JPH08333209A - Antibacterial composition and method for producing antibacterial material using the same - Google Patents
Antibacterial composition and method for producing antibacterial material using the sameInfo
- Publication number
- JPH08333209A JPH08333209A JP7138209A JP13820995A JPH08333209A JP H08333209 A JPH08333209 A JP H08333209A JP 7138209 A JP7138209 A JP 7138209A JP 13820995 A JP13820995 A JP 13820995A JP H08333209 A JPH08333209 A JP H08333209A
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- Prior art keywords
- antibacterial
- resin
- silver
- antibacterial composition
- producing
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
- Paper (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Laminated Bodies (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
(57)【要約】
【目的】 樹脂の透明性や樹脂表面の平滑性を損なうこ
となく、樹脂をはじめ各種材料に、容易に抗菌性を付与
する方法を提供する。
【構成】 銀、銅および亜鉛の少なくとも一種のチオス
ルファト錯体の水溶液を非水溶媒に分散させたエマルシ
ョン抗菌性組成物を熱硬化牲樹脂に混合し、硬化させて
抗菌性の付与された樹脂成形体を得る。また、同抗菌性
組成物を塗料樹脂中に混合し、これを被塗装物に塗装し
て抗菌性の付与された塗装皮膜を形成する。さらには、
上記チオスルファト錯体の水溶液を水性塗料中に混合
し、これを被塗装物に塗装して抗菌性の付与された塗装
皮膜を形成する。(57) [Summary] [Purpose] To provide a method for easily imparting antibacterial properties to various materials including a resin without impairing the transparency of the resin and the smoothness of the resin surface. [Structure] A resin molded article having an antibacterial property imparted by mixing an emulsion antibacterial composition in which an aqueous solution of at least one thiosulfato complex of silver, copper and zinc is dispersed in a non-aqueous solvent with a thermosetting resin and curing the mixture. To get In addition, the antibacterial composition is mixed with a paint resin, and this is applied to an object to be coated to form a coating film having antibacterial properties. Furthermore,
An aqueous solution of the above-mentioned thiosulfato complex is mixed with an aqueous paint, and this is applied to an object to be coated to form a coating film having antibacterial properties.
Description
【０００１】[0001]
【産業上の利用分野】本発明は、溶液状の抗菌性組成物
および同組成物を用いて抗菌性の付与された抗菌性材料
を製造する方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solution-shaped antibacterial composition and a method for producing an antibacterial material having antibacterial properties using the composition.
【０００２】[0002]
【従来の技術】近年、合成樹脂製品が多用されるにいた
り、例えば、台所用品等のように衛生面で注意を払う必
要がある分野に用いられる場合に、合成樹脂表面の菌に
よる汚染が問題となってきている。また、建築用資材と
して使用されているコーキング材表面に菌や黴がはえ、
衛生面であるいは外観が悪くなる等の問題が生じてい
る。その対策として、合成樹脂中に抗菌性組成物を混入
し、合成樹脂表面にこの組成物を溶出させて樹脂表面の
殺菌を行う方法が用いられている。また、合成樹脂中の
抗菌・抗黴性組成物を積極的に溶出させ、この樹脂表面
およびその周囲に対して抗菌・抗黴効果を得るために
は、チアベンダゾール等の有機抗菌抗黴性組成物が用い
られる。2. Description of the Related Art In recent years, when synthetic resin products are frequently used, and when they are used in fields in which hygiene is required, such as kitchen appliances, contamination of the surface of the synthetic resin by bacteria is a problem. Is becoming. In addition, fungi and mold flies on the surface of caulking materials used as building materials,
There are problems such as hygiene and poor appearance. As a countermeasure, there is used a method in which an antibacterial composition is mixed into a synthetic resin and the composition is eluted on the surface of the synthetic resin to sterilize the resin surface. Further, in order to positively elute the antibacterial / antifungal composition in the synthetic resin and obtain an antibacterial / antifungal effect on the resin surface and its surroundings, an organic antibacterial / antifungal composition such as thiabendazole is used. Is used.
【０００３】また、抗菌性組成物もその表面の永久的か
つ完全な殺菌性を保証するものでないため、定期的な表
面殺菌を行う方が、より清潔性を維持できる。この場合
の表面殺菌として、従来より一般的に次亜塩素酸ナトリ
ウム等の塩素系漂白剤がよく用いられる。さらに、植物
抽出物の中には、テルペン系化合物が抗菌効果を有する
ことが知られている。この種の化合物を用いた技術とし
て、白せん菌の治療剤作成（特開昭６３−３０４２４号
公報）、植物からフィトンチッドを取り出して冷蔵庫に
取り付けた、防臭防黴ユニット付冷蔵庫（特開昭６１−
２２８２８３公報）、空気清浄器（特開昭６１−２６８
９３４公報）が開示されている。Further, since the antibacterial composition does not guarantee the permanent and complete bactericidal property of the surface, periodical surface sterilization can maintain more cleanliness. As the surface sterilization in this case, a chlorine-based bleaching agent such as sodium hypochlorite has generally been used conventionally. Furthermore, among plant extracts, terpene compounds are known to have antibacterial effects. As a technique using this kind of compound, a therapeutic agent for Trichophyton is prepared (Japanese Patent Laid-Open No. 63-30424), and a phytoncide is taken out from a plant and attached to a refrigerator. −
228283), an air purifier (Japanese Patent Laid-Open No. 61-268).
934).
【０００４】[0004]
【発明が解決しようとする課題】しかし、有機抗菌抗黴
材料は揮発性を有するため、これを合成樹脂に含有させ
ると、この合成樹脂の周囲環境が汚染され、またこの合
成樹脂の表面と接触した排液中には、抗菌抗黴材料が含
有されており、これが排水環境汚染の原因となり、さら
に、下水処理中の活性汚泥に影響を及ぼすなどの問題が
ある。また、銀イオン（Ａｇ+）を用いた銀系抗菌剤
は、台所で常用する漂白剤を用いると、銀イオンが塩素
系漂白剤中の塩素イオンと反応し不溶性の塩化銀を生成
する。さらに、この塩化銀は光反応活性が高いためすぐ
に金属銀、酸化銀に変化することにより、黒変するのみ
ならず、抗菌性能を低下させるという問題点があった。
また、樹脂中に混練した場合、銀塩安定化のため用いる
担持体の屈折率が混練樹脂のそれと異なるため、樹脂を
不透明にさせたり、担持体の吸湿性により成形樹脂表面
の平滑性を損なうなどの問題点もあった。さらに、植物
抽出物の場合、植物内に存在する物質の多くは芳香性物
質であり、揮発性を有するため、これら物質を樹脂に混
入しようとしても、樹脂の成形時の加熱により蒸発する
ため、混入することができないという問題がある。However, since the organic antibacterial and antifungal material has volatility, if it is contained in the synthetic resin, the surrounding environment of the synthetic resin is polluted and the surface of the synthetic resin is contacted. The effluent contains antibacterial and antifungal materials, which causes pollution of wastewater environment, and has a problem that it affects activated sludge during sewage treatment. As for a silver-based antibacterial agent using silver ions (Ag + ), when a bleaching agent commonly used in the kitchen is used, the silver ions react with chlorine ions in the chlorine-based bleaching agent to produce insoluble silver chloride. Further, since this silver chloride has a high photoreactive activity, there is a problem that it immediately changes to metallic silver or silver oxide, so that it not only turns black, but also reduces the antibacterial performance.
Further, when kneaded in a resin, the refractive index of the carrier used for stabilizing the silver salt is different from that of the kneaded resin, so that the resin becomes opaque and the hygroscopicity of the carrier impairs the smoothness of the molding resin surface. There were also problems such as. Furthermore, in the case of a plant extract, most of the substances present in the plant are aromatic substances and have volatility, so even if you try to mix these substances into the resin, they will evaporate due to the heating during molding of the resin. There is a problem that it cannot be mixed.
【０００５】[0005]
【課題を解決するための手段】本発明の抗菌性組成物
は、銀、銅、および亜鉛よりなる群から選択される少な
くとも一種の金属のチオスルファト錯体の水溶液からな
るものである。ここに用いるチオスルファト金属錯体
は、銀錯体で説明すると、酢酸銀、硫酸銀および硝酸銀
の少なくとも一種の可溶性銀塩を純水に溶解し、その溶
液に亜硫酸カリウムとチオ硫酸カリウムチオまたは硫酸
ナトリウムと亜硫酸ナトリウムを順次添加して溶解する
ことにより調製することができる。また、チオ硫酸ナト
リウムまたはチオ硫酸カリウムの飽和溶液に少なくとも
一種の可溶性銀塩を溶解する方法、亜硫酸ナトリウムま
たは亜硫酸カリウムの飽和溶液に少なくとも一種の可溶
性銀塩を溶解した後、チオ硫酸ナトリウムまたはチオ硫
酸カリウムを溶解する方法によって調製することができ
る。The antibacterial composition of the present invention comprises an aqueous solution of a thiosulfato complex of at least one metal selected from the group consisting of silver, copper and zinc. The thiosulfato metal complex used here is described as a silver complex. At least one soluble silver salt of silver acetate, silver sulfate and silver nitrate is dissolved in pure water, and potassium sulfite and potassium thiosulfate thio or sodium sulfate and sulfite are added to the solution. It can be prepared by sequentially adding and dissolving sodium. A method of dissolving at least one soluble silver salt in a saturated solution of sodium thiosulfate or potassium thiosulfate, a method of dissolving at least one soluble silver salt in a saturated solution of sodium sulfite or potassium sulfite, and then dissolving sodium thiosulfate or thiosulfate It can be prepared by a method of dissolving potassium.
【０００６】銀イオン、亜硫酸イオンおよびチオ硫酸イ
オンを構成成分とするチオスルファト銀錯体の水溶液に
おいては、亜硫酸イオンおよびチオ硫酸イオンの銀イオ
ンに対するモル比がそれぞれ１〜６および１〜１８であ
ることが好ましい。また、さらに、チオスルファト亜鉛
錯体を含むことが好ましい。このチオスルファト亜鉛錯
体を形成するための亜鉛塩としては、酢酸亜鉛、硫酸亜
鉛および硝酸亜鉛の少なくとも一種の可溶性亜鉛塩が好
ましい。さらに、上記のチオスルファト金属錯体の水溶
液をｐＨ６〜８に保つのが好ましい。ｐＨ調整には、上
記溶液に酢酸、クエン酸、酒石酸などのカルボン酸、あ
るいはほう酸、燐酸などの無機物弱酸を添加する。In an aqueous solution of a thiosulfato silver complex containing silver ion, sulfite ion and thiosulfate ion as constituents, the molar ratio of sulfite ion and thiosulfate ion to silver ion is 1 to 6 and 1 to 18, respectively. preferable. Further, it is preferable that a thiosulfatozinc complex is further included. As the zinc salt for forming the thiosulfato zinc complex, at least one soluble zinc salt of zinc acetate, zinc sulfate and zinc nitrate is preferable. Furthermore, it is preferable to keep the aqueous solution of the thiosulfato metal complex at pH 6 to 8. To adjust the pH, a carboxylic acid such as acetic acid, citric acid or tartaric acid, or a weak inorganic acid such as boric acid or phosphoric acid is added to the above solution.
【０００７】また、本発明は、銀、銅、および亜鉛より
なる群から選択される少なくとも一種の金属のチオスル
ファト錯体の水溶液を非水溶媒に分散させたエマルショ
ンからなる抗菌性組成物を提供する。The present invention also provides an antibacterial composition comprising an emulsion in which an aqueous solution of a thiosulfato complex of at least one metal selected from the group consisting of silver, copper and zinc is dispersed in a non-aqueous solvent.
【０００８】さらに、本発明は、上記の抗菌性組成物を
用いて各種の抗菌性材料を製造する方法を提供する。す
なわち、上記の水溶液を用いる場合は、これを水性塗料
中に混合し、この塗料を被塗装物に塗装して抗菌性の付
与された塗装皮膜を形成する。また、上記の水溶液を抄
紙工程で添加することにより、抗菌性の付与された紙を
製造する。さらに、上記の水溶液を抄紙後の乾燥工程あ
るいは塗工工程、さらには完成後に、紙に添着して抗菌
性の付与された紙を製造する。Further, the present invention provides a method for producing various antibacterial materials using the above antibacterial composition. That is, when the above-mentioned aqueous solution is used, this is mixed with an aqueous paint, and this paint is applied to an object to be coated to form a coating film having antibacterial properties. Further, by adding the above-mentioned aqueous solution in the papermaking process, paper with antibacterial properties is produced. Further, the above-mentioned aqueous solution is applied to the paper after the paper making process for drying or coating, and after completion, to produce a paper having antibacterial properties.
【０００９】また、上記のエマルションからなる抗菌性
組成物を用いる場合は、この抗菌性組成物を熱硬化牲樹
脂に混合し、硬化させて抗菌性の付与された樹脂成形体
を製造する。さらに、この抗菌性組成物を塗料樹脂中に
混合し、これを被塗装物に塗装して抗菌性の付与された
塗装皮膜を形成する。ここにおいて、上記のエマルショ
ンの分散媒である非水溶媒は、前記熱硬化性樹脂、塗料
樹脂またはそれらの溶媒と相溶するものであることを要
する。なお、上記塗装皮膜と金属基地面の間に、含水率
の低い樹脂塗膜を設けることが好ましい。When the antibacterial composition comprising the above emulsion is used, the antibacterial composition is mixed with a thermosetting resin and cured to produce a resin molded article having antibacterial properties. Further, this antibacterial composition is mixed with a coating resin, and this is applied to an object to be coated to form a coating film having antibacterial properties. Here, the non-aqueous solvent that is the dispersion medium of the emulsion needs to be compatible with the thermosetting resin, the coating resin, or the solvent thereof. A resin coating film having a low water content is preferably provided between the coating film and the surface of the metal matrix.
【００１０】[0010]
【作用】本発明で抗菌性組成物として用いるチオスルフ
ァト金属錯体の水溶液は、その錯体の安定性が高いため
担持体を必要とせず、従って樹脂中に混練した場合、樹
脂の透明性、樹脂表面の平滑性などの樹脂固有の特性を
そのまま維持させることができる。特に、可溶性銀塩の
水溶液に、亜硫酸塩を添加して亜硫酸錯体を形成させた
後、さらにチオ硫酸塩を加えて形成したチオスルファト
銀錯体は、安定性が向上している。この際、亜硫酸塩お
よびチオ硫酸塩と銀の比率を制御することでさらに安定
性を向上させることができる。具体的には、原料中のチ
オ硫酸イオンと銀イオンのモル比（Ｓ2Ｏ3 2-）／（Ａｇ
+）を１から１８、亜硫酸イオンと銀イオンのモル比
（ＳＯ3 2-）／（Ａｇ+）を１から６にすることにより、
生成する抗菌性組成物の安定性、とりわけ耐光・耐熱変
色性を向上させることができる。また、ｐＨを６〜８に
制御することで一層の安定性を向上させることができ
る。The aqueous solution of the thiosulfato metal complex used as the antibacterial composition in the present invention does not require a carrier because the complex is highly stable. Therefore, when it is kneaded in the resin, the transparency of the resin and the resin surface The characteristics peculiar to the resin such as smoothness can be maintained as they are. In particular, a thiosulfato silver complex formed by adding a sulfite salt to an aqueous solution of a soluble silver salt to form a sulfite complex and then adding a thiosulfate salt has improved stability. At this time, the stability can be further improved by controlling the ratio of silver with the sulfite or thiosulfate. Specifically, the molar ratio of thiosulfate ion to silver ion in the raw material (S 2 O 3 2− ) / (Ag
+ ) From 1 to 18 and the molar ratio (SO 3 2 − ) / (Ag + ) of sulfite ion to silver ion from 1 to 6,
It is possible to improve the stability of the resulting antibacterial composition, especially the light resistance and heat discoloration resistance. Further, the stability can be further improved by controlling the pH to 6-8.
【００１１】本発明の抗菌性組成物は、担体を使用する
ことが困難な材料や、紙のように繊維に直接添着できる
材料にも、適用が可能である。さらに、本発明の抗菌性
組成物は、溶液状であることから、液体状の樹脂や塗料
中に容易に分散させて抗菌性を付与することができる。
また、銀を錯体化して安定化させているため、安定した
抗菌作用が得られる。さらに、環境中に溶出しても環境
汚染の原因となりにくい。また、塩素濃度の高い雰囲気
中で使用しても変色抗菌性能の低下がみられにくい。The antibacterial composition of the present invention can be applied to a material for which a carrier is difficult to use or a material such as paper which can be directly attached to a fiber. Furthermore, since the antibacterial composition of the present invention is in the form of a solution, it can be easily dispersed in a liquid resin or paint to impart antibacterial properties.
Further, since silver is complexed and stabilized, a stable antibacterial action can be obtained. Further, even if it is eluted into the environment, it is unlikely to cause environmental pollution. Further, even when used in an atmosphere with a high chlorine concentration, discoloration antibacterial performance is unlikely to deteriorate.
【００１２】また、原料中の酢酸銀の代わりに硫酸銀を
用いることにより、生成溶液状抗菌性組成物中の酢酸残
留をなくし、溶液状抗菌性組成物の酢酸臭および溶液状
抗菌性組成物の加熱加工時の酢酸臭を除去できる。金属
基地面に銀を含む抗菌性塗装膜を設けた場合、金属表面
と塗装膜が接し、その部分に水が介在すると局部電池を
形成し、金属のイオン化傾向が銀よりも高い場合、腐食
現象を引き起こす。ただし、金属がアルミニウムの場合
は、表面にアルミナ層を形成し、腐食を起こしにくい。
そこで、金属表面に水を含みにくい樹脂を用いた絶縁層
を設けることで、銀を含む塗装膜を形成しても腐食を起
こしにくくなる。Further, by using silver sulfate in place of silver acetate in the raw material, residual acetic acid in the produced solution type antibacterial composition is eliminated, and the acetic acid odor of the solution type antibacterial composition and the solution type antibacterial composition are eliminated. The acetic acid odor during heat processing can be removed. When an antibacterial coating film containing silver is provided on the metal base surface, the metal surface contacts the coating film, and if water intervenes in that part, a local battery is formed.If the metal ionization tendency is higher than silver, the corrosion phenomenon occurs. cause. However, when the metal is aluminum, an alumina layer is formed on the surface and corrosion is unlikely to occur.
Therefore, by providing an insulating layer made of a resin that does not easily contain water on the metal surface, corrosion is less likely to occur even when a coating film containing silver is formed.
【００１３】[0013]
［実施例１］まず、酢酸銀の水溶液を調製した。酢酸銀
（ＣＨ3ＣＯＯＡｇ）は溶解度が小さいので、飽和溶解
度に近い７．７ｇ／ｌを６０℃以下の温度で溶解した。
この溶解工程において、６０℃を越える温度では酢酸銀
が分解するので、６０℃以下室温以上の温度範囲が好ま
しい。次に、亜硫酸ナトリウム（Ｎａ2ＳＯ3）を酢酸銀
１モルにたいして３モルの割合で添加し、充分溶解させ
た後、チオ硫酸ナトリウム（Ｎａ2Ｓ2Ｏ3）を酢酸銀１
モルに対して１２モルの割合で添加し溶解させた。この
時の溶解工程は４０℃〜室温の温度範囲が好ましい。Example 1 First, an aqueous solution of silver acetate was prepared. Since silver acetate (CH 3 COOAg) has a low solubility, 7.7 g / l, which is close to the saturated solubility, was dissolved at a temperature of 60 ° C. or lower.
In this melting step, silver acetate is decomposed at a temperature higher than 60 ° C., so a temperature range of 60 ° C. or lower and room temperature or higher is preferable. Next, sodium sulfite (Na 2 SO 3 ) was added at a ratio of 3 mol with respect to 1 mol of silver acetate and sufficiently dissolved, and then sodium thiosulfate (Na 2 S 2 O 3 ) was added to 1 mol of silver acetate.
It was added and dissolved in a ratio of 12 mol with respect to mol. The melting step at this time is preferably in the temperature range of 40 ° C. to room temperature.
【００１４】このようにして調製されたチオスファト銀
錯体の水溶液に、酢酸亜鉛を亜鉛／銀比率が２になるよ
うに添加し、溶解させた。これに酢酸を加えてｐＨを
７．０に調製した。こうして溶液状抗菌性組成物を得
た。表１は、上記と同様にして酢酸銀に対する亜硫酸塩
およびチオ硫酸塩のモル比を変えて各種の抗菌性組成物
を調製し、その抗菌性や安定性などのついて評価した結
果を示す。Zinc acetate was added to and dissolved in the aqueous solution of the thiosphato silver complex thus prepared so that the zinc / silver ratio was 2. Acetic acid was added to this to adjust the pH to 7.0. Thus, a solution type antibacterial composition was obtained. Table 1 shows the results of evaluation of antibacterial properties and stability of various antibacterial compositions prepared by changing the molar ratio of sulfite and thiosulfate to silver acetate in the same manner as described above.
【００１５】[0015]
【表１】 [Table 1]
【００１６】なお、評価基準は以下のとおりである。 黒変：溶液調製中あるいは調製後に、溶液に色調変化が
ある。 ▲ ：やや溶液に色調変化がある。 △ ：実用上差し支えのない抗菌性がある。 ○ ：抗菌性、色調とも良好。 ◎ ：抗菌性、色調ともに良好、とりわけ耐光性極めて
良好。 粘凋：乾燥後、その表面に粘凋性あるいは若干の吸湿性
がある。The evaluation criteria are as follows. Blackening: There is a change in color tone of the solution during or after preparation. ▲: There is a slight change in color tone of the solution. Δ: It has antibacterial properties that are practically acceptable. ○: Good antibacterial property and color tone. ⊚: Both antibacterial property and color tone are excellent, and especially light resistance is extremely good. Stickiness: After drying, the surface has stickiness or some hygroscopicity.
【００１７】本実施例では、ｐＨ調節のために酢酸を用
いたが、クエン酸、酒石酸などのカルボン酸、あるいは
ほう酸、燐酸などの無機弱酸を添加しても溶液の安定性
は若干低下するが実用上差し支えがない。また、実施例
では酢酸銀を銀原料として用いたが、その代わりに硫酸
銀を用いても同様の抗菌性能が得られた。硫酸銀を用い
ることにより、生成する溶液状抗菌性組成物中の酢酸残
留をなくし、酢酸臭およびこれを樹脂と混練する際の酢
酸臭を除去することができる。さらに、銀錯体のカチオ
ンとしてナトリウムを用いたが、カリウムを用いても実
用上差し支えのない耐熱性が得られる。In this embodiment, acetic acid was used for adjusting the pH, but the stability of the solution is slightly lowered even if a carboxylic acid such as citric acid or tartaric acid or an inorganic weak acid such as boric acid or phosphoric acid is added. There is no practical problem. Further, although silver acetate was used as a silver raw material in the examples, similar antibacterial performance was obtained by using silver sulfate instead. By using silver sulfate, the acetic acid odor and the acetic acid odor when kneading the acetic acid and the resin can be eliminated by eliminating the residual acetic acid in the resulting solution antibacterial composition. Furthermore, although sodium was used as the cation of the silver complex, even if potassium is used, heat resistance that is practically acceptable will be obtained.
【００１８】［実施例２］実施例１の溶液状抗菌性組成
物１００重量部を界面活性剤のラウリン酸カリウム１重
量部とともに、非水溶媒のキシレン１００重量部中に分
散・乳化させ、非水溶媒に抗菌性材料を分散させたエマ
ルション抗菌性組成物を得た。[Example 2] 100 parts by weight of the solution type antibacterial composition of Example 1 was dispersed and emulsified in 100 parts by weight of xylene which is a non-aqueous solvent together with 1 part by weight of potassium laurate as a surfactant. An emulsion antibacterial composition having an antibacterial material dispersed in a water solvent was obtained.
【００１９】［実施例３］実施例２のエマルション抗菌
性組成物を、その銀換算重量にして１.５重量部相当を
不飽和ポリエステル樹脂１００重量部に添加し、均一に
分散させ、さらに硬化剤、着色剤、骨材などと共に成形
型に注型し、１２０℃で１時間加熱して硬化させ、抗菌
性を付与した樹脂成形体を得た。 ［実施例４］実施例２のエマルション抗菌性組成物を、
その銀換算重量にして１.５重量部相当をウレタン樹脂
塗料１００重量部に配合し、均一に分散させた。この塗
料を溶媒で希釈し、下塗り層を設けた金属表面に約２０
μｍの塗膜厚みにスプレー塗装した。Example 3 The emulsion antibacterial composition of Example 2 was added to 100 parts by weight of unsaturated polyester resin in an amount equivalent to 1.5 parts by weight in terms of silver, and uniformly dispersed and further cured. The mixture was cast into a mold together with the agent, colorant, aggregate, etc., and heated at 120 ° C. for 1 hour to be cured to obtain an antibacterial resin molded body. [Example 4] The emulsion antibacterial composition of Example 2 was
The equivalent of 1.5 parts by weight in terms of silver was mixed with 100 parts by weight of the urethane resin coating material and uniformly dispersed. This paint is diluted with a solvent, and about 20 is applied to the metal surface provided with the undercoat layer.
It was spray coated to a coating thickness of μm.
【００２０】［実施例５］実施例１の溶液状抗菌性組成
物を水分散アクリル−スチロールエマルジョン樹脂塗料
に加えて均一に分散させた。溶液状抗菌性組成物の添加
割合は、樹脂分１００重量部に対して銀換算重量にして
１.５重量部相当である。この分散液を木質生地表面に
約３０μｍの塗膜厚みで刷毛塗り塗装した。 ［実施例６］製紙工程は、パルプ化工程、調成工程、抄
造工程、加工工程および仕上げ工程からなる。この抄造
工程に用いるパルプの中にサイズ剤などと共に実施例１
の溶液状抗菌性組成物を繊維分換算１００重量部に対
し、銀換算重量にして１.５重量部の割合となるよう配
合し、均一に分散させ、丸網抄紙装置で抄紙し、抗菌性
の付与された紙を得た。なお、抄紙装置には、防錆処理
が施されている。Example 5 The solution type antibacterial composition of Example 1 was added to a water-dispersed acrylic-styrene emulsion resin coating material and uniformly dispersed. The addition ratio of the solution type antibacterial composition is equivalent to 1.5 parts by weight in terms of silver weight with respect to 100 parts by weight of the resin content. This dispersion was brush-painted on the surface of the wooden material with a coating thickness of about 30 μm. [Example 6] The papermaking process includes a pulping process, a preparation process, a papermaking process, a processing process, and a finishing process. Example 1 together with a sizing agent in the pulp used in this papermaking process
The solution-type antibacterial composition was blended in an amount of 1.5 parts by weight in terms of silver with respect to 100 parts by weight of fiber content, uniformly dispersed, and paper-made with a net paper machine to obtain antibacterial properties. To obtain a paper. It should be noted that the paper machine is rustproofed.
【００２１】［実施例７］製紙工程の最終工程で紙に塗
料を塗布する。この塗料中に、カオリンなどの顔料と共
に実施例１の溶液状抗菌性組成物を添加し、抗菌性の付
与された紙を製造した。 ［比較例１］溶液状抗菌性組成物を用いない他は実施例
３と同様にして、不飽和ポリエステル樹脂を硬化し、成
形体を得た。[Embodiment 7] A coating material is applied to paper in the final step of the paper manufacturing process. The solution type antibacterial composition of Example 1 was added to this paint together with a pigment such as kaolin to prepare an antibacterial paper. Comparative Example 1 An unsaturated polyester resin was cured in the same manner as in Example 3 except that the solution type antibacterial composition was not used to obtain a molded product.
【００２２】以上実施例３〜７および比較例１の樹脂成
形体などの各サンプルについて、以下に示す抗黴試験、
抗菌試験を行った。その結果を表２に示す。表２より、
実施例３〜７のサンプルは、いずれも実用的な抗菌・抗
黴性能を有することがわかる。For each of the samples such as the resin moldings of Examples 3 to 7 and Comparative Example 1, the following antifungal test,
An antibacterial test was conducted. The results are shown in Table 2. From Table 2,
It is understood that the samples of Examples 3 to 7 all have practical antibacterial and antifungal properties.
【００２３】抗黴試験：日本工業規格のカビ抵抗牲試験
（ＪＩＳ Ｚ ２９１１）の繊維製品用防黴試験による
ハローテスト法に準じ、１４日後に評価した。用いた黴
は、クラドスポリウム クラドスポリオイデス（Clados
porium cladosporioides)、ケトミウム グロボサム（C
haetomium globosum）、ペニシリウム シトリナム（Pe
nicillium citrinum）、およびアスペリギルス ニゲル
（Asperigillus niger）の４種である。 抗菌試験：エスケリチア コ−ライ（Escherichia col
i）、スタフィロコックス アウレウス（Staphylococcu
s aureus）、およびバチルス サブチリス（Bacillus s
ubtillis）の各菌約１０4ｃｆｕ／ｍｌを懸濁させた液
滴０．２ｍｌをサンプルの表面に滴下し、温度３７℃、
湿度９０％以上の環境で２４時間放置後、生存菌数を計
測し、１０2以上の菌数減少が見られた場合効果ありと
した。Anti-mildew test: Evaluation was carried out 14 days later in accordance with the halo test method based on the mildew resistance test for textile products of the Japanese Industrial Standards (JIS Z 2911). The mold used was Cladosporium Clados
porium cladosporioides), ketodium globosum (C
haetomium globosum), Penicillium citrinum (Pe
nicillium citrinum) and Asperigillus niger. Antibacterial test: Escherichia col
i), Staphylococcu aureus
aureus), and Bacillus subtilis (Bacillus s)
ubtillis), each of which is a suspension of about 10 4 cfu / ml of bacteria, 0.2 ml of droplets is dropped on the surface of the sample, and the temperature is 37 ° C.
After being left for 24 hours in an environment with a humidity of 90% or more, the number of surviving bacteria was measured, and when a decrease in the number of bacteria of 10 2 or more was observed, it was judged to be effective.
【００２４】[0024]
【表２】 [Table 2]
【００２５】［実施例８］実施例１の処方と異なる溶液
状抗菌性組成物の製法について説明する。まず、酢酸銀
を４０〜５０℃において７．７ｇ／ｌの割合で純水に溶
解し、次いで、この溶液に酢酸銀１モルに対して３モル
の亜硫酸ナトリウム、次に３モルのチオ硫酸ナトリウム
をそれぞれ添加して溶解させた。このように調製された
溶液状抗菌性組成物について、実施例１と同様の使用用
途を試みた結果、同様あるいはそれ以上の効果が得られ
た。[Example 8] A method for producing a solution type antibacterial composition different from the formulation of Example 1 will be described. First, silver acetate was dissolved in pure water at a rate of 7.7 g / l at 40 to 50 ° C., and then 3 mol of sodium sulfite and then 3 mol of sodium thiosulfate were added to the solution. Were added and dissolved. The solution type antibacterial composition thus prepared was tested for its intended use in the same manner as in Example 1, and as a result, the same or higher effect was obtained.
【００２６】[0026]
【発明の効果】以上のように本発明の溶液状抗菌性組成
物は、組成物そのものの安定性が高いため担持体を必要
とせず、樹脂中に混練した場合、担持体に起因する弊害
を生じることなく、すなわち樹脂の透明性、樹脂表面の
平滑性をそのまま維持することができる。また、従来の
抗菌剤のように担持体の粒度にとらわれることなく、各
種材料に容易に抗菌性を付与することができる。As described above, the solution-type antibacterial composition of the present invention does not require a carrier because the composition itself has high stability, and when kneaded in a resin, the harmful effect caused by the carrier is eliminated. It does not occur, that is, the transparency of the resin and the smoothness of the resin surface can be maintained as they are. Further, unlike the conventional antibacterial agents, the antibacterial property can be easily imparted to various materials regardless of the particle size of the carrier.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０８Ｋ 5/56 ＫＣＦ Ｃ０８Ｋ 5/56 ＫＣＦ Ｃ０８Ｌ 101/00 Ｃ０８Ｌ 101/00 Ｄ２１Ｈ 19/00 Ｄ２１Ｈ 1/10 21/14 ７０４ 19/10 1/34 Ａ 21/36 5/22 Ｄ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI Technical display location C08K 5/56 KCF C08K 5/56 KCF C08L 101/00 C08L 101/00 D21H 19/00 D21H 1 / 10 21/14 704 19/10 1/34 A 21/36 5/22 D
Claims (10)
される少なくとも一種の金属のチオスルファト錯体の水
溶液からなる抗菌性組成物。1. An antibacterial composition comprising an aqueous solution of a thiosulfato complex of at least one metal selected from the group consisting of silver, copper and zinc.
イオンを構成成分とするチオスルファト銀錯体の水溶液
からなり、前記亜硫酸イオンおよびチオ硫酸イオンの銀
イオンに対するモル比がそれぞれ１〜６および１〜１８
である抗菌性組成物。2. An aqueous solution of a thiosulfato silver complex having silver ions, sulfite ions and thiosulfate ions as constituent components, wherein the molar ratios of the sulfite ions and thiosulfate ions to the silver ions are 1 to 6 and 1 to 18, respectively.
An antibacterial composition which is
求項２記載の抗菌性組成物。3. The antibacterial composition according to claim 2, further comprising a thiosulfatozinc complex.
される少なくとも一種の金属のチオスルファト錯体の水
溶液を非水溶媒に分散させたエマルションからなる抗菌
性組成物。4. An antibacterial composition comprising an emulsion in which an aqueous solution of a thiosulfato complex of at least one metal selected from the group consisting of silver, copper and zinc is dispersed in a non-aqueous solvent.
樹脂に混合し、硬化させて抗菌性の付与された樹脂成形
体を得る抗菌性材料の製造方法。5. A method for producing an antibacterial material, which comprises mixing the antibacterial composition according to claim 4 with a thermosetting resin and curing the resin to obtain a resin molded article having antibacterial properties.
中に混合し、これを被塗装物に塗装して抗菌性の付与さ
れた塗装皮膜を形成する抗菌性材料の製造方法。6. A method for producing an antibacterial material, which comprises mixing the antibacterial composition according to claim 4 in a coating resin and coating the same on an object to be coated to form a coating film having antibacterial properties.
中に混合し、これを被塗装物に塗装して抗菌性の付与さ
れた塗装皮膜を形成する抗菌性材料の製造方法。7. A method for producing an antibacterial material, which comprises mixing the antibacterial composition according to claim 1 in an aqueous paint and coating the same on an object to be coated to form a coating film having antibacterial properties.
け、この樹脂塗膜上に前記塗装皮膜を形成する請求項６
または７記載の抗菌性材料の製造方法。8. A resin coating film having a low water content is provided on a metal matrix surface, and the coating film is formed on the resin coating film.
Alternatively, the method for producing the antibacterial material according to item 7.
で添加することにより、抗菌性を付与された紙を得る抗
菌性材料の製造方法。9. A method for producing an antibacterial material, which comprises adding the antibacterial composition according to claim 1 in a papermaking process to obtain paper having antibacterial properties.
の紙に添着して抗菌性の付与された紙を得る抗菌性材料
の製造方法。10. A method for producing an antibacterial material, which comprises attaching the antibacterial composition according to claim 1 to a paper after papermaking to obtain paper having antibacterial properties.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13820995A JP3682932B2 (en) | 1995-06-05 | 1995-06-05 | Method for producing antibacterial material |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13820995A JP3682932B2 (en) | 1995-06-05 | 1995-06-05 | Method for producing antibacterial material |
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| Publication Number | Publication Date |
|---|---|
| JPH08333209A true JPH08333209A (en) | 1996-12-17 |
| JP3682932B2 JP3682932B2 (en) | 2005-08-17 |
Family
ID=15216639
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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| JP2003529630A (en) * | 1999-12-15 | 2003-10-07 | スィー．アール． バード インコーポレイテッド | Polymer composition containing silver salt colloid |
| GB2449893A (en) * | 2007-06-07 | 2008-12-10 | Aguacure Ltd | Antimicrobial composition |
| JP2019081988A (en) * | 2017-10-31 | 2019-05-30 | 日本製紙株式会社 | Functional material and use thereof |
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Also Published As
| Publication number | Publication date |
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| JP3682932B2 (en) | 2005-08-17 |
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