JP2017164006A - Antibacterial toothbrush - Google Patents

Antibacterial toothbrush Download PDF

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JP2017164006A
JP2017164006A JP2016049218A JP2016049218A JP2017164006A JP 2017164006 A JP2017164006 A JP 2017164006A JP 2016049218 A JP2016049218 A JP 2016049218A JP 2016049218 A JP2016049218 A JP 2016049218A JP 2017164006 A JP2017164006 A JP 2017164006A
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antibacterial
resin
silver
antibacterial toothbrush
toothbrush according
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JP6840328B2 (en
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渡辺 秀司
Hideji Watanabe
秀司 渡辺
源之助 木村
Gennosuke Kimura
源之助 木村
顕一 山本
Kenichi Yamamoto
顕一 山本
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KANPO SHIKA IGAKU KENKYUSHO KK
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KANPO SHIKA IGAKU KENKYUSHO KK
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Abstract

PROBLEM TO BE SOLVED: To provide an antibacterial toothbrush including brush hairs having a small content of a metal as an antibacterial agent, a high safety for a human body, high in an antimicrobial action, and continuous in antimicrobial activity.SOLUTION: An antibacterial toothbrush has brush hairs made of a resin containing gold (Au) and silver (Ag).SELECTED DRAWING: None

Description

本発明は、抗菌性歯ブラシに関する。   The present invention relates to an antibacterial toothbrush.

歯ブラシは日常的に口腔内で使用されるものだが、その保管時における衛生面については十分な配慮が為されているとは言えない。
どこにでも存在する黄色ブドウ球菌、緑膿菌等は誤嚥性肺炎の起因菌としても知られている。歯ブラシは使用後も湿った状態にあるため、細菌やカビが繁殖しやすい。細菌等が付着した歯ブラシを使用すれば、誤嚥性肺炎の危険性が高まるばかりでなく、口腔を清潔にするどころか、外部から細菌を口腔内に入れることにもなってしまう。
Although toothbrushes are routinely used in the oral cavity, it cannot be said that sufficient consideration has been given to hygiene during storage.
Staphylococcus aureus and Pseudomonas aeruginosa present everywhere are also known as causative bacteria of aspiration pneumonia. Because the toothbrush remains moist after use, bacteria and molds are easy to propagate. The use of a toothbrush with bacteria attached not only increases the risk of aspiration pneumonia, but also causes the bacteria to enter the oral cavity from the outside rather than cleansing the oral cavity.

現代では「抗菌(性)」を謳った歯ブラシ、殺菌機能付きの歯ブラシケース、歯ブラシ除菌器、歯ブラシ用のUV殺菌器等が市販されているが、抗菌力が十分でなかったり、効果が持続しなかったり、機器が高価だったり、使用が面倒だったりするものが多い。   In modern times, toothbrushes with antibacterial properties, toothbrush cases with sterilization function, toothbrush sanitizers, UV sterilizers for toothbrushes, etc. are available on the market, but their antibacterial activity is not sufficient or the effect is sustained. There are many things that are not done, equipment is expensive, and use is troublesome.

有機系抗菌剤は、それ自体の抗菌力は高いが熱に弱く、高分子材料に混合して繊維を製造することが困難である。また、水分や油分と接触すると分解したり、流出したりしてしまい、抗菌力が持続しない。   An organic antibacterial agent has high antibacterial power per se, but is weak against heat, and it is difficult to mix with a polymer material to produce a fiber. In addition, when it comes into contact with moisture or oil, it decomposes or flows out, and the antibacterial activity does not last.

これに対し、無機系抗菌剤は熱に強く、分解し難いため、水分等と接触しても抗菌力が持続し易い。無機系抗菌剤をバインダーによって繊維表面に付着させた繊維(例えば、特許文献1)や、無機系抗菌剤を繊維製造時に樹脂に練り込み紡糸した繊維(例えば、特許文献2)が知られている。   On the other hand, since the inorganic antibacterial agent is resistant to heat and hardly decomposes, the antibacterial activity is easily maintained even when it comes into contact with moisture or the like. A fiber in which an inorganic antibacterial agent is adhered to the fiber surface with a binder (for example, Patent Document 1) and a fiber in which an inorganic antibacterial agent is kneaded into a resin during fiber production and spun (for example, Patent Document 2) are known. .

銀イオン等の抗菌性金属イオンを担持したゼオライトを繊維製造時に樹脂に練り込み紡糸する方法が提案されている(例えば、特許文献3)が、常に水分に曝されながら擦られる歯ブラシ毛には適していない。
また、歯ブラシ毛として持続的な抗菌力と機械的特性を備えることを目的として、シリコン酸化物でコーティングされた抗菌性金属粒子をポリブチレンテレフタレートに均一に含浸することも提案されている(特許文献4)。
There has been proposed a method in which a zeolite carrying an antibacterial metal ion such as silver ion is kneaded into a resin during fiber production and then spun (for example, Patent Document 3), but is suitable for toothbrush hair that is constantly rubbed while exposed to moisture. Not.
In addition, for the purpose of providing sustained antibacterial power and mechanical properties as a toothbrush, it has also been proposed to uniformly impregnate polybutylene terephthalate with antibacterial metal particles coated with silicon oxide (Patent Document) 4).

特開平5−057002号公報Japanese Patent Laid-Open No. 5-057002 特開2004−190197号公報JP 2004-190197 A 特公平6−94534号公報Japanese Patent Publication No. 6-94534 特開2007−159727号公報JP 2007-159727 A

現在市販されている「抗菌(性)」を謳った歯ブラシは、ブラシ毛表面に抗菌剤をコーティングしているものであり、抗菌力が不十分であったり、抗菌力が持続しないという問題点を有している。
また、無機系抗菌剤である銀(Ag)を含有する従来の抗菌性樹脂繊維では、銀を3.3重量%(33,000重量ppm)の濃度で添加しなければ十分な抗菌活性は得られなかった。
本発明は、抗菌剤である金属の含有量が少なく、人体への安全性が高い、抗菌力が高く、抗菌力が持続するブラシ毛を有する抗菌性歯ブラシを提供することを目的とする。
Toothbrushes that are currently marketed with “antibacterial (sex)” are coated with an antibacterial agent on the surface of the brush bristle, and have the problem that the antibacterial activity is insufficient or does not last. Have.
In addition, a conventional antibacterial resin fiber containing silver (Ag), which is an inorganic antibacterial agent, has sufficient antibacterial activity unless silver is added at a concentration of 3.3 wt% (33,000 wt ppm). I couldn't.
An object of the present invention is to provide an antibacterial toothbrush having a brush with a low content of a metal that is an antibacterial agent, high safety to the human body, high antibacterial activity, and sustained antibacterial activity.

本発明によれば、以下の抗菌性歯ブラシ及び抗菌性歯ブラシ毛の製造方法が提供される。
1.金(Au)及び銀(Ag)を含有する樹脂からなるブラシ毛を有する抗菌性歯ブラシ。
2.前記樹脂が、さらに多孔質担体を含有する1に記載の抗菌性歯ブラシ。
3.前記多孔質担体が、銀イオン及び/又は亜鉛イオンを担持した多孔質担体である2に記載の抗菌性歯ブラシ。
4.前記銀イオン及び/又は亜鉛イオンの多孔質担体への担持量が、1.0〜30重量%の範囲内である3に記載の抗菌性歯ブラシ。
5.前記多孔質担体が、ゼオライト、ヒドロキシアパタイト及びリン酸ジルコニウムからなる群から選択される2〜4のいずれかに記載の抗菌性歯ブラシ。
6.前記多孔質担体が、ゼオライトである2〜5のいずれかに記載の抗菌性歯ブラシ。
7.前記ゼオライトの平均粒径が、0.1〜30μmの範囲内である6に記載の抗菌性歯ブラシ。
8.前記樹脂が、ポリエステル系樹脂である1〜7のいずれかに記載の抗菌性歯ブラシ。
9.前記樹脂が、ポリブチレンテレフタレート(PBT)である1〜8のいずれかに記載の抗菌性歯ブラシ。
10.前記ブラシ毛中の金の濃度が、50〜5000重量ppmの範囲内である1〜9のいずれかに記載の抗菌性歯ブラシ。
11.前記ブラシ毛中の銀の濃度が、100〜5000重量ppmの範囲内である1〜10のいずれかに記載の抗菌性歯ブラシ。
12.前記樹脂中における、銀イオン及び/又は亜鉛イオンを担持した多孔質担体の濃度が、1000〜5000重量ppmの範囲内である項1〜11のいずれかに記載の抗菌性歯ブラシ。
13.前記ブラシ毛の毛先から0.5mmの部分の太さが、0.01〜0.05mmの範囲内である1〜12のいずれかに記載の抗菌性歯ブラシ。
14.金粉、銀粉、並びに銀イオン及び/又は亜鉛イオンを担持した多孔質担体を樹脂と混合して樹脂混合物を得る工程、及び
得られた樹脂混合物を200〜280℃で圧出させて糸状とする工程
を有する抗菌性歯ブラシ毛の製造方法。
15.前記樹脂混合物を得る工程が、前記金粉、銀粉、並びに銀イオン及び/又は亜鉛イオンを担持した多孔質担体の前記樹脂中の合計濃度が、前記樹脂混合物の約10倍であるマスターバッチ樹脂混合物を製造する工程、及び
前記マスターバッチ樹脂混合物にさらに前記樹脂を加えて希釈して前記樹脂混合物を得る工程
からなる14に記載の抗菌性歯ブラシ毛の製造方法。
According to the present invention, the following antibacterial toothbrush and method for producing antibacterial toothbrush hair are provided.
1. An antibacterial toothbrush having brush bristles made of a resin containing gold (Au) and silver (Ag).
2. 2. The antibacterial toothbrush according to 1, wherein the resin further contains a porous carrier.
3. 3. The antibacterial toothbrush according to 2, wherein the porous carrier is a porous carrier carrying silver ions and / or zinc ions.
4). 4. The antibacterial toothbrush according to 3, wherein the amount of silver ions and / or zinc ions supported on the porous carrier is in the range of 1.0 to 30% by weight.
5). The antibacterial toothbrush according to any one of 2 to 4, wherein the porous carrier is selected from the group consisting of zeolite, hydroxyapatite, and zirconium phosphate.
6). The antibacterial toothbrush according to any one of 2 to 5, wherein the porous carrier is zeolite.
7). 6. The antibacterial toothbrush according to 6, wherein the zeolite has an average particle size in the range of 0.1 to 30 μm.
8). The antibacterial toothbrush in any one of 1-7 whose said resin is a polyester-type resin.
9. The antibacterial toothbrush in any one of 1-8 whose said resin is polybutylene terephthalate (PBT).
10. The antibacterial toothbrush in any one of 1-9 whose density | concentration of the gold in the said bristle is in the range of 50-5000 weight ppm.
11. The antibacterial toothbrush in any one of 1-10 whose density | concentration of the silver in the said bristle is in the range of 100-5000 weight ppm.
12 Item 12. The antibacterial toothbrush according to any one of Items 1 to 11, wherein the concentration of the porous carrier supporting silver ions and / or zinc ions in the resin is in the range of 1000 to 5000 ppm by weight.
13. The antibacterial toothbrush in any one of 1-12 whose thickness of the 0.5-mm part from the bristles of the said bristle is in the range of 0.01-0.05 mm.
14 A step of mixing gold powder, silver powder, and a porous carrier carrying silver ions and / or zinc ions with a resin to obtain a resin mixture, and a step of extruding the obtained resin mixture at 200 to 280 ° C. to form a yarn A method for producing antibacterial toothbrush bristles.
15. The step of obtaining the resin mixture is a master batch resin mixture in which the total concentration in the resin of the gold powder, silver powder, and a porous carrier supporting silver ions and / or zinc ions is about 10 times that of the resin mixture. 15. The method for producing an antibacterial toothbrush according to 14, comprising a step of producing, and a step of further adding and diluting the resin to the master batch resin mixture to obtain the resin mixture.

本発明によれば、抗菌剤である金属の含有量が少なく、人体への安全性が高い、抗菌力が高く、抗菌力が持続するブラシ毛を有する抗菌性歯ブラシが提供できる。   ADVANTAGE OF THE INVENTION According to this invention, the antibacterial toothbrush which has the bristle with little metal content which is an antibacterial agent, high safety to a human body, high antibacterial power, and antibacterial power lasting can be provided.

本発明の抗菌性歯ブラシは、金(Au)及び銀(Ag)を含有する樹脂からなるブラシ毛を有することを特徴とする。
種々の金属が抗菌活性を有することが知られているが、抗菌活性が高い代表的な金属をその抗菌性の強さの順に示すと次のようになる。
Cu>Ag>Au>Pb>Pt>Ni>Al>Sn>Zn
これらの金属は人体に対しても毒性を示す。上記金属のうち、比較的安全性が高いとされているのはAg、Au及びPtであるが、Agの抗菌活性はAuやPtに比べて非常に強い。そのため、抗菌剤として一般にAgがよく使用されている。
The antibacterial toothbrush of the present invention is characterized by having brush bristles made of a resin containing gold (Au) and silver (Ag).
Various metals are known to have antibacterial activity. Typical metals having high antibacterial activity are shown in the order of their antibacterial strength as follows.
Cu>Ag>Au>Pb>Pt>Ni>Al>Sn> Zn
These metals are also toxic to the human body. Among the above metals, Ag, Au and Pt are considered to be relatively safe, but the antibacterial activity of Ag is much stronger than Au and Pt. Therefore, Ag is often used as an antibacterial agent.

しかし、上述したように金属は人体に対しても毒性を示すため、金属を抗菌剤として使用する場合にその合計使用量は少ない方が好ましいと言える。
従来は、所望の抗菌活性を得るために、Agをブラシ毛の3.3重量%(33,000ppm)と高い濃度で配合することが必要であった。
Auの抗菌活性はAgに比べて非常に弱いが、AgとAuを併用すると、それぞれが非常に少量であっても、顕著に高い抗菌活性を示すことを本発明者らは見出した。つまり、銀と金の相乗作用により抗菌活性が顕著に向上することを見出した。これにより、抗菌剤としての金属の合計量を減らすことが可能になり、人体への毒性も抑えることが可能になった。
However, as described above, since the metal is toxic to the human body, it can be said that it is preferable that the total amount used is small when the metal is used as an antibacterial agent.
Conventionally, in order to obtain a desired antibacterial activity, it was necessary to mix Ag at a high concentration of 3.3% by weight (33,000 ppm) of the brush hair.
Although the antibacterial activity of Au is very weak compared to Ag, the present inventors have found that when Ag and Au are used in combination, the antibacterial activity is remarkably high even in a very small amount. That is, it has been found that the antibacterial activity is remarkably improved by the synergistic action of silver and gold. As a result, the total amount of metals as antibacterial agents can be reduced, and toxicity to the human body can be suppressed.

金属金及び金属銀は純度99.9%以上のものを使用することが好ましい。
ブラシ毛樹脂中の金の濃度は、50〜5000重量ppmの範囲内であることが好ましく、100〜4000重量ppmの範囲内であることがより好ましく、150〜3000ppmの範囲内であることがさらに好ましい。
It is preferable to use metal gold and metal silver having a purity of 99.9% or more.
The gold concentration in the bristle resin is preferably in the range of 50 to 5000 ppm by weight, more preferably in the range of 100 to 4000 ppm by weight, and further in the range of 150 to 3000 ppm. preferable.

ブラシ毛樹脂中の銀の濃度は、100〜5000重量ppmの範囲内であることが好ましく、200〜4000重量ppmの範囲内であることがより好ましく、300〜3000ppmの範囲内であることがさらに好ましい。   The concentration of silver in the brush bristle resin is preferably in the range of 100 to 5000 ppm by weight, more preferably in the range of 200 to 4000 ppm by weight, and further in the range of 300 to 3000 ppm. preferable.

本発明の抗菌性歯ブラシのブラシ毛の原料樹脂には、さらに多孔質担体を配合することが好ましい。多孔質担体は、抗菌剤である金及び銀を樹脂中に均一に分散させるのに役立つ。   It is preferable to further mix a porous carrier with the raw material resin for the bristles of the antibacterial toothbrush of the present invention. The porous carrier serves to uniformly disperse the antibacterial gold and silver in the resin.

多孔質担体は、銀イオン及び/又は亜鉛イオンを担持した多孔質担体であることが好ましい。
さらに、本発明では、金及び銀に加えて多孔質単体に担持された銀イオン及び/又は亜鉛イオンも樹脂に練り込むことでより優れた抗菌性が得られるため好ましい。
本発明の抗菌性歯ブラシでは、抗菌性を有する銀イオン及び/又は亜鉛イオンを多孔質担体に担持させ、これを樹脂に練り込むことで金及び銀をブラシ毛中に均質に分散させることが可能となり、抗菌性を大きく向上させることができる。
The porous carrier is preferably a porous carrier carrying silver ions and / or zinc ions.
Furthermore, in the present invention, in addition to gold and silver, silver ions and / or zinc ions supported on a porous simple substance are kneaded into the resin, so that more excellent antibacterial properties can be obtained.
In the antibacterial toothbrush of the present invention, antibacterial silver ions and / or zinc ions are supported on a porous carrier and kneaded into a resin, whereby gold and silver can be uniformly dispersed in the bristles. Thus, the antibacterial properties can be greatly improved.

多孔質担体としては、ゼオライト、ヒドロキシアパタイト及びリン酸ジルコニウム等が好ましく、ゼオライトが特に好ましい。ゼオライトはアルミノケイ酸塩からなるものが好ましい。   As the porous carrier, zeolite, hydroxyapatite, zirconium phosphate and the like are preferable, and zeolite is particularly preferable. The zeolite is preferably composed of an aluminosilicate.

ゼオライトの平均粒径は、微細な歯ブラシ毛の製造に適した範囲を選択すればよいが、0.1〜30μmの範囲内であることが好ましく、1.0〜10μmの範囲内であることがより好ましく、2.0〜5.0μmの範囲内であることがさらに好ましい。ゼオライトの粒径が大きすぎると、微細なブラシ毛に均一に存在させることができないおそれがある。   The average particle diameter of the zeolite may be selected within a range suitable for the production of fine toothbrush hairs, but is preferably in the range of 0.1 to 30 μm, and is preferably in the range of 1.0 to 10 μm. More preferably, it is further in the range of 2.0 to 5.0 μm. When the particle diameter of zeolite is too large, there is a possibility that it cannot be uniformly present in fine brush hairs.

樹脂としては、ブラシ毛として使用できる繊維を形成でき、口腔内に用いることができるものであればよい。機械的強度、多孔質担体との混合の容易性からポリエステル系樹脂であることが好ましく、ポリブチレンテレフタレート(PBT)であることが特に好ましい。ポリブチレンテレフタレートは、歯ブラシ毛に適した適度な柔軟性と機械的強度を有している。   Any resin that can form fibers that can be used as brush hairs and that can be used in the oral cavity may be used. In view of mechanical strength and ease of mixing with a porous carrier, a polyester-based resin is preferable, and polybutylene terephthalate (PBT) is particularly preferable. Polybutylene terephthalate has appropriate flexibility and mechanical strength suitable for toothbrush hair.

ブラシ毛樹脂中の、銀イオン及び/又は亜鉛イオンを担持した多孔質担体の濃度は1000〜5000重量ppmの範囲内であることが好ましく、2000〜4000重量ppmの範囲内であることがより好ましい。濃度が低いと金及び銀の分散が不均一となるおそれがある。濃度が高くてもそれ以上の効果は期待できない可能性があり、製造コストが高くなるため好ましくない。   The concentration of the porous carrier carrying silver ions and / or zinc ions in the brush bristle resin is preferably in the range of 1000 to 5000 ppm by weight, more preferably in the range of 2000 to 4000 ppm by weight. . If the concentration is low, the dispersion of gold and silver may be non-uniform. Even if the concentration is high, there is a possibility that no further effect can be expected, which is not preferable because the production cost increases.

銀イオン及び/又は亜鉛イオンの多孔質担体への担持量は、1.0〜30重量%であることが好ましく、5.0〜20重量%であることがより好ましく、6.0〜12重量%であることがさらに好ましい。担持量が低いと十分な抗菌力が得られないおそれがある。   The amount of silver ions and / or zinc ions supported on the porous carrier is preferably 1.0 to 30% by weight, more preferably 5.0 to 20% by weight, and 6.0 to 12% by weight. % Is more preferable. If the supported amount is low, sufficient antibacterial power may not be obtained.

銀イオン及び亜鉛イオンは、担体であるゼオライト近傍に細菌やカビ等の細胞が位置すると、ゼオライトから解離分散によって細菌やカビの細胞膜に到達し、この細胞膜のタンパク質に吸着されるとともに、細胞の構造破壊を起こして細菌やカビ等のエネルギー代謝を不能にして菌自体を死滅させる作用を有する。   When cells such as bacteria and mold are located in the vicinity of the carrier zeolite, silver ions and zinc ions reach the cell membrane of bacteria and mold by dissociation and dispersion from the zeolite, and are adsorbed to the proteins of the cell membrane and the cell structure. It has the effect of causing destruction and disabling the energy metabolism of bacteria and molds and killing the bacteria themselves.

また、担持されている金属イオンによる作用とは別に、ゼオライト自体による殺菌作用もある。ゼオライトはSiO、Al等の金属酸化物からなっており、この骨格構造に結合されている酸素が部分的に活性酸素に転換され、上記金属イオンによる作用と同様に、細菌やカビの細胞膜等のタンパク質層に吸着されて、強力な殺菌効果を示す。 In addition to the action of the supported metal ions, there is also a bactericidal action by the zeolite itself. Zeolites are composed of metal oxides such as SiO 2 and Al 2 O 3 , and oxygen bonded to this skeletal structure is partially converted into active oxygen. It is adsorbed on a protein layer such as a cell membrane and exhibits a strong bactericidal effect.

本発明の抗菌性歯ブラシは、金、銀、さらには銀イオン及び/又は亜鉛イオン担持ゼオライトが樹脂中に均一に分散して存在し、ブラッシングによって歯ブラシ毛が摩耗しても、抗菌力は持続する。   In the antibacterial toothbrush of the present invention, gold, silver, and also zeolites carrying silver ions and / or zinc ions are uniformly dispersed in the resin, and the antibacterial activity is maintained even if the toothbrush bristles are worn by brushing. .

ブラシ毛の直径は、所望のブラシの硬さ(柔軟性)に応じて適宜決定すればよいが、通常は0.15〜0.22mmの範囲内、好ましくは0.18〜0.21mmの範囲内である。   The diameter of the brush bristles may be appropriately determined according to the desired hardness (flexibility) of the brush, but is usually in the range of 0.15 to 0.22 mm, preferably in the range of 0.18 to 0.21 mm. Is within.

歯ブラシ毛としてのブラッシング効果を高めるため、ブラシ毛の先端は円錐形に加工されていることが好ましい。円錐形に加工されていることによって、歯周ポケット内までブラシ毛が入り込み易くなり、歯磨き効果が高くなる。   In order to enhance the brushing effect as the toothbrush bristles, it is preferable that the tip of the bristles be processed into a conical shape. By being processed into a conical shape, it becomes easier for the bristles to enter the periodontal pocket, and the tooth brushing effect is enhanced.

ブラシ毛の先端は、毛先から0.5mmの部分の太さが、0.01〜0.05mmの範囲内であることが好ましく、0.02〜0.04mmの範囲内であることがより好ましい。   The tip of the bristles preferably has a thickness of 0.5 mm from the bristles within a range of 0.01 to 0.05 mm, more preferably within a range of 0.02 to 0.04 mm. preferable.

次に、本発明の抗菌性歯ブラシ毛の製造方法は、
金粉、銀粉、並びに銀イオン及び/又は亜鉛イオンを担持した多孔質担体を樹脂と混合して樹脂混合物を得る工程、及び
得られた樹脂混合物を200〜280℃で圧出させて糸状とする工程
を有することを特徴とする。
Next, the method for producing the antibacterial toothbrush of the present invention is as follows.
A step of mixing gold powder, silver powder, and a porous carrier carrying silver ions and / or zinc ions with a resin to obtain a resin mixture, and a step of extruding the obtained resin mixture at 200 to 280 ° C. to form a yarn It is characterized by having.

上記樹脂混合物を得る工程は、前記金粉、銀粉、並びに銀イオン及び/又は亜鉛イオンを担持した多孔質担体の前記樹脂中の合計濃度が、前記樹脂混合物の約10倍であるマスターバッチ樹脂混合物を製造する工程、及び
前記マスターバッチ樹脂混合物にさらに前記樹脂を加えて希釈して前記樹脂混合物を得る工程
からなることが好ましい。
The step of obtaining the resin mixture comprises a masterbatch resin mixture in which the total concentration in the resin of the gold powder, silver powder, and the porous carrier supporting silver ions and / or zinc ions is about 10 times that of the resin mixture. It is preferable to comprise a step of producing, and a step of adding the resin to the masterbatch resin mixture and diluting it to obtain the resin mixture.

パウダー状のゼオライトを樹脂に混合する場合、多量の樹脂中に少量のゼオライトを均一に分散することは難く、抗菌性が偏った樹脂組成物となる場合がある。
ゼオライトが均一に分散された樹脂組成物とするために、濃度が約10重量%となるように濃度の高いマスターバッチ樹脂混合物を製造し、このマスターバッチ樹脂混合物にさらに樹脂を加えてゼオライトが所望の濃度となるように希釈して歯ブラシ毛製造用樹脂組成物とすることが好ましい。
When powdery zeolite is mixed with a resin, it is difficult to uniformly disperse a small amount of zeolite in a large amount of resin, and a resin composition with a biased antibacterial property may be obtained.
In order to obtain a resin composition in which zeolite is uniformly dispersed, a master batch resin mixture having a high concentration is produced so that the concentration is about 10% by weight, and a resin is further added to the master batch resin mixture to obtain a desired zeolite. It is preferable to dilute it so that it may become the density | concentration of and to set it as the resin composition for toothbrush manufacturing.

金粉の樹脂への混合量は、樹脂1トンに対して100g〜5kgの範囲であることが好ましく、150g〜4kgの範囲であることがより好ましい。   The amount of gold powder mixed in the resin is preferably in the range of 100 g to 5 kg, more preferably in the range of 150 g to 4 kg, per ton of resin.

銀粉の樹脂への混合量は、樹脂1トンに対して100g〜5kgの範囲であることが好ましく、300g〜4kgの範囲であることがより好ましい。   The mixing amount of the silver powder into the resin is preferably in the range of 100 g to 5 kg, more preferably in the range of 300 g to 4 kg with respect to 1 ton of resin.

銀イオン及び/又は亜鉛イオンを担持した多孔質担体の樹脂への混合量は、樹脂1トンに対して1〜5kgの範囲であることが好ましく、2〜4kgの範囲であることがより好ましい。   The mixing amount of the porous carrier carrying silver ions and / or zinc ions into the resin is preferably in the range of 1 to 5 kg, more preferably in the range of 2 to 4 kg with respect to 1 ton of resin.

銀イオン及び/又は亜鉛イオンをゼオライトに担持させる方法は、公知の方法を用いればよく、例えば、金属イオン(銀イオン、亜鉛イオン)のイオン交換処理等が挙げられる。
より具体的には、銀イオン、亜鉛イオンの水溶液に、適当なpH条件でゼオライトを添加し、ゼオライト中のイオン交換可能なイオンの一部又は全部を銀イオン、亜鉛イオンで置換させ、イオン交換終了後、水洗し、加熱乾燥すればよい。
As a method for supporting silver ions and / or zinc ions on zeolite, a known method may be used, and examples thereof include ion exchange treatment of metal ions (silver ions and zinc ions).
More specifically, zeolite is added to an aqueous solution of silver ions and zinc ions under an appropriate pH condition, and a part or all of the ion-exchangeable ions in the zeolite are replaced with silver ions and zinc ions, and ion exchange is performed. After completion, it may be washed with water and dried by heating.

銀イオン及び/又は亜鉛イオンを担持したゼオライトは、市販品を用いてもよい。   A commercial product may be used as the zeolite carrying silver ions and / or zinc ions.

上記のようにして得られた樹脂組成物は、200〜280℃、好ましくは220〜260℃の温度で圧出させて糸状にする。糸状に成形する方法は、歯ブラシ毛を形成し得る公知の方法を用いればよい。   The resin composition obtained as described above is extruded at a temperature of 200 to 280 ° C., preferably 220 to 260 ° C., to form a thread. A known method capable of forming toothbrush bristles may be used as the method for forming the yarn.

ブラシ毛の端部を円錐形に加工することが好ましい。ブラシ毛の先端を円錐形に加工するには、当業界で通常用いる加工方法を用いればよい。
このようにして得られたブラシ毛に対し、洗浄、乾燥等の仕上げを行い、ブラシ柄に植毛することで本発明の抗菌性歯ブラシを得ることができる。
It is preferable to process the ends of the bristle into a conical shape. In order to process the tip of the bristles into a conical shape, a processing method usually used in the art may be used.
The antibacterial toothbrush of the present invention can be obtained by finishing the brush bristles thus obtained, such as washing and drying, and planting the brush bristles.

本発明の抗菌性歯ブラシは、抗菌作用を有する金、銀、並びに銀イオン及び/又は亜鉛イオンがブラシ毛を構成する樹脂中に均一に分散されているため、ブラッシング等によって摩耗しても抗菌力が低下しない。
本発明の抗菌性歯ブラシは、身の回りのどこにでも存在する黄色ブドウ球菌等の細菌やかびの繁殖を抑制することができる。
The antibacterial toothbrush of the present invention has antibacterial activity even when it is worn by brushing or the like because gold, silver, and silver ions and / or zinc ions having antibacterial action are uniformly dispersed in the resin constituting the bristles. Does not drop.
The antibacterial toothbrush of the present invention can suppress the growth of bacteria such as Staphylococcus aureus and fungi that exist everywhere around us.

以下、抗菌性歯ブラシ毛の製造実施例、及び黄色ブドウ球菌に対する抗菌力試験例を示して、本発明をより具体的に説明する。   Hereinafter, the present invention will be described more specifically by showing production examples of antibacterial toothbrush bristles and examples of antibacterial activity tests against S. aureus.

製造例:銀イオン及び亜鉛イオン担持ゼオライト粉末の製造
A型ゼオライト50gを蒸留水400mLに加えて撹拌し、スラリー状にした。このゼオライトスラリーに硝酸を加えてpH7.2に調整した。蒸留水100mLに硝酸銀5g及び硝酸亜鉛3gを加えて金属塩水溶液を調製した。この金属塩水溶液をゼオライトスラリーに加えて55℃で3時間撹拌し、金属イオン(銀イオン及び亜鉛イオン)のイオン交換処理を行った。イオン交換後のスラリーを遠心分離し、沈殿物を蒸留水で水洗し、乾燥し、粉砕して平均粒径が2.6μmの銀イオン及び亜鉛イオンを担持したゼオライト粉末を得た。
Production Example: Production of zeolite powder carrying silver ions and zinc ions 50 g of A-type zeolite was added to 400 mL of distilled water and stirred to form a slurry. Nitric acid was added to the zeolite slurry to adjust to pH 7.2. An aqueous metal salt solution was prepared by adding 5 g of silver nitrate and 3 g of zinc nitrate to 100 mL of distilled water. This aqueous metal salt solution was added to the zeolite slurry and stirred at 55 ° C. for 3 hours to perform ion exchange treatment of metal ions (silver ions and zinc ions). The slurry after ion exchange was centrifuged, and the precipitate was washed with distilled water, dried, and pulverized to obtain a zeolite powder carrying silver ions and zinc ions having an average particle diameter of 2.6 μm.

実施例1:抗菌性歯ブラシ毛の製造
純度99.9%の金粉180g、純度99.9%の銀粉400g、並びに銀イオン及び亜鉛イオンを担持したゼオライト粉末3.0kgを、ポリブチレンテレフタレート(PBT)に添加し、均一になるように混練し、合計100kgのマスターバッチ樹脂混合物を製造した。マスターバッチ樹脂混合物にさらにPBTを加えて均一に混合し、歯ブラシ毛製造用樹脂組成物(歯ブラシ毛素材)1000kgを得た。
Example 1 Production of Antibacterial Toothbrush Bristles 180 g of gold powder with a purity of 99.9%, 400 g of silver powder with a purity of 99.9%, and 3.0 kg of zeolite powder supporting silver ions and zinc ions were added to polybutylene terephthalate (PBT). And knead | mixed so that it might become uniform, and the masterbatch resin mixture of a total of 100 kg was manufactured. To the master batch resin mixture, PBT was further added and mixed uniformly to obtain 1000 kg of a resin composition (toothbrush bristle material) for toothbrush bristle production.

得られた樹脂組成物を220〜260℃の温度で圧出させて繊維状とし、元糸を製造した。元糸の直径は0.19±0.1mmであった。この元糸を長さ31(±1.0mm)にカッティングし、両先端を円錐形に加工した。加工した先端から0.5mmの部分の太さは0.03mmであった。   The obtained resin composition was extruded at a temperature of 220 to 260 ° C. to form a fiber, and a base yarn was produced. The diameter of the base yarn was 0.19 ± 0.1 mm. This base yarn was cut to a length of 31 (± 1.0 mm), and both ends were processed into a conical shape. The thickness of the 0.5 mm portion from the processed tip was 0.03 mm.

試験例1:歯ブラシ毛製造用樹脂の黄色ブドウ球菌に対する抗菌力試験
実施例1で製造した歯ブラシ毛製造用樹脂組成物を用い、大きさ約3cm×3cm×厚み約7mmのプレートを製造し、試験用検体として用いた。
Test Example 1: Antibacterial activity test of resin for producing toothbrush hair against Staphylococcus aureus Using the resin composition for producing toothbrush hair produced in Example 1, a plate having a size of about 3 cm × 3 cm × about 7 mm in thickness was produced and tested. It was used as a test sample.

<抗菌力試験方法>
JIS Z 2801:2010「抗菌加工製品−抗菌性試験方法・抗菌効果」5 試験方法を参考にして、検体の抗菌力試験を行った。
検体は消毒用アルコールに約1分間浸漬して、検体表面に付着している雑菌を除去してから試験に供した。
規定に従い、大きさ約30mm×30mm×厚さ約0.09mmのポリエチレンフィルムを比較対照として用いた。
試験はStaphylococcus aureus subsp. aureus NBRC 12732(黄色ブドウ球菌)及びEscherichia coli
(大腸菌)で行った。
<Antimicrobial test method>
JIS Z 2801: 2010 “Antibacterial processed product—antibacterial test method / antibacterial effect” 5 The antibacterial activity test of the specimen was performed with reference to the test method.
The specimen was immersed in disinfecting alcohol for about 1 minute to remove the germs adhering to the specimen surface and then used for the test.
According to regulations, a polyethylene film having a size of about 30 mm × 30 mm × thickness of about 0.09 mm was used as a comparative control.
The test was performed using Staphylococcus aureus subsp. aureus NBRC 12732 (S. aureus) and Escherichia coli
(E. coli).

検体及び比較対照の上に、それぞれ試験菌液0.1mLを乗せてポリエチレンフィルムを被せ、35℃で24時間培養した後の生菌数を測定した。結果を表1に示す。   On the specimen and the comparative control, 0.1 mL of the test bacterial solution was placed and covered with a polyethylene film. The results are shown in Table 1.

Figure 2017164006
Figure 2017164006

比較対照では、24時間後も生菌数が殆ど変わらないのに比べ、検体では24時間後には、生菌数が検出限界未満となっており、実施例1で製造した歯ブラシ毛用樹脂は、黄色ブドウ球菌及び大腸菌に対して非常に高い抗菌力を示すことがわかる。   In the comparative control, the viable cell count is less than the detection limit after 24 hours in the specimen compared to the viable cell count after 24 hours, and the toothbrush resin produced in Example 1 is It can be seen that it exhibits very high antibacterial activity against S. aureus and E. coli.

実施例2:抗菌性歯ブラシ毛の製造
純度99.9%の金粉180g、純度99.9%の銀粉400g、並びに銀イオン及び亜鉛イオンを担持したゼオライト粉末3.0kgを、ポリブチレンテレフタレート(PBT)に添加し、均一になるように混練し、合計100kgのマスターバッチ樹脂混合物を製造した。マスターバッチ樹脂混合物にさらにPBTを加えて均一に混合し、歯ブラシ毛製造用樹脂組成物(歯ブラシ毛素材)1000kgを得た。
樹脂組成物中の金の濃度は約180重量ppm、銀の濃度は約400ppmであった。
Example 2 Production of Antibacterial Toothbrush Bristles 180 g of gold powder with a purity of 99.9%, 400 g of silver powder with a purity of 99.9%, and 3.0 kg of zeolite powder supporting silver ions and zinc ions were added to polybutylene terephthalate (PBT). And knead | mixed so that it might become uniform, and the masterbatch resin mixture of a total of 100 kg was manufactured. To the master batch resin mixture, PBT was further added and mixed uniformly to obtain 1000 kg of a resin composition (toothbrush bristle material) for toothbrush bristle production.
The concentration of gold in the resin composition was about 180 ppm by weight, and the concentration of silver was about 400 ppm.

得られた樹脂組成物を220〜260℃の温度で圧出させて繊維状とし、元糸を製造した。元糸の直径は0.19±0.1mmであった。この元糸を長さ31(±1.0mm)にカッティングし、両先端を円錐形に加工した。加工した先端から0.5mmの部分の太さは0.03mmであった。   The obtained resin composition was extruded at a temperature of 220 to 260 ° C. to form a fiber, and a base yarn was produced. The diameter of the base yarn was 0.19 ± 0.1 mm. This base yarn was cut to a length of 31 (± 1.0 mm), and both ends were processed into a conical shape. The thickness of the 0.5 mm portion from the processed tip was 0.03 mm.

比較例:銀のみを抗菌剤として用いた抗菌性歯ブラシ毛の製造
銀の濃度が3.3重量%(33,000重量ppm)の歯ブラシ毛製造用樹脂組成物を用いた以外は実施例2と同様にして歯ブラシ毛を製造した。
Comparative Example: Production of antibacterial toothbrush using only silver as an antibacterial agent Example 2 except that a resin composition for producing toothbrush having a silver concentration of 3.3 wt% (33,000 wtppm) was used. Similarly, toothbrush bristles were produced.

試験例2:歯ブラシ毛製造用樹脂の黄色ブドウ球菌に対する抗菌力試験
実施例2で製造した歯ブラシ毛及び比較例で製造した歯ブラシ毛を、それぞれ5cm×5cmに敷き詰めたものを試験用検体として用い、試験例1と同様の方法で抗菌力試験を行った。
規定に従い、大きさ約30mm×30mm×厚さ約0.09mmのポリエチレンフィルムを比較対照として用いた。
試験はStaphylococcus aureus subsp. aureus NBRC 12732(黄色ブドウ球菌)及びEscherichia coli
(大腸菌)で行った。
Test Example 2: Antibacterial activity test of the resin for producing toothbrush hair against Staphylococcus aureus Using the toothbrush hair produced in Example 2 and the toothbrush hair produced in the comparative example, each spread as 5 cm × 5 cm as a test specimen, An antibacterial activity test was performed in the same manner as in Test Example 1.
According to regulations, a polyethylene film having a size of about 30 mm × 30 mm × thickness of about 0.09 mm was used as a comparative control.
The test was performed using Staphylococcus aureus subsp. aureus NBRC 12732 (S. aureus) and Escherichia coli
(E. coli).

実施例2の検体、比較例の検体及び比較対照の上に、それぞれ試験菌液0.4mLを乗せてポリエチレンフィルム(被覆フィルム;表面積16cm)を被せ、35℃で24時間培養した後の生菌数を測定した。
抗菌活性値は、次の式で計算出した。
抗菌活性値=U−A
:比較対照の試験片1cm当たりの24時間培養後の生菌数の常用対数値
:検体1cm当たりの24時間培養後の生菌数の常用対数値
ここで、抗菌活性値が2.0以上で、抗菌活性ありと評価される。
結果を表2に示す。
The test sample solution of Example 2, the test sample of the comparative example, and the comparative control were each placed with 0.4 mL of the test bacterial solution, covered with a polyethylene film (coated film; surface area of 16 cm 2 ), and then cultured at 35 ° C. for 24 hours. The number of bacteria was measured.
The antibacterial activity value was calculated by the following formula.
Antibacterial activity value = U t −A t
U t : Common logarithm of the number of viable bacteria after 24 hours culture per 1 cm 2 of the test specimen for comparison
A t: here 24 hours common logarithm value of the number of living bacteria after culture per sample 1 cm 2, with the antimicrobial activity value of 2.0 or more is evaluated that there is antibacterial activity.
The results are shown in Table 2.

Figure 2017164006
Figure 2017164006

黄色ぶどう球菌については、銀のみを抗菌剤として用いた比較例では、銀が33,000重量ppmと高濃度で添加されてはじめて、抗菌活性ありと評価される抗菌活性値の下限値2.0であった。これに対し、金を約180重量ppm及び銀を約400重量ppmの濃度で添加した実施例2では、金属の合計濃度が約580重量ppmと極めて低い濃度であるにもかかわらず抗菌活性値が5.0と非常に高かった。
同様に、大腸菌についても、比較例では抗菌活性値が5.0であったのに対し、実施例2では抗菌活性が6.2であった。
As for Staphylococcus aureus, in the comparative example using only silver as an antibacterial agent, the lower limit 2.0 of the antibacterial activity value evaluated as having antibacterial activity is only after silver is added at a high concentration of 33,000 ppm by weight. Met. On the other hand, in Example 2 in which gold was added at a concentration of about 180 ppm by weight and silver at a concentration of about 400 ppm by weight, the antibacterial activity value was low even though the total concentration of metals was about 580 ppm by weight. It was very high at 5.0.
Similarly, for E. coli, the antibacterial activity value was 5.0 in the comparative example, whereas the antibacterial activity was 6.2 in Example 2.

表2の結果から、従来の銀のみを抗菌剤として添加した場合には、銀を多量に使用する必要があったが、本発明によれば、銀及び金を抗菌剤として用いることで、金と銀の相乗効果として銀が少量であっても高い抗菌活性が得られることがわかる。
本発明によって、銀に比べて抗菌活性が弱い金を少量併用することによって、銀の添加量が少なくても抗菌活性が顕著に向上し、これにより抗菌剤である金属の合計添加量を顕著に少なく抑えることができ、人体への安全性が高い、抗菌性ブラシ毛の生産が可能となった。
From the results of Table 2, when only conventional silver was added as an antibacterial agent, it was necessary to use a large amount of silver, but according to the present invention, by using silver and gold as an antibacterial agent, It can be seen that, as a synergistic effect of silver and silver, high antibacterial activity can be obtained even with a small amount of silver.
According to the present invention, by using a small amount of gold having a weak antibacterial activity compared with silver, the antibacterial activity is remarkably improved even if the addition amount of silver is small, thereby significantly increasing the total addition amount of metals as antibacterial agents. The production of antibacterial brush hair that can be reduced to a low level and highly safe for the human body has become possible.

本発明によれば、抗菌力が長く持続するブラシ毛を有する抗菌性歯ブラシが提供され、歯ブラシを清潔に保持でき、身の回りに存在する細菌やカビによる感染の予防、さらには誤嚥性肺炎の予防に非常に有用である。
本発明によれば、特別な手段や手間を必要とせずに歯ブラシの衛生を保持することができるため、介護の現場において特に有用である。
また、本発明によれば、抗菌剤である金属の含有量が少なく、人体への安全性が高い、抗菌性歯ブラシが生産できる。
ADVANTAGE OF THE INVENTION According to this invention, the antibacterial toothbrush which has the bristles which have long lasting antibacterial activity is provided, the toothbrush can be kept clean, the prevention of the infection by bacteria and mold existing around, and the prevention of aspiration pneumonia Very useful to.
According to the present invention, the hygiene of the toothbrush can be maintained without requiring any special means or labor, and thus it is particularly useful in the field of care.
In addition, according to the present invention, an antibacterial toothbrush having a low content of metal as an antibacterial agent and having high safety to the human body can be produced.

Claims (15)

金(Au)及び銀(Ag)を含有する樹脂からなるブラシ毛を有する抗菌性歯ブラシ。   An antibacterial toothbrush having brush bristles made of a resin containing gold (Au) and silver (Ag). 前記樹脂が、さらに多孔質担体を含有する請求項1に記載の抗菌性歯ブラシ。   The antibacterial toothbrush according to claim 1, wherein the resin further contains a porous carrier. 前記多孔質担体が、銀イオン及び/又は亜鉛イオンを担持した多孔質担体である請求項2に記載の抗菌性歯ブラシ。   The antibacterial toothbrush according to claim 2, wherein the porous carrier is a porous carrier carrying silver ions and / or zinc ions. 前記銀イオン及び/又は亜鉛イオンの多孔質担体への担持量が、1.0〜30重量%の範囲内である請求項3に記載の抗菌性歯ブラシ。   The antibacterial toothbrush according to claim 3, wherein the amount of silver ions and / or zinc ions supported on the porous carrier is in the range of 1.0 to 30% by weight. 前記多孔質担体が、ゼオライト、ヒドロキシアパタイト及びリン酸ジルコニウムからなる群から選択される請求項2〜4のいずれかに記載の抗菌性歯ブラシ。   The antibacterial toothbrush according to any one of claims 2 to 4, wherein the porous carrier is selected from the group consisting of zeolite, hydroxyapatite, and zirconium phosphate. 前記多孔質担体が、ゼオライトである請求項2〜5のいずれかに記載の抗菌性歯ブラシ。   The antibacterial toothbrush according to any one of claims 2 to 5, wherein the porous carrier is zeolite. 前記ゼオライトの平均粒径が、0.1〜30μmの範囲内である請求項6に記載の抗菌性歯ブラシ。   The antibacterial toothbrush according to claim 6, wherein an average particle diameter of the zeolite is in a range of 0.1 to 30 µm. 前記樹脂が、ポリエステル系樹脂である請求項1〜7のいずれかに記載の抗菌性歯ブラシ。   The antibacterial toothbrush according to any one of claims 1 to 7, wherein the resin is a polyester resin. 前記樹脂が、ポリブチレンテレフタレート(PBT)である請求項1〜8のいずれかに記載の抗菌性歯ブラシ。   The antibacterial toothbrush according to any one of claims 1 to 8, wherein the resin is polybutylene terephthalate (PBT). 前記ブラシ毛中の金の濃度が、50〜5000重量ppmの範囲内である請求項1〜9のいずれかに記載の抗菌性歯ブラシ。   The antibacterial toothbrush according to any one of claims 1 to 9, wherein a gold concentration in the brush bristles is in a range of 50 to 5000 ppm by weight. 前記ブラシ毛中の銀の濃度が、100〜5000重量ppmの範囲内である請求項1〜10のいずれかに記載の抗菌性歯ブラシ。   The antibacterial toothbrush according to any one of claims 1 to 10, wherein a concentration of silver in the brush bristles is in a range of 100 to 5000 ppm by weight. 前記樹脂中における、銀イオン及び/又は亜鉛イオンを担持した多孔質担体の濃度が、1000〜5000重量ppmの範囲内である請求項1〜11のいずれかに記載の抗菌性歯ブラシ。   The antibacterial toothbrush according to any one of claims 1 to 11, wherein a concentration of the porous carrier supporting silver ions and / or zinc ions in the resin is in a range of 1000 to 5000 ppm by weight. 前記ブラシ毛の毛先から0.5mmの部分の太さが、0.01〜0.05mmの範囲内である請求項1〜12のいずれかに記載の抗菌性歯ブラシ。   The antibacterial toothbrush according to any one of claims 1 to 12, wherein a thickness of a portion 0.5 mm from a tip of the brush hair is within a range of 0.01 to 0.05 mm. 金粉、銀粉、並びに銀イオン及び/又は亜鉛イオンを担持した多孔質担体を樹脂と混合して樹脂混合物を得る工程、及び
得られた樹脂混合物を200〜280℃で圧出させて糸状とする工程
を有する抗菌性歯ブラシ毛の製造方法。
A step of mixing gold powder, silver powder, and a porous carrier carrying silver ions and / or zinc ions with a resin to obtain a resin mixture, and a step of extruding the obtained resin mixture at 200 to 280 ° C. to form a yarn A method for producing antibacterial toothbrush bristles.
前記樹脂混合物を得る工程が、前記金粉、銀粉、並びに銀イオン及び/又は亜鉛イオンを担持した多孔質担体の前記樹脂中の合計濃度が、前記樹脂混合物の約10倍であるマスターバッチ樹脂混合物を製造する工程、及び
前記マスターバッチ樹脂混合物にさらに前記樹脂を加えて希釈して前記樹脂混合物を得る工程
からなる請求項14に記載の抗菌性歯ブラシ毛の製造方法。
The step of obtaining the resin mixture is a master batch resin mixture in which the total concentration in the resin of the gold powder, silver powder, and a porous carrier supporting silver ions and / or zinc ions is about 10 times that of the resin mixture. The method for producing an antibacterial toothbrush according to claim 14, comprising a step of producing, and a step of further adding the resin to the master batch resin mixture to dilute to obtain the resin mixture.
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