JP4368966B2 - Dissolvable glass composition for adding resin moldings having antibacterial properties and resin moldings using the same - Google Patents
Dissolvable glass composition for adding resin moldings having antibacterial properties and resin moldings using the same Download PDFInfo
- Publication number
- JP4368966B2 JP4368966B2 JP09330499A JP9330499A JP4368966B2 JP 4368966 B2 JP4368966 B2 JP 4368966B2 JP 09330499 A JP09330499 A JP 09330499A JP 9330499 A JP9330499 A JP 9330499A JP 4368966 B2 JP4368966 B2 JP 4368966B2
- Authority
- JP
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- Prior art keywords
- resin
- glass composition
- antibacterial
- resin moldings
- component
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000011347 resin Substances 0.000 title claims description 42
- 229920005989 resin Polymers 0.000 title claims description 42
- 230000000844 anti-bacterial effect Effects 0.000 title claims description 26
- 239000000203 mixture Substances 0.000 title claims description 22
- 239000011521 glass Substances 0.000 title claims description 16
- 238000000465 moulding Methods 0.000 title claims description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims 1
- 230000000996 additive effect Effects 0.000 claims 1
- 230000000845 anti-microbial effect Effects 0.000 claims 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 7
- 239000003513 alkali Substances 0.000 description 7
- 229910052725 zinc Inorganic materials 0.000 description 7
- 239000011701 zinc Substances 0.000 description 7
- 239000003242 anti bacterial agent Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 229920001684 low density polyethylene Polymers 0.000 description 3
- 239000004702 low-density polyethylene Substances 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical group [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 241000588724 Escherichia coli Species 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 description 1
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
-
- 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
- C03C4/0035—Compositions for glass with special properties for soluble glass for controlled release of a compound incorporated in said glass
-
- 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
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
- C03C8/04—Frit compositions, i.e. in a powdered or comminuted form containing zinc
-
- 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
- C03C2204/00—Glasses, glazes or enamels with special properties
- C03C2204/02—Antibacterial glass, glaze or enamel
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Glass Compositions (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
【０００１】
【産業上の利用分野】
本発明は、溶解性ガラスに係る抗菌剤に関するものであって、さらには、この抗菌剤を樹脂などに複合して用いることができるものである。
【０００２】
【従来技術】
近年、樹脂成形品に抗菌性を付与する試みが各方面でなされている。ところが、一般的には抗菌剤として１００〜１５０℃で分解してしまう有機系のものが使用されているので、原料中に抗菌剤を混入しようとしても樹脂成形時の加熱に耐えることができない。このため成形後に製品の表面に抗菌処理を施すものがほとんどであり、その処理コストが高くなるうえ、短期間の使用により脱落し易い等の問題があった。そこで、樹脂への練り込み温度により変化を受けることのない抗菌性を有する抗菌剤として溶解性ガラスが注目されている。これは、溶解性ガラスの中に抗菌成分を示す金属イオンを含有させて抗菌効果を発揮させるものである。その中に抗菌成分として亜鉛を含有させるものがあるが、従来のものはガラス中の亜鉛含有率が低く、十分な抗菌効果が得られていなかった。そのため、樹脂に抗菌性を付与する際、ガラス粉末を多量に添加する必要があった。その結果、
樹脂に対する添加量が多くなることにより、最終製品でのコストアップを招いたり、また最悪の事態として樹脂の強度の劣化を引き起こす可能性があった。一方で、溶解性ガラスはその組成中に、一般的なＳｉＯ２、アルカリ成分が含有されているものが用いられてきたが、ガラス中にアルカリ成分を含有することにより、アルカリ成分を嫌う樹脂には使用不可能であった。一方で、亜鉛量を多く含む化合物としてホウ酸亜鉛があるが、ホウ酸亜鉛のままでは、耐水性、耐熱性等の物性に支障があり、その改善が求められていた。
【０００３】
【発明が解決しようとする課題】
本発明は、上記したような問題点を解決して、従来の亜鉛含有溶解性ガラスより更に含有率が高い抗菌性を有する溶解性ガラスを提供することにより、樹脂に対する添加率を低く抑え、製品のコストアップを最小限に抑えることを可能にすることであり、さらに樹脂の強度劣化を最小限に抑えるようにすることである。
【０００４】
【課題を解決するための手段】
上記を解決するためになされた本発明の抗菌性を有する樹脂成形体添加用溶解性ガラス組成物は、組成がｗｔ％表示でＢ２Ｏ３：２０〜５０％、ＺｎＯ：５０〜８０％を含有し、ＳｉＯ２及びアルカリ成分を含まない物である。好ましくは上記組成物を主成分として、ＲＯ成分（ここで、ＲＯ成分とはＣａＯ、ＭｇＯなどのアルカリ土類から選ばれた少なくとも一種以上のものをいう）を１０ｗｔ％以下含有する方がよい。さらに、Ａｇ２Ｏを２ｗｔ％以下の割合で含有することが望まれる。また、これらのガラス組成物の粉末の平均粒径が１〜３０μｍであることを特徴とするものである。一方で、本発明の抗菌性を有する樹脂成形体は、上記ガラス組成物の粉末を樹脂に対して０．１〜１０ｗｔ％含有することを特徴とするものである。
【０００５】
【発明実施の形態】
以下に本発明の実施の形態を詳細に説明する。
本発明で用いられる溶解性ガラス組成物は、組成がｗｔ％表示でＢ２Ｏ３：２０〜５０％、ＺｎＯ：５０〜８０％を主成分として、ＲＯ成分を０〜１０ｗｔ％、Ａｇ２Ｏを０〜２ｗｔ％含有するものである。ここで、組成限定理由について説明すると、Ｂ２Ｏ３が２０ｗｔ％以下では、ガラス骨格となるものが不足しガラス化しないためであり、５０ｗｔ％以上では亜鉛含有量が低下してしまい、従来製品と変わらないものとなってしまうからである。ＺｎＯが５０ｗｔ％以下では従来製品と変化が無く、８０％以上ではガラス骨格となるＢ２Ｏ３量が不足してしまう。ＲＯ成分は、亜鉛を含有した抗菌性を有するガラス組成物の水に対する溶解速度をコントロールするために添加するのがよい。ここで、アルカリ成分を使用しないのは、樹脂によってアルカリ成分を嫌うものがあり、その樹脂にも使用するためにアルカリ成分は使用しない。さらに、Ａｇ２Ｏは、抗菌効果向上のために、含有させることが好ましいが、２ｗｔ％以上では、樹脂混合時に変色する可能性が高くなるためよくない。これらガラス組成物の粉末の平均粒径は１〜３０μｍであることが好ましい。１μｍ以下では、樹脂中への分散が困難となるからである。逆に５０μｍ以上では、樹脂に添加する場合、樹脂の強度劣化を十分に抑えることができないからである。一方で、亜鉛を含有した抗菌性を有するガラス組成物の樹脂に対する添加率において、０．１ｗｔ％以下では充分な抗菌効果が発揮されず、１０ｗｔ％以上は樹脂の物性を劣化する恐れがあり、また抗菌効果の面からも必要ない。
【０００６】
【実施例】
実施例を下記に示す。
表１に示すように実施例１〜３、比較例１，２についてそれぞれ原料を調合し、ルツボを使用し１３００℃にて０．５〜１Ｈｒ溶融した後急冷し、粉砕して平均粒径２０μｍ程度にしたのち、ＬＤＰＥ樹脂，ＰＰ樹脂に各０．３ｗｔ％添加して抗菌評価用のサンプルとした。ｗｔ％で表示する。
【０００７】
【表１】
抗菌試験として、作成したサンプル上に菌液を滴下し、３５℃にて２４時間放置した後、サンプル上の菌液を洗い流し培地に塗布し、３５℃にて放置後生菌数をカウントした。試験菌は大腸菌、黄色ブドウ球菌を使用した。その結果をＬＤＰＥ樹脂，ＰＰ樹脂についてそれぞれ表２、表３および表４、表５に示す。
【０００９】
【表２】
ＬＤＰＥ樹脂
【表３】
【表４】
ＰＰ樹脂
【表５】
以上のように非常に少量で抗菌効果を発揮する。
【００１４】
【発明の効果】
以上に説明したように本発明の抗菌性を有する溶解性ガラス組成物とそれを用いた樹脂成形体によれば、樹脂に対し少量添加で十分な抗菌効果をもたらすことが出来る。また、無アルカリガラスであるため、樹脂を選ばず全ての樹脂に使用が可能になる。
よって本発明は従来の問題点を一掃した抗菌性を有する溶解性ガラス組成物とそれを用いた樹脂成形体として価値が高く、業界に寄与するところは極めて大きいものがある。[0001]
[Industrial application fields]
The present invention relates to an antibacterial agent relating to a soluble glass, and further, this antibacterial agent can be used in combination with a resin or the like.
[0002]
[Prior art]
In recent years, various attempts have been made to impart antibacterial properties to resin molded products. However, since an organic type that decomposes at 100 to 150 ° C. is generally used as an antibacterial agent, even if an antibacterial agent is mixed into the raw material, it cannot withstand the heating during resin molding. For this reason, most of the products are subjected to antibacterial treatment after molding, and the treatment cost is high, and there are problems such as easy removal due to short-term use. Thus, soluble glass has attracted attention as an antibacterial agent having antibacterial properties that is not affected by the kneading temperature of the resin. This is one in which a metal ion indicating an antibacterial component is contained in the soluble glass to exert an antibacterial effect. Among them, there are those containing zinc as an antibacterial component, but the conventional one has a low zinc content in the glass and a sufficient antibacterial effect has not been obtained. Therefore, it was necessary to add a large amount of glass powder when imparting antibacterial properties to the resin. as a result,
Increasing the amount added to the resin may increase the cost of the final product, and in the worst case, may cause deterioration of the strength of the resin. On the other hand, in the composition of the soluble glass, those containing general SiO 2 and an alkali component have been used in its composition. However, by containing an alkali component in the glass, the soluble glass is a resin that dislikes the alkali component. Was unusable. On the other hand, there is zinc borate as a compound containing a large amount of zinc. However, with zinc borate as it is, physical properties such as water resistance and heat resistance are hindered, and improvement thereof has been demanded.
[0003]
[Problems to be solved by the invention]
The present invention solves the above-mentioned problems and provides a soluble glass having antibacterial properties having a higher content rate than the conventional zinc-containing soluble glass, thereby suppressing the addition rate to the resin, It is possible to minimize the cost increase of the resin, and to minimize the deterioration of the strength of the resin.
[0004]
[Means for Solving the Problems]
The soluble glass composition for resin molded article addition having antibacterial properties of the present invention made to solve the above contains B2O3: 20-50%, ZnO: 50-80% in terms of wt%, It does not contain SiO 2 and alkali components. It is preferable to contain 10 wt% or less of an RO component (wherein the RO component is at least one selected from alkaline earths such as CaO and MgO) with the composition as a main component. Furthermore, it is desirable to contain Ag2O at a ratio of 2 wt% or less. Moreover, the average particle diameter of the powder of these glass compositions is 1-30 micrometers, It is characterized by the above-mentioned. On the other hand, the resin molded body having antibacterial properties of the present invention is characterized in that the glass composition powder is contained in an amount of 0.1 to 10 wt% with respect to the resin.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, embodiments of the present invention will be described in detail.
Soluble glass composition used in the present invention, B 2 O 3 composition in wt% Display: 20~50%, ZnO: as a main component 50 to 80%, 0-10 wt% of RO components, Ag 2 O In an amount of 0 to 2 wt%. Here, the reason for limiting the composition will be described. If B 2 O 3 is 20 wt% or less, the glass skeleton is insufficient and the glass does not vitrify, and if it is 50 wt% or more, the zinc content decreases, and the conventional product This is because it will not change. If ZnO is 50 wt% or less, there is no change from the conventional product, and if it is 80% or more, the amount of B 2 O 3 that becomes a glass skeleton is insufficient. The RO component is preferably added to control the dissolution rate of zinc-containing antibacterial glass composition in water. Here, the reason why the alkali component is not used is that the resin dislikes the alkali component depending on the resin, and the alkali component is not used because it is also used for the resin. Furthermore, Ag 2 O is preferably contained for improving the antibacterial effect, but if it is 2 wt% or more, it is not good because the possibility of discoloration during resin mixing increases. The average particle size of the glass composition powder is preferably 1 to 30 μm. This is because if it is 1 μm or less, dispersion in the resin becomes difficult. On the other hand, when the thickness is 50 μm or more, the strength deterioration of the resin cannot be sufficiently suppressed when added to the resin. On the other hand, in the addition ratio of zinc-containing antibacterial glass composition to the resin, a sufficient antibacterial effect is not exhibited at 0.1 wt% or less, and the physical properties of the resin may be degraded at 10 wt% or more, Moreover, it is not necessary from the aspect of antibacterial effect.
[0006]
【Example】
Examples are shown below.
As shown in Table 1, raw materials were prepared for each of Examples 1 to 3 and Comparative Examples 1 and 2, melted at 1300 ° C. at 0.5 to 1 Hr using a crucible, rapidly cooled, pulverized, and average particle size of 20 μm. Then, 0.3 wt% of each was added to the LDPE resin and PP resin to prepare a sample for antibacterial evaluation. Displayed in wt%.
[0007]
[Table 1]
As an antibacterial test, the bacterial solution was dropped on the prepared sample and allowed to stand at 35 ° C. for 24 hours. Then, the bacterial solution on the sample was washed off and applied to the medium, and after standing at 35 ° C., the number of viable bacteria was counted. As test bacteria, Escherichia coli and Staphylococcus aureus were used. The results are shown in Table 2, Table 3, Table 4, and Table 5 for LDPE resin and PP resin, respectively.
[0009]
[Table 2]
LDPE resin
[Table 3]
[Table 4]
PP resin
[Table 5]
As described above, it exhibits an antibacterial effect in a very small amount.
[0014]
【The invention's effect】
As described above, according to the soluble glass composition having antibacterial properties of the present invention and the resin molded body using the same, a sufficient antibacterial effect can be brought about by adding a small amount to the resin. In addition, since it is alkali-free glass, it can be used for all resins regardless of the resin.
Therefore, the present invention is highly valuable as a soluble glass composition having antibacterial properties that eliminates the conventional problems and a resin molded article using the same, and has a great contribution to the industry.
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP09330499A JP4368966B2 (en) | 1999-03-31 | 1999-03-31 | Dissolvable glass composition for adding resin moldings having antibacterial properties and resin moldings using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP09330499A JP4368966B2 (en) | 1999-03-31 | 1999-03-31 | Dissolvable glass composition for adding resin moldings having antibacterial properties and resin moldings using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000281380A JP2000281380A (en) | 2000-10-10 |
| JP4368966B2 true JP4368966B2 (en) | 2009-11-18 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP09330499A Expired - Lifetime JP4368966B2 (en) | 1999-03-31 | 1999-03-31 | Dissolvable glass composition for adding resin moldings having antibacterial properties and resin moldings using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4368966B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4388282B2 (en) | 2003-01-24 | 2009-12-24 | 東亞合成株式会社 | Silver-based glassy antibacterial agent with excellent antibacterial effect |
| JP2011231052A (en) * | 2010-04-28 | 2011-11-17 | Kracie Home Products Ltd | Skin care external preparation composition |
| CN118324414B (en) * | 2024-06-11 | 2024-08-20 | 安徽正合雅聚新材料科技有限公司 | Silver-carrying glass antibacterial agent for high-transparency ABS resin |
-
1999
- 1999-03-31 JP JP09330499A patent/JP4368966B2/en not_active Expired - Lifetime
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| Publication number | Publication date |
|---|---|
| JP2000281380A (en) | 2000-10-10 |
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