JPH08325112A - Antibacterial composition and production of antibacterial resin composition - Google Patents
Antibacterial composition and production of antibacterial resin compositionInfo
- Publication number
- JPH08325112A JPH08325112A JP7137027A JP13702795A JPH08325112A JP H08325112 A JPH08325112 A JP H08325112A JP 7137027 A JP7137027 A JP 7137027A JP 13702795 A JP13702795 A JP 13702795A JP H08325112 A JPH08325112 A JP H08325112A
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- Prior art keywords
- resin
- antibacterial
- composition
- weight
- emulsion
- Prior art date
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、抗菌性組成物、および
抗菌性樹脂組成物の製造方法に関する。FIELD OF THE INVENTION The present invention relates to an antibacterial composition and a method for producing an antibacterial resin 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材料を混入し、
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
抗黴材料を積極的に溶出させ、この樹脂表面およびその
周囲に対して殺菌殺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材料が用いられる。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, mix antibacterial material into synthetic resin,
A method of sterilizing the resin surface by eluting this composition on the surface of the synthetic resin is used. Further, an organic antibacterial / antifungal material such as thiabendazole is used in order to positively elute the antibacterial / antifungal material in the synthetic resin and obtain a bactericidal and fungicidal effect on the surface of the resin and its surroundings.
【０００３】また、抗菌性材料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６１−２
２８２８３公報）、空気清浄器（特開昭６１−２６８９
３４公報）が開示されている。Further, since the antibacterial material does not guarantee the permanent and complete sterilization 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. Techniques using this compound include preparation of a therapeutic agent for Trichophyton (JP-A-63-30424), a refrigerator with an odor-preventing and anti-mold unit in which phytoncide is taken out from a plant and attached to a refrigerator (JP-A-61-2).
28283), an air purifier (Japanese Patent Laid-Open No. 61-2689).
34 publication).
【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、そ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、植物抽出物は、その多くは芳香性物質で揮発性を有
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 a synthetic resin, the surrounding environment is contaminated and the organic resin is contacted with the surface of the synthetic resin. The liquid contains an antibacterial and antifungal material, which causes pollution of wastewater environment and further has a problem that it affects activated sludge during sewage treatment. In addition, since most plant extracts are aromatic substances and have volatility, even if an attempt is made to mix these substances into a resin, they will not evaporate due to evaporation due to heating during resin molding.
【０００５】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
し、さらに塩化銀の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、抗菌性
材料を樹脂に混練する場合、樹脂中に均一に分散する混
練技術が必要で、そのために分散助剤、混練温度条件の
検討と共に、混練工数が必要となり、抗菌処理のための
コストアップにつながっていた。A silver-based antibacterial agent using silver ions (Ag + ) produces an insoluble silver chloride by reacting silver ions with chlorine ions in the chlorine-based bleaching agent when a bleaching agent commonly used in the kitchen is used. Furthermore, since 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, when an antibacterial material is kneaded with a resin, a kneading technique to uniformly disperse the resin in the resin is required. Therefore, it is necessary to examine the dispersion aid and the kneading temperature condition, as well as the kneading man-hour, and the cost for antibacterial treatment It was up.
【０００６】本発明は、安定した抗菌効果を示す樹脂成
形体を与える抗菌性組成物を提供することを目的とす
る。また、本発明は、汎用の樹脂と容易に混練すること
ができる抗菌性樹脂組成物を提供することを目的とす
る。An object of the present invention is to provide an antibacterial composition which gives a resin molded product having a stable antibacterial effect. Another object of the present invention is to provide an antibacterial resin composition that can be easily kneaded with a general-purpose resin.
【０００７】[0007]
【課題を解決するための手段】本発明の抗菌性組成物
は、銀、亜鉛および銅よりなる群から選ばれる少なくと
も一種の金属のチオスルファト錯体の水溶液に、無機酸
化物のコロイド粒子および樹脂エマルジョンを分散させ
てなるものである。また、本発明の抗菌性組成物は、
銀、亜鉛および銅よりなる群から選ばれた少なくとも一
種の金属のチオスルファト錯体を前記金属換算量で０．
１〜１０重量部含む水溶液１００重量部、固形分０．１
〜５０重量部相当の無機酸化物のコロイド溶液、および
樹脂分０．５〜５０重量部相当の樹脂エマルジョンから
なる。ここで、前記コロイド粒子としては、二酸化珪
素、ベーマイト、アルミナ、および酸化チタンよりなる
群から選ばれるものが好ましい。The antibacterial composition of the present invention comprises colloidal particles of an inorganic oxide and a resin emulsion in an aqueous solution of a thiosulfato complex of at least one metal selected from the group consisting of silver, zinc and copper. It is dispersed. Further, the antibacterial composition of the present invention,
A thiosulfato complex of at least one metal selected from the group consisting of silver, zinc and copper is added in an amount of 0.
100 parts by weight of aqueous solution containing 1 to 10 parts by weight, solid content 0.1
.About.50 parts by weight of an inorganic oxide colloidal solution and a resin content of 0.5 to 50 parts by weight of a resin emulsion. Here, the colloidal particles are preferably selected from the group consisting of silicon dioxide, boehmite, alumina, and titanium oxide.
【０００８】本発明の抗菌性樹脂組成物の製造方法は、
上記の抗菌性組成物を前記エマルジョン樹脂と相溶性の
ある樹脂ペレットと混合し、乾燥するものである。ま
た、本発明の抗菌性樹脂組成物の製造方法は、上記の抗
菌性組成物を乾燥して前記樹脂を造粒するものである。
本発明に用いるエマルジョン樹脂は、ポリスチレン樹
脂、アクリル樹脂あるいはアクリル・スチロール共重合
体樹脂などの熱可塑性樹脂である。The method for producing the antibacterial resin composition of the present invention comprises:
The above-mentioned antibacterial composition is mixed with resin pellets compatible with the emulsion resin and dried. Further, the method for producing an antibacterial resin composition of the present invention is to dry the above antibacterial composition to granulate the resin.
The emulsion resin used in the present invention is a thermoplastic resin such as polystyrene resin, acrylic resin, or acrylic / styrene copolymer resin.
【０００９】本発明の抗菌性組成物は、以下のようにし
て調製することができる。まず、銀、銅、および亜鉛か
ら選ばれた少なくとも一種の金属の水溶性塩、好ましく
は酢酸塩、硫酸塩および硝酸塩の少なくとも一種を純水
に溶解し、その溶液に亜硫酸ナトリウムまたは亜硫酸カ
リウム、およびチオ硫酸ナトリウムまたはチオ硫酸カリ
ウムをそれぞれ順次添加して溶解させ、チオスルファト
金属錯体溶液を調製する。この水溶液中の金属錯体の量
は、金属換算値で水溶液１００重量部当たり０．１〜１
０重量部が適当である。また、前記錯体を形成させるた
めの亜硫酸塩およびチオ硫酸塩は、それぞれ金属１モル
当たり１〜６モルおよび１〜１８モルが適当である。次
に、無機酸化物微粒子を懸濁させたコロイド溶液を前記
水溶液に添加し、混合して無機酸化物微粒子を分散さ
せ、さらに樹脂エマルジョンを添加し、混合して均一に
分散させる。The antibacterial composition of the present invention can be prepared as follows. First, a water-soluble salt of at least one metal selected from silver, copper, and zinc, preferably acetate, at least one of sulfates and nitrates is dissolved in pure water, sodium sulfite or potassium sulfite in the solution, and Sodium thiosulfate or potassium thiosulfate are sequentially added and dissolved to prepare a thiosulfato metal complex solution. The amount of the metal complex in this aqueous solution is 0.1 to 1 per 100 parts by weight of the aqueous solution in terms of metal.
0 parts by weight is suitable. Further, the sulfite and the thiosulfate for forming the complex are appropriately 1 to 6 mol and 1 to 18 mol per mol of the metal, respectively. Next, a colloidal solution in which inorganic oxide fine particles are suspended is added to the above aqueous solution, mixed to disperse the inorganic oxide fine particles, and further a resin emulsion is added, mixed and uniformly dispersed.
【００１０】この抗菌性組成物を用いて樹脂組成物を得
るには、上記エマルジョンの樹脂と相溶性を有する熱可
塑性樹脂のペレットを前記分散液に加え、樹脂溶融温度
以下の温度で乾燥することにより、熱可塑性樹脂ペレッ
トの表面に、エマルジョンとして添加された樹脂および
無機酸化物微粒子をこの微粒子に担持された錯体ととも
に被着させる。ここに用いる熱可塑性樹脂ペレットの量
は、前記抗菌性組成物におけるチオスルファト金属錯体
を前記金属換算量で０．１〜１０重量部含む水溶液１０
０重量部に対して２００〜１０，０００重量部が適当で
ある。また、上記のように、前記抗菌性組成物を乾燥、
造粒することによっても抗菌性樹脂組成物を得ることが
できる。これらの抗菌性樹脂組成物は、いわゆるマスタ
ーバッチとして汎用樹脂に混練することにより、抗菌性
の付与された樹脂成形体を与える。To obtain a resin composition using this antibacterial composition, pellets of a thermoplastic resin having compatibility with the resin of the above emulsion are added to the above dispersion liquid and dried at a temperature below the resin melting temperature. Thus, the resin and the inorganic oxide fine particles added as an emulsion are adhered to the surface of the thermoplastic resin pellet together with the complex supported on the fine particles. The amount of the thermoplastic resin pellets used here is an aqueous solution containing 0.1 to 10 parts by weight of the thiosulfato metal complex in the antibacterial composition in terms of the metal.
200 to 10,000 parts by weight is suitable for 0 parts by weight. Also, as described above, drying the antibacterial composition,
The antibacterial resin composition can also be obtained by granulating. These antibacterial resin compositions give a resin molded article having antibacterial properties when kneaded with a general-purpose resin as a so-called masterbatch.
【００１１】[0011]
【作用】本発明では、チオスルファト銀錯体、チオスル
ファト亜鉛錯体、またはチオスルファト銅錯体、あるい
はこれらの混合物を抗菌性成分として用いる。これらの
錯体は、安定であることから光安定性が得られるばかり
でなく、錯体がアニオンを形成することから塩素に対し
ての安定性が確保される。本発明の抗菌性組成物は、上
記の錯体の水溶液に、無機酸化物のコロイド粒子および
樹脂エマルジョンを分散させたもので、前記無機酸化物
微粒子による錯体の担持効果により、さらに熱安定性が
得られる。無機酸化物微粒子は、粒径約０．０１〜１０
μｍであることが好ましい。粒径が０．０１μｍ未満で
は担持効果が少なく、一方１０μｍを越えると樹脂成形
体表面で肉眼での識別が可能となり、表面のザラツキの
原因となる。In the present invention, a thiosulfato silver complex, a thiosulfato zinc complex, a thiosulfato copper complex, or a mixture thereof is used as an antibacterial component. Since these complexes are stable, not only is photostability obtained, but also because the complexes form anions, stability to chlorine is secured. The antibacterial composition of the present invention is obtained by dispersing colloidal particles of an inorganic oxide and a resin emulsion in an aqueous solution of the above complex, and the effect of supporting the complex by the fine particles of the inorganic oxide provides further thermal stability. To be The inorganic oxide fine particles have a particle size of about 0.01 to 10
It is preferably μm. If the particle size is less than 0.01 μm, the carrying effect is small, while if it exceeds 10 μm, the surface of the resin molded product can be visually identified, which causes the surface roughness.
【００１２】また、本発明の抗菌性組成物は、無機酸化
物の微粒子とともにエマルジョン状態の樹脂が分散して
いるので、これを乾燥することにより、無機酸化物の微
粒子がほぼ均一に分散した抗菌性樹脂組成物を得ること
ができる。樹脂エマルジョンを分散させていないものを
乾燥すると、無機酸化物微粒子の二次粒子凝集が起こ
り、結果として樹脂分散に用いた場合大きな凝集体にな
ってしまうのである。本発明の抗菌性樹脂組成物は、加
熱することで軟化し、その周囲に樹脂を配置することで
その樹脂中への均一分散が容易ともなる。In the antibacterial composition of the present invention, since the resin in the emulsion state is dispersed together with the fine particles of the inorganic oxide, the antibacterial composition in which the fine particles of the inorganic oxide are almost uniformly dispersed is dried. Resin composition can be obtained. When the resin emulsion in which the resin emulsion is not dispersed is dried, secondary particles of the inorganic oxide fine particles aggregate, resulting in large aggregates when used for resin dispersion. The antibacterial resin composition of the present invention is softened by heating, and by disposing a resin around it, it becomes easy to uniformly disperse the resin in the resin.
【００１３】[0013]
【実施例】以下、本発明をその実施例によりさらに詳し
く説明する。 ［実施例１］本実施例では、可溶性金属塩として酢酸銀
を用いた例を示す。まず、酢酸銀（ＣＨ3ＣＯＯＡｇ）
の水溶液を調製した。酢酸銀は溶解度が小さいので、溶
解度に近い７．７ｇ／ｌを６０℃以下の温度で溶解し
た。この溶解工程を６０℃を越える温度で行うと、酢酸
銀が分解するので、６０℃以下室温の範囲が好ましい。
次に、この酢酸銀の水溶液に、亜硫酸ナトリウム（Ｎａ
2ＳＯ3）を酢酸銀１ｇに対して２．７ｇの割合で添加
し、充分溶解させた後、チオ硫酸ナトリウム（Ｎａ2Ｓ2
Ｏ3）を酢酸銀１ｇに対して６．６ｇの割合で添加し、
溶解させた。次いで、酢酸亜鉛を亜鉛換算量にして、前
記銀量の２倍量を添加した。こうしてチオスルファト銀
錯体およびチオスルファト亜鉛錯体を含む抗菌性溶液を
得た。この時の溶解工程は、４０℃〜室温の温度範囲で
行うのが好ましい。The present invention will be described in more detail with reference to its examples. [Example 1] In this example, silver acetate is used as a soluble metal salt. First, silver acetate (CH 3 COOAg)
Was prepared. Since silver acetate has a low solubility, 7.7 g / l, which is close to the solubility, was dissolved at a temperature of 60 ° C. or lower. If this dissolving step is carried out at a temperature higher than 60 ° C., silver acetate is decomposed, so that the temperature is preferably 60 ° C. or lower and room temperature.
Next, add sodium sulfite (Na
2 SO 3 ) was added at a ratio of 2.7 g to 1 g of silver acetate and sufficiently dissolved, and then sodium thiosulfate (Na 2 S 2
O 3 ) was added at a ratio of 6.6 g to 1 g of silver acetate,
Dissolved. Next, zinc acetate was made into a zinc conversion amount, and twice the amount of the above silver was added. Thus, an antibacterial solution containing a silver thiosulfato complex and a zinc thiosulfato complex was obtained. The melting step at this time is preferably performed in a temperature range of 40 ° C. to room temperature.
【００１４】この抗菌性溶液１００重量部に対して、ベ
ーマイトのコロイド溶液（固形分：約１０％、日産化学
製コロイダルシリカＡＳ−２００）を２０重量部の割合
で添加し、攪拌して均一に混合した。ここに用いたコロ
イドのベーマイトは、約０．１μｍの粒径を有する。次
に、この分散液にアクリルースチレン共重合体樹脂の水
分散エマルション（樹脂分：５０％）を、前記抗菌性溶
液１００重量部に対し２０重量部の割合で添加し、攪拌
して均一に混合し、抗菌性組成物を得た。To 100 parts by weight of this antibacterial solution, 20 parts by weight of a colloidal solution of boehmite (solid content: about 10%, colloidal silica AS-200 manufactured by Nissan Chemical Co., Ltd.) was added, and the mixture was uniformly stirred. Mixed. The colloidal boehmite used here has a particle size of about 0.1 μm. Next, an aqueous dispersion emulsion of acrylic-styrene copolymer resin (resin content: 50%) was added to this dispersion at a ratio of 20 parts by weight with respect to 100 parts by weight of the antibacterial solution, and the mixture was stirred to be uniform. The mixture was mixed to obtain an antibacterial composition.
【００１５】上記抗菌性組成物に、前記アクリルースチ
レン共重合体樹脂と相溶性のある樹脂として、スチレン
樹脂のペレットを前記抗菌性溶液換算１００重量部に対
して３３３重量部の割合で添加し、攪拌して均一に混合
した後、乾燥して抗菌性樹脂組成物を得た。この乾燥
は、抗菌性材料が分解しないように、圧力は常圧で温度
は６０℃とした。なお、圧力は１０-4Ｐａ〜常圧、温度
は４０℃〜１２０℃が好ましい。このようにして得た抗
菌性樹脂組成物は、長期の保管、保存に耐え得るよう
に、耐湿、減圧パックで梱包することが好ましい。As a resin compatible with the acrylic-styrene copolymer resin, styrene resin pellets were added to the above antibacterial composition at a ratio of 333 parts by weight to 100 parts by weight of the antibacterial solution. Then, the mixture was stirred and uniformly mixed, and then dried to obtain an antibacterial resin composition. In this drying, the pressure was normal pressure and the temperature was 60 ° C. so that the antibacterial material was not decomposed. The pressure is preferably 10 −4 Pa to normal pressure, and the temperature is preferably 40 ° C. to 120 ° C. The antibacterial resin composition thus obtained is preferably packaged in a moisture-proof, reduced-pressure pack so as to withstand long-term storage and storage.
【００１６】上記の方法で製造した抗菌性樹脂組成物
を、ポリスチレン樹脂の成形時に、ナチュラル樹脂２０
重量部に対して１重量部の割合で均一に分散させ、射出
成形機で２２０℃の加工温度で樹脂を成形し、成形体を
得た。この樹脂成形体について、下記に示すような抗菌
試験および抗黴試験を行った。その結果、表１に示すよ
うに、実用上充分な抗菌および抗黴性能を示した。さら
に、上記原料中のナトリウム塩の一部をカリウム塩に置
き換えることにより、全部をカリウム塩に置き換えたも
のよりは特性の若干劣るものの実用上は差し支えのない
抗菌性材料が得られた。本実施例では、可溶性金属塩と
して酢酸銀および酢酸亜鉛を用いたが、いずれか一方、
またはその他の可溶性塩を用いてもよい。また、亜鉛塩
または銅塩を用いても、銀塩を用いたものより特性が若
干劣るものの実用上は差し支えのない抗菌性材料が得ら
れた。The antibacterial resin composition produced by the above-mentioned method is applied to the natural resin 20 when the polystyrene resin is molded.
It was uniformly dispersed in a ratio of 1 part by weight with respect to parts by weight, and the resin was molded by an injection molding machine at a processing temperature of 220 ° C. to obtain a molded body. The resin molded product was subjected to the following antibacterial test and antifungal test. As a result, as shown in Table 1, practically sufficient antibacterial and antifungal properties were exhibited. Furthermore, by replacing a part of the sodium salt in the above raw material with a potassium salt, an antibacterial material which is slightly inferior to the one in which all of the sodium salt is replaced with a potassium salt but has no problem in practical use was obtained. In this example, silver acetate and zinc acetate were used as the soluble metal salt, but one of
Alternatively, other soluble salts may be used. Further, even if the zinc salt or the copper salt is used, an antibacterial material which is slightly inferior to the one using the silver salt but has no problem in practical use was obtained.
【００１７】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をサンプルの樹脂成形体上に滴下し、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 textiles 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)
0.2 ml of a suspension of about 10 4 cfu / ml of each bacterium of ubtillis) was dripped on the resin molded product of the sample, and left for 24 hours in an environment of temperature 37 ° C. and humidity of 90% or more, and then surviving bacteria The number was counted, and when a decrease in the number of bacteria of 10 2 or more was observed, it was considered to be effective.
【００１８】［比較例１］実施例１で調製した抗菌性溶
液から酢酸銀および酢酸亜鉛を除いた溶液を作成した。
この溶液を実施例１の抗菌性溶液の代わりに用いてポリ
スチレン樹脂の成形体を得た。この樹脂成形体について
も同様の抗菌試験を行った。Comparative Example 1 A solution was prepared by removing silver acetate and zinc acetate from the antibacterial solution prepared in Example 1.
This solution was used in place of the antibacterial solution of Example 1 to obtain a polystyrene resin molded body. The same antibacterial test was performed on this resin molded product.
【００１９】［実施例２］実施例１と同様の方法で調製
したアクリルースチレン共重合体樹脂の水分散エマルシ
ョンを含む抗菌性組成物を乾燥、造粒して抗菌性樹脂組
成物を得た。この乾燥は、抗菌性材料が分解しないよう
に、圧力は常圧で温度は６０℃とした。なお、圧力は１
０-4Ｐａ〜常圧、温度は４０℃〜１２０℃が好ましい。
このようにして得た抗菌性樹脂組成物は、長期の保管、
保存に耐え得るように耐湿、減圧パックで梱包すること
が好ましい。上記の方法で製造した抗菌性樹脂組成物
を、ポリスチレン樹脂の成形時に、成形体重量を１００
重量部とした時、成形体中の銀換算重量で０．０１５重
量部になるようナチュラル樹脂中に均一に分散させ、射
出成形機で成形し成形体を得た。この樹脂成形体につい
て、実施例１と同様の抗菌試験および抗黴試験を行った
ところ、実用上充分な抗菌・抗黴性能を示した。[Example 2] An antibacterial composition containing an aqueous dispersion emulsion of an acrylic-styrene copolymer resin prepared in the same manner as in Example 1 was dried and granulated to obtain an antibacterial resin composition. . In this drying, the pressure was normal pressure and the temperature was 60 ° C. so that the antibacterial material was not decomposed. The pressure is 1
It is preferable that the pressure is 0 −4 Pa to normal pressure and the temperature is 40 to 120 ° C.
The antibacterial resin composition thus obtained is stored for a long time,
It is preferable to pack in a moisture-proof and vacuum pack so that it can be stored. When the polystyrene resin is molded with the antibacterial resin composition produced by the above method, the weight of the molded body is 100%.
When the amount was parts by weight, it was uniformly dispersed in a natural resin so that the weight of silver in the formed product was 0.015 parts by weight, and the product was molded by an injection molding machine to obtain a molded product. When the resin molded product was subjected to the same antibacterial test and antifungal test as in Example 1, it showed practically sufficient antibacterial and antifungal properties.
【００２０】[0020]
【表１】 [Table 1]
【００２１】［実施例３］実施例１に記した製造方法を
基本とし、各種条件を変更して樹脂成形体を作成し、そ
の抗菌性能、製造時の作業性、および色調表面状態を主
体とする成形仕上がり外観について評価した。その結果
を表２に示す。なお、抗菌性能の評価は、次のようにし
た。すなわち、約１０4ｃｆｕ／ｍｌの大腸菌または黄
色ぶどう状菌を懸濁させた液滴０．２ｍｌをサンプルの
樹脂成形体上に滴下し、温度３７℃、湿度９０％以上の
環境で２４時間放置後、生存菌数を計測した。そして、
１０3を越える菌数減少が見られた場合を○印、１０3〜
１０2の菌数減少が見られた場合を△印、菌数減少が１
０2未満の場合を×印でそれぞれ表した。外観、作業性
については、良好を○印、やや変色がみられるものを△
印で表した。[Example 3] Based on the manufacturing method described in Example 1, various conditions were changed to prepare a resin molded article, and its antibacterial performance, workability at the time of manufacturing, and color tone surface state were mainly used. The appearance of the finished molded product was evaluated. The results are shown in Table 2. The antibacterial performance was evaluated as follows. That is, 0.2 ml of a droplet in which about 10 4 cfu / ml of Escherichia coli or yellow vine was suspended was dropped on the resin molded body of the sample, and left for 24 hours in an environment of temperature 37 ° C. and humidity 90% or more. After that, the number of surviving bacteria was counted. And
When a decrease in the number of bacteria exceeding 10 3 is observed, a circle indicates 10 3 ~
When the decrease in the number of bacteria of 10 2 is seen, it is marked with △, and the decrease in the number of bacteria is 1
The case of less than 0 2 is represented by x. Regarding the appearance and workability, ○ indicates good and △ indicates slight discoloration.
It is indicated by a mark.
【００２２】[0022]
【表２】 [Table 2]
【００２３】表中、抗菌成分濃度は、抗菌性溶液（金属
錯体の水溶液）中における錯体化金属種換算値の濃度で
表している。また、コロイド濃度は、抗菌性溶液１００
重量部に対するコロイド溶液（固形分１０％）の割合を
表す。エマルジョン濃度は、抗菌性溶液１００重量部に
対する樹脂エマルジョン（樹脂分５０％）の割合を表
す。In the table, the concentration of the antibacterial component is represented by the concentration of the complexed metal species conversion value in the antibacterial solution (metal complex aqueous solution). Also, the colloid concentration is 100% antibacterial solution.
It represents the ratio of the colloidal solution (solid content 10%) to parts by weight. The emulsion concentration represents the ratio of the resin emulsion (resin content 50%) to 100 parts by weight of the antibacterial solution.
【００２４】[0024]
【発明の効果】以上のように本発明の抗菌性組成物は、
抗菌性材料そのものの安定性が高いため、液状でも安定
で、かつ容易に抗菌性材料の濃度の高い樹脂組成物を与
える。また、本発明の抗菌性樹脂組成物は、抗菌性材料
を高濃度に含むことができるため、これをいわゆるマス
ターバッチとして利用することにより、容易に汎用樹脂
に混練して抗菌性樹脂成形体を得ることができる。この
ように液体の抗菌性組成物からマスターバッチを作成す
るため、混練操作工程の削減が可能となる。本発明の抗
菌性樹脂組成物により抗菌性を付与された樹脂成形体
は、抗菌性材料である錯体の担体となる無機酸化物粒子
が微粒子であるから、樹脂の透明性や樹脂表面の平滑性
が損なわれることがなく、安定した抗菌作用を発揮す
る。また、抗菌性材料の徐放性と熱安定性が得られる。
さらに、塩素濃度の高い雰囲気中で使用しても、変色や
抗菌性能の低下がみられにくい。As described above, the antibacterial composition of the present invention is
Since the antibacterial material itself has high stability, a resin composition that is stable even in a liquid state and easily has a high concentration of the antibacterial material is provided. Further, since the antibacterial resin composition of the present invention can contain the antibacterial material in a high concentration, by utilizing this as a so-called masterbatch, the antibacterial resin molding can be easily kneaded into a general-purpose resin. Obtainable. Since the masterbatch is prepared from the liquid antibacterial composition as described above, the number of kneading operation steps can be reduced. The resin molded body having antibacterial properties imparted by the antibacterial resin composition of the present invention has fine particles of the inorganic oxide particles serving as a carrier of the complex which is an antibacterial material, and therefore has transparency of the resin and smoothness of the resin surface. Stable antibacterial action without being damaged. In addition, the sustained release property and heat stability of the antibacterial material can be obtained.
Furthermore, even when used in an atmosphere with a high chlorine concentration, discoloration and deterioration of antibacterial performance are unlikely to occur.
───────────────────────────────────────────────────── 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 Ａ０１Ｎ 55/02 Ａ０１Ｎ 55/02 Ｇ 59/06 59/06 Ｚ 59/16 59/16 Ｚ Ｃ０８Ｋ 5/56 ＫＣＦ Ｃ０８Ｋ 5/56 ＫＣＦ Ｃ０８Ｌ 101/00 ＬＳＹ Ｃ０８Ｌ 101/00 ＬＳＹ (72)発明者 西野 敦 大阪府門真市大字門真1006番地 松下電器 産業株式会社内 (72)発明者 大井戸 彦文 大阪府門真市大字門真1006番地 松下電器 産業株式会社内 (72)発明者 竹村 勝喜 大阪府門真市大字門真1006番地 松下電器 産業株式会社内─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI Technical display area A01N 55/02 A01N 55/02 G 59/06 59/06 Z 59/16 59/16 Z C08K 5 / 56 KCF C08K 5/56 KCF C08L 101/00 LSY C08L 101/00 LSY (72) Inventor Atsushi Nishino 1006 Kadoma, Kadoma City, Osaka Prefecture Matsushita Electric Industrial Co., Ltd. (72) Hikofumi Oido Osaka Prefecture 1006 Kadoma, Kadoma-shi, Matsushita Electric Industrial Co., Ltd. (72) Inventor, Katsuki Takemura 1006 Kadoma, Kadoma, Osaka Prefecture Matsushita Electric Industrial Co., Ltd.
Claims (5)
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
に、無機酸化物のコロイド粒子および樹脂エマルジョン
を分散させてなる抗菌性組成物。1. An antibacterial composition comprising colloidal particles of an inorganic oxide and a resin emulsion dispersed in an aqueous solution of a thiosulfato complex of at least one metal selected from the group consisting of silver, zinc and copper.
た少なくとも一種の金属のチオスルファト錯体を前記金
属換算量で０．１〜１０重量部含む水溶液１００重量
部、固形分０．１〜５０重量部相当の無機酸化物のコロ
イド溶液、および樹脂分０．５〜５０重量部相当の樹脂
エマルジョンからなる抗菌性組成物。2. 100 parts by weight of an aqueous solution containing 0.1 to 10 parts by weight of the thiosulfato complex of at least one metal selected from the group consisting of silver, zinc and copper in terms of the metal, and a solid content of 0.1 to 50. An antibacterial composition comprising a colloidal solution of an inorganic oxide corresponding to parts by weight and a resin emulsion corresponding to a resin content of 0.5 to 50 parts by weight.
マイト、アルミナ、および酸化チタンよりなる群から選
ばれる請求項１または２記載の抗菌性組成物。3. The antibacterial composition according to claim 1, wherein the colloidal particles are selected from the group consisting of silicon dioxide, boehmite, alumina, and titanium oxide.
前記エマルジョン樹脂と相溶性のある樹脂ペレットと混
合し、乾燥することを特徴とする抗菌性樹脂組成物の製
造方法。4. A method for producing an antibacterial resin composition, which comprises mixing the antibacterial composition according to claim 1 or 2 with resin pellets compatible with the emulsion resin and drying the mixture.
乾燥して前記樹脂を造粒することを特徴とする抗菌性樹
脂組成物の製造方法。5. A method for producing an antibacterial resin composition, which comprises drying the antibacterial composition according to claim 1 or 2 to granulate the resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13702795A JP3585059B2 (en) | 1995-06-02 | 1995-06-02 | Antimicrobial composition and method for producing antimicrobial resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13702795A JP3585059B2 (en) | 1995-06-02 | 1995-06-02 | Antimicrobial composition and method for producing antimicrobial resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08325112A true JPH08325112A (en) | 1996-12-10 |
| JP3585059B2 JP3585059B2 (en) | 2004-11-04 |
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ID=15189140
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13702795A Expired - Fee Related JP3585059B2 (en) | 1995-06-02 | 1995-06-02 | Antimicrobial composition and method for producing antimicrobial resin composition |
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| Country | Link |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100478494B1 (en) * | 2002-06-12 | 2005-05-17 | 황승수 | Master batch containing silver colloid |
| KR101039043B1 (en) * | 2009-12-08 | 2011-06-03 | 주식회사 아이즌 | Zinc sulfied nano particle compositions, anti-bacteria and anti-filamentous fungi polymer masterbatches and methods of the preparation of the same |
| WO2012111894A1 (en) * | 2011-02-18 | 2012-08-23 | (주)더몰론코리아 | Pellet-type antibacterial masterbatch |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109097856B (en) * | 2018-08-15 | 2020-11-06 | 晋大纳米科技（厦门）有限公司 | Copper-based antibacterial master batch and preparation method thereof |
-
1995
- 1995-06-02 JP JP13702795A patent/JP3585059B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100478494B1 (en) * | 2002-06-12 | 2005-05-17 | 황승수 | Master batch containing silver colloid |
| KR101039043B1 (en) * | 2009-12-08 | 2011-06-03 | 주식회사 아이즌 | Zinc sulfied nano particle compositions, anti-bacteria and anti-filamentous fungi polymer masterbatches and methods of the preparation of the same |
| WO2011071261A3 (en) * | 2009-12-08 | 2011-11-10 | 주식회사 아이즌 | Zinc sulfide nanoparticle composition, antibacterial and anti-fungicidal polymer resin master batch containing same, and preparation method thereof |
| WO2012111894A1 (en) * | 2011-02-18 | 2012-08-23 | (주)더몰론코리아 | Pellet-type antibacterial masterbatch |
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| Publication number | Publication date |
|---|---|
| JP3585059B2 (en) | 2004-11-04 |
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