhance the antibacterial effect.

[0014]

According to the first aspect of the present invention, a tree is provided.
An inorganic antibacterial agent is kneaded in a fat material, and the inorganic antibacterial agent is mixed.
The fungicide has a refractive index equal to or close to the refractive index of the resin material.
Silver thiosulfato complex salt supported on a carrier with a refractive index
After that, at least a part of the surface has a refractive index of the resin material.
Coating material having the same or similar refractive index to
Antibacterial composite characterized by being coated with
It is.

According to a second aspect of the present invention, the resin material is a coating material.
Antibacterial properties, characterized by being a material used as the main ingredient
Complex.

According to a third aspect of the present invention, the adhesive is kneaded.
An antibacterial compound characterized by the fact that

According to the present invention , the inorganic antibacterial agent has high safety to the human body and the environment.

[0018]

[0019]

[0020]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below based on embodiments.

Example 1 In Example 1, an antibacterial transparent resin will be described.

First, a method for producing the antibacterial agent used in the present invention will be described.

A mixture 4 of 100 parts by weight of a water-soluble silver salt such as silver acetate, sodium sulfite and sodium bisulfite
50 parts by weight, and a water-soluble salt of sodium thiosulfate 30
0 parts by weight was added to and dissolved in water containing no chlorine, and mixed with sufficient stirring to obtain an aqueous solution of a silver thiosulfato complex.

The carrier for the antibacterial agent used in this embodiment is "JI
SZ0701 Silica gel desiccant for packaging "
Type silica gel powder. The B-type silica gel powder has a low moisture absorption rate at low humidity, a high moisture absorption rate at high humidity, and a high total moisture absorption at high humidity, and has an average particle size of about 3 μm.

The silica gel powder was dried at 180 ° C. for 2 hours or more. The silver thiosulfato complex solution was mixed with 100 parts by weight of silica gel so as to be 2 parts by weight as a silver component. Next, the water absorbed in the solvent and the carrier was promptly removed. Next, this was pulverized to a predetermined particle size to obtain silica gel carrying an antibacterial material.

After 100 parts by weight of the above silica gel is dispersed in a solution obtained by diluting 100 parts by weight of tetraethoxysilane as a reactive organosilicon compound in ethyl alcohol, pure water is added thereto to hydrolyze the tetraethoxysilane. And at least part of the surface of the silica gel was coated. Next, this was dried to obtain a silver silica gel-based antibacterial agent.

Next, 3 parts by weight of the above-mentioned silver silica gel antibacterial agent and 3 parts by weight of calcium stearate were mixed with 100 parts by weight of the melamine resin, and pressed at about 150 ° C.
Baking and curing at ℃ for 2 hours to obtain an antibacterial transparent resin.
This antibacterial transparent resin was subjected to an antibacterial test by the following method. Table 1 shows the results.

The antibacterial test was performed using E. coli (Escherichia col
i), Staphylococcus aureus (Staphylococcus aureus)
The method was based on the method of dropping bacteria. Evaluation was performed 3 days later.

The antibacterial transparent resin was subjected to a discoloration test by heating during molding, a discoloration test by exposure to ultraviolet light, and a discoloration test by immersion in a chlorine-based detergent, as compared with the resin to which no antibacterial agent was added. Was.

The transparency of the molded article was determined by the color state after molding, the heat discoloration during molding was determined by the change in the resin surface color after molding at 150 ° C., and the UV exposure test was determined by exposure to a sunshine weatherometer for 2000 hours. For the resin surface color change and the chlorine-based detergent immersion test, the resin surface color change after immersion in a 5% aqueous solution of sodium hypochlorite for 100 hours was examined. The results are shown in Table 2.

Table 1 shows that the antibacterial transparent resin of this example has practical antibacterial performance.

From Table 2, it can be seen that the antibacterial transparent resin of this example has practical discoloration resistance.

[0033]

[Table 1]

[0034]

[Table 2]

Example 2 In Example 2, a silver zeolite-based antibacterial agent was prepared in the same manner using zeolite instead of silica gel as a carrier, and used as an antibacterial agent.

3 parts by weight of a silver zeolite antibacterial agent and 3 parts by weight of calcium stearate are mixed with 100 parts by weight of a urea resin, pressed at about 150 ° C., and then baked at 100 ° C. for 2 hours to obtain an antibacterial transparent resin. .

An antibacterial test was carried out on this antibacterial transparent resin in the same manner as in Example 1. The result is the same as that of Example 1, and it is understood that it has practical antibacterial performance.

Further, the results of the discoloration test by heating at the time of molding, the results of the discoloration test by exposure to ultraviolet light, and the discoloration test by immersion in a chlorine-based detergent were compared with those of the resin to which the antibacterial agent was not added. A test was performed in the same manner as in Example 1. It can be seen that the result is similar to that of Example 1 and has practical discoloration resistance.

The antibacterial transparent resin of the above embodiment has silver, which is highly safe to the human body and the environment, supported on silica gel or the like as a thiosulfatosilver complex salt, and the surface is coated with a coating material. , Which has the effect of stabilizing the antibacterial effect on the resin surface for a long period of time. The antibacterial agent kneaded in the resin exerts an antibacterial action on bacteria approaching the vicinity of the resin surface.

Next, the main transparent resin material, silica gel,
Table 3 shows the refractive index of zeolite.

[0041]

[Table 3]

By using an antibacterial agent using silica gel or zeolite powder having the same refractive index as that of the transparent resin material shown in Table 3 as a carrier, the resin surface has an antibacterial effect and the transparency is impaired. You can not. Here, since the refractive index of silica gel or zeolite is in the range of 1.3 to 1.7, the refractive index of the transparent resin material is also in the range of 1.3 to 1.7 (close to 1.3 or 1.7). Other transparent resin materials can be used as long as the refractive index is out of this range.

The surface of the resin is exposed to chlorine-based chemicals and ultraviolet rays because it is used in various detergents and places exposed to sunlight, but the antibacterial agent in the resin is formed by coating a hydrolyzate of tetraalkoxysilane. As a result, the antimicrobial component is less likely to be directly affected by chlorine or ultraviolet light, and thus can have stable antimicrobial action and discoloration resistance.

Example 3 In Example 3, an antibacterial paint containing an antibacterial transparent resin as a main component will be described.

First, a silver silica gel antibacterial agent is prepared in the same manner as in Example 1.

Next, 40 parts by weight of vinyl chloride resin, 25 parts by weight of methanol, 10 parts by weight of ethyl acetate and 25 parts of toluene
1 part by weight of the above-mentioned silver silica gel antibacterial agent is mixed and stirred with
Obtain antibacterial paint. The antibacterial paint was spray-coated on SUS304 having a hairline and was dried and cured at room temperature for 48 hours, and subjected to an antibacterial test by the following method. Table 4 shows the results.

The antibacterial test was performed using E. coli (Escherichia col
i), Staphylococcus aureus (Staphylococcus aureus)
The method was based on the method of dropping bacteria. Evaluation was performed 3 days later.

The antibacterial paint is a conventional organic paint using a conventional organic antibacterial agent using phenol;
Compared to a paint without an antimicrobial agent, a transparency test after coating drying, a discoloration test by exposure to ultraviolet light, and a discoloration test by immersion in a chlorine-based detergent were performed.

Regarding the transparency of the coated product, the state of the hairline and the color were measured. The UV exposure test was performed by examining the change in the color of the coated surface after exposure to a sunshine weatherometer for 2000 hours. The chlorine-based detergent immersion test was performed using hypochlorite. The coating surface color change after immersion in a 5% aqueous solution of sodium acid for 100 hours was examined, and the results are shown in Table 5.

Table 4 shows that the antibacterial paint of this example has practical antibacterial performance.

From Table 5, it can be seen that the antibacterial paint of this example has practical discoloration resistance.

[0052]

[Table 4]

[0053]

[Table 5]

Example 4 In Example 4, a silver zeolite antibacterial agent was prepared in the same manner using zeolite instead of silica gel as a carrier, and used as an antibacterial agent.

25 parts by weight of styrene resin, 5 parts by weight of rosin,
5 parts by weight of soybean oil, 35 parts by weight of xylol and toluene 3
One part by weight of the silver zeolite-based antibacterial agent is mixed and stirred with 0 part by weight to obtain an antibacterial paint. This antibacterial paint is SUS304
, And dried and cured at room temperature for 48 hours, and subjected to an antibacterial test by the following method.

An antibacterial test was conducted on this antibacterial paint in the same manner as in Example 3. The result is the same as that of Example 3, and it can be seen that it has practical antibacterial performance.

Further, the antibacterial paint was compared with a paint to which no antibacterial agent was added and a conventional antibacterial paint using an organic antibacterial agent. A discoloration test by immersion in a detergent was performed in the same manner as in Example 3. It can be seen that the result is similar to that of Example 3 and has practical discoloration resistance.

As described above, the antibacterial paint of the present embodiment has silver, which is highly safe to the human body and the environment, supported on silica gel or the like as a thiosulfato silver complex salt, and is coated on the surface. , Which has the effect of stably maintaining the antibacterial effect in the paint for a long period of time. The antibacterial agent kneaded in the paint has an antibacterial effect on bacteria approaching the vicinity of the paint surface.

Here, as the transparent resin material which is the main material of the coating material, there is the same one as shown in Table 3 above.

By using the above-mentioned antibacterial agent using silica gel or zeolite powder having a refractive index similar to that of the transparent resin material shown in Table 3 as a carrier, the transparency of the paint is not impaired, and Does not impair the texture. Also in this case, the refractive index of the transparent resin material is in the range of 1.3 to 1.7 of silica gel or zeolite (the refractive index may be outside this range if the refractive index is close to 1.3 or 1.7). For example, another transparent resin material can be used.

The painted surface is exposed to chlorine-based chemicals and ultraviolet rays because it is used in various detergents and places exposed to sunlight, but the antibacterial agent in the antibacterial paint is a hydrolyzate of tetraalkoxysilane. The coating makes the antimicrobial component less likely to be directly affected by chlorine or ultraviolet light, so that it can have stable antimicrobial action and discoloration resistance.

Example 5 In Example 5, a film-shaped antibacterial transparent resin will be described.

First, a silver silica gel antibacterial agent is prepared in the same manner as in Example 1.

Next, 3 parts by weight of the above-mentioned silver silica gel antibacterial agent and 3 parts by weight of calcium stearate were mixed with 100 parts by weight of polyvinylidene chloride resin, and about 1 part by using an extruder.
A masterbatch was made at 80 ° C. This was applied to a molding machine to form a film having a thickness of 0.25 mm. This antibacterial food packaging transparent resin film was subjected to an antibacterial test by the following method in comparison with a conventional resin film. Table 6 shows the results.

The antibacterial test was performed using E. coli (Escherichia col
i), Staphylococcus aureus (Staphylococcus aureus)
The method was based on the method of dropping bacteria. Evaluation was performed 3 days later.

From Table 6, it was confirmed that the transparent resin film of this example had practical antibacterial performance.

[0067]

[Table 6]

Example 6 In Example 6, 100 parts by weight of polyvinyl chloride resin was mixed with 3 parts by weight of a silver silica gel antibacterial agent and 3 parts by weight of calcium stearate prepared in the same manner as in Example 5, and extruded. A masterbatch was made at about 170 ° C. using a machine. This is applied to a molding machine and has a thickness of 0.
A 25 mm film was made. An antibacterial test was conducted on this transparent resin film for antibacterial food packaging in the same manner as in Example 5. The result was the same as that of Example 5, and it was confirmed that it had practical antibacterial performance.

Example 7 In Example 7, 100 parts by weight of a polyvinyl acetate resin was mixed with 3 parts by weight of a silver silica gel antibacterial agent and 3 parts by weight of calcium stearate prepared in the same manner as in Example 5, and extruded. A masterbatch was made at about 170 ° C. using a machine. This was applied to a molding machine to form a film having a thickness of 0.25 mm. An antibacterial test was conducted on this transparent resin film for antibacterial food packaging in the same manner as in Example 5. The result was the same as that of Example 5, and it was confirmed that it had practical antibacterial performance. (Example 8) In Example 8, a silver zeolite-based antibacterial agent was prepared in the same manner using zeolite instead of silica gel as a carrier and used as an antibacterial agent.

3 parts by weight of the above-mentioned silver zeolite antibacterial agent and 3 parts by weight of calcium stearate were added to 100 parts by weight of polyethylene resin.
The parts by weight were mixed and a masterbatch was made at about 180 ° C. using an extruder. This is put on a molding machine and thickness is 0.2
A 5 mm film was made. An antibacterial test was conducted on this transparent resin film for antibacterial food packaging in the same manner as in Example 5. The result was the same as that of Example 5, and it was confirmed that it had practical antibacterial performance.

Further, the quality of the transparent resin film for the antibacterial food packaging of the above example was tested according to JIS Z 1707, and a predetermined standard was obtained.

As described above, the transparent resin film for the antibacterial food packaging of the above embodiment has silver having a high antibacterial action which is highly safe for the human body and the environment, supported on silica gel or the like as a silver thiosulfato complex salt. It has a structure in which an antibacterial agent capable of maintaining a stable effect for a long time is dispersed in a transparent resin film for food packaging. The antibacterial agent kneaded in the transparent resin film has an antibacterial effect on bacteria approaching the vicinity of the surface of the transparent resin film.

Next, Table 7 shows the refractive indexes of the transparent resin materials, silica gel and zeolite used for the transparent resin film.

[0074]

[Table 7]

By using the above-mentioned antibacterial agent using silica gel or zeolite powder having a refractive index similar to that of the transparent resin material shown in Table 7 as a carrier, the transparency of the film is maintained in a state where antibacterial performance is imparted. You can do it. Also in this case, the refractive index of the transparent resin material is in the range of 1.3 to 1.7 of silica gel or zeolite (the refractive index may be outside this range if the refractive index is close to 1.3 or 1.7). For example, another transparent resin material can be used.

In the above embodiment, the transparent resin film is used for food packaging, but the application is not limited to this.

(Embodiment 9) In Embodiment 9, an antibacterial adhesive will be described.

First, a silver silica gel antibacterial agent is prepared in the same manner as in Example 1.

Next, 60 parts by weight of urea, 30% formalin 2
Then, an appropriate amount of sodium hydroxide is added and p.
Neutralize to H7. After boiling, the mixture is refluxed for 10 minutes, 0.26 parts of formic acid is added, and the mixture is boiled for 3 hours to obtain a urea adhesive. To this, 6 parts by weight of the above-mentioned silver silica gel antibacterial agent is added to obtain an antibacterial adhesive. This adhesive was applied to rawan material and dried and cured at room temperature for 24 hours. As a comparison, a conventional organic adhesive using phenol and an adhesive without an antibacterial agent were used in the following method. An antibacterial test was performed. Table 8 shows the results.

The antibacterial test was performed using E. coli (Escherichia col
i), Staphylococcus aureus (Staphylococcus aureus)
The method was based on the method of dropping bacteria. Evaluation was performed 3 days later.

The antibacterial adhesive was subjected to a discoloration test by exposure to ultraviolet light after coating and drying and a discoloration test by immersion in a chlorine-based detergent, in comparison with a conventional organic adhesive and an adhesive to which no antibacterial agent was added. Was. Table 9 shows the results.
Shown in

For the UV exposure test, the color change of the coated surface after 2,000 hours exposure to sunshine weatherometer was examined. For the chlorine-based detergent immersion test, the color change of the coated surface after immersion in a 5% aqueous solution of sodium hypochlorite for 100 hours was examined. .

Further, in order to examine the deterioration of the adhesive strength due to bacterial contamination, an antibacterial adhesive and an antimicrobial-free adhesive were used to bond the Rawan agent, and the adhesive was used in an environment with a relative humidity of 95% and an air temperature of 35 ° C. After standing for a week, the compressive shear bond strength was examined. Table 10 shows the results.

Table 8 shows that the antimicrobial adhesive of this example has practical antimicrobial performance.

Table 9 shows that the antibacterial adhesive of this example has practical discoloration resistance.

From Table 10, it can be seen that the antibacterial adhesive of this example has a practical adhesive strength.

[0087]

[Table 8]

[0088]

[Table 9]

[0089]

[Table 10]

Example 10 In Example 10, a silver zeolite-based antibacterial agent was prepared in the same manner using zeolite instead of silica gel as a carrier, and used as an antibacterial agent.

25 parts by weight of styrene resin, 5 parts by weight of rosin,
5 parts by weight of soybean oil, 35 parts by weight of xylol and toluene 3
One part by weight of the above-mentioned silver zeolite-based antibacterial agent is mixed and stirred with 0 parts by weight to obtain an antibacterial adhesive. This antibacterial adhesive is SUS3
04 was spray-coated, and dried and cured at room temperature for 48 hours, and subjected to an antibacterial test by the following method.

An antibacterial test was performed on this antibacterial adhesive in the same manner as in Example 9. The result is the same as that of Example 9, and it can be seen that it has practical antibacterial performance.

Further, the antibacterial adhesive was compared with the adhesive to which no antibacterial agent was added, and the transparency after coating and drying was improved.
A discoloration test by exposure to ultraviolet light and a discoloration test by immersion in a chlorine-based detergent were performed in the same manner as in Example 9. It can be seen that the result is the same as that of Example 9 and has practical discoloration resistance.

As described above, the antibacterial adhesive of the above-mentioned embodiment has a silver thiosulfato complex salt, which is highly safe for the human body and the environment, supported on silica gel or the like, so that the effect can be stably maintained for a long period of time. Has a structure dispersed in an adhesive. The antibacterial agent kneaded in the adhesive has an antibacterial effect on bacteria on the application surface or in contact with the adhesion surface. Also, with respect to an adhesive bonded with an antibacterial adhesive, if a solvent such as water is present in the adhesive itself or in the surroundings, the antibacterial agent transferred in the solvent can exert an antibacterial effect. The antibacterial effect on the adhesive surface is a function that suppresses the growth of bacteria on the adhesive surface, which makes it possible to weaken the adhesive surface due to the invasion of bacteria into the adhesive and to suppress the deterioration of the adhesive strength. Becomes

The adhesive surface is exposed to chlorine-based chemicals and ultraviolet rays because it is used in various detergents and places exposed to sunlight, but the antibacterial agent in the antibacterial adhesive is a hydrolyzate of tetraalkoxysilane. Since the antibacterial component is hardly directly affected by chlorine or ultraviolet light by the coating of the, it is possible to have stable antibacterial action and discoloration resistance.

Since the antibacterial agent in the antibacterial adhesive is coated with a hydrolyzate of tetraalkoxysilane, the antibacterial component is hardly directly affected by chlorine and ultraviolet rays, so that the discoloration can be suppressed.

(Example 11) In Example 11, an antibacterial resin molded product will be described.

The antibacterial particles used in Example 11 are characterized in that a silver thiosulfato complex salt is supported on silica gel, and a part or all of the surface is coated with a coating material.

Next, a method for producing silver silica gel antibacterial particles will be described.

First, 100 parts by weight of a water-soluble silver salt such as silver acetate is added to and dissolved in water containing no chlorine, 450 parts by weight of a mixture of sodium sulfite and sodium bisulfite, and 300 parts by weight of a water-soluble salt of sodium thiosulfate. The parts were sequentially mixed and dissolved with sufficient stirring to obtain an aqueous solution of a silver thiosulfato complex. The weight of sodium thiosulfate is indicated as the weight of the hydrate _{Na 2 S 2 O 3 · 5H} 2 O.

In this example, the carrier used for the silver silica gel antibacterial particles is a B-type silica gel powder described in "JIS Z 0701 Silica Gel Desiccant for Packaging". The B-type silica gel powder is a silica gel powder having a low moisture absorption rate at low humidity, a high moisture absorption rate at high humidity, and a high total moisture absorption at high humidity, and its particle size can be controlled. In this embodiment, the average particle size is about 30 μm.

The silica gel powder was dried at 180 ° C. for 2 hours or more. The silver thiosulfato complex solution was mixed with 100 parts by weight of silica gel so as to be 2 parts by weight as a silver component. Next, the water absorbed in the solvent and the carrier was promptly removed. Next, this was pulverized to a predetermined particle size to obtain silica gel carrying an antibacterial material.

Next, 100 parts by weight of the above silica gel was dispersed in a solution of 100 parts by weight of tetraethoxysilane diluted and mixed with 100 parts by weight of ethyl alcohol as a coating material, and 20 parts by weight of pure water was added thereto. The tetraethoxysilane was hydrolyzed to coat at least a part of the surface of the silica gel. Next, this was dried to obtain silver silica gel antibacterial particles.

Next, an antibacterial resin molded product (or molded product)
As the base resin, polypropylene is used as a thermoplastic resin. The antibacterial resin molded product of the present invention is formed by mixing silver silica gel antibacterial particles and resin in a conventional manner into pellets,
It is molded by injection molding or the like.

The composition is as shown in Table 11.

[0106]

[Table 11]

The antibacterial performance of the above molded antibacterial resin was evaluated by the following test method.

According to the above embodiment, width 2 cm, length 3 c
A test plate having a thickness of 2 mm and a thickness of 2 mm was molded. Further, a comparative control test plate in which the particle size of the silver silica gel antibacterial particles was 3 μm was produced in the same manner as in Example 11 above.
0.2 ml of a phosphate buffer containing 4.5 × 10 ⁵ (viable cells / ml) of Escherichia-coli 3301 is dropped on a test plate, and allowed to stand at 37 ° C. After a certain period of time, the bacterial solution on the test plate is placed in a petri dish, and poured with a normal agar medium for general bacteria (manufactured by Nissui Pharmaceutical Co., Ltd.) at 40 ° C. When the agar solidifies, it is cultured at 37 ° C. for 18 hours and the number of colonies is counted. The standing time is set several times, and the time change of the viable cell count is measured.

Table 12 shows the results of the antibacterial test when the antibacterial particles having a particle size of 3 μm were added to the thermoplastic resin and when the particles had a particle size of 30 μm.

[0110]

[Table 12]

(Example 12) In the same manner as in Example 11, silver silica gel-based antibacterial particles were prepared, and an antibacterial resin molded product was produced using unsaturated polyester which is a thermosetting resin as a base resin. I do. The composition is as shown in Table 13.

[0112]

[Table 13]

The antibacterial performance of the above antibacterial resin molded product was evaluated by the following test method.

According to the above embodiment, width 2 cm, length 3 c
A test plate having a thickness of 2 mm and a thickness of 2 mm was molded. Further, a comparative control test plate in which the particle size of the silver silica gel-based antibacterial particles was 3 μm was produced in the same manner as in Example 12 above.
0.2 ml of a phosphate buffer containing 45 × 10 ⁵ (viable cells / ml) of Escherichia-coli 3301 is dropped on a test plate, and allowed to stand at 37 ° C. After a certain period of time, the bacterial solution on the test plate is placed in a petri dish, and poured with a normal agar medium for general bacteria (manufactured by Nissui Pharmaceutical Co., Ltd.) at 40 ° C.
When the agar solidifies, it is cultured at 37 ° C. for 18 hours, and the number of colonies is counted. The standing time is set several times, and the time change of the viable cell count is measured.

Table 14 shows the results of the antibacterial test when the antibacterial particles having a particle size of 3 μm were added to the thermosetting resin and when the particle size was 30 μm.

[0116]

[Table 14]

(Example 13) A silver silica gel viscose solution having a composition of 100% by weight of a viscose liquid prepared by a known method and the same concentration of 20% by weight of silver silica gel-based antibacterial particles as in Example 11 was 0.1 mm in diameter. Spinning from a spinning hole having 2,200 holes in a spinning funnel filled with spinning water.
The mixture was extruded at a discharge rate of 50 ml / min, and was sufficiently coagulated in a spinning funnel. The temperature and flow rate of the used spinning water are 3
0 ° C., 15 l / l. Then, 1.4
The fiber surface is regenerated by passing through a 0.3% by weight aqueous sulfuric acid solution for 0.3 seconds. The spun yarn is washed with water and desulfurized with sodium sulfide. Perform washing, dyeing, washing, and oil treatment. This is cut to a length of about 0.5 mm, and this is used as antibacterial particles (rayon).

As a base resin of the antibacterial resin molded product, polypropylene is used as a thermoplastic resin. The obtained rayon antibacterial particles and resin are mixed by a conventional method to form a pellet, and then molded by injection molding or the like.

The antibacterial performance of the above antibacterial resin molded product was evaluated by the following test method.

According to the above embodiment, width 2 cm, length 3 c
A test plate having a thickness of 2 mm and a thickness of 2 mm was molded. Further, a comparative test plate using rayon particles obtained from rayon fibers to which no silver silica gel-based antibacterial particles were added was produced in the same manner as the above production method. Escherichia coli
-coli 3301) was dropped on a test plate, and 0.2 ml of a phosphate buffer solution containing 4.5 × 10 ⁵ (viable cell count / ml) was dropped on the test plate.
Leave at 7 ° C. After a certain period of time, the bacterial solution on the test plate is placed in a petri dish, and poured with a normal agar medium for general bacteria (manufactured by Nissui Pharmaceutical Co., Ltd.) at 40 ° C. When the agar solidifies, it is cultured at 37 ° C. for 18 hours and the number of colonies is counted. The standing time is set several times, and the time change of the viable cell count is measured.

Table 15 shows the results of the antibacterial test when the rayon particles were added to the thermoplastic resin and when the rayon particles were added to the thermoplastic resin.

[0122]

[Table 15]

As described above, in the antibacterial resin molded product of the above embodiment, by setting the particle size of the antibacterial particles to 30 μm or more, the number of outcrops of the mixed antibacterial particles on the surface of the molded product as it is can be obtained. Therefore, the antibacterial effect can be increased as compared with the related art, regardless of whether the base resin is a thermosetting resin or a thermoplastic resin.

Further, by making the melting point of the antibacterial particles higher than the melting point of the base resin, the number of outcrops of the antibacterial particles can be increased.

In general, it is necessary that the resin molded article has antibacterial properties under use conditions such that a liquid containing bacteria that is harmful or uncomfortable to the human body is in contact with the resin molded article. . Therefore, the antibacterial resin molded product formed by mixing the antibacterial particles into the resin has an antibacterial property by the antibacterial particles exposed on the surface of the resin molded product eluting silver ions into a liquid in contact with the resin. It is based on the mechanism of action that is exerted.

However, since the particle size of the antibacterial particles to be mixed into the resin has conventionally been about 0.5 to 10 μm, the antibacterial particles near the resin surface were easily buried. This tendency is more remarkable as the particle size is smaller. Therefore, the antibacterial particles on the surface and near the surface of the molded resin article were almost covered with the resin and did not contribute to the elution of silver, and the antibacterial ability was reduced. The reason that the antibacterial particles are buried inside the resin is
This is because the presence or absence of the head angle of the particles (outcrop) is determined by the interaction between the surface tension and viscosity of the resin at the time of curing the resin and the mobility of the particles. There are a wide variety of types of resins generally used, and thus the surface tension and viscosity of the resins have different values. By adding antibacterial particles having a particle size of about 30 μm or more, the composition can be applied to any resin, the outcrop of the antibacterial particles can be expanded, and the elution amount of silver ions can be increased.

On the other hand, when a thermosetting resin is used as a base material, the effect of increasing the particle size described above increases. The reason will be described below. In general, thermosetting resin molded by compression molding has the property of shrinking after curing, so when antibacterial particles are added, the resin molded product is formed by the presence of antibacterial particles near the surface as in the above-described operation. A crater-like depression occurs on the surface of the slab. Next, the resin surrounding the particles near the surface also shrinks due to the effect of shrinkage at the time of curing, whereby the effect of particle outcrop further increases.

Therefore, by incorporating antibacterial particles having a particle size of 30 μm or more into the thermosetting resin, it is possible to increase the outcrop of the antibacterial particles due to shrinkage during curing of the resin.

Further, if the melting point of the antibacterial particles is higher than the melting point of the base resin and the particle system is 30 μm or more, the above-mentioned effects can be applied to any substance of the antibacterial particles in the above description. Is done. As an example, a particle obtained by cutting rayon fiber to which silver silica gel-based antibacterial particles of an arbitrary particle size has been added is used as a new antibacterial particle, and this is added to a base resin to form a stone-patterned antibacterial resin molded product. And the like.

In the above embodiment, polypropylene was used as the thermoplastic resin used for the antibacterial resin molded product. However, the present invention is not limited to this. For example, polyethylene, polyvinyl chloride, polystyrene, polyvinyl acetate, polyvinyl alcohol,
Polymethacryl alcohol, polybutene, polyvinyl butyral, polyvinylidene chloride, polyacrylate, polyacrylonitrile, acrylonitrile styrene butadiene (ABS), acrylonitrile styrene, ethylene-vinyl acetate, polytetrafluoroethylene, polychlorotetrafluoroethylene, acetal Resin, chlorinated polyether resin, polypropylene oxide,
Polo epichlorohydrin, polyester, polyamide,
Polycarbonate, polyphenylene oxide, polysulfone, polyurethane, styrene butadiene, or the like may be used.

In the above embodiments, the unsaturated polyester is used as the thermosetting resin. However, the present invention is not limited to this. For example, a phenol resin, a urea resin, a melamine resin, an epoxy resin, a diallyl phthalate resin, a polyester resin, or the like may be used. You may.

In each of the above embodiments, a silver thiosulfato complex was used as the inorganic antibacterial agent in each case. However, the present invention is not limited to this, and other silver antibacterial agents may be used. Alternatively, other inorganic antibacterial agents such as copper-based and zinc-based may be used.

Further, in each of the above embodiments, a hydrolyzate of tetraethoxysilane was used as a coating material for the carrier in each case. However, the present invention is not limited to this. May be used. Alternatively, another coating material may be used as long as the above effects are not impaired.
In this case, for example, when used for an antibacterial transparent resin, the refractive index of the coating material may be the same as or close to the refractive index of the transparent resin material.

[0134]

As is apparent from the above description, the present invention has the advantages that microbial contamination can be prevented and the safety to humans and the environment can be enhanced.

Further, since a carrier having a refractive index equal to or close to that of the transparent resin material is used for the carrier of the inorganic antibacterial agent, there is an advantage that transparency is not impaired.

Further, there is an advantage that the adhesive strength can be prevented from deteriorating due to the invasion of microorganisms into the adhesive.

Further, there is an advantage that the appearance of the antibacterial particles on the surface of the antibacterial resin molded product can be increased and the antibacterial effect can be increased.

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Atsushi Nishino 1006 Kadoma, Kazuma, Osaka Prefecture Inside Matsushita Electric Industrial Co., Ltd. (56) References JP 5-17617 (JP, A) JP 5-230325 (JP, A) JP 5-78602 (JP, A) JP 4-300975 (JP, A) Japanese Unexamined Patent Publication No. Hei 4-231063 (JP, A) Japanese Unexamined Patent Publication No. Hei 5-140331 (JP, A) Japanese Unexamined Patent Publication No. Sho 49-98854 (JP, A) Japanese Unexamined Patent Publication No. Hei 3-296566 (JP, A) Japanese Unexamined Patent Publication No. Hei 2-132166 JP-A-63-372 (JP, A) JP-A-3-84066 (JP, A) JP-A-2-269141 (JP, A) JP-A-1-246204 (JP, A) JP-A-64-24860 (JP, A) JP-A-2-286770 (JP, A) JP-A-1 -263175 (JP, A) JP-A-5-201817 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 1/00-101/16 C08K 3/00-13/08 C09D 5/00-201/10 C09J 5/00-201/10 A01N 59/16

Claims (3)

(57) [Claims] An inorganic antibacterial agent is kneaded in a resin material.
The inorganic antibacterial agent has the same refractive index as the resin material.
Or silver thiosulfate as a carrier with a refractive index close to that
After supporting the complex salt, at least a part of its surface is
Has a refractive index equal to or close to the refractive index of the resin material
An antibacterial composite characterized by being coated with a coating material . Wherein said resin material is antibacterial multiple of claim 1, characterized in that the material used for the main component of the paint
Compound . 3. The method according to claim 2, wherein the adhesive is kneaded.
That claim 1 antimicrobial composite according.