WO2016152442A1 - Antibacterial glass and resin molded article using same - Google Patents

Antibacterial glass and resin molded article using same Download PDF

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Publication number
WO2016152442A1
WO2016152442A1 PCT/JP2016/056620 JP2016056620W WO2016152442A1 WO 2016152442 A1 WO2016152442 A1 WO 2016152442A1 JP 2016056620 W JP2016056620 W JP 2016056620W WO 2016152442 A1 WO2016152442 A1 WO 2016152442A1
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Prior art keywords
antibacterial
glass
resin
resin molded
antibacterial glass
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PCT/JP2016/056620
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French (fr)
Japanese (ja)
Inventor
益田　紀彰
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日本電気硝子株式会社
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Priority to CN201680011400.XA priority Critical patent/CN107250074A/en
Publication of WO2016152442A1 publication Critical patent/WO2016152442A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/14—Silica-free oxide glass compositions containing boron
    • C03C3/145—Silica-free oxide glass compositions containing boron containing aluminium or beryllium
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C12/00—Powdered glass; Bead compositions
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/16—Silica-free oxide glass compositions containing phosphorus
    • C03C3/19—Silica-free oxide glass compositions containing phosphorus containing boron
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/40—Glass
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/34—Shaped forms, e.g. sheets, not provided for in any other sub-group of this main group
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof

Definitions

  • the present invention relates to antibacterial glass and a resin molded product using the same.
  • Resin molded products such as toothbrushes, soap holders, troughs, washstands, and bathtubs are used for a long time under high humidity conditions, so bacteria and sputum are prone to multiply.
  • the resin is conventionally filled with an antibacterial agent, which is used as a resin molded product.
  • antibacterial agents that use Ag ions with high antibacterial properties are often used.
  • zeolite powder supporting Ag ions water-soluble glass powder containing Ag 2 O in the glass composition, and the like are known. It has been.
  • the antibacterial sustained performance deteriorates.
  • the resin molded product is used for a long period of time under a high humidity condition, the antibacterial sustained performance is likely to be insufficient. This phenomenon is attributed to the fact that Ag metal colloid has a lower antibacterial property than Ag ions.
  • the present invention has been made in view of the above circumstances, does not cause a problem in appearance when it is a resin molded product, is inexpensive, and has high antimicrobial durability, and resin molding using the same It is to create a product.
  • the inventor introduced the above technical problem by introducing a small amount of Ag 2 O and a predetermined amount of Al 2 O 3 into the B 2 O 3 —MgO-based glass.
  • the present invention has been found out that it can be solved, and is proposed as the present invention. That is, the antibacterial glass of the present invention has a glass composition in terms of mol%, B 2 O 3 40-60%, MgO 10-32%, Ag 2 O 0.05-0.5%, Al 2 O 3 It contains 2 to 10%.
  • the antibacterial glass of the present invention contains 40 mol% or more of B 2 O 3 , 10 mol% or more of MgO, and 0.05 to 0.5 mol% of Ag 2 O in the glass composition. Thereby, after suppressing an increase in cost, antimicrobial sustainability can be improved. Furthermore, since the content of Ag 2 O is small, problems such as discoloration due to ultraviolet irradiation hardly occur.
  • the antibacterial glass of the present invention contains 2 mol% or more of Al 2 O 3 in the glass composition.
  • Ag can be stably held in an ion state in the glass.
  • the antibacterial action of Ag ions can be effectively exhibited.
  • the antibacterial glass of the present invention preferably further contains 2 to 15 mol% of ZnO as a glass composition. If it does in this way, stability of glass can be raised. Moreover, Zn ion elutes and antibacterial property can be improved.
  • the antibacterial glass of the present invention preferably further contains 0.1 to 5 mol% of CaO as a glass composition. If it does in this way, stability of glass can be raised.
  • the antibacterial glass of the present invention preferably further contains 0.1 to 10 mol% of P 2 O 5 as a glass composition. If it does in this way, stability of glass can be raised. Moreover, it becomes easy to hold Ag stably in an ionic state.
  • the antibacterial glass of the present invention preferably contains 0 to 5 mol% of Na 2 O as a glass composition. If it does in this way, stability of glass can be raised. Moreover, it becomes easy to hold Ag stably in an ionic state.
  • the antibacterial glass of the present invention is preferably in a powder form.
  • antimicrobial glass of the present invention preferably has an average particle diameter D 50 is 0.5 ⁇ 25 [mu] m.
  • the “average particle diameter D 50 ” refers to a value measured with a laser diffractometer, and in the volume-based cumulative particle size distribution curve measured by the laser diffraction method, the accumulated amount is accumulated from the smaller particle.
  • the particle diameter is 50%.
  • the resin molded product of the present invention is a resin molded product containing antibacterial glass, and the antibacterial glass is preferably the above antibacterial glass.
  • the resin molded product of the present invention preferably has an antibacterial glass content of 0.01 to 20% by mass.
  • the antibacterial glass of the present invention does not cause a problem in appearance when it is a resin molded product, is inexpensive, and has a high antibacterial sustainability. Therefore, the antibacterial glass of the present invention is suitable as an antibacterial agent to be filled in a resin molded product, and particularly suitable as an antibacterial agent to be filled in a resin molded product such as a toothbrush, a soap dish, a tub, a wash basin, and a bathtub. is there.
  • the antibacterial glass of the present invention has a glass composition in terms of mol%, B 2 O 3 40-60%, MgO 10-32%, Ag 2 O 0.05-0.5%, Al 2 O 3 2- It is characterized by containing 10%.
  • the reason for limiting the content range of each component as described above will be described below.
  • % display means mol%.
  • B 2 O 3 is a glass-forming component and a component that can adjust antimicrobial persistence.
  • the content of B 2 O 3 is 40 to 60%, preferably 45 to 60%. If the content of B 2 O 3 is too small, vitrification becomes difficult and water resistance becomes too high, and the elution amount of Ag ions decreases, so that the antibacterial sustainability tends to decrease. On the other hand, if the content of B 2 O 3 is too large, the water resistance is excessively decreased and the elution amount of Ag ions becomes excessive, so that the antibacterial durability is likely to be decreased.
  • MgO is a component that assists in vitrification, and is a component that lowers the high temperature viscosity while maintaining water resistance.
  • the content of MgO is 10 to 32%, preferably 12 to 30%. If the content of MgO is too small, the water resistance is lowered and the elution rate of Ag ions is increased, so that the resin molded product is likely to be discolored. On the other hand, when there is too much content of MgO, vitrification will become difficult.
  • Ag 2 O is a component that enhances antibacterial properties.
  • the content of Ag 2 O is 0.05 to 0.5%, preferably 0.1 to 0.5%.
  • the content of Ag 2 O is too small, it becomes difficult to enjoy the effect of the above.
  • the content of Ag 2 O is too large, problems such as resin discoloration due to ultraviolet irradiation tend to occur, and the raw material cost tends to increase.
  • Al 2 O 3 is a component that assists in vitrification, and is a component that stably keeps the Ag component in an ionic state in the glass.
  • Al exists in the glass in an oxygen tetracoordinate like Si.
  • Al is a trivalent cation in the glass and has one valence less than that of Si, so it has a negative ion (-1) charge due to the charge balance with oxygen ions. Existing.
  • Ag ions are monovalent cations and are stably supported on the Al sites of monovalent negative ions in a state of charge compensation.
  • the content of Al 2 O 3 is 2 to 10%, preferably 4 to 8%.
  • ZnO is a component that assists in vitrification and is a component that imparts antibacterial properties as Zn ions.
  • the ZnO content is preferably 2 to 15%, more preferably 5 to 15%. When there is too little content of ZnO, antibacterial property will fall easily. On the other hand, when there is too much content of ZnO, vitrification will become difficult.
  • CaO is a component that helps vitrification.
  • the content of CaO is preferably 0.1 to 5%, more preferably 0.5 to 4%. When there is too little content of CaO, it will become difficult to receive the said effect. On the other hand, when there is too much content of CaO, vitrification will become difficult.
  • P 2 O 5 is a glass forming component and is a component that stably keeps the Ag component in an ionic state in the glass. Furthermore, it is a component that can control the water resistance and optimize the elution rate of Ag ions.
  • the content of P 2 O 5 is preferably 0.1 to 10%, more preferably 1 to 7%. When the content of P 2 O 5 is too small, it becomes difficult to enjoy the above-mentioned effects. On the other hand, when the content of P 2 O 5 is too large, the water resistance decreases unduly, it becomes difficult to optimize the dissolution rate of the Ag ions.
  • Na 2 O is a component that helps vitrification, and is a component that lowers the high temperature viscosity. Furthermore, it is a component that can control the water resistance and optimize the elution rate of Ag ions.
  • the content of Na 2 O is preferably 0 to 5%, more preferably 0.1 to 3%. However, when the content of Na 2 O exceeds 3%, there is a risk of adversely affecting the curing characteristics of the resin.
  • SiO 2 is a glass forming component.
  • the content of SiO 2 is preferably 0 to 3%, more preferably 0 to 1%. When the content of SiO 2 is too large, the dissolution rate of the Ag ion is liable to decrease.
  • ZrO 2 , SrO, BaO, TiO 2 , CeO 2 and the like may be introduced in total or individually, preferably up to 5%, particularly up to 1%. .
  • the shape of the antibacterial glass of the present invention is not particularly limited.
  • the shape can be a powder shape, a fiber shape, a flake shape, or the like.
  • a powder shape that is, a glass powder is particularly preferable.
  • the specific surface area is increased, so that high antibacterial properties can be obtained.
  • the average particle diameter D 50 of the glass powder is preferably 0.5 ⁇ 25 [mu] m, more preferably 5 ⁇ 20 [mu] m.
  • the average particle diameter D 50 of the glass powder is too small, the glass powder particles are aggregated, hardly kneaded with a resin or the like. Moreover, when it is set as a resin molded product, it may flow out into warm water or the like and may not contribute to the antibacterial properties of the resin molded product.
  • the average particle diameter D 50 of the glass powder is too large, the amount of elution of Ag ion and Zn ion per unit mass is reduced, the antimicrobial persistence is liable to decrease.
  • the resin molded product of the present invention is a resin molded product containing antibacterial glass, and the antibacterial glass is preferably the above antibacterial glass.
  • the content of the antibacterial glass is preferably 0.01 to 20% by mass, more preferably 0.05 to 5% by mass.
  • the antibacterial glass is added excessively, the antibacterial property does not increase so much, which is disadvantageous in terms of cost.
  • thermoplastic resin a thermosetting resin, or the like
  • resin a thermoplastic resin, a thermosetting resin, or the like
  • the antibacterial glass surface can be made oleophilic by silane coupling treatment or the like in order to enhance the dispersibility of the antibacterial glass.
  • silane coupling agent include amino silane, epoxy silane, methacryl silane, ureido silane, and isocyanate silane.
  • the resin molded article of the present invention may contain various additives (colloidal silica, zinc oxide, alumina, white carbon, tin oxide, titanium oxide, silicon oxide, etc.) in addition to the antibacterial glass.
  • various additives colloidal silica, zinc oxide, alumina, white carbon, tin oxide, titanium oxide, silicon oxide, etc.
  • Table 1 shows examples of the present invention (sample Nos. 1 to 5) and comparative examples (sample No. 6).
  • Each sample was produced as follows. First, glass raw materials were prepared so as to have the glass composition shown in the table, mixed well, then placed in a platinum-rhodium alloy crucible and melted at 1200 to 1350 ° C. for 3 hours. After melting, it was formed into a film having a thickness of about 0.7 mm. The obtained glass film was pulverized by a ball mill, through mesh 75 micron sieve to obtain a glass powder having an average particle diameter D 50 shown in the table. The average particle diameter D 50 of the glass powder is a value measured by Shimadzu Corporation laser diffractometer.
  • the elution amount of silver ions into pure water was evaluated as follows. 3 g of the above glass powder was placed in 30 g of pure water and held at 50 ° C. for 16 hours, and then the glass powder was collected by filtration and dried at 120 ° C. for 2 hours. Next, 0.4 g of glass powder treated with pure water was again put into 40 g of pure water and shaken in a thermostatic bath set at 35 ° C. for 24 hours. Finally, the aqueous solution was collected by filtration, and the elution amount of silver ions in the aqueous solution was evaluated by ICP emission analysis. In addition, the elution amount of the silver ion in aqueous solution was evaluated by the same method also about the glass powder which was not processed with the pure water of 50 degreeC.
  • sample no. The elution amount of silver ions 1 to 5 was 25.1 ppm / m 2 or more after the treatment with pure water at 50 ° C., similarly to the case before the treatment with pure water at 50 ° C.
  • sample No. 6 was treated with pure water at 50 ° C., the silver ion elution amount decreased to 10.6 ppm / m 2 .
  • antibacterial properties were evaluated as follows. In other words, in accordance with the test method “antibacterial activity evaluation test method minimum growth inhibitory concentration measurement method I (1998 revised edition) MIC measurement method by liquid medium dilution method” established by the Antibacterial Product Technology Council, antibacterial properties are exhibited as MIC values. evaluated. The results are shown in Table 1.
  • the MIC value is 200 ( ⁇ g / ml) or less, and the standard value 800 ( ⁇ g / ml) or less as the antibacterial agent shown by the Antibacterial Product Technical Council I met.
  • the antibacterial sustainability test was carried out by the Antibacterial Product Technology Council, “Antibacterial power test method for antibacterial processed products I (1998 version) film adhesion method: JISZ2801”. Specifically, the above-mentioned resin molded product was immersed in warm water at 50 ° C. for 16 hours, and the above antibacterial test was conducted. In this test method, when the test bacterium is Escherichia coli, if the antibacterial activity value is 2.0 or more, it is evaluated as “antibacterial”. Thereafter, the appearance of the resin molded product was visually observed.
  • sample no. Nos. 1 to 5 had an antibacterial activity value of 2 or more even after being immersed in warm water, and had good antibacterial persistence. Moreover, the color tone of the resin molded product after being immersed in warm water maintained the same milky white color as before being immersed in warm water, and yellowing by Ag metal colloid was not recognized. On the other hand, sample No. No. 6 had an antibacterial activity value of less than 2 after being immersed in warm water, and its antibacterial durability was low.
  • the antibacterial glass of the present invention is suitable as an antibacterial agent to be filled into a resin molded product, and particularly suitable as an antibacterial agent to be filled into a resin molded product such as a toothbrush, a soap bowl, a tub, a wash basin, and a bathtub.
  • the antibacterial glass of the present invention can be applied to antibacterial applications such as antibacterial glazes such as glass articles and ceramic articles, and antibacterial paints such as metal articles.

Abstract

The present invention addresses the technical problem of inventing: a low-cost antibacterial glass which does not cause a problem in appearance if used for a resin molded article, and which has high sustainability of antibacterial activity; and a resin molded article which uses this antibacterial glass. In order to solve the above-mentioned problem, an antibacterial glass according to the present invention is characterized by having a glass composition which contains, in mol%, 40-60% of B2O3, 10-32% of MgO, 0.05-0.5% of Ag2O and 2-10% of Al2O3.

Description

抗菌性ガラス及びこれを用いた樹脂成形品Antibacterial glass and resin molded product using the same
　本発明は、抗菌性ガラス及びこれを用いた樹脂成形品に関する。 The present invention relates to antibacterial glass and a resin molded product using the same.
　歯ブラシ、石鹸入れ、たらい、洗面台、浴槽等の樹脂成形品は、高湿度の条件下で長期間使用されるため、細菌や黴が増殖し易い。 Resin molded products such as toothbrushes, soap holders, troughs, washstands, and bathtubs are used for a long time under high humidity conditions, so bacteria and sputum are prone to multiply.
　細菌や黴の増殖を抑えるために、従来から、樹脂に抗菌剤を充填し、これを樹脂成形品としている。 In order to suppress the growth of bacteria and sputum, the resin is conventionally filled with an antibacterial agent, which is used as a resin molded product.
　また、抗菌剤には、抗菌性が高いＡｇイオンを利用したものが多く用いられており、例えばＡｇイオンを担持させたゼオライト粉末、ガラス組成中にＡｇ２Ｏを含む水溶性ガラス粉末等が知られている。 In addition, antibacterial agents that use Ag ions with high antibacterial properties are often used. For example, zeolite powder supporting Ag ions, water-soluble glass powder containing Ag 2 O in the glass composition, and the like are known. It has been.
　ところが、従来のＡｇイオンを含む抗菌剤は、高価である。更に、ガラス組成中にＡｇ２Ｏを導入すると、長期間の使用により、ガラスが紫外線や熱等の作用で変色する傾向がある。これは、ＡｇイオンがＡｇ金属コロイドに変化することによる。この傾向は、樹脂成形品が白色の場合に顕在化し易くなる。 However, conventional antibacterial agents containing Ag ions are expensive. Furthermore, when Ag 2 O is introduced into the glass composition, the glass tends to discolor due to the action of ultraviolet rays, heat or the like due to long-term use. This is because Ag ions are changed to Ag metal colloids. This tendency is easily manifested when the resin molded product is white.
　更に、ＡｇイオンからＡｇ金属コロイドに変化すると、抗菌持続性能が劣化する。特に、樹脂成形品を高湿度の条件下で長期間使用する場合に、抗菌持続性能が不十分になる可能性が高い。この現象は、Ａｇ金属コロイドが、Ａｇイオンよりも抗菌性が低いことに起因する。 Furthermore, when the Ag ion is changed to Ag metal colloid, the antibacterial sustained performance deteriorates. In particular, when the resin molded product is used for a long period of time under a high humidity condition, the antibacterial sustained performance is likely to be insufficient. This phenomenon is attributed to the fact that Ag metal colloid has a lower antibacterial property than Ag ions.
　本発明は、上記事情に鑑みなされたものであり、樹脂成形品とした場合に外観上の問題を発生させず、安価であり、しかも抗菌持続性が高い抗菌性ガラス及びこれを用いた樹脂成形品を創案することである。 The present invention has been made in view of the above circumstances, does not cause a problem in appearance when it is a resin molded product, is inexpensive, and has high antimicrobial durability, and resin molding using the same It is to create a product.
　本発明者は、種々の実験を行った結果、Ｂ２Ｏ３－ＭｇＯ系ガラスに少量のＡｇ２Ｏを導入すると共に、所定量のＡｌ２Ｏ３を導入することにより、上記技術的課題を解決し得ることを見出し、本発明として提案するものである。すなわち、本発明の抗菌性ガラスは、ガラス組成として、モル％表示で、Ｂ２Ｏ３　４０～６０％、ＭｇＯ　１０～３２％、Ａｇ２Ｏ　０．０５～０．５％、Ａｌ２Ｏ３　２～１０％を含有することを特徴とする。 As a result of various experiments, the inventor introduced the above technical problem by introducing a small amount of Ag 2 O and a predetermined amount of Al 2 O 3 into the B 2 O 3 —MgO-based glass. The present invention has been found out that it can be solved, and is proposed as the present invention. That is, the antibacterial glass of the present invention has a glass composition in terms of mol%, B 2 O 3 40-60%, MgO 10-32%, Ag 2 O 0.05-0.5%, Al 2 O 3 It contains 2 to 10%.
　本発明の抗菌性ガラスは、ガラス組成中にＢ２Ｏ３を４０モル％以上、ＭｇＯを１０モル％以上、且つＡｇ２Ｏを０．０５～０．５モル％含む。これにより、コストの上昇を抑えた上で、抗菌持続性を高めることができる。更にＡｇ２Ｏの含有量が少ないため、紫外線の照射による変色等の問題も生じ難い。 The antibacterial glass of the present invention contains 40 mol% or more of B 2 O 3 , 10 mol% or more of MgO, and 0.05 to 0.5 mol% of Ag 2 O in the glass composition. Thereby, after suppressing an increase in cost, antimicrobial sustainability can be improved. Furthermore, since the content of Ag 2 O is small, problems such as discoloration due to ultraviolet irradiation hardly occur.
　更に、本発明の抗菌性ガラスは、ガラス組成中にＡｌ２Ｏ３を２モル％以上含む。これにより、ガラス内でＡｇをイオン状態として安定に保持することができる。結果として、Ａｇ２Ｏの含有量が少量であっても、Ａｇイオンの抗菌作用を効果的に発揮させることが可能になる。 Furthermore, the antibacterial glass of the present invention contains 2 mol% or more of Al 2 O 3 in the glass composition. Thereby, Ag can be stably held in an ion state in the glass. As a result, even if the content of Ag 2 O is small, the antibacterial action of Ag ions can be effectively exhibited.
　第二に、本発明の抗菌性ガラスは、更に、ガラス組成として、ＺｎＯを２～１５モル％含有することが好ましい。このようにすれば、ガラスの安定性を高めることができる。またＺｎイオンが溶出して、抗菌性を高めることができる。 Second, the antibacterial glass of the present invention preferably further contains 2 to 15 mol% of ZnO as a glass composition. If it does in this way, stability of glass can be raised. Moreover, Zn ion elutes and antibacterial property can be improved.
　第三に、本発明の抗菌性ガラスは、更に、ガラス組成として、ＣａＯを０．１～５モル％含有することが好ましい。このようにすれば、ガラスの安定性を高めることができる。 Third, the antibacterial glass of the present invention preferably further contains 0.1 to 5 mol% of CaO as a glass composition. If it does in this way, stability of glass can be raised.
　第四に、本発明の抗菌性ガラスは、更に、ガラス組成として、Ｐ２Ｏ５を０．１～１０モル％含有することが好ましい。このようにすれば、ガラスの安定性を高めることができる。またＡｇをイオン状態として安定に保持し易くなる。 Fourth, the antibacterial glass of the present invention preferably further contains 0.1 to 10 mol% of P 2 O 5 as a glass composition. If it does in this way, stability of glass can be raised. Moreover, it becomes easy to hold Ag stably in an ionic state.
　第五に、本発明の抗菌性ガラスは、ガラス組成として、Ｎａ２Ｏを０～５モル％含有することが好ましい。このようにすれば、ガラスの安定性を高めることができる。またＡｇをイオン状態として安定に保持し易くなる。 Fifth, the antibacterial glass of the present invention preferably contains 0 to 5 mol% of Na 2 O as a glass composition. If it does in this way, stability of glass can be raised. Moreover, it becomes easy to hold Ag stably in an ionic state.
　第六に、本発明の抗菌性ガラスは、粉末形状であることが好ましい。 Sixth, the antibacterial glass of the present invention is preferably in a powder form.
　第七に、本発明の抗菌性ガラスは、平均粒子径Ｄ５０が０．５～２５μｍであることが好ましい。ここで、「平均粒子径Ｄ５０」とは、レーザー回折装置で測定した値を指し、レーザー回折法により測定した際の体積基準の累積粒度分布曲線において、その積算量が粒子の小さい方から累積して５０％である粒子径を表す。 Seventh, antimicrobial glass of the present invention preferably has an average particle diameter D 50 is 0.5 ~ 25 [mu] m. Here, the “average particle diameter D 50 ” refers to a value measured with a laser diffractometer, and in the volume-based cumulative particle size distribution curve measured by the laser diffraction method, the accumulated amount is accumulated from the smaller particle. The particle diameter is 50%.
　第八に、本発明の樹脂成形品は、抗菌性ガラスを含む樹脂成形品であって、抗菌性ガラスが、上記の抗菌性ガラスであることが好ましい。 Eighth, the resin molded product of the present invention is a resin molded product containing antibacterial glass, and the antibacterial glass is preferably the above antibacterial glass.
　第九に、本発明の樹脂成形品は、抗菌性ガラスの含有量が０．０１～２０質量％であることが好ましい。 Ninth, the resin molded product of the present invention preferably has an antibacterial glass content of 0.01 to 20% by mass.
　本発明の抗菌性ガラスは、樹脂成形品とした場合に外観上の問題を発生させず、安価であり、しかも抗菌持続性が高い。よって、本発明の抗菌性ガラスは、樹脂成形品に充填される抗菌剤として好適であり、特に歯ブラシ、石鹸入れ、たらい、洗面台、浴槽等の樹脂成形品に充填される抗菌剤として好適である。 The antibacterial glass of the present invention does not cause a problem in appearance when it is a resin molded product, is inexpensive, and has a high antibacterial sustainability. Therefore, the antibacterial glass of the present invention is suitable as an antibacterial agent to be filled in a resin molded product, and particularly suitable as an antibacterial agent to be filled in a resin molded product such as a toothbrush, a soap dish, a tub, a wash basin, and a bathtub. is there.
　本発明の抗菌性ガラスは、ガラス組成として、モル％表示で、Ｂ２Ｏ３　４０～６０％、ＭｇＯ　１０～３２％、Ａｇ２Ｏ　０．０５～０．５％、Ａｌ２Ｏ３　２～１０％を含有すること特徴とする。上記のように各成分の含有範囲を限定した理由を下記に示す。なお、各成分の含有範囲の説明において、％表示はモル％を意味する。 The antibacterial glass of the present invention has a glass composition in terms of mol%, B 2 O 3 40-60%, MgO 10-32%, Ag 2 O 0.05-0.5%, Al 2 O 3 2- It is characterized by containing 10%. The reason for limiting the content range of each component as described above will be described below. In addition, in description of the containing range of each component,% display means mol%.
　Ｂ２Ｏ３は、ガラス形成成分であり、また抗菌持続性を調整し得る成分である。Ｂ２Ｏ３の含有量は４０～６０％、好ましくは４５～６０％である。Ｂ２Ｏ３の含有量が少な過ぎると、ガラス化が困難になると共に、耐水性が高くなり過ぎて、Ａｇイオンの溶出量が少なくなるため、抗菌持続性が低下し易くなる。一方、Ｂ２Ｏ３の含有量が多過ぎると、耐水性が低下し過ぎて、Ａｇイオンの溶出量が過大になるため、抗菌持続性が低下し易くなる。 B 2 O 3 is a glass-forming component and a component that can adjust antimicrobial persistence. The content of B 2 O 3 is 40 to 60%, preferably 45 to 60%. If the content of B 2 O 3 is too small, vitrification becomes difficult and water resistance becomes too high, and the elution amount of Ag ions decreases, so that the antibacterial sustainability tends to decrease. On the other hand, if the content of B 2 O 3 is too large, the water resistance is excessively decreased and the elution amount of Ag ions becomes excessive, so that the antibacterial durability is likely to be decreased.
　ＭｇＯは、ガラス化を助ける成分であり、また耐水性を維持した状態で高温粘性を下げる成分である。ＭｇＯの含有量は１０～３２％、好ましくは１２～３０％である。ＭｇＯの含有量が少な過ぎると、耐水性が低下して、Ａｇイオンの溶出速度が大きくなるため、樹脂成形品の変色が生じ易くなる。一方、ＭｇＯの含有量が多過ぎると、ガラス化が困難になる。 MgO is a component that assists in vitrification, and is a component that lowers the high temperature viscosity while maintaining water resistance. The content of MgO is 10 to 32%, preferably 12 to 30%. If the content of MgO is too small, the water resistance is lowered and the elution rate of Ag ions is increased, so that the resin molded product is likely to be discolored. On the other hand, when there is too much content of MgO, vitrification will become difficult.
　Ａｇ２Ｏは、抗菌性を高める成分である。Ａｇ２Ｏの含有量は０．０５～０．５％、好ましくは０．１～０．５％である。Ａｇ２Ｏの含有量が少な過ぎると、上記の効果を享受し難くなる。一方、Ａｇ２Ｏの含有量が多過ぎると、紫外線の照射による樹脂の変色等の問題が生じ易くなり、また原料コストが高騰し易くなる。 Ag 2 O is a component that enhances antibacterial properties. The content of Ag 2 O is 0.05 to 0.5%, preferably 0.1 to 0.5%. When the content of Ag 2 O is too small, it becomes difficult to enjoy the effect of the above. On the other hand, when the content of Ag 2 O is too large, problems such as resin discoloration due to ultraviolet irradiation tend to occur, and the raw material cost tends to increase.
　Ａｌ２Ｏ３は、ガラス化を助ける成分であり、またガラス内でＡｇ成分をイオン状態として安定に保持する成分である。Ａｌは、ガラス内ではＳｉと同じく酸素４配位で存在する。Ａｌは、ガラス内で３価のカチオンであり、Ｓｉの４価と比較して価数が１つ少ないため、酸素イオンとの電荷バランスにより、マイナスイオン（－１）の電荷を持った状態で存在している。一方、Ａｇイオンは、１価のカチオンであり、１価のマイナスイオンのＡｌサイトに電荷補償の状態で安定的に担持される。なお、Ａｇイオンは、イオン状態では抗菌性が高いものの、非常に還元性が高いため、周辺から電子を奪って、容易にイオン状態から金属状態に変化する性質を有する。そして、Ａｇイオンは、イオン状態では抗菌性が高いものの、金属状態に変化すると抗菌性が著しく低下してしまう。Ａｌ２Ｏ３の含有量が少な過ぎると、上記の効果を享受し難くなる。一方、Ａｌ２Ｏ３の含有量が多過ぎると、耐水性が高くなり過ぎて、Ａｇイオンの溶出量が少なくなるため、抗菌持続性が低下し易くなる。よって、Ａｌ２Ｏ３の含有量は２～１０％、好ましくは４～８％である。 Al 2 O 3 is a component that assists in vitrification, and is a component that stably keeps the Ag component in an ionic state in the glass. Al exists in the glass in an oxygen tetracoordinate like Si. Al is a trivalent cation in the glass and has one valence less than that of Si, so it has a negative ion (-1) charge due to the charge balance with oxygen ions. Existing. On the other hand, Ag ions are monovalent cations and are stably supported on the Al sites of monovalent negative ions in a state of charge compensation. In addition, although Ag ion has high antibacterial property in an ionic state, since it is very reducible, it has a property which takes an electron from the periphery and changes easily from an ionic state to a metallic state. And although Ag ion has high antibacterial property in an ion state, when it changes to a metal state, antibacterial property will fall remarkably. When the content of Al 2 O 3 is too small, it becomes difficult to enjoy the effect of the above. On the other hand, when the content of Al 2 O 3 is too large, too high water resistance, since the elution amount of Ag ions is reduced, the antimicrobial persistence is liable to decrease. Therefore, the content of Al 2 O 3 is 2 to 10%, preferably 4 to 8%.
　上記成分以外にも、以下の成分を含んでもよい。 In addition to the above components, the following components may be included.
　ＺｎＯは、ガラス化を助ける成分であり、またＺｎイオンとして抗菌性を付与する成分である。ＺｎＯの含有量は、好ましくは２～１５％、より好ましくは５～１５％である。ＺｎＯの含有量が少な過ぎると、抗菌性が低下し易くなる。一方、ＺｎＯの含有量が多過ぎると、ガラス化が困難になる。 ZnO is a component that assists in vitrification and is a component that imparts antibacterial properties as Zn ions. The ZnO content is preferably 2 to 15%, more preferably 5 to 15%. When there is too little content of ZnO, antibacterial property will fall easily. On the other hand, when there is too much content of ZnO, vitrification will become difficult.
　ＣａＯは、ガラス化を助ける成分である。ＣａＯの含有量は、好ましくは０．１～５％、より好ましくは０．５～４％である。ＣａＯの含有量が少な過ぎると、上記効果を享受し難くなる。一方、ＣａＯの含有量が多過ぎると、ガラス化が困難になる。 CaO is a component that helps vitrification. The content of CaO is preferably 0.1 to 5%, more preferably 0.5 to 4%. When there is too little content of CaO, it will become difficult to receive the said effect. On the other hand, when there is too much content of CaO, vitrification will become difficult.
　Ｐ２Ｏ５は、ガラス形成成分であり、またガラス内でＡｇ成分をイオン状態として安定に保持する成分である。更に耐水性を制御して、Ａｇイオンの溶出速度を適正化し得る成分である。Ｐ２Ｏ５の含有量は、好ましくは０．１～１０％、より好ましくは１～７％である。Ｐ２Ｏ５の含有量が少な過ぎると、上記効果を享受し難くなる。一方、Ｐ２Ｏ５の含有量が多過ぎると、耐水性が不当に低下して、Ａｇイオンの溶出速度を適正化し難くなる。 P 2 O 5 is a glass forming component and is a component that stably keeps the Ag component in an ionic state in the glass. Furthermore, it is a component that can control the water resistance and optimize the elution rate of Ag ions. The content of P 2 O 5 is preferably 0.1 to 10%, more preferably 1 to 7%. When the content of P 2 O 5 is too small, it becomes difficult to enjoy the above-mentioned effects. On the other hand, when the content of P 2 O 5 is too large, the water resistance decreases unduly, it becomes difficult to optimize the dissolution rate of the Ag ions.
　Ｎａ２Ｏは、ガラス化を助ける成分であり、また高温粘性を低下させる成分である。更に耐水性を制御して、Ａｇイオンの溶出速度を適正化し得る成分である。Ｎａ２Ｏの含有量は、好ましくは０～５％、より好ましくは０．１～３％である。但し、Ｎａ２Ｏの含有量が３％を超えると、樹脂の硬化特性等に悪影響を及ぼす虞が生じる。 Na 2 O is a component that helps vitrification, and is a component that lowers the high temperature viscosity. Furthermore, it is a component that can control the water resistance and optimize the elution rate of Ag ions. The content of Na 2 O is preferably 0 to 5%, more preferably 0.1 to 3%. However, when the content of Na 2 O exceeds 3%, there is a risk of adversely affecting the curing characteristics of the resin.
　ＳｉＯ２は、ガラス形成成分である。ＳｉＯ２の含有量は、好ましくは０～３％、より好ましくは０～１％である。ＳｉＯ２の含有量が多過ぎると、Ａｇイオンの溶出速度が低下し易くなる。 SiO 2 is a glass forming component. The content of SiO 2 is preferably 0 to 3%, more preferably 0 to 1%. When the content of SiO 2 is too large, the dissolution rate of the Ag ion is liable to decrease.
　上記成分以外にも、他の成分を含んでもよく、例えば、ＺｒＯ２、ＳｒＯ、ＢａＯ、ＴｉＯ２、ＣｅＯ２等を合量又は個別に好ましくは５％まで、特に１％まで導入してもよい。 In addition to the above components, other components may be included. For example, ZrO 2 , SrO, BaO, TiO 2 , CeO 2 and the like may be introduced in total or individually, preferably up to 5%, particularly up to 1%. .
　本発明の抗菌性ガラスでは、特に形状は限定されず、例えば、粉末形状、繊維形状、フレーク形状等の形状とすることができる。その中でも、特に粉末形状、つまりガラス粉末が好ましい。ガラス粉末とすれば、比表面積が大きくなるため、高い抗菌性を得ることができる。 The shape of the antibacterial glass of the present invention is not particularly limited. For example, the shape can be a powder shape, a fiber shape, a flake shape, or the like. Among these, a powder shape, that is, a glass powder is particularly preferable. When the glass powder is used, the specific surface area is increased, so that high antibacterial properties can be obtained.
　ガラス粉末の平均粒子径Ｄ５０は、好ましくは０．５～２５μｍ、より好ましくは５～２０μｍである。ガラス粉末の平均粒子径Ｄ５０が小さ過ぎると、ガラス粉末同士が凝集して、樹脂等と混練し難くなる。また樹脂成形品とした場合に、温水等に流出して、樹脂成形品の抗菌性に寄与できない虞が生じる。一方、ガラス粉末の平均粒子径Ｄ５０が大き過ぎると、単位質量当りのＡｇイオンやＺｎイオンの溶出量が少なくなり、抗菌持続性が低下し易くなる。 The average particle diameter D 50 of the glass powder is preferably 0.5 ~ 25 [mu] m, more preferably 5 ~ 20 [mu] m. When the average particle diameter D 50 of the glass powder is too small, the glass powder particles are aggregated, hardly kneaded with a resin or the like. Moreover, when it is set as a resin molded product, it may flow out into warm water or the like and may not contribute to the antibacterial properties of the resin molded product. On the other hand, when the average particle diameter D 50 of the glass powder is too large, the amount of elution of Ag ion and Zn ion per unit mass is reduced, the antimicrobial persistence is liable to decrease.
　本発明の樹脂成形品は、抗菌性ガラスを含む樹脂成形品であって、抗菌性ガラスが、上記の抗菌性ガラスであることが好ましい。本発明の樹脂成形品において、抗菌性ガラスの含有量は、好ましくは０．０１～２０質量％、より好ましくは０．０５～５質量％である。抗菌性ガラスの含有量が少な過ぎると、樹脂成形品に十分な抗菌性を付与することが困難になる。一方、抗菌性ガラスの含有量が多過ぎると、樹脂中に均一に分散させることが困難になり、マスターバッチ成形を行い難くなる。更に、抗菌性ガラスを過剰に添加しても、抗菌性があまり上昇しないため、コスト的に不利である。 The resin molded product of the present invention is a resin molded product containing antibacterial glass, and the antibacterial glass is preferably the above antibacterial glass. In the resin molded product of the present invention, the content of the antibacterial glass is preferably 0.01 to 20% by mass, more preferably 0.05 to 5% by mass. When there is too little content of antibacterial glass, it will become difficult to provide sufficient antibacterial property to a resin molded product. On the other hand, when there is too much content of antibacterial glass, it will become difficult to disperse | distribute uniformly in resin, and it will become difficult to perform masterbatch shaping | molding. Furthermore, even if the antibacterial glass is added excessively, the antibacterial property does not increase so much, which is disadvantageous in terms of cost.
　樹脂として、熱可塑性樹脂、熱硬化性樹脂等が使用可能である。例えば、ポリオレフィン系樹脂、ポリカーボネート樹脂、ＡＢＳ樹脂、ＡＳ樹脂、ポリアミド系樹脂、ポリウレタン系樹脂、ポリビニルアルコール樹脂、ポリエステル樹脂、ポリエチレンテレフタレート樹脂、ポリエチレンオキシド系樹脂、ポリフェニルサルファイド系樹脂、アクリル樹脂、メラミン樹脂、フェノール系樹脂、エポキシ系樹脂、ユリア系樹脂、ポリイミド系樹脂、脂肪族系ナイロン樹脂、ポリ塩化ビニル系樹脂、ポリ塩化ビニデン樹脂、酢酸ビニル系樹脂、フッ素系樹脂、シリコーン系樹脂、主要なエンジニアリングプラスティック等やこれらの複合体に使用可能である。またガラス繊維、ボロン繊維、炭素繊維で強化された樹脂にも適用可能である。 As the resin, a thermoplastic resin, a thermosetting resin, or the like can be used. For example, polyolefin resin, polycarbonate resin, ABS resin, AS resin, polyamide resin, polyurethane resin, polyvinyl alcohol resin, polyester resin, polyethylene terephthalate resin, polyethylene oxide resin, polyphenyl sulfide resin, acrylic resin, melamine resin , Phenolic resin, epoxy resin, urea resin, polyimide resin, aliphatic nylon resin, polyvinyl chloride resin, polyvinylidene chloride resin, vinyl acetate resin, fluorine resin, silicone resin, main engineering It can be used for plastics and the like and composites thereof. It can also be applied to resins reinforced with glass fibers, boron fibers, and carbon fibers.
　熱可塑性樹脂や熱硬化性樹脂へ抗菌性ガラスを充填する場合、抗菌性ガラスの分散性を高めるために、抗菌性ガラス表面をシランカップリング処理等で親油性にすることができる。これにより、抗菌性ガラスの含有量が少なくても、熱可塑性樹脂等に抗菌性を付与することができる。なお、シランカップリング剤としては、アミノシラン、エポキシシラン、メタクリルシラン、ウレイドシラン、イソシアネートシラン等が挙げられる。 When antibacterial glass is filled into a thermoplastic resin or a thermosetting resin, the antibacterial glass surface can be made oleophilic by silane coupling treatment or the like in order to enhance the dispersibility of the antibacterial glass. Thereby, even if there is little content of antimicrobial glass, antimicrobial property can be provided to a thermoplastic resin etc. Examples of the silane coupling agent include amino silane, epoxy silane, methacryl silane, ureido silane, and isocyanate silane.
　本発明の樹脂成形品は、抗菌性ガラス以外にも、各種の添加物（コロイダルシリカ、酸化亜鉛、アルミナ、ホワイトカーボン、酸化錫、酸化チタン、酸化珪素等）を含んでいてもよい。 The resin molded article of the present invention may contain various additives (colloidal silica, zinc oxide, alumina, white carbon, tin oxide, titanium oxide, silicon oxide, etc.) in addition to the antibacterial glass.
　以下、本発明を実施例に基づいて説明する。なお、以下の実施例は単なる例示である。本発明は、以下の実施例に何ら限定されない。 Hereinafter, the present invention will be described based on examples. The following examples are merely illustrative. The present invention is not limited to the following examples.
　表１は、本発明の実施例（試料Ｎｏ．１～５）と比較例（試料Ｎｏ．６）を示している。 Table 1 shows examples of the present invention (sample Nos. 1 to 5) and comparative examples (sample No. 6).
Figure JPOXMLDOC01-appb-T000001
  
Figure JPOXMLDOC01-appb-T000001
  
　次のようにして、各試料を作製した。まず、表中のガラス組成になるように、ガラス原料を調合し、十分に混合した後、白金－ロジウム合金坩堝に入れ、１２００～１３５０℃で３時間溶融した。溶融後、約０．７ｍｍ厚のフィルム状に成形した。得られたガラスフィルムをボールミルにより粉砕し、目開き７５ミクロンの篩を通して、表中に示す平均粒子径Ｄ５０のガラス粉末を得た。なお、ガラス粉末の平均粒子径Ｄ５０は、島津製作所社製レーザー回折測定装置により測定した値である。 Each sample was produced as follows. First, glass raw materials were prepared so as to have the glass composition shown in the table, mixed well, then placed in a platinum-rhodium alloy crucible and melted at 1200 to 1350 ° C. for 3 hours. After melting, it was formed into a film having a thickness of about 0.7 mm. The obtained glass film was pulverized by a ball mill, through mesh 75 micron sieve to obtain a glass powder having an average particle diameter D 50 shown in the table. The average particle diameter D 50 of the glass powder is a value measured by Shimadzu Corporation laser diffractometer.
　以下のようにして、銀イオンの純水中への溶出量を評価した。上記のガラス粉末３ｇを３０ｇの純水中に入れて、５０℃で１６時間保持した後、濾過によりガラス粉末を採取し、１２０℃で２時間乾燥した。次に、純水で処理したガラス粉末０．４ｇを再度、４０ｇの純水中に入れて、３５℃に設定した恒温槽中で２４時間振とうさせた。最後に、濾過により水溶液を採取し、ＩＣＰ発光分析法により、水溶液中の銀イオンの溶出量を評価した。なお、５０℃の純水で処理していないガラス粉末についても、同様の方法により水溶液中の銀イオンの溶出量を評価した。 The elution amount of silver ions into pure water was evaluated as follows. 3 g of the above glass powder was placed in 30 g of pure water and held at 50 ° C. for 16 hours, and then the glass powder was collected by filtration and dried at 120 ° C. for 2 hours. Next, 0.4 g of glass powder treated with pure water was again put into 40 g of pure water and shaken in a thermostatic bath set at 35 ° C. for 24 hours. Finally, the aqueous solution was collected by filtration, and the elution amount of silver ions in the aqueous solution was evaluated by ICP emission analysis. In addition, the elution amount of the silver ion in aqueous solution was evaluated by the same method also about the glass powder which was not processed with the pure water of 50 degreeC.
　表１から分かるように、試料Ｎｏ．１～５の銀イオンの溶出量は、５０℃の純水で処理した後も、５０℃の純水で処理する前と同様にして、２５．１ｐｐｍ／ｍ２以上であった。一方、試料Ｎｏ．６は、５０℃の純水で処理すると、銀イオンの溶出量が１０．６ｐｐｍ／ｍ２まで減少した。 As can be seen from Table 1, sample no. The elution amount of silver ions 1 to 5 was 25.1 ppm / m 2 or more after the treatment with pure water at 50 ° C., similarly to the case before the treatment with pure water at 50 ° C. On the other hand, sample No. 6 was treated with pure water at 50 ° C., the silver ion elution amount decreased to 10.6 ppm / m 2 .
　以下のようにして、抗菌性を評価した。つまり抗菌製品技術協議会の定める試験法「抗菌剤の抗菌力評価試験法最小発育阻止濃度測定法I（１９９８年度改訂版）液体培地希釈法によるＭＩＣ測定法」に則り、ＭＩＣ値として抗菌性を評価した。その結果を表１に示す。 The antibacterial properties were evaluated as follows. In other words, in accordance with the test method “antibacterial activity evaluation test method minimum growth inhibitory concentration measurement method I (1998 revised edition) MIC measurement method by liquid medium dilution method” established by the Antibacterial Product Technology Council, antibacterial properties are exhibited as MIC values. evaluated. The results are shown in Table 1.
　表１から分かるように、試料Ｎｏ．１～６は、試験菌が大腸菌及び黄色ブドウ球菌の場合、ＭＩＣ値が２００（μｇ／ｍｌ）以下であり、抗菌製品技術協議会が示す抗菌剤としての基準値８００（μｇ／ｍｌ）以下を満たしていた。 As can be seen from Table 1, sample no. 1 to 6, when the test bacteria are Escherichia coli and Staphylococcus aureus, the MIC value is 200 (μg / ml) or less, and the standard value 800 (μg / ml) or less as the antibacterial agent shown by the Antibacterial Product Technical Council I met.
　次に、実際に樹脂に混練、充填して、樹脂成形品とした場合の抗菌持続性と外観品位を評価した。具体的には、各試料に係るガラス粉末（０．２質量％）とポリプロピレン樹脂とを混合し、約５０×５０×２ｍｍの板状に成形し、その抗菌持続性と外観品位を評価した。その結果を表１に示す。 Next, the antibacterial sustainability and appearance quality when the resin was actually kneaded and filled into a resin molded product were evaluated. Specifically, glass powder (0.2% by mass) and polypropylene resin according to each sample were mixed and formed into a plate shape of about 50 × 50 × 2 mm, and the antibacterial durability and appearance quality were evaluated. The results are shown in Table 1.
　抗菌持続性試験は、抗菌製品技術協議会の「抗菌加工製品の抗菌力試験法I（１９９８年度版）フィルム密着法：ＪＩＳＺ２８０１」で行った。具体的には、上記樹脂成形品を５０℃の温水中に１６時間浸漬して、上記の抗菌性試験を行った。なお、この試験法では、試験菌が大腸菌の場合、抗菌活性値が２．０以上であれば、「抗菌性あり」と評価される。その後、樹脂成形品の外観を目視で観察した。 The antibacterial sustainability test was carried out by the Antibacterial Product Technology Council, “Antibacterial power test method for antibacterial processed products I (1998 version) film adhesion method: JISZ2801”. Specifically, the above-mentioned resin molded product was immersed in warm water at 50 ° C. for 16 hours, and the above antibacterial test was conducted. In this test method, when the test bacterium is Escherichia coli, if the antibacterial activity value is 2.0 or more, it is evaluated as “antibacterial”. Thereafter, the appearance of the resin molded product was visually observed.
　表１から分かるように、試料Ｎｏ．１～５は、温水に浸漬した後も、抗菌活性値が２以上を示しており、良好な抗菌持続性を有していた。また、温水に浸漬した後の樹脂成形品の色調は、温水に浸漬する前と同じ乳白色を維持しており、Ａｇ金属コロイドによる黄変は認められなかった。一方、試料Ｎｏ．６は、温水に浸漬した後に抗菌活性値が２未満になり、抗菌持続性が低かった。 As can be seen from Table 1, sample no. Nos. 1 to 5 had an antibacterial activity value of 2 or more even after being immersed in warm water, and had good antibacterial persistence. Moreover, the color tone of the resin molded product after being immersed in warm water maintained the same milky white color as before being immersed in warm water, and yellowing by Ag metal colloid was not recognized. On the other hand, sample No. No. 6 had an antibacterial activity value of less than 2 after being immersed in warm water, and its antibacterial durability was low.
　本発明の抗菌性ガラスは、樹脂成形品に充填される抗菌剤として好適であり、特に歯ブラシ、石鹸入れ、たらい、洗面台、浴槽等の樹脂成形品に充填される抗菌剤として好適である。本発明の抗菌性ガラスは、これ以外にも、例えばガラス物品、セラミック物品等の抗菌性釉薬、金属物品等の抗菌性塗料等の抗菌用途に適用可能である。 The antibacterial glass of the present invention is suitable as an antibacterial agent to be filled into a resin molded product, and particularly suitable as an antibacterial agent to be filled into a resin molded product such as a toothbrush, a soap bowl, a tub, a wash basin, and a bathtub. In addition to this, the antibacterial glass of the present invention can be applied to antibacterial applications such as antibacterial glazes such as glass articles and ceramic articles, and antibacterial paints such as metal articles.

Claims (9)

  1. 　ガラス組成として、モル％表示で、Ｂ２Ｏ３　４０～６０％、ＭｇＯ　１０～３２％、Ａｇ２Ｏ　０．０５～０．５％、Ａｌ２Ｏ３　２～１０％を含有することを特徴とする抗菌性ガラス。 The glass composition contains B 2 O 3 40 to 60%, MgO 10 to 32%, Ag 2 O 0.05 to 0.5%, and Al 2 O 3 2 to 10% in terms of mol%. Antibacterial glass.
  2. 　更に、ガラス組成として、ＺｎＯを２～１５モル％含有することを特徴とする請求項１に記載の抗菌性ガラス。 The antibacterial glass according to claim 1, further comprising 2 to 15 mol% of ZnO as a glass composition.
  3. 　更に、ガラス組成として、ＣａＯを０．１～５モル％含有することを特徴とする請求項１又は２に記載の抗菌性ガラス。 The antibacterial glass according to claim 1 or 2, further comprising 0.1 to 5 mol% of CaO as a glass composition.
  4. 　更に、ガラス組成として、Ｐ２Ｏ５を０．１～１０モル％含有することを特徴とする請求項１～３の何れかに記載の抗菌性ガラス。 The antibacterial glass according to any one of claims 1 to 3, further comprising 0.1 to 10 mol% of P 2 O 5 as a glass composition.
  5. 　ガラス組成として、Ｎａ２Ｏを０～５モル％含有することを特徴とする請求項１～４の何れかに記載の抗菌性ガラス。 The antibacterial glass according to any one of claims 1 to 4, wherein the glass composition contains 0 to 5 mol% of Na 2 O.
  6. 　粉末形状であることを特徴とする請求項１～５の何れかに記載の抗菌性ガラス。 The antibacterial glass according to any one of claims 1 to 5, which is in a powder form.
  7. 　平均粒子径Ｄ５０が０．５～２５μｍであることを特徴とする請求項６に記載の抗菌性ガラス。 The antibacterial glass according to claim 6, wherein the average particle diameter D 50 is 0.5 to 25 µm.
  8. 　抗菌性ガラスを含む樹脂成形品であって、
    　抗菌性ガラスが、請求項１～７の何れかに記載の抗菌性ガラスであることを特徴とする樹脂成形品。     A resin molded product containing antibacterial glass,
    A resin molded product, wherein the antibacterial glass is the antibacterial glass according to any one of claims 1 to 7.
  9. 　抗菌性ガラスの含有量が０．０１～２０質量％であることを特徴とする請求項８に記載の樹脂成形品。 The resin molded product according to claim 8, wherein the content of the antibacterial glass is 0.01 to 20% by mass.
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JP2001247337A (en) * 1999-12-28 2001-09-11 Ishizuka Glass Co Ltd Glass composition for imparting antimicrobial properties, antimicrobial polymer composite material using the same and formed bodies of antimicrobial polymer composite material
JP2004359755A (en) * 2003-06-03 2004-12-24 Ishizuka Glass Co Ltd Antimicrobial resin composition and its molding

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JP2001247337A (en) * 1999-12-28 2001-09-11 Ishizuka Glass Co Ltd Glass composition for imparting antimicrobial properties, antimicrobial polymer composite material using the same and formed bodies of antimicrobial polymer composite material
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