JP4764685B2 - Antibacterial agent, resin composition containing the same and molding material - Google Patents

Antibacterial agent, resin composition containing the same and molding material Download PDF

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JP4764685B2
JP4764685B2 JP2005272110A JP2005272110A JP4764685B2 JP 4764685 B2 JP4764685 B2 JP 4764685B2 JP 2005272110 A JP2005272110 A JP 2005272110A JP 2005272110 A JP2005272110 A JP 2005272110A JP 4764685 B2 JP4764685 B2 JP 4764685B2
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glass
antibacterial
resin composition
resin
phosphate
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JP2007084450A (en
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秀樹 遠藤
浩一 示野
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Asahi Fiber Glass Co Ltd
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    • 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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • 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
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
    • C03C3/066—Glass compositions containing silica with less than 40% silica by weight containing boron 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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
    • C03C3/068—Glass compositions containing silica with less than 40% silica by weight containing boron containing rare earths
    • 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
    • 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
    • C03C3/17—Silica-free oxide glass compositions containing phosphorus containing aluminium or beryllium

Description

本発明は、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、及び該樹脂組成物から成形してなる成形品に関する。   The present invention relates to an antibacterial agent containing phosphate glass, a resin composition containing the antibacterial agent, and a molded product formed from 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。しかし、酸化銀は価格が高いともに、ＡｇＯ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。   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. However, while silver oxide is expensive, AgO-containing glass powder tends to discolor due to the action of ultraviolet rays or heat when used for a long time. This tendency is particularly problematic when the resin product is white or transparent.

一方、ＺｎＯも水に溶出すると抗菌作用を有することが知られており、ＺｎＯを主成分とするガラスが抗菌剤が提案されている。この種のＺｎＯを含むガラス抗菌剤として、例えば、特許文献１や特許文献２が知られている。   On the other hand, ZnO is also known to have an antibacterial action when eluted in water, and an antibacterial agent has been proposed for glass containing ZnO as a main component. For example, Patent Document 1 and Patent Document 2 are known as glass antibacterial agents containing this type of ZnO.

特許文献１には、Ｐ２Ｏ５：４０〜５５モル％、ＺｎＯ：３５〜４５モル％、Ａｌ２Ｏ３：５〜１５モル％、Ｂ２Ｏ３：１〜１０モル％のＺｎＯ−Ｐ2Ｏ5系のガラス抗菌剤が開示されている。また、特許文献２においても、ＺｎＯ ２５〜７０％、Ｐ2Ｏ5 ５〜４０％、Ｂ2Ｏ3 ０〜３５％、ＳｉＯ2 ０〜２０％、ＭｇＯ ０〜３０％、ＣａＯ ０〜３０％、ＳｒＯ ０〜２０％、ＢａＯ ０〜１５％、Ｌｉ2Ｏ ０〜２５％、Ｎａ2Ｏ ０〜２５％、Ｋ2Ｏ ０〜２５％、ＴｉＯ2 ０〜２０％、ＺｒＯ2 ０〜１０％、Ｌａ2Ｏ3 ０〜２０％、Ａｌ2Ｏ3 ０〜１５％の組成を有するＺｎＯ−Ｐ2Ｏ5系ガラスからなる抗菌剤が開示されている。
これらのＺｎＯ−Ｐ2Ｏ5系のガラス抗菌剤は、ガラスの原料費が安価であり、また、樹脂製品に充填しても紫外線や熱等による変色を起こさないという特徴がある。 Patent Document 1 includes ZnO—P of P 2 O 5 : 40 to 55 mol%, ZnO: 35 to 45 mol%, Al 2 O 3 : 5 to 15 mol%, B 2 O 3 : 1 to 10 mol%. A 2 O 5 -based glass antimicrobial agent is disclosed. Also in Patent Document 2, ZnO 25-70%, P 2 O 5 5-40%, B 2 O 3 0-35%, SiO 2 0-20%, MgO 0-30%, CaO 0-30% , SrO 0~20%, BaO 0~15% , Li 2 O 0~25%, Na 2 O 0~25%, K 2 O 0~25%, TiO 2 0~20%, ZrO 2 0~10% An antibacterial agent made of ZnO—P 2 O 5 glass having a composition of La 2 O 3 0 to 20% and Al 2 O 3 0 to 15% is disclosed.
These ZnO—P 2 O 5 -based glass antibacterial agents are characterized in that the raw material cost of glass is low, and even when filled in resin products, they do not cause discoloration due to ultraviolet rays or heat.

しかしながら、これらの従来知られるＺｎＯ−Ｐ2Ｏ5系のガラス抗菌剤は、初期の抗菌性能はともかくとして、湿潤条件における耐水性や長期間における耐光性は必ずしも優れたものではなく、なお、改善の余地があった。
特開平８−１７５８４３号公報 特開平１１−１００２２８号公報 However, these conventionally known ZnO—P 2 O 5 -based glass antibacterial agents are not necessarily excellent in water resistance under wet conditions and long-term light resistance, apart from initial antibacterial performance. There was room for.
JP-A-8-175743 Japanese Patent Laid-Open No. 11-100288

本発明は、抗菌性能とともに、耐水性や耐光性に優れた抗菌性能を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、及び該樹脂組成物からなる成形材料を提供することを目的とする。   The present invention relates to a phosphate-based novel glass antibacterial agent having antibacterial performance that is excellent in water resistance and light resistance in addition to antibacterial performance, a resin composition containing the antibacterial agent, and a molding material comprising the resin composition The purpose is to provide.

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必須的に含有するリン酸塩系のガラスが、初期の抗菌性能とともに、耐水性や耐光性に優れた抗菌性能を有することを見出した。また、本発明者は、上記の必須成分に加えて、Ａｌ２Ｏ３、Ｂ２Ｏ３、ＭｇＯ、ＣａＯ、ＢａＯ、及びＳｎＯをさらに含有させることにより、その抗菌性能を改善できることも見出した。 As a result of intensive studies to achieve the above object, the inventor of the present invention includes ZnO and P 2 O 5 in a specific ratio as a glass composition, and in addition, Li 3 O and Na 2 O, which are SO 3 and alkali metals. It has been found that phosphate glass, which essentially contains K 2 O at a specific ratio, has antibacterial performance excellent in water resistance and light resistance as well as initial antibacterial performance. The present inventor has also found that the antibacterial performance can be improved by further adding Al 2 O 3 , B 2 O 3 , MgO, CaO, BaO, and SnO in addition to the above essential components.

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、Ｐ２Ｏ５：２２〜２７％、ＺｎＯ：１０〜５５％、ＳＯ３：３〜１８％、Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ：５〜３５％（但し、Ｌｉ２Ｏ：０〜１５％、Ｎａ２Ｏ：３〜１５％、Ｋ２Ｏ：０〜１０％）、Ａｌ２Ｏ３：０〜５％、Ｂ２Ｏ３：０〜１５％、ＭｇＯ：０〜１５％、ＣａＯ：０〜１５％、ＢａＯ：０〜１５％、及びＳｎＯ：０〜１５％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）リン酸塩系ガラスが、酸化物基準のモル％表示で、Ｐ２Ｏ５：２２〜２７％、ＺｎＯ：２５〜４０％、ＳＯ３：８〜１８％、Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ：２５〜３５％（ただし、Ｌｉ２Ｏ：０〜１５％、Ｎａ２Ｏ：３〜１５％、Ｋ２Ｏ：０〜１０％）、Ａｌ２Ｏ３：０〜５％、Ｂ２Ｏ３：０〜１５％、ＭｇＯ：０〜１５％、ＣａＯ：０〜１５％、ＢａＯ：０〜１５％、及びＳｎＯ：０〜１５％を有することを特徴とする上記（１）に記載の抗菌剤。
（３）リン酸塩系ガラスが平均粒径（Ｄ５０）が０．５〜２０μｍの粉末である上記（１）又は（２）に記載の抗菌剤。
（４）樹脂１００質量部に対して０．１〜２０質量部添加されて使用されることを特徴とする上記（１）〜（３）のいずれかにに記載の抗菌剤。
（５）抗菌剤を含む樹脂組成物であって、抗菌剤が酸化物基準のモル％表示で、Ｐ２Ｏ５：２２〜２７％、ＺｎＯ：１０〜５５％、ＳＯ３：３〜１８％、Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ：５〜３５％（但し、Ｌｉ２Ｏ：０〜１５％、Ｎａ２Ｏ：３〜１５％、Ｋ２Ｏ：０〜１０％）、Ａｌ２Ｏ３：０〜５％、Ｂ２Ｏ３：０〜１５％、ＭｇＯ：０〜１５％、ＣａＯ：０〜１５％、ＢａＯ：０〜１５％、及びＳｎＯ：０〜１５％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。
（６）リン酸塩系ガラスが酸化物基準のモル％表示で、Ｐ２Ｏ５：２２〜２７％、ＺｎＯ：２５〜４０％、ＳＯ３：８〜１８％、Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ：２５〜３５％（ただし、Ｌｉ２Ｏ：０〜１５％、Ｎａ２Ｏ：３〜１５％、Ｋ２Ｏ：０〜１０％）、Ａｌ２Ｏ３：０〜５％、Ｂ２Ｏ３：０〜１５％、ＭｇＯ：０〜１５％、ＣａＯ：０〜１５％、ＢａＯ：０〜１５％、及びＳｎＯ：０〜１５％を有することを特徴とする上記（５）に記載の樹脂組成物。
（７）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（５）又は（６）に記載の樹脂組成物。
（８）樹脂１００質量部に対してリン酸塩系ガラス１〜２０質量部を含有することを特徴とする上記（５）〜（７）のいずれかに記載の樹脂組成物。
（９）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（５）〜（８）のいずれかに記載の樹脂組成物。
（１０）上記（５）〜（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) by mol% based on oxides, P 2 O 5: 22~27% , ZnO: 10~55%, SO 3: 3~18%, Li 2 O + Na 2 O + K 2 O: 5~35% ( However, Li 2 O: 0~15%, Na 2 O: 3~15%, K 2 O: 0~10%), Al 2 O 3: 0~5%, B 2 O 3: 0~15%, An antibacterial agent comprising a phosphate glass having MgO: 0 to 15%, CaO: 0 to 15%, BaO: 0 to 15%, and SnO: 0 to 15%.
(2) Phosphate-based glass expressed in mol% based on oxide, P 2 O 5 : 22 to 27%, ZnO: 25 to 40%, SO 3 : 8 to 18%, Li 2 O + Na 2 O + K 2 O: 25 to 35% (although, Li 2 O: 0~15%, Na 2 O: 3~15%, K 2 O: 0~10%), Al 2 O 3: 0~5%, B 2 O 3 : 0-15%, MgO: 0-15%, CaO: 0-15%, BaO: 0-15%, and SnO: 0-15%, The antibacterial according to (1) above Agent.
(3) The antibacterial agent according to (1) or (2), wherein the phosphate glass is a powder having an average particle diameter (D50) of 0.5 to 20 μm.
(4) The antibacterial agent according to any one of (1) to (3) above, wherein 0.1 to 20 parts by mass is added to 100 parts by mass of the resin.
(5) A resin composition containing an antibacterial agent, wherein the antibacterial agent is expressed in terms of mol% based on oxide, P 2 O 5 : 22 to 27%, ZnO: 10 to 55%, SO 3 : 3 to 18% Li 2 O + Na 2 O + K 2 O: 5 to 35% (however, Li 2 O: 0 to 15%, Na 2 O: 3 to 15%, K 2 O: 0 to 10%), Al 2 O 3 : 0 Phosphate-based glass having ˜5%, B 2 O 3 : 0-15%, MgO: 0-15%, CaO: 0-15%, BaO: 0-15%, and SnO: 0-15%. A resin composition characterized by being.
(6) salt-based glass phosphate represented by mol% based on oxides, P 2 O 5: 22~27% , ZnO: 25~40%, SO 3: 8~18%, Li 2 O + Na 2 O + K 2 O : 25% to 35% (however, Li 2 O: 0~15%, Na 2 O: 3~15%, K 2 O: 0~10%), Al 2 O 3: 0~5%, B 2 O 3 : 0-15%, MgO: 0-15%, CaO: 0-15%, BaO: 0-15%, and SnO: 0-15%, The resin composition as described in (5) above object.
(7) The resin composition according to the above (5) or (6), wherein the phosphate glass is a powder having an average particle diameter (D50) of 0.5 to 20 μm.
(8) The resin composition as described in any one of (5) to (7) above, which contains 1 to 20 parts by mass of a phosphate glass with respect to 100 parts by mass of the resin.
(9) The resin composition as described in any one of (5) to (8) above, wherein the resin is a thermosetting resin, a thermoplastic resin, rubber, or an elastomer.
(10) A molded product obtained by molding the resin composition according to any one of (5) to (8).

本発明によれば、抗菌性能とともに、耐水性や耐光性に優れた抗菌性野を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、及び該樹脂組成物から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 having an antibacterial field excellent in water resistance and light resistance as well as antibacterial performance, a resin composition containing the antibacterial agent, and molding from the resin composition A molded product is 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、Ｐ２Ｏ５：２２〜２７％、ＺｎＯ：１０〜５５％、ＳＯ３：３〜１８％、Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ：５〜３５％（但し、Ｌｉ２Ｏ：０〜１５％、Ｎａ２Ｏ：３〜１５％、Ｋ２Ｏ：０〜１０％）、Ａｌ２Ｏ３：０〜５％、Ｂ２Ｏ３：０〜１５％、ＭｇＯ：０〜１５％、ＣａＯ：０〜１５％、ＢａＯ：０〜１５％、及びＳｎＯ：０〜１５％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: 22~27%, ZnO : 10~55%, SO 3: 3~18%, Li 2 O + Na 2 O + K 2 O: 5~35% ( however, Li 2 O: 0~15%, Na 2 O: 3~15%, K 2 O : 0~10%), Al 2 O 3: 0~5%, B 2 O 3: 0~15%, MgO: 0~15%, CaO: 0~15% BaO: 0-15% and SnO: 0-15%.

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及びアルカリ金属成分である。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２２〜２７％である。Ｐ2Ｏ5が２２％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、２７％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１０〜５５％、好ましくは２５〜４０％である。ＺｎＯが１０％よりも少なくなると抗菌作用が弱くなり、５５％を越えるとガラス化が困難になる。 The essential components in the phosphate glass of the present invention are P 2 O 5 , ZnO, SO 3 and an alkali metal component. Among, P 2 O 5 is an essential component to the glass forming, the content thereof is 22 to 27%. If P 2 O 5 is less than 22%, it is difficult to vitrify, and a homogeneous glass cannot be obtained. On the other hand, if it exceeds 27%, the water resistance as glass is lowered, which is not preferable. ZnO is a component exhibiting an antibacterial action, and its content is 10 to 55%, preferably 25 to 40%. When ZnO is less than 10%, the antibacterial action becomes weak, and when it exceeds 55%, 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抗菌性を左右する重要な成分である。その含有量は３〜１８％、好ましくは８〜１８％である。ＳＯ３が３％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。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 affects the antibacterial properties. Its content is 3 to 18%, preferably 8 to 18%. SO 3 decreases the solubility of glass to be obtained with less than 3%, the antibacterial activity is weakened. 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、５〜３５％好ましくは２５〜３５％である。該合計の含有量が５％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、３５％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％、Ｎａ２Ｏが３〜１５％、及びＫ２Ｏは０〜１０％である。 Further, an alkali metal Li 2 O, Na 2 O, and K 2 O are components that help melt the glass. The total content of Li 2 O + Na 2 O + K 2 O is 5 to 35%, preferably 25 to 35%. When the total content is less than 5%, the glass is not sufficiently melted and hardly vitrified. On the other hand, when the total content is more than 35%, the water resistance as glass is remarkably lowered, which is not preferable. As the individual components of the alkali metal, Li 2 O is 0 to 15% Na 2 O 3 to 15% and K 2 O is 0 to 10%.

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。Ｂ２Ｏ３は、ガラス形成成分であり、ガラス融解の補助の作用を有する。その含有量は、０〜１５％、好ましくは０〜１０％である。Ｂ2Ｏ3が１５％を超えるとガラスの化学耐久性が悪くなる。 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%, melting of the glass becomes more difficult and a homogeneous glass cannot be obtained. B 2 O 3 is a glass forming component and has a function of assisting glass melting. Its content is 0-15%, preferably 0-10%. If B 2 O 3 exceeds 15%, the chemical durability of the glass is deteriorated.

また、ＣａＯ及びＢａＯは、いずれもガラスの溶融を助ける成分であり、その含有量は、ＣａＯが０〜１５％、及びＢａＯが０〜１５％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、ＭｇＯが０〜１５％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％である。   Moreover, CaO and BaO are components that assist melting of the glass, and the contents thereof are 0 to 15% for CaO and 0 to 15% for BaO. MgO is a component that aids melting of the glass and is a component that improves water resistance. The content of MgO is 0 to 15%. SnO is a component having a function of improving the durability of the glass, and its content is 0 to 15%.

本発明のリン酸塩系ガラスとしては、なかでも、Ｐ２Ｏ５：２２〜２７％、ＺｎＯ：２５〜４０％、ＳＯ３：８〜１８％、Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ：２５〜３５％（ただし、Ｌｉ２Ｏ：０〜１５％、Ｎａ２Ｏ：３〜１５％、Ｋ２Ｏ：０〜１０％）、Ａｌ２Ｏ３：０〜５％、Ｂ２Ｏ３：０〜１５％、ＭｇＯ：０〜１５％、ＣａＯ：０〜１５％、ＢａＯ：０〜１５％、及びＳｎＯ：０〜１５％を有するものが好ましい。かかる組成のリン酸塩系ガラスは、特に、抗菌性が後記する実施例に見られるように顕著に優れている。 As the phosphate glass of the present invention, P 2 O 5 : 22 to 27%, ZnO: 25 to 40%, SO 3 : 8 to 18%, Li 2 O + Na 2 O + K 2 O: 25 to 35, among others. % (However, Li 2 O: 0 to 15%, Na 2 O: 3 to 15%, K 2 O: 0 to 10%), Al 2 O 3 : 0 to 5%, B 2 O 3 : 0 to 15 %, MgO: 0-15%, CaO: 0-15%, BaO: 0-15%, and SnO: 0-15% are preferred. The phosphate glass having such a composition is particularly excellent in antibacterial properties as seen in Examples described later.

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Ｓｒ、Ｔｉ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、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 Sr, Ti, Fe, Co, Ni, Cu, 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、バルーンなど適宜選ぶことができる。特に比表面積が大きくなり、高い抗菌効果が得られるので粉末で用いることが好ましい。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。   The form of the phosphate glass of the present invention can be appropriately selected from fibers, powders, flakes, balloons and the like. In particular, the specific surface area becomes large and a high antibacterial effect is obtained, so that it is preferable to use it in powder form. 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.

本発明の抗菌剤を構成するリン酸塩系ガラスの耐水性は、以下の方法により求める。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、浸漬後の試料を秤量し、質量損失を測定する。浸漬前の質量に対する質量損失の割合を百分率として、ガラスの耐水性を評価する。本発明の抗菌剤のリン酸塩系ガラスは、２価のＺｎイオンを溶出し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０．０２〜５．０質量％、特に好ましくは０．０２〜２．０質量％が好適である。耐水性が０．０２％よりも小さいと、２価のＺｎ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り、２．０％よりも大きいと、ガラスとしての耐水性が不十分となり、溶出しやすくなり、好ましくない。   The water resistance of the phosphate glass constituting the antibacterial agent of the present invention is determined by the following method. A glass cullet (a plate of about 15 mm square and a thickness of about 6 mm) 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, and the sample after immersion is weighed. Measure the mass loss. The water resistance of the glass is evaluated using the ratio of mass loss to the mass before immersion as a percentage. Since the phosphate glass of the antibacterial agent of the present invention exhibits antibacterial properties by eluting divalent Zn ions, it achieves both water resistance as glass and elution properties for expressing antibacterial properties. The water resistance is preferably 0.02 to 5.0% by mass, particularly preferably 0.02 to 2.0% by mass. If the water resistance is less than 0.02%, the elution amount of divalent Zn ions is small, making it difficult to sufficiently exhibit antibacterial properties. If the water resistance is more than 2.0%, the water resistance as glass is low. Insufficient and easy to elute, which is not preferable.

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てリン酸塩系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。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。   The phosphate-based glass constituting the antibacterial agent of the present invention is prepared by mixing and melting glass raw materials and solidifying them using a known method and apparatus so as to obtain a desired glass composition. A glass cullet can be prepared and pulverized to a predetermined average particle size. Examples of the method for grinding phosphate glass cullet include wet grinding such as media stirring mill, colloid mill and wet ball mill, and dry grinding such as jet mill, dry ball mill and roll crusher. May be used. 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, 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.

本発明の抗菌剤は上記に限られるものではなく、例えば、ガラスやセラミックの抗菌性釉薬、金属の抗菌性塗料等、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 for various antibacterial applications such as glass and ceramic antibacterial glazes and metal antibacterial paints.

本発明の樹脂組成物における抗菌剤の含有量は、樹脂１００質量部に対して好ましくは０．１〜２０質量部であり、特に０．５〜１０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 preferably 0.1 to 20 parts by mass, particularly preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the resin. 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が好ましい。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 the antibacterial agent in the present invention is preferably 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０．２〜２．０質量％である。付与量が０．２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２．０質量％より多いと前記樹脂へのリン酸塩系ガラス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 application is determined. The solid content is preferably 0.2 to 2.0% by mass based on the standard. When the applied amount is less than 0.2% by mass, it is difficult to sufficiently improve the handling property and the adhesion property with the resin when handling the glass. On the other hand, when the applied amount is more than 2.0% by mass, the dispersion of the phosphate glass in the resin is likely to be lowered, which is not preferable.

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それら以外の添加剤とを、混合することにより得られる。   The resin composition containing the antibacterial agent of the present invention is obtained by mixing a resin, a phosphate glass, and additives other than those blended as necessary.

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、混合と同時の溶融（例えば溶融混練）又は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。   In particular, when the resin is a thermoplastic resin or a thermoplastic elastomer, the molding material is obtained by a method similar to the conventional method for producing a resin composition, such as melting at the same time as mixing (for example, melt kneading) or melt kneading after mixing. As a resin composition can be obtained. 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。その成形の方法としては、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 of the present invention, which is a molding material, can be molded into various molded products 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。   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. The product is manufactured.

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。また、本発明の抗菌剤は、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、塗料などにも用いることができる。   Examples of the molded article include sanitary products such as toilets, bathtubs, and washstands, kitchen products, stationery, and toys. The antibacterial agent of the present invention can also be used for film materials, sheet materials, electrical appliance housing materials, paper products, textile products, paints, and the like.

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。   Examples of the present invention will be described below, but the present invention should not be construed as being limited thereto.

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）抗菌性試験：
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。抗菌性の評価は、該ＪＩＳ規定に定義される抗菌活性値で判定し、抗菌効果を有する抗菌活性値２．０以上を○とし、抗菌活性値２．０未満を×として、ランク評価した。
（２）耐水性テスト後の抗菌性試験：
９０±５℃で１６時間の温水中に浸漬する条件で処理した試験片について、上記と同様の抗菌性試験を行った。
（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た。
（４）Ｉｚｏｄ衝撃試験：
ＡＳＴＭ−Ｄ２５６に従って、厚さ３ｍｍのノッチ付き試験片について、Ｉｚｏｄ衝撃試験を行った。 The various characteristic values below were measured as follows.
(1) Antibacterial test:
According to JIS Z2801 5.2, an antibacterial test was performed using Staphylococcus aureus and Escherichia coli as test bacteria in accordance with the antibacterial processed product standard. The antibacterial evaluation was evaluated based on the antibacterial activity value defined in the JIS regulations, and the rank was evaluated with an antibacterial activity value of 2.0 or more having an antibacterial effect as ◯ and an antibacterial activity value of less than 2.0 as x.
(2) Antibacterial test after water resistance test:
An antibacterial test similar to the above was performed on a test piece treated under conditions of immersion in warm water at 90 ± 5 ° C. for 16 hours.
(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. The ratio of the mass loss to the mass before immersion was taken as a percentage.
(4) Izod impact test:
According to ASTM-D256, an Izod impact test was performed on a test piece with a thickness of 3 mm.

（リン酸塩ガラス粉末の調製）
Ｐ２Ｏ５：２４．３％、ＺｎＯ：３１．９％、ＳＯ３：１５．８％、Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ：２７．０％（但し、Ｌｉ２Ｏ：９．０％、Ｎａ２Ｏ：１０．５％、Ｋ２Ｏ：７．５％）及びＡｌ２Ｏ３：１．０％の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、リン酸塩系ガラスＡとなるカレットを作製した。ガラスの耐水性は、０．７％であった。前記カレットを粉砕し、平均粒径（Ｄ５０）が２μｍのガラス粉末を得た。 (Preparation of phosphate glass powder)
P 2 O 5: 24.3%, ZnO: 31.9%, SO 3: 15.8%, Li 2 O + Na 2 O + K 2 O: 27.0% ( however, Li 2 O: 9.0%, Na 2 O: 10.5%, K 2 O: 7.5%) and Al 2 O 3 : 1.0%, glass raw materials are mixed, melted, and solidified by melting. A cullet to be an acid salt glass A was produced. The water resistance of the glass was 0.7%. The cullet was pulverized to obtain a glass powder having an average particle diameter (D50) of 2 μm.

また、Ｐ２Ｏ５：２４．９％、ＺｎＯ：４０．５％、ＳＯ３：９．３％、Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ：１４．２％（但し、Ｌｉ２Ｏ：４．１％、Ｎａ２Ｏ：５．７％、Ｋ２Ｏ：７．５％）、Ａｌ２Ｏ３：１．５％及びＢ２Ｏ３：９．６％の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、リン酸塩系ガラスＢとなるカレットを作製した。ガラスの耐水性は、０．０３％であった。前記カレットを粉砕し、平均粒径（Ｄ５０）が２μｍのガラス粉末をそれぞれ得た。 Further, P 2 O 5: 24.9% , ZnO: 40.5%, SO 3: 9.3%, Li 2 O + Na 2 O + K 2 O: 14.2% ( however, Li 2 O: 4.1% Na 2 O: 5.7%, K 2 O: 7.5%), Al 2 O 3 : 1.5%, and B 2 O 3 : 9.6%. A cullet to be a phosphate glass B was prepared by solidifying after mixing and melting. The water resistance of the glass was 0.03%. The cullet was pulverized to obtain glass powders each having an average particle size (D50) of 2 μm.

比較例として、モル％表示で、Ｐ２Ｏ５：２７．０％、ＺｎＯ：２６．０％、ＳＯ３：２０．０％、Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ：２７．０％（但し、Ｌｉ２Ｏ：９．０％、Ｎａ２Ｏ：１０．５％、Ｋ２Ｏ：７．５％）の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、リン酸塩系ガラスＣとなるカレットを作製した。ガラスの耐水性は、１５％であった。前記カレットを粉砕し、平均粒径（Ｄ５０）が２μｍのガラス粉末を得た。 As a comparative example, P 2 O 5 : 27.0%, ZnO: 26.0%, SO 3 : 20.0%, Li 2 O + Na 2 O + K 2 O: 27.0% (in terms of mol%) 2 O: 9.0%, Na 2 O: 10.5%, K 2 O: 7.5%) By mixing and melting the glass raw materials and solidifying them, phosphoric acid is obtained. A cullet to be a salt glass C was produced. The water resistance of the glass was 15%. The cullet was pulverized to obtain a glass powder having an average particle diameter (D50) of 2 μm.

また、Ｐ２Ｏ５：４５．０％、ＺｎＯ：４５．０％及びＬｉ２Ｏ：１０．０％の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、リン酸塩系ガラスＤとなるカレットを作製した。ガラスの耐水性は、４０％であった。前記カレットを粉砕し、平均粒径（Ｄ５０）が２μｍのガラス粉末を得た。 Further, by mixing and melting glass raw materials so as to have a glass composition of P 2 O 5 : 45.0%, ZnO: 45.0% and Li 2 O: 10.0%, A cullet to be an acid salt glass D was produced. The water resistance of the glass was 40%. The cullet was pulverized to obtain a glass powder having an average particle diameter (D50) of 2 μm.

（ポリプロピレン樹脂組成物）
実施例１
ポリプロピレン樹脂（ＰＰ：Ｊ−７００ＧＰ、出光興産社製）９９質量部とリン酸塩系ガラスＡのガラス粉末（平均粒径２μｍ）１質量部とを混合した後、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て実施例１となるペレット状の樹脂組成物を得た。この樹脂組成物を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℃にて成形し、ポリプロピレン樹脂組成物の厚さ３ｍｍの平板成形品を得た。 (Polypropylene resin composition)
Example 1
After mixing 99 parts by mass of a polypropylene resin (PP: J-700GP, manufactured by Idemitsu Kosan Co., Ltd.) and 1 part by mass of a glass powder of phosphate glass A (average particle size 2 μm), biaxial with a cylinder set temperature of 200 ° C. The pellet-shaped resin composition used in Example 1 was obtained by melt-kneading using an extruder. The resin composition 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. to obtain a 3 mm-thick flat plate molded product of the polypropylene resin composition.

実施例２〜３、比較例１〜３
表１に記載の配合組成にて、実施例１と同様の方法によって、実施例２〜３及び比較例１〜３のとなるポリプロピレン樹脂組成物の成形品をそれぞれ得た。 Examples 2-3 and Comparative Examples 1-3
Molded products of the polypropylene resin compositions to be Examples 2 to 3 and Comparative Examples 1 to 3 were obtained in the same manner as in Example 1 with the blending composition shown in Table 1.

これらの成形品から試験片を得て、ＩＺＯＤ衝撃試験、初期の抗菌性試験及び耐水性テスト後の抗菌性試験を行った。また、成形品の変色を目視で判定し、それらの評価結果をあわせて表１に示す。なお、リン酸塩系ガラスを含まない比較例３は、抗菌性試験の対照サンプルとして用いた。   Test pieces were obtained from these molded articles, and an IZOD impact test, an initial antibacterial test, and an antibacterial test after a water resistance test were performed. Further, the discoloration of the molded product is visually determined, and the evaluation results are shown in Table 1. In addition, the comparative example 3 which does not contain phosphate glass was used as a control sample for the antibacterial test.

Figure 0004764685
Figure 0004764685

本発明のリン酸塩系ガラスＡを含む実施例１及び２は、初期及び耐水性テスト後の抗菌性試験で抗菌活性値がそれぞれ２．０以上を示した。リン酸塩系ガラスＢを含む実施例３は、初期及び耐水性テスト後の抗菌性試験で抗菌活性値がそれぞれ２．０以上を示した。本発明の組成範囲外のリン酸塩系ガラスＣを含む比較例１は、初期の抗菌性試験では抗菌活性値が２．０以上を示したものの、耐水性テスト後の大腸菌の抗菌性試験では、抗菌活性値が２．０未満であった。また、本発明の組成範囲外のリン酸塩系ガラスＤを含む比較例２は、初期の抗菌性試験では抗菌活性値が２．０以上を示したものの、耐水性テスト後の抗菌性試験では、抗菌活性値が２．０未満であり、また、成形品に変色があった。   In Examples 1 and 2 containing the phosphate glass A of the present invention, the antibacterial activity value was 2.0 or more in the initial and antibacterial tests after the water resistance test, respectively. In Example 3 including the phosphate glass B, the antibacterial activity value was 2.0 or more in the initial and antibacterial tests after the water resistance test. Comparative Example 1 containing phosphate glass C outside the composition range of the present invention showed an antibacterial activity value of 2.0 or more in the initial antibacterial test, but in the antibacterial test of Escherichia coli after the water resistance test. The antibacterial activity value was less than 2.0. Further, Comparative Example 2 containing phosphate glass D outside the composition range of the present invention showed an antibacterial activity value of 2.0 or more in the initial antibacterial test, but in the antibacterial test after the water resistance test. The antibacterial activity value was less than 2.0, and the molded product was discolored.

（不飽和ポリエステル樹脂組成物）
実施例４〜５及び比較例４〜５
表２に記載の配合組成にて、各成分を混合し、ガラス繊維（繊維径１５μｍ、長さ２５ｍｍ）に含浸させて、シートモールディングコンパウンド（ＳＭＣ）をそれぞれ得た。この時、得られるＳＭＣ中のガラス繊維の含有割合が２５質量％であった。なお、表２における不飽和ポリエステル樹脂は、イソフタル酸とポリエチレングリコールとプロピレングリコールとを原料として製造されたものである。なお、表２中の「ポリスチレン溶液」は、スチレンモノマー６９質量％含有溶液であり、「改質剤」はポリエチレンパウダーである。また、表２中の略号はそれぞれ以下を意味する。
ＴＢＩＣ：ターシャリブチルイソプロピルアルコール
ｐｈｒ：樹脂成分１００質量部としたときの質量部
各ＳＭＣを成形温度１４０℃、加圧保持時間４分、チャージ面積５０％で２２ｃｍ角、厚み３mmの平板に成形して、実施例４〜５及び比較例４〜５となる不飽和ポリエステル樹脂組成物の成形品をそれぞれ得た。これらの成形品から試験片を得て、初期の抗菌性試験及び耐水性テスト後の抗菌性試験を行い、その評価結果を表３に示す。なお、リン酸塩系ガラスを含まない比較例５は、抗菌性試験の対照サンプルとして用いた。 (Unsaturated polyester resin composition)
Examples 4-5 and Comparative Examples 4-5
In the blending composition shown in Table 2, each component was mixed and impregnated into glass fiber (fiber diameter 15 μm, length 25 mm) to obtain a sheet molding compound (SMC). At this time, the content rate of the glass fiber in SMC obtained was 25 mass%. The unsaturated polyester resin in Table 2 is produced using isophthalic acid, polyethylene glycol and propylene glycol as raw materials. The “polystyrene solution” in Table 2 is a solution containing 69% by mass of styrene monomer, and the “modifier” is polyethylene powder. Moreover, the symbol in Table 2 means the following, respectively.
TBIC: Tertiary butyl isopropyl alcohol phr: parts by mass when the resin component is 100 parts by mass Each SMC is molded into a flat plate having a molding temperature of 140 ° C., a pressure holding time of 4 minutes, a charge area of 50%, a 22 cm square and a thickness of 3 mm. Thus, molded articles of unsaturated polyester resin compositions to be Examples 4 to 5 and Comparative Examples 4 to 5 were obtained. Test pieces were obtained from these molded products, and the initial antibacterial test and the antibacterial test after the water resistance test were conducted. The evaluation results are shown in Table 3. In addition, the comparative example 5 which does not contain phosphate glass was used as a control sample for the antibacterial test.

Figure 0004764685
Figure 0004764685

Figure 0004764685
Figure 0004764685

本発明のリン酸塩系ガラスＡ及びＢを含む実施例４及び５は、初期及び耐水性テスト後の抗菌性試験で抗菌活性値がそれぞれ２．０以上を示した。本発明の組成範囲外のリン酸塩系ガラスＣを含む比較例４は、初期の抗菌性試験では黄色ぶどう球菌の抗菌活性値が２．０以上を示したものの、初期の大腸菌の抗菌活性値が２．０未満であり、耐水性テスト後の抗菌性試験の抗菌活性値も２．０未満であった。   In Examples 4 and 5 including the phosphate glasses A and B of the present invention, the antibacterial activity value was 2.0 or more in the initial and antibacterial tests after the water resistance test, respectively. In Comparative Example 4 containing phosphate glass C outside the composition range of the present invention, the antibacterial activity value of Staphylococcus aureus was 2.0 or more in the initial antibacterial test, but the initial antibacterial activity value of Escherichia coli Was less than 2.0, and the antibacterial activity value of the antibacterial test after the water resistance test was also less than 2.0.

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. Examples thereof include sanitary products such as toilets, bathtubs, washstands, kitchen products, stationery, toys, electrical appliances, paper products, textile products, and the like.

Claims (10)

酸化物基準のモル％表示で、Ｐ２Ｏ５：２２〜２７％、ＺｎＯ：１０〜５５％、ＳＯ３：３〜１８％、Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ：５〜３５％（但し、Ｌｉ２Ｏ：０〜１５％、Ｎａ２Ｏ：３〜１５％、Ｋ２Ｏ：０〜１０％）、Ａｌ２Ｏ３：０〜５％、Ｂ２Ｏ３：０〜１５％、ＭｇＯ：０〜１５％、ＣａＯ：０〜１５％、ＢａＯ：０〜１５％、及びＳｎＯ：０〜１５％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。 As represented by mol% based on oxides, P 2 O 5: 22~27% , ZnO: 10~55%, SO 3: 3~18%, Li 2 O + Na 2 O + K 2 O: 5~35% ( however, Li 2 O: 0-15%, Na 2 O: 3-15%, K 2 O: 0-10%), Al 2 O 3 : 0-5%, B 2 O 3 : 0-15%, MgO: 0 An antibacterial agent comprising a phosphate-based glass having -15%, CaO: 0-15%, BaO: 0-15%, and SnO: 0-15%. リン酸塩系ガラスが、酸化物基準のモル％表示で、Ｐ２Ｏ５：２２〜２７％、ＺｎＯ：２５〜４０％、ＳＯ３：８〜１８％、Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ：２５〜３５％（ただし、Ｌｉ２Ｏ：０〜１５％、Ｎａ２Ｏ：３〜１５％、Ｋ２Ｏ：０〜１０％）、Ａｌ２Ｏ３：０〜５％、Ｂ２Ｏ３：０〜１５％、ＭｇＯ：０〜１５％、ＣａＯ：０〜１５％、ＢａＯ：０〜１５％、及びＳｎＯ：０〜１５％を有することを特徴とする請求項１に記載の抗菌剤。 Phosphate glass is expressed in terms of mol% based on oxide, P 2 O 5 : 22 to 27%, ZnO: 25 to 40%, SO 3 : 8 to 18%, Li 2 O + Na 2 O + K 2 O: 25 35% (although, Li 2 O: 0~15%, Na 2 O: 3~15%, K 2 O: 0~10%), Al 2 O 3: 0~5%, B 2 O 3: 0 The antibacterial agent according to claim 1, which has -15%, MgO: 0 to 15%, CaO: 0 to 15%, BaO: 0 to 15%, and SnO: 0 to 15%. リン酸塩系ガラスが平均粒径（Ｄ５０）が０．５〜２０μｍの粉末である請求項１又は２に記載の抗菌剤。   The antibacterial agent according to claim 1 or 2, wherein the phosphate glass is a powder having an average particle size (D50) of 0.5 to 20 µm. 樹脂１００質量部に対して０．１〜２０質量部添加されて使用されることを特徴とする請求項１〜３のいずれかに記載の抗菌剤。   The antibacterial agent according to any one of claims 1 to 3, wherein the antibacterial agent is used by adding 0.1 to 20 parts by mass with respect to 100 parts by mass of the resin. 抗菌剤を含む樹脂組成物であって、抗菌剤が酸化物基準のモル％表示で、Ｐ２Ｏ５：２２〜２７％、ＺｎＯ：１０〜５５％、ＳＯ３：３〜１８％、Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ：５〜３５％（但し、Ｌｉ２Ｏ：０〜１５％、Ｎａ２Ｏ：３〜１５％、Ｋ２Ｏ：０〜１０％）、Ａｌ２Ｏ３：０〜５％、Ｂ２Ｏ３：０〜１５％、ＭｇＯ：０〜１５％、ＣａＯ：０〜１５％、ＢａＯ：０〜１５％、及びＳｎＯ：０〜１５％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。 A resin composition containing an antibacterial agent, wherein the antibacterial agent is expressed in terms of mol% based on oxide, P 2 O 5 : 22 to 27%, ZnO: 10 to 55%, SO 3 : 3 to 18%, Li 2 O + Na 2 O + K 2 O: 5~35% ( however, Li 2 O: 0~15%, Na 2 O: 3~15%, K 2 O: 0~10%), Al 2 O 3: 0~5% , B 2 O 3: 0~15% , MgO: 0~15%, CaO: 0~15%, BaO: 0~15%, and SnO: it is a phosphate-based glass having a 0-15% A resin composition characterized. リン酸塩系ガラスが酸化物基準のモル％表示で、Ｐ２Ｏ５：２２〜２７％、ＺｎＯ：２５〜４０％、ＳＯ３：８〜１８％、Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ：２５〜３５％（ただし、Ｌｉ２Ｏ：０〜１５％、Ｎａ２Ｏ：３〜１５％、Ｋ２Ｏ：０〜１０％）、Ａｌ２Ｏ３：０〜５％、Ｂ２Ｏ３：０〜１５％、ＭｇＯ：０〜１５％、ＣａＯ：０〜１５％、ＢａＯ：０〜１５％、及びＳｎＯ：０〜１５％を有することを特徴とする請求項５に記載の樹脂組成物。 As represented by mol% of salt based glass phosphate oxide basis, P 2 O 5: 22~27% , ZnO: 25~40%, SO 3: 8~18%, Li 2 O + Na 2 O + K 2 O: 25~ 35% (however, Li 2 O: 0 to 15%, Na 2 O: 3 to 15%, K 2 O: 0 to 10%), Al 2 O 3 : 0 to 5%, B 2 O 3 : 0 The resin composition according to claim 5, wherein the resin composition has 15%, MgO: 0 to 15%, CaO: 0 to 15%, BaO: 0 to 15%, and SnO: 0 to 15%. 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請求項５又は６に記載の樹脂組成物。   The resin composition according to claim 5 or 6, wherein the phosphate glass is a powder having an average particle diameter (D50) of 0.5 to 20 µm. 樹脂１００質量部に対してリン酸塩系ガラスが１〜２０質量部を含有することを特徴とする請求項５〜７のいずれかに記載の樹脂組成物。   The resin composition according to any one of claims 5 to 7, wherein the phosphate glass contains 1 to 20 parts by mass with respect to 100 parts by mass of the resin. 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請求項５〜８のいずれかに記載の樹脂組成物。   The resin composition according to claim 5, wherein the resin is a thermosetting resin, a thermoplastic resin, rubber, or an elastomer. 請求項５〜９のいずれかに記載の樹脂組成物を成形してなる成形品。   A molded article formed by molding the resin composition according to claim 5.
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