JPH11100227A - Anti-fungus agent and resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an anti-fungus agent having high anti-fungus activity and composed of a ZnO based glass hardly causing devitrification or phase separation and a resin composition containing the same. SOLUTION: This anti-fungus agent is composed of the ZnO-P2 O5 based glass having a composition by mol of 46-80% ZnO, 5-50% P2 O5 , 0-30% B2 O3 + SiO2 , 0-40% RO (RO represents one or more kinds of MgO, CaO, SrO, BaO) and 0-20% R2 O CRAO represents one or more kinds of Li2 O, Na2 O, K2 O). The resin composition is prepared by incorporating the anti-fungus agent in a resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antibacterial agent made of glass and a resin composition containing the same.

[0002]

2. Description of the Related Art Resin products used around water, such as wash basins, sinks, bathtubs, tubs, soap tubs, toothbrushes, etc., are exposed to high humidity for a long period of time, so that bacteria and fungi easily multiply. BACKGROUND ART In order to suppress the growth of bacteria and fungi, an antibacterial agent has been conventionally mixed with a resin. Many inorganic antibacterial agents that utilize silver oxide are used.
For example, zeolite powder carrying silver oxide, and soluble glass powder containing AgO in the composition are known. However, silver oxide is expensive and the amount of use may be limited. Further, AgO-containing glass powder is not preferable because it tends to be discolored by the action of ultraviolet rays or heat when used for a long time.
This tendency tends to be a problem particularly when the resin product is white.

On the other hand, it is known that ZnO also has an antibacterial action when eluted in water, and glass containing ZnO as a main component has been proposed as an antibacterial agent. As this kind of antibacterial agent, for example, Japanese Patent Application Laid-Open No. 8-175584 discloses ZnO-P ₂
O ₅ -Al ₂ O ₃ -B consisting ₂ O ₃ based glass antimicrobial agents are disclosed. This type of glass is characterized in that the raw material cost is low, and no discoloration due to ultraviolet rays, heat, or the like occurs even when filled in a resin product.

[0004]

The antibacterial action of the ZnO-based glass is due to Zn ⁺⁺ ions eluted from the glass, and it is expected that the more ZnO contained in the glass, the stronger the antibacterial activity. However, when the ZnO content is large, the glass tends to be unstable, and devitrification and phase separation tend to occur during molding. Therefore, finding a glass composition containing as much ZnO as possible and having high stability is an issue for obtaining a ZnO-based glass having high antibacterial ability.

An object of the present invention is to provide an antibacterial agent made of a ZnO-based glass having a high antibacterial ability and hardly causing devitrification and phase separation, and a resin composition containing the same.

[0006]

The antimicrobial agent of the present invention comprises mo
46~80% ZnO in the l% display, P ₂ O ₅ 5~50
%, B ₂ O ₃ + SiO ₂ 0 to 30%, RO (RO is M
gO, CaO, SrO, BaO)
%, R ₂ O (R ₂ O is 1 of Li ₂ O, Na ₂ O, K ₂ O)
ZnO-P ₂ O ₅ having a seed or higher) 0-20% of the composition
It is characterized by being made of a system glass.

[0007] The resin composition of the present invention is a resin composition containing an antimicrobial agent, wherein the antimicrobial agent has a mol%
46~80% ZnO in the display, P ₂ O ₅ 5~50%,
B ₂ O ₃ + SiO ₂ 0-30%, RO (RO is Mg
O, CaO, SrO, BaO)
%, R ₂ O (R ₂ O is 1 of Li ₂ O, Na ₂ O, K ₂ O)
ZnO-P ₂ O ₅ having a seed or higher) 0-20% of the composition
It is characterized by being made of a system glass.

[0008]

The antibacterial agent of the present invention has a Zn solubility of a suitable
Consisting O-P ₂ O ₅ based glass. ZnO is a major factor that provides antibacterial properties, and elutes as Zn ⁺⁺ ions to impart antibacterial properties to the resin. P ₂ O ₅ is a glass forming oxide, and is an essential component for obtaining a glass having a ZnO component and having solubility.

Next, the reason why the composition range of the glass is limited as described above will be described.

[0010] The content of ZnO is 46-80%, preferably 50-70%. When the content of ZnO is less than 46%, the antibacterial effect becomes weak, and when it exceeds 80%, vitrification becomes difficult.

[0011] P ₂ O ₅ is a glass-forming component, and its content is 5 to 50%, preferably 8 to 40%. P ₂
If O ₅ is less than 5%, vitrification tends to be difficult, and if it exceeds 50%, water resistance is deteriorated and an appropriate elution amount is exceeded. As a result, antibacterial properties cannot be maintained for a long period of time. The service life is undesirably short.

B ₂ O ₃ and SiO ₂ are glass-forming components, and their content is 0 to 30% in total, preferably ₃ to ₂ %.
3%. If the total amount exceeds 30%, the water resistance of the glass deteriorates, and phase separation easily occurs. Note that B ₂
The content of O ₃ is 0 to 23%, and the content of SiO ₂ is 0 to 8%.
%.

RO (RO is MgO, CaO, SrO, B
aO) is a component that assists the melting of glass,
Its content is 0-40% in total, preferably 3-25%
It is. When RO exceeds 40%, the glass becomes unstable. Preferably, the content of MgO is 0 to 5%, the content of CaO is 0 to 25%, the content of SrO is 0 to 5%, and the content of BaO is 0 to 5%.

R ₂ O (R ₂ O is Li ₂ O, Na ₂ O, K
₂ O 1 or more) is a component to assist the melting of the glass,
Its content is 0-20%, preferably 0-10%. If R ₂ O exceeds 20%, the glass becomes unstable.
Preferably, the content of Li ₂ O is 0 to 6%, the content of Na ₂ O is 0 to 6%, and the content of K ₂ O is 0 to 6%.

Various components other than those described above can be added.

For example, TiO ₂ and ZrO ₂ are combined up to 20% in order to adjust the acid resistance and alkali resistance of the glass.
Preferably, it can be added up to 5%. If the total amount of these components exceeds 20%, the glass becomes difficult to melt.
La ₂ O ₃ is up to 20% to help the glass melt
Preferably, it can be added up to 10%. La ₂ O ₃
Exceeds 20%, the glass tends to be devitrified.

However, in the present invention, it is better to avoid adding Al ₂ O ₃ as much as possible. As a result of the investigation by the present inventors,
In ZnO-P ₂ O ₅ based glass, 46Mo the ZnO
When the content is 1% or more, it has been found that as the content of Al ₂ O ₃ increases, the glass tends to become an obstacle in obtaining a homogeneous glass. Therefore, to obtain a stable glass containing a large amount of ZnO,
It is desirable that Al ₂ O ₃ is not contained, or if Al ₂ O ₃ is contained, the content is limited to a small amount, especially 4% or less.

The antibacterial agent of the present invention can be provided in various forms such as, for example, a powder, a fiber, and a flake.
Above all, when provided in the form of a powder, the specific surface area increases, so that a high antibacterial effect can be obtained. In the case of powder, it is preferable that the powder has an average particle diameter of 1 to 20 μm, preferably 2 to 20 μm. That is, the average particle size of the powder is 1
If it is smaller than 20 μm, it becomes difficult to manufacture powder.
This is because if it is larger, the elution amount of Zn ⁺⁺ ion per unit weight becomes small, which is not preferable.

The antibacterial agent of the present invention can be used for filling a thermosetting resin or a thermosetting resin. For example, phenolic resin, polyester resin, melamine resin,
Urea resin, diallyl phthalate resin, epoxy resin, silicone resin, vinyl chloride resin, vinyl acetate resin, polyethylene resin, polystyrene resin,
It can be used for a polypropylene resin, an acrylic resin, a polyurethane resin, a SAN resin, an ABS resin, a polycarbonate resin, a fluorine resin, a polyimide resin, a polyphenylsulfide resin, and a composite thereof. Among these resins, acrylic resins, polyester resins, melamine resins, ABS resins used for applications such as sanitary containers, and ABS resins, and silicone resins used for applications such as sealing materials can be used for filling. preferable.

The antibacterial agent of the present invention is not limited to resin filling, but can be used for various antibacterial applications such as antibacterial glaze of glass or ceramic, antibacterial paint of metal and the like.

The resin composition of the present invention comprises the ZnO-
It contains an antibacterial agent made of P ₂ O ₅ glass, and its content is 0.1 to 70% by volume, particularly 0.1 to 1% by volume.
Desirably, it is 0% by volume. The reason for limiting the content in this manner is that if the content is less than 0.1% by volume, it becomes difficult to impart sufficient antibacterial properties to the resin. On the other hand, as the content of the antibacterial agent increases, the antibacterial activity increases. However, when the content exceeds 10% by volume, the antibacterial activity hardly changes. When the content exceeds 70% by volume, resin molding becomes difficult.

Examples of the resin include a phenol resin, a polyester resin, a melamine resin, a urea resin, a diallyl phthalate resin, an epoxy resin, a silicone resin, a vinyl chloride resin, a vinyl acetate resin,
Polyethylene resin, polystyrene resin, polypropylene resin, acrylic resin, polyurethane resin, S
AN resin, ABS resin, polycarbonate-based resin, fluorine-based resin, polyimide-based resin, polyphenylsulfide-based resin, and the like, and composites thereof can be used. Among these resins, acrylic resins, polyester resins, melamine resins, A
It is preferable to use a silicone resin used for applications such as a BS resin and a sealing material.

In the resin composition of the present invention, various additives usually contained in a resin can be appropriately contained in addition to the antibacterial agent.

[0024]

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

Tables 1 and 2 show examples of the present invention (sample N
o. 1 to 10).

[0026]

[Table 1]

[0027]

[Table 2]

Each sample was prepared as follows.

First, zinc phosphate, ammonium phosphate, boric acid, pure silica, magnesium phosphate, calcium phosphate,
Strontium carbonate, barium carbonate, lithium phosphate,
After thoroughly mixing potassium phosphate, sodium phosphate, titanium oxide, zirconium oxide, and lanthanum oxide to a predetermined mixing amount, put into a platinum-rhodium alloy crucible,
Melted at 200-1300 ° C. for 4 hours. After melting, it was formed into a film-like cullet having a thickness of about 1 mm by a water-cooled roller. This is crushed by a ball mill, and the opening 1
After passing through a 05 micron sieve, the average particle size of the glass powder is 7 to 8 with an air-permeable specific surface area measuring device (manufactured by Shimadzu Corporation).
It adjusted so that it might be set to micrometer, and the sample was obtained. When the obtained samples were evaluated with an optical microscope, no devitrification or phase separation was observed in any of the samples.

Further, the polyester resin powder and the above glass were mixed at a volume ratio of 95: 5, formed into a plate of about 10 cm, and evaluated for antibacterial properties and appearance of the resin.
The results are shown in each table.

As is clear from the table, the No. 1 of the embodiment of the present invention. The resin plates using the samples Nos. 1 to 10 exhibited good antibacterial properties, and no deterioration in appearance was observed even after the accelerated test.

The antibacterial properties were evaluated as follows. First, gelatin containing bacteria adjusted so that Escherichia coli was present at a rate of 2 × 10 ³ / cm ² was processed into a sheet shape, and this was stuck on a resin plate. Then 100 at 35 ° C
After culturing for a period of time, the number of bacteria was measured, and those with less than 10 viable bacteria were regarded as good, and those with 10 or more viable bacteria were regarded as defective. Regarding the appearance of the resin, an acceleration test (immersing the resin plate in water and boiling for 500 hours) was performed. Thereafter, the surface of the resin was compared with that before the test, and those maintaining the initial gloss were evaluated as good, and those that became cloudy and lost the gloss were evaluated as poor.

[0033]

As described above, the antibacterial agent of the present invention is stable as glass and can impart sufficient antibacterial properties when filled in a resin. Moreover, it does not adversely affect the appearance of the resin product. Therefore, it is preferable for resin filling.

The resin composition of the present invention has antibacterial properties and does not deteriorate its appearance. Therefore wash basins, sinks, bathtubs, tubs, soap boxes,
It can be suitably used for applications such as resin products such as toothbrushes and sealing materials around water.

Claims (10)

[Claims] (1) a ZnO of 46 to 80% in mol%;
_{P 2 O 5 5~50%, B} 2 O 3 + SiO 2 0~30
%, RO (RO is 1 of MgO, CaO, SrO, BaO)
0-40%, R ₂ O (R ₂ O is Li ₂ O, N
a ₂ O, K ₂ O 1 or more) antimicrobial agent characterized in that it consists of ZnO-P ₂ O ₅ based glass having a 0-20% of the composition. 2. The antibacterial agent according to claim 1, which is provided in the form of a powder. 3. The antibacterial agent according to claim 2, wherein the average particle size is 1 to 20 μm. 4. The antibacterial agent according to claim 1, which is used for filling a resin. 5. A polyester resin, an acrylic resin,
The antibacterial agent according to claim 4, which is filled in a melamine resin, an ABS resin, or a silicone resin. 6. A resin composition containing an antimicrobial agent, wherein the antimicrobial agent is ZnO 46 to 80 in mol%.
%, P ₂ O ₅ 5 to 50%, B ₂ O ₃ + SiO ₂ 0
30%, RO (RO is MgO, CaO, SrO, BaO
0-40%, R ₂ O (R ₂ O is Li ₂ O,
Na ₂ O, K ₂ O 1 or more) the resin composition characterized in that it consists of ZnO-P ₂ O ₅ based glass having a 0-20% of the composition. 7. The resin composition according to claim 6, wherein the antibacterial agent is contained in the form of a powder. 8. The resin composition according to claim 7, wherein the average particle size of the antibacterial agent is 1 to 20 μm. 9. The resin composition according to claim 6, wherein the content of the antibacterial agent is 0.1 to 70% by volume. 10. The resin composition according to claim 6, wherein the resin is a polyester resin, an acrylic resin, a melamine resin, an ABS resin or a silicone resin.