JP3159485B2 - Inorganic antibacterial agent, production method thereof and antibacterial resin composition - Google Patents
Inorganic antibacterial agent, production method thereof and antibacterial resin compositionInfo
- Publication number
- JP3159485B2 JP3159485B2 JP23050491A JP23050491A JP3159485B2 JP 3159485 B2 JP3159485 B2 JP 3159485B2 JP 23050491 A JP23050491 A JP 23050491A JP 23050491 A JP23050491 A JP 23050491A JP 3159485 B2 JP3159485 B2 JP 3159485B2
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- Japan
- Prior art keywords
- antibacterial agent
- antibacterial
- resin
- inorganic antibacterial
- zeolite
- Prior art date
- 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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Description
【０００１】[0001]
【産業上の利用分野】本発明は、無機質抗菌剤、その製
造方法及び抗菌性樹脂組成物に関する。さらに言えば、
ゼオライト粒子に微細な抗菌性金属粉末を担持させた無
機質抗菌剤、その製造方法及び該抗菌剤を合成樹脂に配
合させてなる抗菌性樹脂組成物に係るものである。The present invention relates to an inorganic antibacterial agent, a method for producing the same, and an antibacterial resin composition. Furthermore,
The present invention relates to an inorganic antibacterial agent in which fine antibacterial metal powder is supported on zeolite particles, a method for producing the same, and an antibacterial resin composition obtained by blending the antibacterial agent with a synthetic resin.
【０００２】[0002]
【従来の技術】従来より、銀や銅の金属やそのイオンが
殺菌抗菌作用を有することは知られている。最近、この
抗菌作用を応用した各種の無機質抗菌剤の開発が盛んに
行われている。例えば、特開昭60−181002号公報には、
天然または合成のゼオライトをカチオン交換により銀、
銅または亜鉛等の抗菌性イオンと置換して得られる抗菌
性ゼオライトが開示されている。また、特開昭63−2658
0号公報や特開平1−257124号公報には前記抗菌性金属イ
オンと同時にアンモニウムイオンを担持して耐変色性を
改善した抗菌性ゼオライトを開示している。他方、前記
抗菌性金属をゼオライト担体に化学メッキ法により担持
させた抗菌性組成物が知られている(特開平2−268104号
公報)。2. Description of the Related Art It has been known that silver and copper metals and their ions have a bactericidal and antibacterial action. Recently, various inorganic antibacterial agents utilizing this antibacterial action have been actively developed. For example, JP-A-60-181002 discloses that
Silver, by cation exchange of natural or synthetic zeolite
An antibacterial zeolite obtained by substituting an antibacterial ion such as copper or zinc is disclosed. Also, JP-A-63-2658
No. 0 and JP-A-1-257124 disclose an antibacterial zeolite having improved discoloration resistance by carrying ammonium ions simultaneously with the antibacterial metal ions. On the other hand, an antimicrobial composition in which the antimicrobial metal is supported on a zeolite carrier by a chemical plating method is known (Japanese Patent Application Laid-Open No. 2-268104).
【０００３】[0003]
【発明が解決しようとする課題】上記したように抗菌性
の金属やそのイオンをゼオライト担体に担持した無機質
抗菌剤は公知である。これらにおいて、抗菌性金属イオ
ンを担持したいわゆる抗菌性ゼオライトは、一般に金属
を担持したものより、抗菌作用が強いけれども、日光
(特に紫外線)に露光すると、それ自体が著しく変色する
のみならず、これを配合した樹脂は、経時的に褐色に変
色する欠点がある。この点、金属銀を担持したゼオライ
トも同様で、特に化学メッキ法により製造された銀担持
ゼオライトは灰色乃至暗褐色の粉末であって、しかも経
時的に変色する。このような変色は、樹脂や塗料等に使
用する場合、著しく商品価値を下げるため、重大な問題
となっている。しかして、この変色原因は銀イオン等の
感光性によると考えられ、銀またはそのイオンを担持し
た無機質抗菌剤である限り、担体がゼオライトであるか
否かを問わず、耐光性や耐熱性がないことから、優れた
抗菌作用が認められながらも、その使用が著しく制限さ
れていた。本発明者らは、叙上の事実に鑑み、耐光性及
び耐熱性を改善したゼオライト系無機質抗菌剤を鋭意研
究した結果、本発明を完成した。As described above, inorganic antibacterial agents in which an antibacterial metal or its ion is supported on a zeolite carrier are known. In these, so-called antibacterial zeolites carrying antibacterial metal ions generally have stronger antibacterial action than those carrying metals,
When exposed to (especially ultraviolet light), not only does the resin itself significantly change its color, but the resin containing it has the disadvantage of discoloring brown over time. In this respect, the same applies to the zeolite supporting metallic silver. In particular, the silver-supported zeolite produced by the chemical plating method is a gray to dark brown powder and discolors with time. Such discoloration is a serious problem when used in resins, paints and the like, because it significantly lowers the commercial value. However, the cause of this discoloration is considered to be due to the photosensitivity of silver ions, etc., as long as the inorganic antibacterial agent carrying silver or its ions, regardless of whether the carrier is zeolite or not, the light resistance and heat resistance are high. As a result, although its excellent antibacterial effect was recognized, its use was significantly restricted. In view of the facts described above, the present inventors have intensively studied a zeolite-based inorganic antibacterial agent having improved light resistance and heat resistance, and have completed the present invention.
【０００４】すなわち、本発明は、耐光性および耐熱性
の優れたゼオライト系無機質抗菌剤及びその製造方法を
提供することを目的とする。That is, an object of the present invention is to provide a zeolite-based inorganic antibacterial agent having excellent light resistance and heat resistance, and a method for producing the same.
【０００５】本発明の他の目的は、前記抗菌剤を配合し
た樹脂組成物を提供することにある。Another object of the present invention is to provide a resin composition containing the above antibacterial agent.
【０００６】[0006]
【課題を解決するための手段】すなわち、本発明が提供
しようとする無機質抗菌剤は合成ゼオライト担体に微細
な抗菌性金属粉末を圧着担持してなることを構成上の特
徴とするものである。That is, the inorganic antibacterial agent to be provided by the present invention is characterized in that a fine antibacterial metal powder is pressed and supported on a synthetic zeolite carrier.
【０００７】また、本発明が提供しようとする無機質抗
菌剤の製造方法は、合成ゼオライト粉末と抗菌性金属粉
末との混合物を摩砕により均一に混合して微細な抗菌性
金属粉末を合成ゼオライト担体に圧着担持させることを
構成上の特徴とするものである。Further, the present invention provides a method for producing an inorganic antibacterial agent, which comprises mixing a mixture of a synthetic zeolite powder and an antibacterial metal powder uniformly by grinding to form a fine antibacterial metal powder into a synthetic zeolite carrier. It is characterized in that it is held by pressure bonding.
【０００８】さらに本発明が提供しようとする抗菌性樹
脂組成物は合成樹脂１００重量部に対し、前記無機質抗
菌剤を０.０５〜５０重量部含有させてなることを構成
上の特徴とするものである。Further, the antimicrobial resin composition to be provided by the present invention is characterized in that the inorganic antimicrobial agent is contained in an amount of 0.05 to 50 parts by weight based on 100 parts by weight of the synthetic resin. It is.
【０００９】以下、本発明について詳述する。本発明に
おいて、合成ゼオライト担体（以下、単に「ゼオライト
担体」という）としては、例えばゼオライトＡ、ゼオラ
イトＰ、ゼオライトＸ、ゼオライトＹ、アナルサイトま
たはモルデナイトなどが代表的に挙げられる。 Hereinafter, the present invention will be described in detail. In the present invention, synthetic zeolite responsible body (hereinafter, simply "Zeolite
It is a called carrier "), such as zeolite A, zeolite P, zeolite X, zeolite Y, such as anal site or mordenite Ru mentioned typically.
【００１０】これらゼオライトは、一般的にはナトリウ
ムゼオライトがあるが、ナトリウムとイオン交換により
他のカチオンと置換した金属置換型ゼオライトであって
もよい。[0010] These zeolites are generally sodium zeolites, but may be metal-substituted zeolites substituted with other cations by ion exchange with sodium.
【００１１】本発明は、特に次の一般式：The present invention is particularly directed to the following general formula:
【化２】ｘＭn/2Ｏ・Ａｌ2Ｏ3・ｙＳｉＯ2・ｚＨ2Ｏ （式中、０.８≦ｘ≦１.２、１.８≦ｙ≦２０、０≦ｚ
≦２０、ｎは原子価、Ｍは１価または２価カチオンを表
す）で表される金属置換合成ゼオライトであって、残留
ナトリウムがＮａ2Ｏとして１０重量％以下のものが好
適である。また、置換金属イオン(Ｍ)としては、周期律
表ＩＢ族、IIＡ族、IIＢ族またはVIII族の金属イオンが
挙げられ、それらは１種または２種以上であってもよ
い。## STR2 ## xM n / 2 O · Al 2 O 3 · ySiO 2 · zH 2 O ( wherein, 0.8 ≦ x ≦ 1.2,1.8 ≦ y ≦ 20,0 ≦ z
≦ 20, n is a valence, and M is a monovalent or divalent cation), and is preferably a metal-substituted synthetic zeolite having a residual sodium content of 10% by weight or less as Na 2 O. Examples of the substituted metal ion (M) include metal ions of Group IB, IIA, IIB, or VIII of the periodic table, and one or more of them may be used.
【００１２】かかる金属置換ゼオライトを具体的に挙げ
ると、前記合成ゼオライト金属置換体が含まれるが、本
発明では、カルシウム、マグネシウム、亜鉛、銅の金属
イオンから選ばれた１種または２種以上の金属置換ゼオ
ライトＡが耐色性及び耐熱性の面のみならず、経済的な
点からみて特に好ましい。Specific examples of such metal-substituted zeolites include the above-mentioned metal-substituted zeolites. In the present invention, one or more metal ions selected from calcium, magnesium, zinc and copper metal ions are used. The metal-substituted zeolite A is particularly preferable from the viewpoint of not only the color resistance and the heat resistance but also the economy.
【００１３】かかるゼオライトは担体として、粒度分布
がシャープで微細であることが必要であるが、多くの場
合、平均粒子径(Ｄ５０)が０.１〜５μｍの範囲であ
り、且つＤ５０の１／２〜３／２の範囲にある粒度部分
が少なくとも５０重量％であるものが良い。Such a zeolite needs to have a sharp and fine particle size distribution as a carrier. In many cases, the zeolite has an average particle size (D50) in the range of 0.1 to 5 μm and 1/50 of D50. It is preferred that the particle size in the range of 2/3/2 is at least 50% by weight.
【００１４】他方、上記ゼオライト担体に担持すべき抗
菌性金属としては既に公知であり、例えば銀、銅、亜
鉛、錫又はこれらの１種または２種以上を含む合金の粉
末であり、特に銀粉が抗菌力の点から優れている。On the other hand, the antibacterial metal to be supported on the zeolite carrier is already known, and is, for example, powder of silver, copper, zinc, tin or an alloy containing one or more of these, especially silver powder. Excellent in terms of antibacterial power.
【００１５】かかる金属粉のゼオライト担体に対する担
持量は、金属やゼオライトの物性や抗菌剤の用途等によ
って一様ではないが、多くの場合、全重量当り０.０５
〜１０重量％、好ましくは０.５〜５重量％の範囲にあ
る。The amount of the metal powder supported on the zeolite carrier is not uniform depending on the physical properties of the metal or zeolite, the use of the antibacterial agent, etc.
-10% by weight, preferably 0.5-5% by weight.
【００１６】担持量が０.０５重量％未満のときは抗菌
作用が弱く、また、１０重量％を越えると耐色性が悪く
なるのみならず経済的にみても余り実用性がなくなる。When the supported amount is less than 0.05% by weight, the antibacterial effect is weak, and when it exceeds 10% by weight, not only the color fastness is deteriorated but also the economical efficiency becomes too low.
【００１７】本発明に係る無機質抗菌剤は、このような
ゼオライト担体に微細な抗菌性金属粉末が圧着担持され
てなることを特徴としている。The inorganic antibacterial agent according to the present invention is characterized in that a fine antibacterial metal powder is pressed and supported on such a zeolite carrier.
【００１８】ここで、圧着担持されているとは、担体と
金属粉末とが強力セン断力による摩砕と混合作用によっ
て主として物理的に強固に担体粒子表面に付着されてい
ることを意味する。Here, "press-carrying" means that the carrier and the metal powder are physically and strongly mainly adhered to the surface of the carrier particles by the grinding and mixing action by the strong shearing force.
【００１９】従って、化学メッキ方法など金属塩の置換
処理、金属化合物の熱分解処理あるいは真空蒸着の如き
蒸着処理等によって担体に金属粒子を担持させるもので
はない。Therefore, the metal particles are not supported on the carrier by a substitution treatment of a metal salt such as a chemical plating method, a thermal decomposition treatment of a metal compound, or an evaporation treatment such as vacuum evaporation.
【００２０】また、圧着担持の程度は、特に限定はない
けれども、抗菌性金属として銀を使用する場合には、銀
の溶解度(Ｓ)が０.０１≦Ｓ≦５、好ましくは０.０１≦
Ｓ≦１.０の範囲が好ましい。Further, although the degree of the pressure bonding is not particularly limited, when silver is used as the antibacterial metal, the solubility (S) of silver is 0.01 ≦ S ≦ 5, preferably 0.01 ≦ S ≦ 5.
The range of S ≦ 1.0 is preferred.
【００２１】この理由は、Ｓ＜０.０１のときは、抗菌
力が弱くＳ＞５のときは耐色性が悪くなることによる。The reason for this is that when S <0.01, the antibacterial activity is weak, and when S> 5, the color fastness is poor.
【００２２】なお、ここで銀の溶解度とは、抗菌剤試料
１ｇを１００ｍｌの純水中で１５分間撹拌して静置後、
０.２μｍのメンブランフィルターで濾過した濾液中の
銀濃度(ppm)をいう。Here, the solubility of silver means that 1 g of an antibacterial agent sample was stirred in 100 ml of pure water for 15 minutes, allowed to stand,
It refers to the silver concentration (ppm) in the filtrate filtered through a 0.2 μm membrane filter.
【００２３】本発明に係る無機質抗菌剤は前記のとおり
ゼオライト粉末と抗菌性金属粉末との混合物を強力セン
力による摩砕処理することにより、均一に混合して微細
な抗菌性金属粒子をゼオライト粒子に圧着担持させるこ
とにより製造することができる。As described above, the inorganic antibacterial agent according to the present invention is obtained by subjecting a mixture of a zeolite powder and an antibacterial metal powder to a crushing treatment with a strong force to uniformly mix the fine antibacterial metal particles with the zeolite particles. It can be manufactured by supporting by pressure.
【００２４】強力セン断による摩砕は、乾式法または湿
式法のいずれでもよいが、好ましくは前者である。The grinding by high shearing may be either a dry method or a wet method, but the former is preferred.
【００２５】摩砕機は、強力セン断力を伴うものであれ
ば、特に限定はないけれども、ボールミルが工業的に好
ましい。摩砕時間は、機種や原料混合物の物性によって
異なるが、２〜５０時間、好ましくは５〜２４時間の範
囲にある。The mill is not particularly limited as long as it has a strong shearing force, but a ball mill is industrially preferable. The milling time varies depending on the type and physical properties of the raw material mixture, but is in the range of 2 to 50 hours, preferably 5 to 24 hours.
【００２６】かかる粉砕によりゼオライト粒子表面に抗
菌性金属の微粒子が均一に圧着担持されるが、前記した
溶解度(Ｓ)の範囲内になるような摩砕条件を設定するこ
とが望ましい。Although the fine particles of the antibacterial metal are uniformly pressed and supported on the surface of the zeolite particles by the pulverization, it is desirable to set the grinding conditions so that the solubility (S) is within the above-mentioned range.
【００２７】なお、かかる摩砕の際に、後の使用による
分散性や脱アグロメレートをより改善させるために、高
級脂肪酸またはその金属塩やアミドの如き誘導体、界面
活性剤等の表面処理剤で必要により表面処理することが
できる。In order to further improve dispersibility and deagglomeration during subsequent use during grinding, a surface treatment agent such as a higher fatty acid or a derivative thereof such as a metal salt or amide, or a surfactant is required. For surface treatment.
【００２８】本発明に係る無機質抗菌剤は、従来の抗菌
性ゼオライトのような抗菌性金属イオンに依拠する溶出
型抗菌剤とは異なり、不溶出型抗菌剤であるため、耐色
性が著しく改善され、樹脂、ゴム、塗料等、各種基材に
幅広く配合使用して、その抗菌機能を付与させることが
できる。The inorganic antibacterial agent according to the present invention is a non-elutable antibacterial agent unlike a conventional eluting antibacterial agent which relies on an antibacterial metal ion such as an antibacterial zeolite, so that the color resistance is remarkably improved. The antibacterial function can be imparted to a wide variety of base materials such as resins, rubbers, paints and the like.
【００２９】特に、本発明は、各種の合成樹脂に前記抗
菌剤を配合して耐色、耐熱性のある抗菌性樹脂組成物を
提供することができる。In particular, the present invention can provide an antibacterial resin composition having color resistance and heat resistance by blending the above antibacterial agent with various synthetic resins.
【００３０】適用できる樹脂は、特に限定はなく熱可塑
性または熱硬化性の樹脂は勿論のこと、合成ゴムの如き
弾性樹脂であってもよい。The applicable resin is not particularly limited, and may be an elastic resin such as a synthetic rubber as well as a thermoplastic or thermosetting resin.
【００３１】熱可塑性樹脂として代表的なものを挙げる
と、ポリ塩化ビニル、ポリ塩化ビニリデン、塩素化ポリ
オレフィンの如き塩素系樹脂、ポリエチレン、ポリプロ
ピレンの如きポリオレフィン樹脂、ポリスチレン、ポリ
酢酸ビニル、(メタ)アクリル樹脂、ポリアセタール樹脂
の如き他のビニル系樹脂、ポリエステル樹脂、ポリサル
フォン樹脂、フッ素樹脂、ポリアミド樹脂、ポリイミド
樹脂、ポリカーボネート樹脂、アイオレマー樹脂、ケイ
素樹脂あるいはＡＡＳ樹脂、ＡＥＳ樹脂、ＡＳ樹脂、Ａ
ＢＳ樹脂、ＥＶＡ樹脂の如き共重合樹脂等が挙げられ、
それらは、ポリマーアロイの如き１種または２種以上の
複合樹脂であってもよい。Representative thermoplastic resins include chlorinated resins such as polyvinyl chloride, polyvinylidene chloride and chlorinated polyolefin, polyolefin resins such as polyethylene and polypropylene, polystyrene, polyvinyl acetate, and (meth) acrylic. Resin, other vinyl resins such as polyacetal resin, polyester resin, polysulfone resin, fluorine resin, polyamide resin, polyimide resin, polycarbonate resin, iomer resin, silicon resin or AAS resin, AES resin, AS resin, A
BS resin, copolymer resin such as EVA resin, and the like,
They may be one or more composite resins such as polymer alloys.
【００３２】熱硬化性樹脂としては、例えばフェノール
樹脂、エポキシ樹脂、不飽和ポリエステル樹脂、ポリウ
レタン樹脂、メラミン樹脂、尿素樹脂、ジアリルフタレ
ート樹脂、ケイ素樹脂などが挙げられ、それらは１種ま
たは２種以上であってもよい。Examples of the thermosetting resin include a phenol resin, an epoxy resin, an unsaturated polyester resin, a polyurethane resin, a melamine resin, a urea resin, a diallyl phthalate resin, and a silicon resin. It may be.
【００３３】合成ゴムの例としては、ＳＢＲ、ＢＲ、Ｉ
Ｒ、ＮＢＲ、ウレタンゴム、シリコーンゴムなどの弾性
樹脂が挙げられる。Examples of the synthetic rubber include SBR, BR, I
Elastic resins such as R, NBR, urethane rubber, and silicone rubber are exemplified.
【００３４】本発明は、かかる合成樹脂に配合する無機
質抗菌剤は、その物性、特に銀の担持量や、合成樹脂組
成物の用途によって多様に異なるが、多くの場合樹脂１
００重量部に対し、０.０５〜５０重量部の範囲にあ
る。最終組成物にあっては０.０５〜２０重量部、好ま
しくは０.１〜１０重量部であるが、マスターバッチと
して構成される樹脂組成物にあっては５０重量部まで配
合することができる。無機質抗菌剤が０.０５重量部未
満の場合は樹脂組成物の抗菌作用が実質的に得られない
からであり、また、上限は多くの場合経済的理由から制
限され、実用的範囲として設定される。According to the present invention, the inorganic antibacterial agent to be added to such a synthetic resin varies widely depending on its physical properties, in particular, the amount of silver carried and the use of the synthetic resin composition.
It is in the range of 0.05 to 50 parts by weight with respect to 00 parts by weight. In the final composition, it is 0.05 to 20 parts by weight, preferably 0.1 to 10 parts by weight, but in the resin composition constituted as a master batch, it can be added up to 50 parts by weight. . When the amount of the inorganic antibacterial agent is less than 0.05 part by weight, the antibacterial action of the resin composition is not substantially obtained, and the upper limit is often limited for economic reasons and set as a practical range. You.
【００３５】なお、樹脂組成物を調製するに当って各種
の樹脂添加剤と併用しうることができる。In preparing the resin composition, it can be used in combination with various resin additives.
【００３６】例えば、酸化チタン、炭酸カルシウム、シ
リカの如き体質顔料、有機または無機の着色材、可塑
剤、架橋剤、難燃剤、酸化防止剤、熱安定剤、紫外線吸
収剤、帯電防止剤、滑剤などの樹脂添加剤は本発明に係
る無機質抗菌剤とそれぞれ個別にまたは予め調合したワ
ンパック型として必要に応じ併用することができる。For example, extenders such as titanium oxide, calcium carbonate and silica, organic or inorganic coloring agents, plasticizers, crosslinking agents, flame retardants, antioxidants, heat stabilizers, ultraviolet absorbers, antistatic agents, lubricants Such resin additives can be used together with the inorganic antibacterial agent according to the present invention, if necessary, individually or in a one-pack type prepared in advance.
【００３７】本発明に係る樹脂組成物は、従来の銀イオ
ンを担持した無機質抗菌剤が有する露光下での経時変化
による褐変現象が実質的に生じない優れた抗菌作用のゆ
えにその用途は多大である。例えば、食品包装用フィル
ム、各種医療、衛生用器具、装置又はその部品類、各種
容器類、フィルター類、繊維類、合成紙、合成畳、接着
剤等多様な特徴的用途の拡大を図ることができる。The resin composition according to the present invention has a great use because of the excellent antibacterial action of a conventional inorganic antibacterial agent carrying silver ions, which does not substantially cause browning due to aging under exposure. is there. For example, the expansion of various characteristic applications such as food packaging films, various medical and sanitary appliances, devices or parts thereof, various containers, filters, fibers, synthetic paper, synthetic tatami, adhesives, etc. it can.
【００３８】[0038]
【作用】本発明に係る無機質抗菌剤は、前記のとおりゼ
オライト担体に抗菌性金属粉末、特に銀粉を圧着担持し
てなるものであるが、単なる銀粉などに比べて抗菌作用
が強い。また、ゼオライトのもつイオン交換能により銀
イオン等の抗菌性金属イオンを担持して従来の抗菌性ゼ
オライトや他の方法、例えば化学的還元法の如き方法で
金属粉末を担持したものに比べて耐変色性があり、特に
樹脂に配合したものであっても耐変色性、耐熱性が著し
く優れている。The inorganic antibacterial agent according to the present invention is obtained by compressing and supporting an antibacterial metal powder, particularly silver powder, on a zeolite carrier as described above, but has a stronger antibacterial effect than simple silver powder. In addition, the ion exchange capacity of zeolite supports antibacterial metal ions such as silver ions, and is more resistant to antibacterial zeolites than conventional antibacterial zeolites and other methods, such as those supporting metal powder by a method such as chemical reduction. It has discoloration properties, and particularly has excellent discoloration resistance and heat resistance even when blended with resin.
【００３９】本発明に係る抗菌剤の特徴的な抗菌力と諸
耐性を示す作用機構の詳細は不明であるが、次のような
ことが推定できる。すなわち、本発明に係る抗菌剤は、
ゼオライト粉末と抗菌性金属粉末とをボールミルの如き
強力セン断力による摩砕と混合することにより、金属粉
末がより微細化して活性化され、これが非常に大きな比
表面積を有するゼオライト表面に圧着されると共に、他
方ではある種のメカノケミカル的な反応によって結合さ
れて安全かつ活性な抗菌剤を構成することによると考え
られる。The details of the action mechanism of the antibacterial agent according to the present invention exhibiting the characteristic antibacterial activity and various resistances are unknown, but the following can be estimated. That is, the antibacterial agent according to the present invention,
By mixing the zeolite powder and the antibacterial metal powder with grinding by a strong shear force such as a ball mill, the metal powder is made finer and activated, and this is pressed against the zeolite surface having a very large specific surface area At the same time, it is believed that they are combined by certain mechanochemical reactions to form safe and active antimicrobial agents.
【００４０】しかして、ゼオライト担体は、特に、残留
ナトリウムの少ない金属置換型ゼオライトにあっては各
種樹脂に対して耐熱性、耐変色性などの作用があり、他
方で樹脂との屈折率が近いことから透明性にも優れてい
ることから本発明に係る抗菌剤を樹脂に配合すると、諸
耐性の改善された抗菌性樹脂を提供することができる。However, the zeolite carrier has an action such as heat resistance and discoloration resistance with respect to various resins, particularly in the case of metal-substituted zeolites having a low residual sodium, and has a similar refractive index to the resin. Therefore, when the antibacterial agent according to the present invention is blended with the resin because of its excellent transparency, it is possible to provide an antibacterial resin having improved resistance.
【００４１】[0041]
【実施例】本発明をさらに具体的に説明するために以下
に実施例を示す。実施例中の各測定値はそれぞれ次の方
法によって求めた。 (1) 平均粒径 コールターカエンター(コールターエレクトロニクス社
製)を用いアパチャーチューブ３０μｍで測定した。 (2) 組成分析及び銀の溶解度(Ｓ) 原子吸光光度法及びＩＣＰ法によって定量した。 (3) 着色性 肉眼観察による。 (4) 抗菌試験 大腸菌(ＬＦＯ ３３０１)の初濃度５.９×１０5個／ｍ
ｌ液５０ｍｌを減菌したフラスコに入れ、試料粉末また
はこれを配合した試料樹脂板(１ｍｍ×１０ｍｍ×１０
ｍｍ)１０枚を入れ６時間振盪後の生菌数又は減菌率を
みる。なお、減菌率は、この液中の大腸菌数とコントロ
ールの大腸菌数(４.８×１０5個／ｍｌ)を比較して求め
た。 (5) 樹脂の耐色性試験 樹脂テストピースの着色性につき、成型直後の初期着色
及びウェザーメーターで１０時間照射し、照射前と対比
したときの変色性を経時変色としてそれぞれ肉眼観察し
て、次の３段階法で評価した。 ○・・・変色程度の少ないもの △・・・わずかに変色あるもの ×・・・変色著しいものEXAMPLES Examples are shown below to explain the present invention more specifically. Each measured value in the examples was determined by the following method. (1) Average particle size The average particle size was measured with an aperture tube of 30 μm using Coulter Kaenter (manufactured by Coulter Electronics). (2) Composition analysis and silver solubility (S) Quantification was performed by atomic absorption spectrophotometry and ICP. (3) Colorability By visual observation. (4) Antibacterial test Initial concentration of E. coli (LFO 3301) 5.9 × 10 5 / m
50 ml of the solution was placed in a sterilized flask, and the sample powder or a sample resin plate (1 mm × 10 mm × 10
mm) Put 10 plates and shake for 6 hours to check the viable cell count or the sterilization rate. The sterilization rate was determined by comparing the number of E. coli in this solution with the number of control E. coli (4.8 × 10 5 cells / ml). (5) Resin color resistance test Regarding the colorability of the resin test piece, the initial coloration immediately after molding and irradiation with a weather meter for 10 hours, the discoloration when compared with before irradiation as a time-dependent discoloration, each visually observed, Evaluation was made by the following three-step method. ○: little discoloration Δ: slight discoloration ×: remarkable discoloration
【００４２】実施例１〜３ 表１に示す金属置換ゼオライトＡ３７重量部と平均粒径
０.４８μｍの銀粉(同和鉱業(株)製、Ｇ１７)３重量部
との混合物をボールミルに仕込み、２４時間乾式による
摩砕混合を施してそれぞれ無機質抗菌剤を製造した。こ
の抗菌剤の抗菌力は表２に示す結果が得られた。なお、
原料銀粉を比較例１としてその抗菌力を調べた。Examples 1 to 3 A mixture of 37 parts by weight of the metal-substituted zeolite A shown in Table 1 and 3 parts by weight of silver powder having an average particle size of 0.48 μm (G17, manufactured by Dowa Mining Co., Ltd.) was charged into a ball mill, and the mixture was allowed to stand for 24 hours. Each of them was subjected to dry milling and mixing to produce inorganic antibacterial agents. With respect to the antibacterial activity of this antibacterial agent, the results shown in Table 2 were obtained. In addition,
The antibacterial activity of the raw material silver powder as Comparative Example 1 was examined.
【００４３】[0043]
【表１】 [Table 1]
【００４４】比較例２ 試料Ｎo.１のゼオライトＡ１００ｇを純水２００ｍｌに
懸濁させ、分散剤(商品名リポノックス)０.１ｇを加え
て強力撹拌を施して脱アグロメレートしたゼオライトＡ
スラリーを調製した。このスラリーに無電解銀メッキ液
(硝酸銀５ｇを純水に溶解した５０ｍｌ液にアンモニア
でpＨ１１にした銀アンモニウム錯体)を撹拌下徐々に添
加し５０℃まで昇温しながら、アンモニアpＨ８にした
ホルムアルデヒド１０ｍｌを加えて７０℃に昇温し３０
分間撹拌処理した。次いで、常法により分離、水洗及び
乾燥してメッキ法に基づく無機質抗菌剤を得た。Comparative Example 2 100 g of zeolite A of sample No. 1 was suspended in 200 ml of pure water, 0.1 g of a dispersing agent (trade name: Liponox) was added, and zeolite A deagglomerated by vigorous stirring was added.
A slurry was prepared. Electroless silver plating solution
(Silver ammonium complex, pH 11 with ammonia, was added to a 50 ml solution of 5 g of silver nitrate in pure water with stirring), and the temperature was raised to 50 ° C. 30
The mixture was stirred for minutes. Then, separation, washing and drying were performed by a conventional method to obtain an inorganic antibacterial agent based on a plating method.
【００４５】[0045]
【表２】 [Table 2]
【００４６】実施例４〜６、比較例３〜５ 試料抗菌剤２重量部と試料樹脂(ポリプロピレンＭＩ：
８.０、白石化学(株)社製、Ｊ−１５０Ｐ)１００重量部
とをロールで１６０℃において混練した後、射出成型機
にてノズル温度２３０℃、金型温度３０℃で１８０ｍｍ
×５０ｍｍ×１ｍｍのテストピースを作成した。得られ
た樹脂組成物の試料シートの抗菌性及び耐色性等につい
て評価したところ、表３の結果が得られた。Examples 4 to 6, Comparative Examples 3 to 5 2 parts by weight of a sample antibacterial agent and a sample resin (polypropylene MI:
8.0, 100 parts by weight of J-150P manufactured by Shiraishi Chemical Co., Ltd.) were kneaded with a roll at 160 ° C., and then 180 mm at a nozzle temperature of 230 ° C. and a mold temperature of 30 ° C. by an injection molding machine.
× 50 mm × 1 mm test pieces were prepared. When the antibacterial property and the color fastness of the sample sheet of the obtained resin composition were evaluated, the results shown in Table 3 were obtained.
【００４７】[0047]
【表３】 [Table 3]
【００４８】実施例７〜９、比較例６〜８ 表４に示す各種合成樹脂１００重量部に試料抗菌剤２重
量部の配合物を実施例４と同様に射出成型してテストピ
ースを得た。このテストピースの抗菌性と耐色性を評価
したところ表５の結果が得られた。Examples 7 to 9 and Comparative Examples 6 to 8 A mixture of 100 parts by weight of various synthetic resins shown in Table 4 and 2 parts by weight of a sample antibacterial agent was injection molded in the same manner as in Example 4 to obtain a test piece. . When the antibacterial property and the color fastness of this test piece were evaluated, the results shown in Table 5 were obtained.
【００４９】[0049]
【表４】 表４ 合成樹脂 射出成形温度(℃) 低密度ポリエチレン(日本ユニカーGS-360) 210 ナイロン(宇部興産)1013B 240 ポリ塩化ビニル ゼオン103EP 200Table 4 Synthetic resin Injection molding temperature (° C) Low density polyethylene (Nihon Unicar GS-360) 210 Nylon (Ube Industries) 1013B 240 Polyvinyl chloride Zeon 103EP 200
【００５０】[0050]
【表５】 [Table 5]
【００５１】[0051]
【発明の効果】以上のように、本発明に係る無機質抗菌
剤は、安定性のある白色系の優れた抗菌力を有し、これ
を樹脂に配合すると耐熱、耐色性を改善した抗菌性樹脂
組成物を提供することができる。As described above, the inorganic antibacterial agent according to the present invention has a stable white antibacterial activity, and when it is mixed with a resin, the antibacterial activity has improved heat resistance and color resistance. A resin composition can be provided.
フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) A01N 61/00 A01N 25/10 A01N 59/16 A01N 59/20 Continuation of the front page (58) Field surveyed (Int.Cl. 7 , DB name) A01N 61/00 A01N 25/10 A01N 59/16 A01N 59/20
Claims (8)
粉末を圧着担持してなることを特徴とする無機質抗菌
剤。1. An inorganic antibacterial agent comprising a synthetic zeolite carrier and a fine antibacterial metal powder pressed and supported.
粉末を全量当り０．１〜１０重量％担持してなる請求項
１記載の無機質抗菌剤。2. The inorganic antibacterial agent according to claim 1, wherein the synthetic zeolite carrier carries fine antibacterial metal powder in an amount of 0.1 to 10% by weight based on the total amount.
０）が０．１〜５μｍであって、Ｄ５０の１／２から３
／２の範囲にある粒度部分が少なくとも５０重量％であ
る請求項１または２記載の無機質抗菌剤。3. The synthetic zeolite carrier has an average particle size (D5
0) is 0.1 to 5 μm, and is か ら to 3 of D50.
The inorganic antibacterial agent according to claim 1 or 2, wherein the particle size portion in the range of / 2 is at least 50% by weight.
イトを他のカチオンとイオン交換により置換した金属置
換合成ゼオライトである請求項１ないし３のいずれか１
項記載の無機質抗菌剤。4. The synthetic zeolite carrier according to claim 1, wherein the zeolite carrier is a metal-substituted synthetic zeolite obtained by replacing sodium zeolite with another cation by ion exchange.
Item 10. The inorganic antibacterial agent according to the above.
≦２０、０≦ｚ≦２０、Ｍは１価または２価カチオンを
表す）で表されるものであって、残留ナトリウムがＮａ
2Ｏとして１０重量％以下である請求項１ないし４のい
ずれか１項記載の無機質抗菌剤。5. A metal-substituted synthetic zeolite, 2 O (wherein the general formula xM n / 2 O · Al 2 O 3 · ySiO 2 · zH, n is the valence, 0.8 ≦ x ≦ 1.2 1.8 ≦ y
≦ 20, 0 ≦ z ≦ 20, M represents a monovalent or divalent cation), and the residual sodium is Na
The inorganic antibacterial agent according to any one of claims 1 to 4, wherein 2 O is 10% by weight or less.
の混合物を摩砕により均一に混合して微細な抗菌性金属
粉末を合成ゼオライト担体に圧着担持させることを特徴
とする無機質抗菌剤の製造方法。6. A method for producing an inorganic antibacterial agent, wherein a mixture of a synthetic zeolite powder and an antibacterial metal powder is uniformly mixed by grinding, and a fine antibacterial metal powder is pressure-supported on a synthetic zeolite carrier. .
無機質抗菌剤の製造方法。7. The method for producing an inorganic antibacterial agent according to claim 6, wherein the grinding is performed by a ball mill.
無機質抗菌剤を合成樹脂１００重量部に対し、０．０５
〜５０重量部含有させてなる抗菌性樹脂組成物。8. The inorganic antibacterial agent according to claim 1 in an amount of 0.05 to 100 parts by weight of the synthetic resin.
An antimicrobial resin composition containing up to 50 parts by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23050491A JP3159485B2 (en) | 1991-09-10 | 1991-09-10 | Inorganic antibacterial agent, production method thereof and antibacterial resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23050491A JP3159485B2 (en) | 1991-09-10 | 1991-09-10 | Inorganic antibacterial agent, production method thereof and antibacterial resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0570315A JPH0570315A (en) | 1993-03-23 |
| JP3159485B2 true JP3159485B2 (en) | 2001-04-23 |
Family
ID=16908802
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23050491A Expired - Fee Related JP3159485B2 (en) | 1991-09-10 | 1991-09-10 | Inorganic antibacterial agent, production method thereof and antibacterial resin composition |
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| Country | Link |
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|---|---|---|---|---|
| US6357678B1 (en) | 1999-10-29 | 2002-03-19 | Albermarle Corporation | Process for producing ultra finely-divided zeolite powder |
| KR101887205B1 (en) * | 2016-10-25 | 2018-08-09 | 한국생산기술연구원 | Manufacturing method of antibacterial materials using cation exchange reaction and antibacterial materials manufactured therefrom |
| KR102296631B1 (en) * | 2021-01-04 | 2021-09-01 | 주식회사 케이씨씨 | Coating Composition |
| KR102236172B1 (en) * | 2021-01-04 | 2021-04-05 | 주식회사 케이씨씨 | Coating Composition |
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| Publication number | Publication date |
|---|---|
| JPH0570315A (en) | 1993-03-23 |
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