Dissoluble glass, antibacterial resin composition and antibacterial molded article

Description: TECHNICAL FIELD [Detailed description of the invention]

【0001】

[Technical field to which the invention belongs]

The present invention relates to a soluble glass capable of eluting Ag ions, an antibacterial resin composition, and an antibacterial molded product. More specifically, the present invention relates to a soluble glass having less discoloration (yellow) and excellent transparency, antibacterial. The present invention relates to a sex resin composition and an antibacterial molded product.

【0002】

[Conventional technology]

In recent years, in order to impart an antibacterial effect to building materials, home appliances (including TVs, personal computers, mobile phones, video cameras, etc.), miscellaneous goods, packaging materials, etc., a predetermined amount of soluble glass has been mixed into the resin. An antibacterial resin composition is used.

【0003】

As such a soluble glass, a glass water treatment agent capable of eluting Ag ions is disclosed in Japanese Patent Application Laid-Open No. 62-210098. This glass water treatment agent contains monovalent Ag ions in the composition in an amount of 0.2 to 1.5 parts by weight in terms of silver oxide per 100 parts by weight of glass, and B as a glass component.₂ O₃ It is composed of a borosilicate-based soluble glass containing 20 to 70 mol% of. More specifically, in Examples 2 and 3 of the patent gazette, B₂ O₃ 20-30 mol%, ZnO 40 mol%, P₂ O₅ 30-40 mol% and Ag₂ Disclosed is a soluble glass having a composition of 1% by weight of O.

【0004】

Further, Japanese Patent Application Laid-Open No. 1-303150 discloses a transparent film as an antibacterial resin composition using soluble glass capable of eluting Ag ions. This permeable film is a permeable film containing copper ions and / or Ag ions, and in Example 2, B₂ O₃ : 29% by weight, SiO₂ : 51% by weight, Na₂ O: 10% by weight, ZnO: 4% by weight, Al₂ O₃ 1% by weight, Ag₂ Disclosed is a soluble glass consisting of O: 5% by weight.

【0005】

Further, Japanese Patent Application Laid-Open No. 1-313531 discloses a synthetic resin molded body containing soluble glass in the resin as an antibacterial resin composition. Specifically, the synthetic resin molded body is SiO.₂ , B₂ O₃ , P₂ O₅ One or more network-forming oxides of₂ OK₂ Ag as a monovalent Ag in 100 parts by weight of a glass solid composed of one or more mesh-modified oxides of O, CaO, and ZnO.₂ Soluble glass containing 0.1 to 20 parts by weight of O is contained in the resin, and in the examples, SiO₂ : 40 mol%, B₂ O₃ : 50 mol%, Na₂ O: Ag for 100 parts by weight of the mixture consisting of 10 mol%₂ Disclosed is a soluble glass to which 2 parts by weight of O is added.

【0006】

[Problems to be Solved by the Invention]

However, the soluble glass disclosed in Japanese Patent Application Laid-Open No. 62-210098 is B.₂ O₃ It is thought that this is because it contains 20 to 70 mol% of the glass, but there was a problem that the soluble glass became cloudy and had poor transparency. Therefore, when the soluble glass having poor transparency is mixed with the resin or laminated on the surface of the resin molded product, there is a problem that the color and transparency of the resin itself are impaired.

【0007】

Further, the soluble glass disclosed in Japanese Patent Application Laid-Open No. 1-303150 is the same as the soluble glass disclosed in Japanese Patent Application Laid-Open No. 62-210098 B.₂ O₃ This is probably because the soluble glass is cloudy (poor transparency), and the mechanical strength is low. The soluble glass disclosed in the publication is considered to be due to the small amount of ZnO used, but there is a problem that it easily turns yellow due to aging.

【0008】

Further, the soluble glass disclosed in Japanese Patent Application Laid-Open No. 1-313531 is B.₂ O₃ Is used as the main component, and the blending amount of the network-forming oxide and the network-modified oxide is not optimized, the transparency of the soluble glass is lowered, and the composition of the composition is complicated. There were problems such as becoming fragile or lengthening the manufacturing time.

【0009】

Therefore, as a result of diligent studies, the present inventor has become one of the causes of yellowing.₂O₃ It was found that the yellowing of the soluble glass can be prevented without using the above. That is, Ag₂ Although the soluble glass may turn yellow mainly due to O, Ag₂ O, ZnO and P₂ O₅ Are interacting with each other, ZnO and P₂ O₅ The present invention has been completed by finding that the yellowing can be efficiently prevented and the transparency and mechanical strength of the soluble glass can be improved by adding the above amount within a predetermined range.

【0010】

[Means for solving problems]

The present invention is a soluble glass capable of eluting Ag ions, and Ag as a constituent component.₂ O, ZnO and P₂ O₅ And when the total amount of the soluble glass is 100% by weight, Ag₂ O content in the range of 0.2 to 5% by weight, ZnO content in the range of 1 to 50% by weight, and P₂ O₅ The content of the above is set to a value within the range of 30 to 80% by weight. However, Ag₂ O, ZnO and P₂ O₅ If the total amount of is less than 100% by weight, other components such as CaO and Al₂ O₃ And MgO will be satisfied. By constructing the soluble glass in this way, B₂ O₃ It is possible to improve the transparency and mechanical strength of the soluble glass and effectively prevent the yellowing of the soluble glass without using. Also, P₂ O₅ Since the content of the glass is also appropriate, it can be easily dissolved by the surrounding water to uniformly elute Ag ions, and the transparency and mechanical strength of the soluble glass can be improved.

【0011】

Further, in constructing the soluble glass of the present invention, the ZnO content / Ag₂ The weight ratio represented by the O content is preferably set to a value in the range of 1 to 50. Yellowing of soluble glass is mainly Ag₂ Ag is like this because O is involved₂ By determining the ZnO content based on the O content, yellowing of the soluble glass can be prevented more efficiently.

【0012】

Further, in constructing the soluble glass of the present invention, it is preferable that CaO is contained as a constituent component and the content of the CaO is set to a value within the range of 1 to 20% by weight. By forming the soluble glass containing CaO in this way, it is possible to exert an interaction with ZnO and prevent yellowing of the soluble glass more efficiently.

【0013】

Further, in constructing the soluble glass of the present invention, CeO is used as a constituent component.₂ And the CeO₂ It is preferable that the content of is in the range of 0.1 to 5% by weight. By constructing the soluble glass in this way, the transparency and mechanical strength of the soluble glass can be improved, and further, the soluble glass is discolored (blackish) when irradiated with an electron beam. , Brown) can be effectively prevented.

【0014】

Further, in constructing the soluble glass of the present invention, it is preferable that the light transmittance of the soluble glass is set to a value within the range of 50 to 100%. By constructing the soluble glass in this way, there is less risk of impairing the color and transparency of the resin itself, and further, since the soluble glass can be added in a relatively large amount, it can be added for a longer period of time. Therefore, the antibacterial property can be easily controlled. Therefore, from the viewpoint that the transparency when the soluble glass is mixed with the resin or the like can be further improved and the addition amount (usage amount) can be increased, the light transmittance of the soluble glass is 70 to 100%. It is more preferable to set the value within the range, and optimally set the value within the range of 80 to 100%. The light transmittance of the soluble glass is the amount of light transmitted when the soluble glass is processed into a plate with a thickness of 3 mm as an example and visible light having a wavelength of 400 nm to 700 nm is transmitted through the plate glass. Can be calculated by measuring with an absorptiometer.

【0015】

Further, in constructing the soluble glass of the present invention, it is preferable that the soluble glass is in the form of powder and the average particle size of the soluble glass is set to a value within the range of 0.1 to 1000 μm. When a soluble glass having such an average particle size is used, it becomes easy to mix it in the resin, and even when the antibacterial resin composition is molded into a molded product, excellent surface smoothness can be obtained. .. The average particle size of the soluble glass can be easily controlled by combining a pulverization method and a classification method.

【0016】

Further, in constructing the soluble glass of the present invention, it is preferable that the soluble glass is in the form of powder and one of an inorganic substance and / or an organic substance is coated around the soluble glass. By constructing the soluble glass in this way, the elution rate of Ag ions can be easily controlled, and the antibacterial property can be maintained for a long period of time. In addition, the dispersibility of the soluble glass can be improved to make it easier to mix in the resin.

【0017】

Further, another aspect of the present invention is an antibacterial resin composition, characterized in that the above-mentioned soluble glass is mixed in the resin. The antibacterial resin composition thus constructed can elute an appropriate amount of Ag ions by utilizing the surrounding water, and can exhibit an excellent antibacterial effect for a long period of time. Further, such an antibacterial resin composition also has a feature of high transparency.

【0018】

Another aspect of the present invention is an antibacterial molded product, wherein the soluble glass is laminated on the surface of the molded product. The molded product is not particularly limited as long as it can maintain a certain shape, but may be, for example, a molded product made of resin, metal, ceramic, glass, wood, paper, cloth, or the like. It may be a molded product made of.

【0019】

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, embodiments of the soluble glass of the present invention and an antibacterial resin composition using the same will be specifically described.

【0020】

[First Embodiment] The first embodiment of the present invention is a soluble glass, which is Ag.₂ O, ZnO and P₂ O₅ Is included as a constituent component in a predetermined amount. Hereinafter, the components and the like for constituting the soluble glass of the present invention will be specifically described.

【0021】

1.Ag₂O Ag₂ O is an essential component of the soluble glass of the present invention, and the soluble glass can be made into an antibacterial glass by eluting Ag ions. Here, Ag₂ The value of O content in the range of 0.2 to 5% by weight is Ag.₂ This is because when the O content is less than 0.2% by weight, the antibacterial property of the soluble glass becomes insufficient, and a large amount of soluble glass is required to obtain a predetermined antibacterial effect. Meanwhile, Ag₂ This is because if the O content exceeds 5% by weight, the soluble glass is more likely to be discolored, and the cost becomes high, which is economically disadvantageous. Therefore, from the viewpoint of a better balance between the antibacterial property and the discoloration prevention property of the soluble glass, Ag₂ The O content is more preferably set to a value in the range of 1 to 4% by weight, and even more preferably set to a value in the range of 1.5 to 3% by weight.

【0022】

2.ZnO ZnO is an essential constituent of the soluble glass of the present invention and basically functions as a network-modified oxide. However, in addition to this, ZnO also has a function of preventing yellowing of the soluble glass in the present invention. Here, the reason why the ZnO content is set to a value in the range of 1 to 50% by weight is that if the ZnO content is less than 1% by weight, the yellowing prevention effect becomes insufficient, while the yellowing prevention effect becomes insufficient. This is because if the ZnO content exceeds 50% by weight, the transparency of the soluble glass is lowered and the mechanical strength is poor. Therefore, from the viewpoint of better balance between the discoloration prevention property and the transparency of the soluble glass, it is more preferable to set the ZnO content in the range of 2 to 30% by weight, and the optimum value is 3 to 20. The value should be within the range of% by weight.

【0023】

In addition, the content of ZnO, Ag₂ It is preferable to determine it in consideration of the O content. Specifically, ZnO content / Ag₂ The weight ratio represented by the O content is preferably set to a value in the range of 1 to 50. The reason for this is that if the weight ratio is less than 1.0, it may not be possible to effectively prevent yellowing of the soluble glass, while if the weight ratio exceeds 50, the soluble glass may become cloudy. Or, conversely, it may turn yellow. Therefore, it is more preferable that the weight ratio is in the range of 1.5 to 30, and it is more preferable that the weight ratio is in the range of 2 to 10.

【0024】

3.P₂O₅P₂ O₅ Is an essential component of the soluble glass of the present invention and basically functions as a network-forming oxide, but in addition to this, in the present invention, the transparency improving function of the soluble glass and the uniform Ag ion are used. It is also involved in release. Where P₂ O₅ The reason why a value in the range of 30 to 80% by weight is preferable for the content of P is₂ O₅ If the content of is less than 30% by weight, the transparency of the soluble glass may be lowered, or the uniform release property and mechanical strength of Ag ions may be poor, while P₂ O₅ If the content of the glass exceeds 80% by weight, the soluble glass may easily turn yellow, or the curability may be poor, resulting in a decrease in mechanical strength. Therefore, from the viewpoint of a better balance between the transparency and anti-discoloration property of the soluble glass, P₂ O₅ The content of the above is more preferably set to a value in the range of 30 to 75% by weight, and optimally set to a value in the range of 30 to 70% by weight.

【0025】

4. Other constituents of soluble glass (1) CaO CaO is an arbitrary constituent component in the soluble glass of the present invention, and when used in the present invention, basically functions as a network-modified oxide. However, CaO can also exert other functions in the present invention, such as lowering the heating temperature when producing soluble glass. Here, it is preferable that the CaO content is set to a value in the range of 1 to 20% by weight. The reason is that if the CaO content is less than 1% by weight, the addition effect (melting temperature lowering effect) may not be exhibited, while if the CaO content exceeds 20% by weight, the solubility may not be exhibited. This is because the transparency of the glass may decrease. Therefore, from the viewpoint of better balance between the effect of lowering the melting temperature of the soluble glass and the transparency, it is more preferable to set the CaO content in the range of 2 to 15% by weight, and optimally 3 to 3 to. The value should be within the range of 12 weights.

【0026】

(2) CeO₂CeO₂ Is an arbitrary constituent component in the soluble glass of the present invention, and basically functions as a network-modified oxide. However, CeO₂ In addition, when used in the present invention, it also exhibits a function of improving the transparency of soluble glass. Also, CeO₂ Can also be added to improve the discoloration property with respect to the electron beam. Here, CeO₂ The content of is preferably set to a value in the range of 0.1 to 5% by weight. The reason is the CeO₂ This is because if the content of is less than 0.1% by weight, the addition effect (transparency improving function) may not be exhibited, while CeO₂ This is because if the content of the above exceeds 5% by weight, the cost becomes high and it may be economically disadvantageous. Therefore, from the viewpoint of a better balance between the economic efficiency of the soluble glass and the anti-discoloration property, CeO₂ The content of the above is more preferably set to a value in the range of 0.2 to 3% by weight, and optimally set to a value in the range of 0.3 to 2% by weight.

【0027】

(3) MgO MgO is an arbitrary constituent component in the soluble glass of the present invention, and basically functions as a network-modified oxide. However, MgO also exhibits a function of improving the transparency of soluble glass when used in the present invention. Here, the MgO content is preferably set to a value in the range of 0.1 to 15% by weight. The reason is that if the MgO content is less than 0.1% by weight, the addition effect (transparency improving function) may not be exhibited, while if the MgO content exceeds 15% by weight, the cost is increased. This is because it may be expensive and economically disadvantageous. Therefore, from the viewpoint of better balance between the economic efficiency of the soluble glass and the anti-discoloration property, it is more preferable to set the MgO content in the range of 0.5 to 12% by weight, and the optimum value is 1 to 10. The value should be within the range of% by weight.

【0028】

(4) Na₂O Na₂ O is an arbitrary constituent component in the soluble glass of the present invention, and when used in the present invention, basically functions as a network-modified oxide. However, Na₂ In addition to this, O also exhibits a function of improving the transparency of soluble glass in the present invention. Here, Na₂ The O content is preferably set to a value in the range of 0.1 to 10% by weight. The reason is that Na₂ This is because if the O content is less than 0.1% by weight, the addition effect (transparency improving function) may not be exhibited, while Na₂ This is because if the O content exceeds 10% by weight, the transparency of the soluble glass may decrease. Therefore, from the viewpoint of a better balance between the transparency and anti-discoloration property of the soluble glass, Na₂ It is more preferable that the O content is in the range of 0.2 to 5% by weight, and optimally, the value is in the range of 0.5 to 3% by weight.

【0029】

(5) Al₂O₃Al₂ O₃ Is an arbitrary constituent component in the soluble glass of the present invention, and when used in the present invention, basically functions as a network-forming oxide. However, in addition to that, Al₂ O₃ Can also exhibit the function of improving the mechanical strength and transparency of the soluble glass in the present invention. Where Al₂ O₃ It is preferable that the content of is in the range of 0.1 to 20% by weight. The reason is the Al₂ O₃ This is because if the content of is less than 0.1% by weight, the addition effect (transparency improving function) may not be exhibited, while Al₂O₃ This is because if the content of the glass exceeds 20% by weight, the transparency of the soluble glass may decrease. Therefore, from the viewpoint of a good balance between the mechanical strength and transparency of the soluble glass, Al₂ O₃ The content of is preferably set to a value in the range of 1 to 15% by weight, more preferably set to a value in the range of 2 to 10% by weight.

【0030】

(6) Other constituents K as a mesh modification component₂ O, SiO₂ , BaO and the like can be added in a predetermined amount within the scope of the object of the present invention.

【0031】

5. Form of soluble glass The form of the soluble glass is not particularly limited, and may be, for example, a particle form, a powder form, a lump form, a rectangular shape, a columnar shape, a polygonal shape, a flat shape, or the like. Further, regarding the form of the soluble glass, it is preferable that the average particle size of the soluble glass is set to a value within the range of 0.1 to 1000 μm. When a soluble glass having such an average particle size is used, it becomes easy to mix it into the resin and it becomes easy to handle it. Further, excellent surface smoothness can be obtained even when an antibacterial resin composition or an antibacterial molded product is used. The average particle size of the soluble glass can be easily controlled by combining a pulverization method and a classification method.

【0032】

Further, regarding the form of the soluble glass, as described above, it is also preferable that the soluble glass is in the form of powder, and the soluble glass is coated with an inorganic substance and / or an organic substance around the soluble glass. By constructing the soluble glass in this way, it is possible to easily control the elution rate of Ag ions and improve the dispersibility of the soluble glass. As the inorganic substance for coating the soluble glass, titanium oxide, ceramic particles and the like are preferable, and similarly, as the organic substance, acrylic particles and the like are preferable.

【0033】

6. Manufacturing method of soluble glass The method for producing the soluble glass in the first embodiment is not particularly limited, but can be specifically produced by the steps shown below.

【0034】

(1) Glass raw material mixing process Ag₂ O, ZnO and P₂ O₅ This is a step in which the glass raw materials such as the above are accurately weighed and then uniformly mixed. When mixing, it is preferable to use a mixing machine (mixer) such as an alumina porcelain crusher, a ball mill, or a propeller mixer.

【0035】

(2) Glass raw material melting process This is a step of producing molten glass by melting uniformly mixed glass raw materials using a glass melting furnace or the like. Adopting a melting temperature of 600 to 1500 ° C and a melting time of 0.1 to 24 hours is possible from the viewpoint of improving production efficiency and yellowing of the soluble glass during manufacturing. It is preferable from the viewpoint that it can be reduced.

【0036】

(3) Soluble glass crushing process This is a step of pulverizing the obtained molten glass into fine particles, that is, the soluble glass of the present invention. Specifically, coarse pulverization (including water pulverization) and fine pulverization are preferable in that glass particles having a uniform particle size can be efficiently obtained. However, depending on the application, it is also preferable to carry out a classification step after such a step. On the other hand, depending on another application, such a step may be omitted. In that case, the soluble glass obtained after the completion of the step (2) can be used as it is as the antibacterial glass.

【0037】

[Second Embodiment] The antibacterial resin composition according to the second embodiment is Ag.₂ O, ZnO and P₂ O₅ A predetermined amount of soluble glass containing the above as a constituent is mixed in the resin (transparent or opaque resin) shown below.

【0038】

1. Transparent resin In preparing the antibacterial resin composition of the present invention, it is possible to mix soluble glass in the transparent resin shown below. Preferred transparent resins include polyethylene resin (PE), polypropylene resin (PP), polyethylene terephthalate resin (PET), polybutylene terephthalate resin (PBT), polycarbonate resin (PC), styrene resin (PS), vinylidene chloride resin, and the like. Vinyl acetate resin , Polyvinyl alcohol resin, fluororesin, polyarylene resin, acrylic resin, epoxy resin, transparent vinyl chloride resin, ionomer resin, polyamide resin, polyacetal resin and the like. When using such a kind of transparent resin, it is preferable to use one having a light transmittance defined by the following formula, specifically within the range of 50 to 100%, and more preferably 80 to 80 to 100. Use one that has a light transmittance within the range of 100%. In addition, the amount of transmitted light and the amount of incident light can be measured using an absorptiometer or a photometer (power meter). At the time of the measurement, as the transparent resin, for example, a plate having a thickness of 1 mm can be used. Light transmittance (%) = transmitted light amount / incident light amount x 100 [0039]

2. Opaque resin Further, in preparing the antibacterial resin composition of the present invention, it is also possible to mix soluble glass in the opaque resin. The following can be mentioned as preferable opaque resins. For example, polyethylene resin (PE), polypropylene resin (PP), polyethylene terephthalate resin (PET), polybutylene terephthalate resin (PBT), polycarbonate resin (PC), styrene resin (PS), vinylidene chloride resin, vinyl acetate resin. , Polyvinyl alcohol resin, fluororesin, polyarylene resin, acrylic resin, epoxy resin, transparent vinyl chloride resin, ionomer resin, polyamide resin, polyacetal resin and other transparent resins, pigments, paints, dyes, etc. One or more of a resin made opaque by adding a predetermined amount of the above, a phenol resin opaque by itself, a melamine resin and the like can be mentioned. When using such a kind of opaque resin, specifically, one having a light transmittance in the range of 0 to 50%, more preferably in the range of 0 to 30% as defined by the above formula. It is preferable to use it.

【0040】

3. Amount of soluble glass mixed (addition amount) In preparing the antibacterial resin composition of the present invention, the amount of soluble glass mixed per 100 parts by weight of the resin is preferably set to a value in the range of 0.01 to 10 parts by weight. The reason for this is that if the amount of the soluble glass mixed is less than 0.01 parts by weight, the antibacterial property may decrease, while if the amount of the soluble glass mixed exceeds 10 parts by weight, the machine of the antibacterial resin composition This is because the target strength may be lowered, mixing may be difficult, or the transparency of the antibacterial resin composition may be lowered. Therefore, from the viewpoint that the balance between the antibacterial property and the mechanical strength of the antibacterial resin composition is more preferable, the amount of the soluble glass mixed per 100 parts by weight of the resin is set to a value within the range of 0.1 to 5 parts by weight. It is more preferable to set the value in the range of 0.3 to 3 parts by weight.

【0041】

4. Manufacturing method of antibacterial resin composition The method for producing the antibacterial resin composition in the second embodiment is not particularly limited, but can be specifically produced by the following steps.

【0042】

(1) Manufacture of soluble glass In the first embodiment, as described above, the soluble glass can be produced by the glass raw material mixing step, the glass raw material melting step, and the soluble glass crushing step.

【0043】

(2) Production of antibacterial resin composition This is a step of accurately weighing the soluble glass and then uniformly mixing it with the resin. Specifically, a stirring and mixing method, a kneading method, a coating method, a diffusion method and the like can be adopted. For example, in the case of the stirring and mixing method, stirring and mixing are performed at room temperature (25 ° C) for 10 minutes to 24 hours. Is preferable. In addition, a mixing machine (mixer) such as an alumina porcelain crusher, ball mill, propeller mixer, triple roll, V blender, etc. is used for mixing, and an organic solvent or lubricant is added to the resin. It is preferable to adjust the viscosity.

【0044】

[Third Embodiment] The antibacterial molded article according to the third embodiment can be configured by laminating the soluble glass according to the first embodiment on the surface of the molded article.

【0045】

1. Antibacterial molded product The form of the antibacterial molded product is not particularly limited, and any antibacterial resin composition may be laminated on the surface of the molded product. Further, the antibacterial resin composition itself may be processed into a predetermined shape to obtain an antibacterial molded product in which the antibacterial resin composition is laminated on the surface of the molded product. The form of the antibacterial molded product can be appropriately adopted depending on the application. For example, the antibacterial resin composition is applied to the surface of the molded product such as a bag, shoes, toys, clothes, underwear, socks, and a bathtub. Anything that is laminated may be used. Further, when the antibacterial resin composition itself is processed into an antibacterial molded product, it is preferably formed into a plate shape, a film shape, a rectangular parallelepiped shape, a rectangular parallelepiped shape, a spherical shape, a rod shape, or a deformed shape.

【0046】

2. Manufacturing method of antibacterial molded products The method for producing the antibacterial molded product in the third embodiment is not particularly limited, but can be specifically produced by the steps shown below.

【0047】

(1) Manufacture of soluble glass In the first embodiment, as described above, the soluble glass can be produced by the glass raw material mixing step, the glass raw material melting step, and the soluble glass crushing step.

【0048】

(2) Production of antibacterial resin composition In the second embodiment, as described above, the antibacterial resin composition can be produced by accurately weighing the soluble glass and then uniformly stirring and mixing the resin with the resin.

【0049】

(3) Manufacture of antibacterial molded products Any material may be used as long as the antibacterial resin composition is laminated on the surface of the molded product. The laminating method is not particularly limited, but a bar coating method, a spray coating method, a knife coating method, a gravure coating method, a dipping method and the like can be adopted. At that time, it is preferable to laminate the antibacterial resin composition on the surface of the molded product to a thickness of 1 to 1000 μm. The reason for this is that if the thickness of the antibacterial resin composition is less than 1 μm, the adhesion to the surface of the molded product may decrease, while if the thickness exceeds 1000 μm, it is difficult to uniformly laminate the articles. This is because it may become, or it may be detached from the surface of the molded product. Therefore, the thickness of the antibacterial resin composition is more preferably set to a value in the range of 3 to 500 μm, and further preferably set to a value in the range of 5 to 100 μm.

【0050】

Further, when the antibacterial resin composition itself is processed into a predetermined shape, the antibacterial resin composition can be easily processed by injection molding using a mold. In that case, it is desirable to perform injection molding at a temperature lower than the decomposition temperature of the resin, but the soluble glass of the present invention does not discolor at about the decomposition temperature of the resin, and as a result, an antibacterial molded product having high transparency. Can be obtained.

【0051】

[Example]

Hereinafter, the present invention will be described in more detail by way of examples. However, the following description illustrates the present invention, and the present invention is not limited to these descriptions.

【0052】

[Example 1] (Creation of soluble glass) When the total amount of soluble glass is 100% by weight, P₂ O₅ The composition ratio of is 68% by weight, the composition ratio of CaO is 10% by weight, the composition ratio of MgO is 8% by weight, the composition ratio of ZnO is 5% by weight, and Al.₂ O₃ Composition ratio of 5% by weight, Ag₂ O composition ratio is 3% by weight, Na₂ O composition ratio is 0.5% by weight, CeO₂ Each glass raw material was uniformly mixed in the crucible using an alumina porcelain crusher so that the composition ratio of the above was 0.5% by weight. Next, using a glass melting furnace, the glass raw material was heated at 1100 ° C. for 1 hour to prepare molten glass. Then, the molten glass taken out from the glass melting furnace was roughly crushed by pouring it into water. Then, after coarsely pulverizing using a mortar (average particle size about 100 μm), finely pulverizing using a vibrating ball mill (average particle size about 5 μm) while checking with a microscope, and using the soluble glass (fine particles) of the present invention. did.

【0053】

(Evaluation of soluble glass) (1) Evaluation 1 (Transparency evaluation 1) The transparency of the obtained soluble glass was judged using a microscope according to the following criteria. The results are shown in Table 1. : Colorless and transparent. Yes: There is some opacity. Δ: There is some whiteness. X: Completely white.

【0054】

(2) Evaluation 2 (Transparency evaluation 2) A red polypropylene plate (thickness 2 mm) was used as a base, and the obtained soluble glass was uniformly placed on this plate. Then, using a microscope, it was judged based on the following criteria whether or not the color of the polypropylene plate could be recognized through the soluble glass. The results are shown in Table 1. : The background color can be completely recognized. Yes: There is a feeling that the background color is slightly blurred. Δ: There is a feeling that the background color is partially blurred. ×: The background color cannot be completely recognized.

【0055】

(3) Evaluation 3 (yellowing evaluation 1) The obtained soluble glass was continuously subjected to ultraviolet rays (black panel temperature: 63 ° C, illuminance: light with a wavelength of 300 to 700 nm, 255 W / m) using an ultraviolet irradiation device (sunshine weather meter).² ) Was irradiated, and the yellowing of the soluble glass was judged according to the following criteria. The yellow denaturation of the soluble glass was measured using a microscope. The results are shown in Table 1. : Colorless and transparent after 100 hours. Yes: It is colorless and transparent after 50 hours. Δ: It is colorless and transparent after 10 hours. ×: Yellowing after 10 hours.

【0056】

(4) Evaluation 4 (yellowing evaluation 2) The obtained soluble glass was immersed in tap water (20 ° C), and the yellowing of the soluble glass was judged according to the following criteria. The yellow denaturation of the soluble glass was measured using a microscope. The results are shown in Table 1. : Colorless and transparent after 1000 hours. Yes: It is colorless and transparent after 500 hours have passed. Δ: Colorless and transparent after 100 hours. ×: Yellowing after 100 hours.

【0057】

(5) Evaluation 5 ~ 8 (antibacterial evaluation) The obtained soluble glass was mixed with polypropylene resin so as to be 0.2% by weight and 0.3% by weight, respectively, to prepare a total of 6 types of resins containing soluble glass. On the other hand, the test bacteria were cultured on a trypticase soy Agar (BBL) agar plate medium at 35 ° C for 24 hours, and the growth settlement was suspended in a 1/500 concentration ordinary bouillon medium (manufactured by Eiken Kagaku Co., Ltd.). Let me, about 1x10⁶ Prepared to CFU / ml. Next, the resin containing soluble glass was molded into test pieces having a thickness of 2 mm, a length of 5 cm, and a width of 5 cm, respectively. Then, 0.5 ml of a suspension of Staphylococcus aureus IFO # 12732 and 0.5 ml of a suspension of Escherichia coli (Escherichia coli ATCC # 8739) were uniformly contacted with the obtained 6 types of test pieces. Further, a polyethylene film (sterilized) was placed on the film, and each was used as a measurement sample by the film cover method. Next, the measurement sample was placed in a constant temperature bath under the conditions of humidity of 95%, temperature of 35 ° C, and 24 hours, and the number of bacteria before the test (growth settlement) and the number of bacteria after the test (growth settlement) were measured, respectively. The measurement was performed and the antibacterial property was evaluated according to the following criteria. The number of bacteria (growth settlement) before the test was 2.6 × 10 for both Staphylococcus aureus and Escherichia coli.⁵ It was (piece / test piece). The results of each are shown in Table 1. In Table 1, evaluation 5 shows the case where the amount of soluble glass added is 0.2% by weight and the test bacterium is Staphylococcus aureus, and evaluation 6 shows the case where the amount of soluble glass added is 0.3% by weight and the test bacterium is yellow. In the case of Staphylococcus aureus, evaluation 7 is the case where the amount of soluble glass added is 0.2 weight and the test bacterium is Escherichia coli, and evaluation 8 is the case where the amount of soluble glass added is 0.3 weight and the test bacterium is Escherichia coli. Is. The same evaluation and description are given in Table 2. : The number of bacteria after the test is less than 1/10000 of the number of bacteria before the test. Yes: The number of bacteria after the test is 1/10000 or more and less than 1/1000 of the number of bacteria before the test. Δ: The number of bacteria after the test is 1/1000 or more and less than 1/100 of the number of bacteria before the test. X: The number of bacteria after the test is 1/100 or more of the number of bacteria before the test.

【0058】

[Examples 2 to 6] (Preparation of Soluble Glass) Soluble glass was prepared so as to have the composition shown in Table 1 under the same preparation conditions as in Example 1. In addition, as compared with Example 1, in Examples 2 and 3, ZnO and P₂ O₅ ZnO / Ag by adjusting the amount of₂ The ratio of O is increased, and in Example 4, the amount of CaO and ZnO added is increased without using MgO, which is relatively expensive. Further, in Example 5, similarly, MgO was not used, and CaO and Al were not used.₂ O₃ The content of is increasing.

【0059】

(Evaluation of Soluble Glass) Under the same evaluation conditions as in Example 1, the obtained soluble glass was evaluated for yellowing and the like. The results are shown in Table 1 (evaluations 1 to 8).

【0060】

[table 1]

<img file="JP2000191339A_D0001.tif" />【0061】

[Comparative Examples 1 to 6] (Preparation of Soluble Glass) In the same manner as in Example 1, soluble glasses were prepared so as to have the compositions shown in Table 2. In addition, in comparison with Example 1, in Comparative Examples 1 to 3, B₂ O₃ Is added in a predetermined amount and the ZnO content is increased (33 to 50% by weight), and in Comparative Examples 4 to 6, B₂ O₃ Is used in a predetermined amount, and ZnO is not added or the amount added is reduced (0 to 5% by weight).

【0062】

(Evaluation of Soluble Glass) Under the same evaluation conditions as in Example 1, the soluble glasses obtained in Comparative Examples 1 to 6 were evaluated for yellowing and the like. The results are shown in Table 2.

【0063】

As is clear from the results, Comparative Examples 1 to 3 are B.₂ O₃ It was confirmed that the obtained soluble glass became cloudy and lacked transparency, probably because the content of ZnO was too high.

【0064】

In addition, Comparative Examples 4 to 6 are B.₂ O₃ On the other hand, it does not contain ZnO, or it seems that it is because of the low content, but the obtained soluble glass is cloudy, lacks transparency, and even yellow. It was confirmed that it was easy to change.

【0065】

[Table 2]

<img file="JP2000191339A_D0002.tif" />【0066】

[Effect of the invention]

As explained above, Ag₂ O, ZnO and P₂ O₅ By containing within the specified range, B₂ O₃ In addition to being able to exhibit excellent antibacterial properties without the use of, the transparency and mechanical strength of the soluble glass have been improved, and yellowing of the soluble glass can be effectively prevented. Further, even if such soluble glass is mixed in the resin or laminated on the surface of the molded product to prepare an antibacterial resin composition or an antibacterial molded product, the color and transparency of the resin and the molded product itself are transparent. The risk of impairing sex has been reduced as much as possible.

【0067】

Further, the soluble glass can be easily processed into a constant shape, and can be made into fine particles having a uniform average particle size. Therefore, the dispersibility is improved, the resin can be mixed more uniformly, and the antibacterial resin composition and the antibacterial molded product can be easily produced. Further, in the soluble glass, the antibacterial resin composition and the antibacterial molded product of the present invention, the antibacterial property can be improved.