JP2008231005A - Antibacterial agent, resin composition containing the same and molded article - Google Patents
Antibacterial agent, resin composition containing the same and molded article Download PDFInfo
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Abstract
Description
本発明は、銀又は銅を含有したリン酸塩系ガラスを含む抗菌剤、該抗菌剤を含む樹脂組成物、及び該樹脂組成物を成形してなる成形品に関する。 The present invention relates to an antibacterial agent containing a phosphate-based glass containing silver or copper, a resin composition containing the antibacterial agent, and a molded article formed by molding the resin composition.
従来から、長時間の高湿の条件下におかれる樹脂製品には、細菌や黴の増殖をおさえるために、樹脂に抗菌剤が添加、含有されている。これらに使用される無機系の抗菌剤としては、酸化銀を利用したものが多く用いられており、例えば、酸化銀を担持させたゼオライト粉末や、組成中に酸化銀を含む溶解性ガラス粉末等が知られている。酸化銀含有ガラス粉末は、長期間使用すると紫外線や熱等の作用で変色する傾向がある。この傾向は樹脂製品が白色や透明である場合には特に問題になりやすい。特許文献１及び特許文献２には、上記の問題点を解決するガラス抗菌剤が開示されている。 Conventionally, in order to suppress the growth of bacteria and sputum, an antibacterial agent is added to and contained in resin products that are subjected to high humidity conditions for a long time. As the inorganic antibacterial agent used in these, those utilizing silver oxide are often used, for example, zeolite powder supporting silver oxide, soluble glass powder containing silver oxide in the composition, etc. It has been known. Silver oxide-containing glass powder tends to discolor due to the action of ultraviolet rays or heat when used for a long period of time. This tendency is particularly problematic when the resin product is white or transparent. Patent Literature 1 and Patent Literature 2 disclose glass antibacterial agents that solve the above problems.
しかしながら、これらの従来知られるガラス抗菌剤は、その製造過程において、１０００℃以上の溶解温度が必要であった。このような製造過程において高温で溶解する場合には、ガラス成分の一部が揮散しガラス組成が変動しやすくなったり、ＮＯＸやＳＯＸ等の腐食性ガスの揮散が増える傾向にあり、また、設備の金属部分の腐食や揮発が増大する可能性が高くなるなどの問題があった。 However, these conventionally known glass antibacterial agents required a melting temperature of 1000 ° C. or higher in the production process. When such dissolved at high temperature in the manufacturing process, there or part becomes volatilized glass composition tends to change the glass component, tends to volatilize is increased corrosive gases such as NO X and SO X, also There was a problem that the possibility of increased corrosion and volatilization of the metal part of the equipment was increased.
本発明は、耐水性や耐光性に優れた抗菌性能を有するとともに、比較的低い溶解温度で製造できるので経済的に製造することができる、銀又は銅を含有するリン酸塩系の新規なガラス抗菌剤、該抗菌剤を含む樹脂組成物、及び該樹脂組成物を成形してなる成形材料を提供することを目的とする。 INDUSTRIAL APPLICABILITY The present invention is a novel phosphate-based glass containing silver or copper, which has antibacterial performance excellent in water resistance and light resistance and can be manufactured economically because it can be manufactured at a relatively low melting temperature. An object is to provide an antibacterial agent, a resin composition containing the antibacterial agent, and a molding material formed by molding the resin composition.
本発明者は、上記目的を達成すべく鋭意検討した結果、ガラス組成として、ＺｎＯ、Ｐ２Ｏ５を特定割合で含み、加えて、ＳＯ３ 及びアルカリ金属である、Ｌｉ２Ｏ、Ｎａ２Ｏ、及びＫ２Ｏをそれぞれ特定割合で含有し、且つ銀又は銅を含有するリン酸塩系のガラスが、耐水性や耐光性に優れた抗菌性能を有するとともに、１０００℃未満の溶融温度で溶解することにより得られことを見出した。 As a result of intensive studies to achieve the above object, the present inventor, as a glass composition, contains ZnO and P 2 O 5 at a specific ratio, and in addition, SO 3 and alkali metals, Li 2 O and Na 2 O. And phosphate glass containing K 2 O at a specific ratio and containing silver or copper have antibacterial performance excellent in water resistance and light resistance and melt at a melting temperature of less than 1000 ° C. And found out that
すなわち、本発明は、かかる新規な知見に基づき本発明に到達したものであり、下記を
特徴とする要旨を有する。
１. 酸化物基準のモル％表示で、Ｐ２Ｏ５：２０〜４０％；ＺｎＯ：５５〜６５％；ＳＯ３：０．５〜１８％；Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ：３〜２０％（但し、Ｌｉ２Ｏ：０〜５％、Ｎａ２Ｏ：３〜１５％、Ｋ２Ｏ：０〜１０％）；Ａｇ２Ｏ若しくはＣｕＯ：０．０５〜１０％；Ａｌ２Ｏ３：０〜５％；ＭｇＯ：０〜１０％；ＣａＯ：０〜１０％；ＢａＯ：０〜１０％、及びＳｎＯ：０〜１０％を有するリン酸塩系ガラスを含むことを特徴とする抗菌剤。
２. Ａｇ２Ｏ：０．０５〜１％若しくはＣｕＯ：０．１〜１０％を有するリン酸塩系ガラスを含む、上記1に記載の抗菌剤。
３. 樹脂１００質量部に対して０．０５〜２０質量部添加されて使用される、上記１又は２に記載の抗菌剤。
４. 抗菌剤を含む樹脂組成物であって、抗菌剤がＰ２Ｏ５：２０〜４０％；ＺｎＯ：５５〜６５％；ＳＯ３：０．５〜１８％；Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ：３〜２０％（但し、Ｌｉ２Ｏ：０〜５％、Ｎａ２Ｏ：３〜１５％、Ｋ２Ｏ：０〜１０％）；Ａｇ２Ｏ若しくはＣｕＯ：０．０５〜１０％；Ａｌ２Ｏ３：０〜５％；ＭｇＯ：０〜１０％；ＣａＯ：０〜１０％；ＢａＯ：０〜１０％、及びＳｎＯ：０〜１０％を有するリン酸塩系ガラスであることを特徴とする樹脂組成物。
５. 抗菌剤が、Ａｇ２Ｏ：０．０５〜１％若しくはＣｕＯ：０．１〜１０％を有するリン酸塩系ガラスである、上記４に記載の抗菌剤。
６. リン酸塩系ガラスが、０．５〜２０μｍの平均粒径（Ｄ５０）を有する粉末である上記４又は５に記載の樹脂組成物。
７. 樹脂１００質量部に対してリン酸塩系ガラスが０．０５〜２０質量部を含有する上記４〜６のいずれかに記載の樹脂組成物。
８. 樹脂が、熱硬化性樹脂、熱可塑性樹脂、ゴム、又はエラストマーであることを特徴とする上記４〜７のいずれかに記載の樹脂組成物。
９. 上記４〜８のいずれかに記載の樹脂組成物を成形してなる成形品。
That is, the present invention has arrived at the present invention based on such novel findings, and has the gist characterized by the following.
1. as represented by mol% based on oxides, P 2 O 5: 20~40% ; ZnO: 55~65%; SO 3: 0.5~18%; Li 2 O + Na 2 O + K 2 O: 3~20% (However, Li 2 O: 0~5%, Na 2 O: 3~15%, K 2 O: 0~10%); Ag 2 O or CuO: 0.05~10%; Al 2 O 3: 0 An antibacterial agent characterized by comprising a phosphate glass having MgO: 0 to 10%; CaO: 0 to 10%; BaO: 0 to 10% and SnO: 0 to 10%.
2. The antibacterial agent according to 1 above, comprising a phosphate-based glass having Ag 2 O: 0.05 to 1% or CuO: 0.1 to 10%.
3. The antibacterial agent according to 1 or 2 above, which is used by adding 0.05 to 20 parts by mass with respect to 100 parts by mass of the resin.
4. A resin composition containing an antibacterial agent, wherein the antibacterial agent is P 2 O 5 : 20 to 40%; ZnO: 55 to 65%; SO 3 : 0.5 to 18%; Li 2 O + Na 2 O + K 2 O : 3-20% (however, Li 2 O: 0~5%, Na 2 O: 3~15%, K 2 O: 0~10%); Ag 2 O or CuO: 0.05 to 10%; Al 2 O 3: 0~5%; MgO : 0~10%; CaO: 0~10%; BaO: 0~10%, and SnO: and characterized in that the phosphate-based glass having a 0-10% Resin composition.
5. The antibacterial agent according to 4 above, wherein the antibacterial agent is phosphate glass having Ag 2 O: 0.05 to 1% or CuO: 0.1 to 10%.
6. The resin composition as described in 4 or 5 above, wherein the phosphate glass is a powder having an average particle diameter (D50) of 0.5 to 20 μm.
7. The resin composition according to any one of 4 to 6 above, wherein the phosphate glass contains 0.05 to 20 parts by mass with respect to 100 parts by mass of the resin.
8. The resin composition according to any one of 4 to 7 above, wherein the resin is a thermosetting resin, a thermoplastic resin, rubber, or an elastomer.
9. A molded product obtained by molding the resin composition according to any one of 4 to 8 above.
本発明によれば、耐水性や耐光性に優れた抗菌性能を有するとともに、経済的に製造することができる、銀又は銅を含有したリン酸塩系の新規なガラス抗菌剤、該抗菌剤を含む樹脂組成物、及び該樹脂組成物を成形してなる成形品が提供される。 According to the present invention, a novel phosphate-based glass antibacterial agent containing silver or copper, which has an antibacterial performance excellent in water resistance and light resistance and can be economically produced, the antibacterial agent A resin composition containing the resin composition and a molded product formed by molding the resin composition are provided.
本発明でおける抗菌剤を構成するリン酸塩系のガラスは、上記のように、酸化物基準のモル％表示（以下、特に断りのない限り、「％」はモル％である）で、Ｐ２Ｏ５：２０〜４０％；ＺｎＯ：５５〜６５％；ＳＯ３：０．５〜１８％；Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ：３〜２０％（但し、Ｌｉ２Ｏ：０〜５％、Ｎａ２Ｏ：３〜１５％、Ｋ２Ｏ：０〜１０％）；Ａｇ２Ｏ若しくはＣｕＯ：０．０５〜１０％；Ａｌ２Ｏ３：０〜５％；ＭｇＯ：０〜１０％；ＣａＯ：０〜１０％；ＢａＯ：０〜１０％、及びＳｎＯ：０〜１０％を有する。 As described above, the phosphate-based glass constituting the antibacterial agent in the present invention is expressed in mol% on the oxide basis (hereinafter, “%” is mol% unless otherwise specified). 2 O 5: 20~40%; ZnO : 55~65%; SO 3: 0.5~18%; Li 2 O + Na 2 O + K 2 O: 3~20% ( however, Li 2 O: 0~5%, Na 2 O: 3~15%, K 2 O: 0~10%); Ag 2 O or CuO: 0.05~10%; Al 2 O 3: 0~5%; MgO: 0~10%; CaO : 0-10%; BaO: 0-10%, and SnO: 0-10%.
なかでも、本発明でおける抗菌剤を構成する好ましいリン酸塩系のガラスは、Ｐ２Ｏ５：２５〜３５％；ＺｎＯ：５５〜６０％；ＳＯ３：１〜１２％；Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ：５〜１０％（但し、Ｌｉ２Ｏ：０〜５％、Ｎａ２Ｏ：４〜９％、Ｋ２Ｏ：１〜６％）；Ａｇ２Ｏ若しくはＣｕＯ：０．１〜５％；Ａｌ２Ｏ３：０〜２％；ＭｇＯ：０〜１％；ＣａＯ：０〜５％；ＢａＯ：０〜２％、及びＳｎＯ：０〜２％を有する。 Among these, preferable phosphate-based glasses constituting the antibacterial agent in the present invention are P 2 O 5 : 25 to 35%; ZnO: 55 to 60%; SO 3 : 1 to 12%; Li 2 O + Na 2. O + K 2 O: 5~10% ( however, Li 2 O: 0~5%, Na 2 O: 4~9%, K 2 O: 1~6%); Ag 2 O or CuO: 0.1 to 5 Al 2 O 3 : 0-2%; MgO: 0-1%; CaO: 0-5%; BaO: 0-2% and SnO: 0-2%.
本発明のリン酸塩系のガラスにおける必須の成分は、Ｐ２Ｏ５、ＺｎＯ、ＳＯ３、アルカリ金属成分および、Ａｇ２Ｏ又はＣｕＯである。このうち、Ｐ２Ｏ５は、ガラス形成に必須な成分であり、その含有量は２０〜４０％で、好ましくは２５〜３５％で、最も好ましくは２７〜３３％である。Ｐ２Ｏ５が２０％よりも少なくなるとガラス化し難くなり、均質なガラスが得られなくなり、一方、４０％より多いと、ガラスとしての耐水性が低下するため好ましくない。また、ＺｎＯは、抗菌作用を示す成分であり、その含有量は５５〜６５％で、好ましくは５５〜６０％である。ＺｎＯが５５％よりも少なくなると抗菌作用が弱くなり、６５％を越えるとガラス化が困難になる。 The essential components in the phosphate-based glass of the present invention are P 2 O 5 , ZnO, SO 3 , an alkali metal component, and Ag 2 O or CuO. Among, P 2 O 5 is an essential component to the glass forming, the content thereof is 20 to 40%, and preferably 25 to 35% and most preferably 27 to 33%. If the P 2 O 5 content is less than 20%, vitrification becomes difficult and a homogeneous glass cannot be obtained. On the other hand, if it exceeds 40%, the water resistance of the glass decreases, which is not preferable. Moreover, ZnO is a component which shows an antibacterial action, The content is 55 to 65%, Preferably it is 55 to 60%. When ZnO is less than 55%, the antibacterial action becomes weak, and when it exceeds 65%, vitrification becomes difficult.
本発明のリン酸塩系ガラスにおいて、ＳＯ３はガラスの溶解性に影響し、かつ抗菌性にも影響与える重要な成分である。その含有量は０．５〜１８％、好ましくは１〜１２％である。ＳＯ３が０．５％よりも少なくなると得られるガラスの溶解性が小さくなり、抗菌作用が弱くなる。また、ガラス溶融時の温度を１０００℃未満にすることが困難となり好ましく無い。一方、含有量が１８％を越えるとガラスとしての耐水性が著しく低下するため、ガラスの溶解性を制御することが困難となり不都合である。 In the phosphate glass of the present invention, SO 3 is an important component that affects the solubility of the glass and also affects the antibacterial properties. Its content is 0.5-18%, preferably 1-12%. When SO 3 is less than 0.5%, the solubility of the obtained glass is reduced, and the antibacterial action is weakened. Moreover, it becomes difficult to make the temperature at the time of glass melting lower than 1000 ° C., which is not preferable. On the other hand, if the content exceeds 18%, the water resistance of the glass is remarkably lowered, which makes it difficult to control the solubility of the glass.
また、アルカリ金属であるＬｉ２Ｏ、Ｎａ２Ｏ、及びＫ２Ｏは、ガラスの溶融を助ける
成分である。その含有量は、Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏの合計で、３〜２０％であり、好ましくは５〜１０％である。該合計の含有量が３％より少ない場合には、ガラスの溶融が不十分となり、ガラス化し難くなり、一方、２０％より多い場合には、ガラスとしての耐水性が著しく低下するため好ましくない。なお、アルカリ金属の個々の成分としては、Ｌｉ２Ｏが０〜１５％、好ましくは０〜５％であり、Ｎａ２Ｏが３〜１５％、好ましくは４〜９％であり及びＫ２Ｏは０〜１０％、好ましくは１〜６％である。
Further, an alkali metal Li 2 O, Na 2 O, and K 2 O are components that help melt the glass. Its content is the sum of Li 2 O + Na 2 O + K 2 O, 3 to 20%, preferably 5-10%. If the total content is less than 3%, the glass is insufficiently melted and hardly vitrified. On the other hand, if the total content is more than 20%, the water resistance of the glass is remarkably lowered. In addition, as individual components of the alkali metal, Li 2 O is 0 to 15%, preferably 0 to 5%, Na 2 O is 3 to 15%, preferably 4 to 9%, and K 2 O Is 0 to 10%, preferably 1 to 6%.
本発明の一形態のリン酸塩系ガラスにおいて、Ａｇ２Ｏは抗菌性を発現する重要な成分であり、その含有量は、０．０５〜１％である。含有量が０．０５％より少ない場合には、抗菌性の発現が不十分となり、一方、１％より多い場合には、樹脂組成物とした場合に赤味の発色があるため好ましくなく、更に得られるガラスが高価となり好ましくない。なかでも、Ａｇ２Ｏの含有量は、０．１〜０．６％が好ましく、０．１〜０．３％が特に好ましい。 In the phosphate glass of one embodiment of the present invention, Ag 2 O is an important component that exhibits antibacterial properties, and its content is 0.05 to 1%. When the content is less than 0.05%, the antibacterial expression becomes insufficient. On the other hand, when the content is more than 1%, it is not preferable because there is a reddish coloring in the resin composition. The resulting glass is expensive and not preferred. Among these, the content of Ag2O is preferably 0.1 to 0.6%, particularly preferably 0.1 to 0.3%.
本発明の別形態のリン酸塩系ガラスにおいて、ＣｕＯは抗菌性を発現する重要な成分であり、その含有量は、０．１〜１０％である。含有量が０．１％より少ない場合には、抗菌性の発現が不十分となり、一方、１０％より多い場合には、ガラスの青色の着色が濃くなり、成形品の用途によって青色の着色が好ましくない場合がある。なかでも、ＣｕＯの含有量は、０．２〜５％が好ましく、０．２〜３．５％が特に好ましい。 In the phosphate glass of another embodiment of the present invention, CuO is an important component that exhibits antibacterial properties, and its content is 0.1 to 10%. When the content is less than 0.1%, the antibacterial effect is insufficient, whereas when the content is more than 10%, the blue coloration of the glass becomes deep, and the blue coloration depends on the use of the molded product. It may not be preferable. Especially, 0.2-5% is preferable and, as for content of CuO, 0.2-3.5% is especially preferable.
本発明のリン酸塩系ガラスにおける任意の成分について説明すると、Ａｌ２Ｏ３は、ガラスの化学耐久性を向上させるために添加する成分であり、その含有量は０〜５％、好ましくは０〜２％である。Ａｌ２Ｏ３が５％を超えると、ガラスの溶融がより困難となり均質なガラスが得られないためである。更にＡｌ２Ｏ３の含有量は０．１％未満であることが、ガラスの溶融温度を上昇させないために好ましい。 The optional components in the phosphate glass of the present invention will be described. Al 2 O 3 is a component added to improve the chemical durability of the glass, and its content is 0 to 5%, preferably 0. ~ 2%. This is because if Al 2 O 3 exceeds 5%, the glass is more difficult to melt and a homogeneous glass cannot be obtained. Further, the content of Al 2 O 3 is preferably less than 0.1% so as not to raise the melting temperature of the glass.
また、ＣａＯは、ガラスの溶融を助ける成分であり、その含有量は０〜１５％、好ましくは０〜５％であり、その含有量が１５％を越えると、ガラスが失透しやすくなるので好ましくない。ＢａＯは、ガラスの溶融を助ける成分であり、その含有量は０〜１５％、好ましくは０〜２％である。ＭｇＯは、ガラスの溶融を助ける成分であり、また耐水性を向上させる成分である。その含有量は０〜１５％、好ましくは０〜１％である。ＳｎＯは、ガラスの耐久性を向上させる機能を有する成分であり、その含有量は０〜１５％、好ましくは０〜１％である。更に、ＣａＯ，ＢａＯ，ＭｇＯおよびＳｎＯの含有量は、いずれも、０．１％未満であることが、ガラスの溶融温度を上昇させるために好ましい。 Further, CaO is a component that aids melting of the glass, and its content is 0 to 15%, preferably 0 to 5%. If the content exceeds 15%, the glass tends to devitrify. It is not preferable. BaO is a component that aids melting of the glass, and its content is 0 to 15%, preferably 0 to 2%. MgO is a component that aids melting of the glass and is a component that improves water resistance. Its content is 0-15%, preferably 0-1%. SnO is a component having a function of improving the durability of the glass, and its content is 0 to 15%, preferably 0 to 1%. Furthermore, it is preferable that the contents of CaO, BaO, MgO and SnO are all less than 0.1% in order to increase the melting temperature of the glass.
本発明の抗菌剤に使用されるリン酸塩系ガラスは、上記以外にＢ、Ｓｒ、Ｔｉ、Ｆｅ、Ｃｏ、Ｎｉ、Ｚｒ、Ｍｏなどの金属酸化物をガラス組成の成分として含有してもよい。 The phosphate glass used for the antibacterial agent of the present invention may contain metal oxides such as B, Sr, Ti, Fe, Co, Ni, Zr, and Mo as components of the glass composition in addition to the above. .
本発明のリン酸塩系ガラスの形態は、繊維、粉末、フレーク、バルーン（中空体）など適宜選ぶことができる。繊維の形態の場合、その太さが好ましくは１〜３０μｍであり、特には６〜２３μｍである。本発明のリン酸塩系ガラスは直接繊維化してもよいし、一旦カレットを製造し、該カレットを繊維化してもよい。かかる本発明のリン酸塩系ガラスの繊維は抗菌性繊維として使用することができる。 The form of the phosphate glass of the present invention can be appropriately selected from fibers, powders, flakes, balloons (hollow bodies) and the like. In the case of a fiber form, the thickness is preferably 1 to 30 μm, particularly 6 to 23 μm. The phosphate glass of the present invention may be directly fiberized, or a cullet may be once produced and the cullet may be fiberized. Such phosphate glass fibers of the present invention can be used as antibacterial fibers.
また、本発明のリン酸塩系ガラスの形態が粉末の場合、比表面積が大きくなり、高い抗菌効果が得られるので好ましい。粉末の場合、平均粒径（Ｄ５０）が０．５〜２０μｍ、好ましくは１〜１０μｍが好適である。平均粒径が０．５μｍより小さいとガラス粉末が製造し難くなり、２０μｍより大きくなると粒子が大きいため、樹脂組成物の表面外観性が劣るため好ましくない。 Moreover, when the form of the phosphate glass of the present invention is a powder, the specific surface area is increased and a high antibacterial effect is obtained, which is preferable. In the case of powder, the average particle diameter (D50) is 0.5 to 20 μm, preferably 1 to 10 μm. If the average particle size is smaller than 0.5 μm, it is difficult to produce glass powder, and if it is larger than 20 μm, the particles are large.
本発明の抗菌剤のリン酸塩系ガラスは、Ｚｎイオン、ＡｇイオンまたはＣｕイオンの溶出を通じて抗菌性を発現することから、ガラスとしての耐水性と、抗菌性を発現するための溶出性とを両立する必要があり、耐水性は好ましくは０．０２〜３．０質量％、特に好ましくは０．０２〜１．０質量％が好適である。耐水性が０．０２％よりも小さいと、Ｚｎイオン、ＡｇイオンまたはＣｕイオンの溶出量が少なく、抗菌性を十分に発揮することが困難となる。また、耐水性が３．０％よりも大きいと、ガラスとしての耐水性が不十分となり、吸湿しやすくなり、ガラスの長期保存や取扱い性が困難になったりするので好ましくない。 Since the phosphate glass of the antibacterial agent of the present invention exhibits antibacterial properties through elution of Zn ions, Ag ions or Cu ions, it has water resistance as glass and elution properties for developing antibacterial properties. The water resistance is preferably 0.02 to 3.0% by mass, particularly preferably 0.02 to 1.0% by mass. If the water resistance is less than 0.02%, the elution amount of Zn ions, Ag ions or Cu ions is small, and it becomes difficult to sufficiently exhibit antibacterial properties. On the other hand, if the water resistance is larger than 3.0%, the water resistance as glass becomes insufficient, it becomes easy to absorb moisture, and long-term storage and handling of the glass become difficult.
本発明の抗菌剤を構成するリン酸塩系ガラスは、既知の方法及び装置を用いて、所望と
するガラス組成となるように、ガラス原料を混合し溶融させてから固化させることにより製造される。リン酸塩系ガラスの粉末は、ガラスのカレットを作製し、所定の平均粒径となるように粉砕することにより得ることができる。リン酸塩系ガラスのカレットを粉砕する方法として、媒体撹拌ミル、コロイドミル、湿式ボールミルなどの湿式粉砕、ジェットミル、乾式ボールミル、ロールクラッシャーなどの乾式粉砕などが挙げられ、複数の粉砕方法を組合せて用いてもよい。
The phosphate glass constituting the antibacterial agent of the present invention is produced by mixing and melting glass raw materials and solidifying them so as to obtain a desired glass composition using a known method and apparatus. . The phosphate glass powder can be obtained by preparing a glass cullet and pulverizing it to a predetermined average particle size. Examples of the method for pulverizing phosphate glass cullet include wet pulverization such as medium stirring mill, colloid mill, and wet ball mill, and dry pulverization such as jet mill, dry ball mill, and roll crusher. May be used.
上記の粉砕方法を用いて、所定の平均粒径を有するガラス粉末を得ることができる。また、粉砕して得られるガラス粉末の平均粒径が上記の好ましい範囲になるように、分級処理を行ってもよい。分級処理としては特に限定されないが、風力式分級機や篩い分け装置等を用いるのが好ましい。 A glass powder having a predetermined average particle diameter can be obtained by using the above pulverization method. Moreover, you may perform a classification process so that the average particle diameter of the glass powder obtained by grind | pulverizing may become said preferable range. Although it does not specifically limit as a classification process, It is preferable to use a wind-type classifier, a sieving apparatus, etc.
本発明のリン酸塩系ガラスの抗菌剤は、熱硬化性樹脂、熱硬化性樹脂、ゴム、エラストマーなどに各種の材料に添加又は充填して使用できる。なかでも、樹脂に充填する場合には、優れた抗菌性を有する樹脂組成物を与える。好ましい樹脂の例としては、ポリプロピレン、ポリエチレンなどのポリオレフィン系樹脂；ポリスチレン系樹脂；ＡＳ（アクリロニトリルースチレン共重合体）樹脂；ＡＢＳ（アクリロニトリル−ブタジエン−スチレン共重合体）樹脂；ポリウレタン系、ポリエステル系などの熱可塑性エラストマー；ＰＢＴ，ＰＥＴなどの熱可塑性ポリエステル系樹脂；不飽和ポリエステル樹脂；アクリル系樹脂；フェノール系樹脂；エポキシ系樹脂；メラミン樹脂；シリコーン系樹脂が挙げられる。これら樹脂のなかでも、特に衛生容器等に用いられるポリオレフィン系樹脂、アクリル系樹脂、メラミン系樹脂、ＡＢＳ樹脂や、シーリング材等に使用されるシリコーン系樹脂が好ましい。 The antibacterial agent of the phosphate glass of the present invention can be used by adding or filling various materials into a thermosetting resin, a thermosetting resin, rubber, an elastomer and the like. Especially, when filling resin, the resin composition which has the outstanding antimicrobial property is given. Examples of preferred resins include polyolefin resins such as polypropylene and polyethylene; polystyrene resins; AS (acrylonitrile-styrene copolymer) resins; ABS (acrylonitrile-butadiene-styrene copolymer) resins; polyurethanes, polyesters, etc. Thermoplastic elastomers such as PBT and PET; unsaturated polyester resins; acrylic resins; phenolic resins; epoxy resins; melamine resins; Among these resins, polyolefin resins, acrylic resins, melamine resins, ABS resins used for sanitary containers and the like, and silicone resins used for sealing materials and the like are particularly preferable.
本発明の樹脂組成物における抗菌剤の含有量は、樹脂１００質量部に対して０．０５〜２０質量部、好ましくは０．１〜１５質量部であり、特に０．１〜５質量部であることが好ましい。含有量が、０．１質量部より少ないと樹脂に十分な抗菌性を付与し難くなる。また、含有量が２０質量部を越えると抗菌力は殆ど変わらなくなり、経済的でないため好ましくない。 The content of the antibacterial agent in the resin composition of the present invention is 0.05 to 20 parts by mass, preferably 0.1 to 15 parts by mass, particularly 0.1 to 5 parts by mass with respect to 100 parts by mass of the resin. Preferably there is. When the content is less than 0.1 parts by mass, it becomes difficult to impart sufficient antibacterial properties to the resin. On the other hand, if the content exceeds 20 parts by mass, the antibacterial activity hardly changes and is not economical, which is not preferable.
更に、本発明で抗菌剤として使用されるリン酸塩系ガラスは、カップリング剤を含む処理剤で表面処理することもできる。この表面処理により、リン酸塩系ガラスと樹脂とから樹脂組成物を得る際や、この樹脂組成物を成形する際に、リン酸塩系ガラスと樹脂との接着性を向上させる。また、リン酸塩系ガラスを取り扱う上で、静電気の発生を抑えてハンドリング性を改善することもできる。また、樹脂とリン酸塩系ガラスとの接着性が向上することにより、樹脂組成物の機械的物性が改善できる。 Furthermore, the phosphate glass used as an antibacterial agent in the present invention can be surface-treated with a treatment agent containing a coupling agent. By this surface treatment, when the resin composition is obtained from the phosphate glass and the resin, or when the resin composition is molded, the adhesion between the phosphate glass and the resin is improved. Moreover, when handling phosphate glass, the generation of static electricity can be suppressed and handling can be improved. Moreover, the mechanical properties of the resin composition can be improved by improving the adhesion between the resin and the phosphate glass.
上記カップリング剤としては、シラン系カップリング剤又はチタネート系カップリング剤などを使用できる。特に、樹脂とガラス粉末との接着性が良好である点からシラン系カップリング剤を用いるのが好ましい。 As the coupling agent, a silane coupling agent or a titanate coupling agent can be used. In particular, it is preferable to use a silane coupling agent from the viewpoint of good adhesion between the resin and the glass powder.
また、上記カップリング剤の成分のリン酸源ガラスへの付与量は、使用される樹脂やリン酸源ガラスなどの種類に応じて選択されるが、付与後のリン酸塩系ガラスの質量を基準にして固形分として、好ましくは０．１〜４質量％、特に好ましくは０．２〜２質量％である。付与量が０．１質量％より少ないとガラスを取り扱う上でのハンドリング性及び樹脂との接着性を充分に改善することが難しくなるので好ましくない。また、付与量が４質量％より多いと、表面処理時にガラスの粉末が２次凝集して固まりになるため前記樹脂への分散を低下させることになり易いので好ましくない。 In addition, the amount of the coupling agent component to be applied to the phosphate source glass is selected according to the type of resin or phosphate source glass used, but the mass of the phosphate-based glass after the application is determined. The solid content is preferably 0.1 to 4% by mass, particularly preferably 0.2 to 2% by mass, based on the standard. When the applied amount is less than 0.1% by mass, it is difficult to sufficiently improve the handling property in handling the glass and the adhesiveness with the resin, which is not preferable. On the other hand, if the applied amount is more than 4% by mass, the glass powder is secondarily agglomerated and hardened during the surface treatment, which is not preferable because dispersion to the resin tends to be reduced.
本発明の抗菌剤を含む樹脂組成物は、樹脂、リン酸塩系ガラス、及び必要に応じて配合される種々の添加剤とを、混合することにより得られる。特に、樹脂が熱可塑性樹脂、熱可塑性エラストマーである場合には、各種成分を混合するとともに溶融（例えば溶融混練）してもよく、また、各種成分の混合後の溶融混練などの従来の樹脂組成物の製造方法と同様の方法により成形材料としての樹脂組成物を得ることができる。配合される樹脂の形態は、特に制限なく、ペレット状、粒状、粉末状、繊維状などの種々の形態を用いることができる。上記各成分を溶融混練した後、押出成形してペレット状又は粒状の成形材料とすることが好ましい。 The resin composition containing the antibacterial agent of the present invention is obtained by mixing a resin, a phosphate glass, and various additives blended as necessary. In particular, when the resin is a thermoplastic resin or a thermoplastic elastomer, various components may be mixed and melted (for example, melt kneading), and a conventional resin composition such as melt kneading after mixing the various components. A resin composition as a molding material can be obtained by a method similar to the method for producing a product. The form of resin to be blended is not particularly limited, and various forms such as pellets, granules, powders, and fibers can be used. After melt-kneading the above components, it is preferable to form by extrusion molding into a pellet-shaped or granular molding material.
成形材料である本発明の抗菌剤を含む樹脂組成物は、従来の樹脂組成物の同様に各種の方法によって成形して成形品とすることができる。その成形方法としては、プレス成形、押出し成形、カレンダ成形、射出成形、引き抜き成形などがある。このような成形方法により、成形品である本発明の樹脂組成物が得られる。また、成形材料である本発明の樹脂組成物を経ることなく、樹脂、リン酸塩系ガラス、及び、さらに必要に応じてそれら以外の添加剤とを、射出成形機や押出し成形機などの成形機中で溶融混合するとともにその溶融混合物を成形して、本発明の成形品を得ることもできる。 The resin composition containing the antibacterial agent of the present invention, which is a molding material, can be molded into a molded product by various methods in the same manner as conventional resin compositions. Examples of the molding method include press molding, extrusion molding, calendar molding, injection molding, and pultrusion molding. By such a molding method, the resin composition of the present invention which is a molded product is obtained. Further, without passing through the resin composition of the present invention, which is a molding material, resin, phosphate glass, and, if necessary, other additives are molded into an injection molding machine or an extrusion molding machine. The molded product of the present invention can also be obtained by melting and mixing in the machine and molding the molten mixture.
例えば、不飽和ポリエステル樹脂などの硬化性樹脂と、硬化剤、低収縮化剤、フィラー、添加剤および増粘剤とを混合したものをガラス繊維などの繊維状補強材に含浸あるいは混練させる方法は、既知の方法、すなわちシートモールディングコンパウンド（ＳＭＣ）やバルクモールディングコンパウンド（ＢＭＣ）の製造方法を使用することができる。前記製造方法により得られる硬化性樹脂組成物、ＳＭＣ、ＢＭＣは、これを既知の方法で製品の形状に成形し、例えば１２０〜１５０℃に加熱し硬化させ、浴槽製品や水まわり製品等の成形品が製造される。成形品としては、例えば、便器、浴槽、洗面台などの衛生関連製品、台所製品、文具、玩具などが挙げられる。 For example, a method of impregnating or kneading a fibrous reinforcing material such as glass fiber with a mixture of a curable resin such as an unsaturated polyester resin and a curing agent, a low shrinkage agent, a filler, an additive, and a thickener. A known method, that is, a method of manufacturing a sheet molding compound (SMC) or a bulk molding compound (BMC) can be used. The curable resin composition, SMC, and BMC obtained by the above manufacturing method are molded into a product shape by a known method, for example, heated to 120 to 150 ° C. to be cured, and molded into a bath product or a water product. Product is manufactured. Examples of the molded article include sanitary products such as toilets, bathtubs, and washstands, kitchen products, stationery, and toys.
本発明の抗菌剤は上記に限られるものではなく、フィルム材、シート材、電化製品のハウジング材、紙製品、繊維製品、塗料などの各種の材料に添加して用いることができる。また、例えば、ガラスやセラミックスの抗菌性釉薬、金属の抗菌性塗料などの種々の抗菌用途に使用可能である。 The antibacterial agent of the present invention is not limited to the above, and can be used by adding to various materials such as film materials, sheet materials, housing materials for electrical appliances, paper products, textile products, paints and the like. Further, it can be used for various antibacterial applications such as antibacterial glazes of glass and ceramics, and metal antibacterial paints.
以下に、本発明の実施例を説明するが、本発明はこれらに限定して解釈されないことはもちろんである。
なお、以下における各種の特性値の測定はそれぞれ次のように行った。
（１）初期の抗菌性試験：
ａ）日本化学療法学会の抗菌力評価試験法の最小発育阻止濃度測定法I（２００３年度版）に従い、液体培地希釈法によるＭＩＣ測定法（以下、ＭＩＣ法とする）で抗菌性試験を実施した。テスト細菌として黄色ぶどう球菌及び大腸菌を用いた。抗菌性の評価は、ＭＩＣ法の判定に従い、試験菌の発育が認められない試料の最低濃度を最小発育阻止濃度として求め、８００μｇ／ｍｌ以下を合格とした。
（２）耐光性試験後の抗菌性試験：
ＪＩＳ−Ｂ７７５３のサンシャインカーボンアーク灯式の耐光性試験装置を用い、水の噴霧無しの６３±３℃で８０時間の条件で処理した試料について、ＪＩＳ Ｚ２８０１ ５．２により、抗菌加工製品規格に従い、テスト細菌として黄色ぶどう球菌及び大腸菌を用いて抗菌性試験を実施した（以下、ＪＩＳ法とする）。抗菌性の評価は、該ＪＩＳ法に定義される抗菌活性値で判定した。抗菌活性値２．０以上を抗菌性があると評価した。
（３）ガラスの耐水性：
ガラスカレット（約１５ｍｍ角で厚さ約６ｍｍの板状体）を試料として秤量し、９０℃の熱湯浴に浸漬し、６時間後に浴から取出し、常温で乾燥後、試料を秤量し、質量損失を測定した。浸漬前の質量に対する質量損失の割合を百分率として算出して、０．０２〜１．０％を○、１．０〜３．０％を△、０．０２％未満及び３．０％超を×としてランク評価した。
（４）樹脂組成物の色調評価：
樹脂組成物の成形品の色調は、日本電色株式会社製Σ９０を用い、ＪＩＳ‐Ｋ‐７１０５方法に準じて、反射法によって厚さ２ｍｍの試験片を測定した。初期の樹脂単体の色調を基準として、色差（△Ｅ）を求めた。
Examples of the present invention will be described below, but the present invention should not be construed as being limited thereto.
The various characteristic values below were measured as follows.
(1) Early antibacterial test:
a) Antibacterial activity test was conducted by the MIC measurement method by liquid medium dilution method (hereinafter referred to as MIC method) according to the minimum growth inhibitory concentration measurement method I (2003 version) of the antibacterial activity evaluation test method of the Japanese Chemotherapy Society . Staphylococcus aureus and Escherichia coli were used as test bacteria. For the evaluation of antibacterial properties, the minimum concentration of the sample in which the growth of the test bacteria was not observed was determined as the minimum growth inhibitory concentration according to the determination of the MIC method, and 800 μg / ml or less was accepted.
(2) Antibacterial test after light resistance test:
Using a JIS-B7753 sunshine carbon arc lamp type light resistance test apparatus, a sample treated under conditions of 63 ± 3 ° C. without water spraying for 80 hours according to JIS Z2801 5.2, in accordance with antibacterial processed product standards, An antibacterial test was carried out using Staphylococcus aureus and Escherichia coli as test bacteria (hereinafter referred to as JIS method). The antibacterial evaluation was determined by the antibacterial activity value defined in the JIS method. An antibacterial activity value of 2.0 or higher was evaluated as antibacterial.
(3) Water resistance of glass:
Glass cullet (a plate of approximately 15 mm square and approximately 6 mm thick) is weighed as a sample, immersed in a hot water bath at 90 ° C., taken out from the bath after 6 hours, dried at room temperature, weighed sample, and mass loss Was measured. Calculate the percentage of mass loss with respect to the mass before immersion as a percentage, 0.02 to 1.0% ○, 1.0 to 3.0% Δ, less than 0.02% and more than 3.0% The rank was evaluated as x.
(4) Color tone evaluation of resin composition:
As the color tone of the molded product of the resin composition, a test piece having a thickness of 2 mm was measured by a reflection method according to JIS-K-7105 method using Σ90 manufactured by Nippon Denshoku Co., Ltd. The color difference (ΔE) was determined based on the initial color tone of the resin alone.
実施例１〜４及び比較例１〜５（リン酸塩ガラス粉末の調製）：
Ｐ２Ｏ５、ＺｎＯ、ＳＯ３、Ｌｉ２Ｏ、Ｎａ２Ｏ、Ｋ２Ｏ、Ｂ２Ｏ３、Ａｌ２Ｏ３、Ａｇ２Ｏ及びＣｕＯからなるガラス組成が表１に示す組成（モル％表示）になるように、ガラス原料を混合し溶融させて固化させることにより、リン酸塩系ガラスからなる実施例１〜４及び比較例１〜５のカレットを作製した。
Examples 1-4 and Comparative Examples 1-5 (Preparation of phosphate glass powder):
The composition (mol%) of the glass composition consisting of P 2 O 5 , ZnO, SO 3 , Li 2 O, Na 2 O, K 2 O, B 2 O 3 , Al 2 O 3 , Ag 2 O and CuO is shown in Table 1. The cullet of Examples 1-4 and Comparative Examples 1-5 which consist of phosphate glass was produced by mixing a glass raw material so that it might become display, making it melt and solidify.
表１には、実施例１〜４及び比較例１〜５のリン酸塩系ガラスについて、溶融温度、失透現象の有無、及び耐水性を示し、さらには、黄色ブドウ球菌及び大腸菌に対する評価の結果も示した。 Table 1 shows the melting temperature, presence or absence of devitrification phenomenon, and water resistance for the phosphate glasses of Examples 1 to 4 and Comparative Examples 1 to 5, and further, the evaluation of Staphylococcus aureus and Escherichia coli. The results are also shown.
また、リン酸塩系ガラスからなる実施例１〜４及び比較例５のカレットをボールミルにより粉砕し、平均粒径（Ｄ５０）が２μｍのガラス粉末を得た。なお、表1中の比較例３における耐水性および抗菌性の結果についての「―」は失透したため測定しなかったことを示す。 Moreover, the cullet of Examples 1-4 and Comparative Example 5 made of phosphate glass was pulverized by a ball mill to obtain glass powder having an average particle diameter (D50) of 2 μm. In Table 1, “−” for the results of water resistance and antibacterial property in Comparative Example 3 indicates that measurement was not performed because of devitrification.
本発明のリン酸塩系ガラスである実施例１〜４のガラスは、いずれも溶解温度が１０００℃未満で得られ、抗菌性試験で最小発育阻止濃度が８００μｇ／ｍｌ以下で合格であった。ＡｇまたはＣｕを含まない比較例１、２および３のガラスは抗菌性が不充分であったり、耐水性が不充分であったりした。また、Ａｇを含有する本発明の組成範囲外の比較例４のガラスは、失透したガラスが得られた。 The glasses of Examples 1 to 4 which are phosphate glasses of the present invention were obtained at melting temperatures of less than 1000 ° C., and passed the anti-bacterial property test with a minimum growth inhibitory concentration of 800 μg / ml or less. The glasses of Comparative Examples 1, 2, and 3 that did not contain Ag or Cu had insufficient antibacterial properties or insufficient water resistance. Moreover, the glass of the comparative example 4 outside the composition range of this invention containing Ag obtained the devitrified glass.
実施例５〜１１及び比較例５（ポリプロピレン樹脂組成物）：
ポリプロピレン樹脂（ＰＰ：Ｊ−７００ＧＰ、プライムポリマー社製）と、上記で得られた実施例１〜４又は比較例５のリン酸塩系ガラスのガラス粉末（平均粒径２μｍ）とを、表２に示す割合にて混合した後、シリンダー設定温度２００℃の２軸押出し機用いて溶融混練し、実施例５〜１１及び比較例６〜７のペレット状の各樹脂組成物を得た。これらの各樹脂組成物を８０℃で５時間乾燥後、射出成形機を用い、シリンダー温度２００℃、金型温度５０℃にて成形することにより、実施例５〜１１及び比較例６〜７のポリプロピレン樹脂製の平板成形品（厚さ２ｍｍ）を得た。
Examples 5 to 11 and Comparative Example 5 (polypropylene resin composition):
Table 2 shows polypropylene resin (PP: J-700GP, manufactured by Prime Polymer Co., Ltd.) and the glass powder (average particle size 2 μm) of the phosphate glass of Examples 1 to 4 or Comparative Example 5 obtained above. Then, the mixture was melt-kneaded using a twin-screw extruder having a cylinder setting temperature of 200 ° C. to obtain pellet-shaped resin compositions of Examples 5 to 11 and Comparative Examples 6 to 7. Each of these resin compositions was dried at 80 ° C. for 5 hours, and then molded using an injection molding machine at a cylinder temperature of 200 ° C. and a mold temperature of 50 ° C., so that Examples 5 to 11 and Comparative Examples 6 to 7 A flat plate molded product (thickness 2 mm) made of polypropylene resin was obtained.
これらの成形品から試験片を切り出し、初期の抗菌性試験及び耐光性試験後の抗菌性試験を行った。その結果を表２に示した。また、成形品の色調評価を行い、それらの評価結果を表３に示す。なお、リン酸塩系ガラスを含まない上記ポリプロビンレン樹脂単体の成形品を参考例として用い、抗菌性試験の対照サンプル及び色調評価のブランクとした。 Test pieces were cut out from these molded products, and an initial antibacterial test and an antibacterial test after the light resistance test were performed. The results are shown in Table 2. Moreover, the color tone evaluation of the molded product was performed, and the evaluation results are shown in Table 3. In addition, the molded article of the said polypropylene resin simple substance which does not contain phosphate glass was used as a reference example, and it was set as the control sample of an antibacterial property test, and the blank of color tone evaluation.
また、本発明の組成範囲外のＡｇ含有量の多いリン酸塩系ガラスを含む比較例６及び７は、初期及び耐光性試験後の抗菌性試験では抗菌活性値がそれぞれ、いずれも２以上を示したものの、耐水性試験後の成形品の色差が大きく、かつ、変色があった。 Further, Comparative Examples 6 and 7 including a phosphate-based glass having a high Ag content outside the composition range of the present invention each had an antibacterial activity value of 2 or more in the initial and antibacterial tests after the light resistance test. Although shown, the color difference of the molded product after the water resistance test was large and there was discoloration.
本発明の抗菌剤は、抗菌性能とともに、耐水性に優れた、またコストも安いので各種の分野に好適に使用でき。それらの例としては、便器、浴槽、洗面台などの衛生関連製品、台所製品、文具、玩具、電化製品、紙製品、繊維製品などの分野が挙げられる。 The antibacterial agent of the present invention is excellent in water resistance as well as antibacterial performance, and is low in cost, so that it can be suitably used in various fields. Examples thereof include sanitary products such as toilets, bathtubs, washstands, kitchen products, stationery, toys, electrical appliances, paper products, textile products, and the like.
Claims (9)
項４又は５に記載の樹脂組成物。 The resin composition according to claim 4 or 5, wherein the phosphate glass is a powder having an average particle diameter (D50) of 0.5 to 20 µm.
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| JP5642325B1 (en) * | 2013-07-02 | 2014-12-17 | 興亜硝子株式会社 | Antibacterial glass |
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| JP2005048170A (en) * | 2003-07-14 | 2005-02-24 | Schott Ag | Use of glass composition for achieving antioxidative effect |
| JP2006518697A (en) * | 2003-02-25 | 2006-08-17 | ショット アクチエンゲゼルシャフト | Antimicrobial action phosphate glass |
| JP2006518696A (en) * | 2003-02-25 | 2006-08-17 | ショット アクチエンゲゼルシャフト | Antimicrobial action sulfophosphate glass |
| JP2008526674A (en) * | 2005-01-08 | 2008-07-24 | ショット アクチエンゲゼルシャフト | Glass powder, in particular biologically active glass powder, and method for producing glass powder, in particular biologically active glass powder |
| JP4764685B2 (en) * | 2005-09-20 | 2011-09-07 | 旭ファイバーグラス株式会社 | Antibacterial agent, resin composition containing the same and molding material |
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| JP2006518697A (en) * | 2003-02-25 | 2006-08-17 | ショット アクチエンゲゼルシャフト | Antimicrobial action phosphate glass |
| JP2006518696A (en) * | 2003-02-25 | 2006-08-17 | ショット アクチエンゲゼルシャフト | Antimicrobial action sulfophosphate glass |
| JP2005048170A (en) * | 2003-07-14 | 2005-02-24 | Schott Ag | Use of glass composition for achieving antioxidative effect |
| JP2008526674A (en) * | 2005-01-08 | 2008-07-24 | ショット アクチエンゲゼルシャフト | Glass powder, in particular biologically active glass powder, and method for producing glass powder, in particular biologically active glass powder |
| JP4764685B2 (en) * | 2005-09-20 | 2011-09-07 | 旭ファイバーグラス株式会社 | Antibacterial agent, resin composition containing the same and molding material |
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| JP5642325B1 (en) * | 2013-07-02 | 2014-12-17 | 興亜硝子株式会社 | Antibacterial glass |
| WO2015001870A1 (en) * | 2013-07-02 | 2015-01-08 | 興亜硝子株式会社 | Antibacterial glass |
| US11006634B2 (en) | 2013-07-02 | 2021-05-18 | Koa Glass Co., Ltd. | Antibacterial glass |
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