JPH0672816A - Antimicrobial agent and antimicrobial resin or rubber composition - Google Patents
Antimicrobial agent and antimicrobial resin or rubber compositionInfo
- Publication number
- JPH0672816A JPH0672816A JP33759491A JP33759491A JPH0672816A JP H0672816 A JPH0672816 A JP H0672816A JP 33759491 A JP33759491 A JP 33759491A JP 33759491 A JP33759491 A JP 33759491A JP H0672816 A JPH0672816 A JP H0672816A
- Authority
- JP
- Japan
- Prior art keywords
- antimicrobial
- resin
- antimicrobial agent
- mol
- rubber
- 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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Links
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- Agricultural Chemicals And Associated Chemicals (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、新規な抗微生物剤に関
する。さらに詳しくは、それ自体無毒性または極めて毒
性が少なく、耐熱性及び耐候性が高く、微粒子でかつ樹
脂、ゴムおよび塗料中への分散性に優れ、更に樹脂、ゴ
ムおよび塗料中へ配合するとそれらの熱安定性を向上さ
せる等の特徴を有する抗微生物剤、具体的には抗菌剤、
抗カビ剤に関する。FIELD OF THE INVENTION The present invention relates to a novel antimicrobial agent. More specifically, it is non-toxic or extremely non-toxic in itself, has high heat resistance and weather resistance, is fine particles, and has excellent dispersibility in resins, rubbers and paints. An antimicrobial agent having characteristics such as improving thermal stability, specifically an antibacterial agent,
Regarding antifungal agents.
【０００２】[0002]
【従来の技術】温度が比較的高く、しかも湿度が高い、
例えば日本のような気候風土は、微生物の繁殖に適して
いる。このため、飲料水、食品等に微生物（細菌）が発
生して、人命に重大な影響をもたらすおそれがある。ま
た食品、化粧品、プラスチックス製品、壁紙、自動車用
内外装品、建材、電線、ケーブル、合成皮革、シーラン
ト、ゴムホース、接着剤、ルーフィング、床材、木材、
塗料等に微生物（カビ）が発生して、変色、悪臭、強度
劣化を生じる。例えば電線であれば漏電につながり、火
災の発生、感電等の危険がある。また微生物による貴重
な文化財の損傷、プラスチックスに発生したカビに起因
する癌、アレルギー性肺炎の発症、発生したバクテリア
を餌とする大量のダニ発生、白癬菌の寄生による水虫、
頑癬の発症等の被害をもたらす。2. Description of the Related Art The temperature is relatively high and the humidity is high.
Climate climates such as Japan are suitable for the reproduction of microorganisms. Therefore, microorganisms (bacteria) may be generated in drinking water, foods, etc., which may seriously affect human life. In addition, food, cosmetics, plastic products, wallpaper, interior and exterior products for automobiles, building materials, electric wires, cables, synthetic leather, sealants, rubber hoses, adhesives, roofing, flooring, wood,
Microbes (mildew) are generated in paints, causing discoloration, bad odor, and strength deterioration. For example, if it is an electric wire, it may lead to electric leakage, which may cause a fire, electric shock, or the like. In addition, damage to valuable cultural properties by microorganisms, cancer caused by mold on plastics, onset of allergic pneumonia, outbreak of a large number of mites that feed on the bacteria that occur, athlete's foot caused by parasitic of Trichophyton,
It causes damage such as the development of psoriasis.
【０００３】上記したような微生物災害を防止する必要
性が近年ますます高まりつつあり、種々の抗微生物剤が
市販されている。これらの抗微生物剤を分類すると、塩
素、臭素、ヨウ素等を含有するハロゲン化合物；亜ヒ酸
銅、酸化第一銅、硝酸銀、銀、銅等を含有するガラス等
の無機化合物；アミン、トリアジン等の窒素化合物；ヒ
素、銅、水銀、錫、亜鉛等の有機金属化合物；イソチア
ゾロン、ピリチオン、チオシアン酸塩等の有機硫黄化合
物；アルキルジメチルベンジルアンモニウム化合物等の
第四級アンモニウム化合物；塩素化フェノール、ビスフ
ェノール、Ｏ−フェニルフェノール等のフェノール化合
物等がある。In recent years, the need to prevent the above-mentioned microbial disasters has been increasing, and various antimicrobial agents are commercially available. When these antimicrobial agents are classified, halogen compounds containing chlorine, bromine, iodine, etc .; inorganic compounds such as glasses containing copper arsenite, cuprous oxide, silver nitrate, silver, copper, etc .; amines, triazines, etc. Nitrogen compounds; organometallic compounds such as arsenic, copper, mercury, tin and zinc; organic sulfur compounds such as isothiazolone, pyrithione and thiocyanate; quaternary ammonium compounds such as alkyldimethylbenzylammonium compounds; chlorinated phenols, bisphenols , O-phenylphenol, and other phenol compounds.
【０００４】[0004]
【発明が解決しようとする課題】最近の傾向として、安
全性と環境に対する影響が重要視され、この傾向は一層
強まるものと考えられている。しかし、既存の抗微生物
剤は、毒性の高いものが多く、しかも水溶性で環境汚染
も無視できないものが多い。As a recent tendency, importance is attached to safety and the influence on the environment, and this tendency is considered to be further strengthened. However, many of the existing antimicrobial agents are highly toxic, water-soluble, and environmental pollution cannot be ignored.
【０００５】さらに既存抗微生物剤の添加は、製品の耐
熱性、耐候性の劣化、樹脂やゴムの加工温度での分解、
発泡、粒子が粗いことに起因する塗料中での分散不良、
製品外観の低下、機械的強度の低下等の問題を生じてい
た。Furthermore, addition of existing antimicrobial agents causes deterioration of heat resistance and weather resistance of products, decomposition of resins and rubbers at processing temperatures,
Poor dispersion in paint due to foaming and coarse particles,
There were problems such as deterioration of product appearance and deterioration of mechanical strength.
【０００６】本発明は、無毒性か無毒性に近く、水や有
機溶媒に不溶もしくは難溶で環境汚染の問題を生じるこ
とがない抗微生物剤の提供を目的とする。さらに本発明
は、それ自体熱および紫外線に対し安定であり、樹脂、
ゴム、塗料中に良く分散し、かつ製品の特徴を損なうこ
とのない抗微生物剤、および該抗微生物剤を含有する樹
脂またはゴム組成物の提供を目的とする。An object of the present invention is to provide an antimicrobial agent which is non-toxic or nearly non-toxic and insoluble or hardly soluble in water or an organic solvent and does not cause a problem of environmental pollution. Further, the present invention is itself stable to heat and ultraviolet light, resin,
An object of the present invention is to provide an antimicrobial agent that is well dispersed in rubber and paint and does not impair the characteristics of the product, and a resin or rubber composition containing the antimicrobial agent.
【０００７】[0007]
【課題を解決するための手段】本発明は、 下記式
（１） （Ｍ1 2+）1-x（Ｍ2 2+）x（ＯＨ）2 （１） ［式中、Ｍ1 2+はＭｇおよび／またはＣａを、Ｍ2 2+はＣ
ｕおよび／またはＺｎを示し、ｘは０.０００１≦ｘ＜
０.９、好ましくは０.０００１≦ｘ＜０.４、さらに好
ましくは０.００１≦ｘ≦０.２の範囲の数を示す］の複
合金属水酸化物を有効成分として含有する抗微生物剤を
提供する。The present invention provides the following formula (1) (M 1 2+ ) 1-x (M 2 2+ ) x (OH) 2 (1) [wherein M 1 2+ is Mg and / or Ca, M 2 2+ is C
u and / or Zn, and x is 0.0001 ≦ x <
0.9, preferably 0.0001 ≤ x <0.4, more preferably 0.0001 ≤ x ≤ 0.2]] as an active ingredient I will provide a.
【０００８】さらに本発明は、樹脂またはゴム１００重
量部に対し、上記抗微生物剤を０.００１〜５０重量
部、好ましくは０.００１〜１５重量部、さらに好まし
くは０.０１〜５重量部含有する抗微生物性樹脂または
ゴム組成物を提供する。Further, in the present invention, 0.001 to 50 parts by weight, preferably 0.001 to 15 parts by weight, more preferably 0.01 to 5 parts by weight of the above-mentioned antimicrobial agent is added to 100 parts by weight of resin or rubber. An antimicrobial resin or rubber composition containing the same is provided.
【０００９】本発明者は、既存の有機系抗微生物剤が毒
性、耐熱性、耐候性に問題があり、他方無機化合物系
は、効果が低く、樹脂やゴムの物性を損なう等の問題が
あることから、銅イオンと亜鉛イオンは毒性が極めて少
ないかもしくは無毒性であること、および安価であるこ
とに着目した。さらにこれら銅および亜鉛系の無機系抗
微生物剤の上記問題の発生する原因について鋭意研究し
た結果、水に対する難溶性にあると推定した。The present inventor has found that existing organic antimicrobial agents have problems in toxicity, heat resistance and weather resistance, while inorganic compound agents have problems such as low effect and impairing physical properties of resins and rubbers. Therefore, we paid attention to the fact that copper ion and zinc ion have very little or no toxicity and are inexpensive. Further, as a result of intensive studies on the causes of the above problems of these copper- and zinc-based inorganic antimicrobial agents, it was presumed that they were poorly soluble in water.
【００１０】即ち、難溶性であるため、有効成分である
銅イオンおよび亜鉛イオンの濃度が効果の出る濃度まで
上昇し難いこと、そして、酸化第一銅、酸化亜鉛等の既
存の抗微生物剤は固体酸性であるため、樹脂およびゴム
の耐熱性、耐候性を劣化させるものと推定した。That is, since it is sparingly soluble, it is difficult to raise the concentration of the active ingredient, copper ion and zinc ion, to a concentration at which the effect is exerted, and existing antimicrobial agents such as cuprous oxide and zinc oxide are Since it is a solid acid, it was presumed that the heat resistance and weather resistance of the resin and rubber would deteriorate.
【００１１】そこで上記無機化合物系抗微生物剤の有す
る問題を同時に解決すべく鋭意研究に努めた結果本発明
を完成した。即ち本発明者は、Ｃａ（ＯＨ）2および／
またはＭｇ（ＯＨ）2に、有効成分であるＣｕ2+および
／またはＺｎ2+を固溶させることにより、Ｃｕ2+および
／またはＺｎ2+を、Ｃａ（ＯＨ）2またはＭｇ（ＯＨ）2
の水に対する溶解性、即ち微溶性〜微難溶性に近いレベ
ルで溶出させることができ、これにより著しく抗微生物
性が向上できることを見いだした。Ｃａ（ＯＨ）2およ
びＭｇ（ＯＨ）2は、固体塩基であるため、樹脂やゴム
の耐熱性、耐候性をむしろ向上させる働きがある。また
本発明の複合金属水酸化物の分解開始温度は約３００℃
以上であり、樹脂やゴムの加工温度での分解、発泡の問
題を生ずることがない。また、銅イオンおよび亜鉛イオ
ン濃度をかなり低く抑えた式（１）の化合物を用いても
抗微生物性が発揮できることによる毒性の一層の低下、
さらには無毒性とできる等の利点を奏することを見いだ
した。また亜鉛イオンを含有する式（１）の化合物は、
白色度に優れ、添加する樹脂等を着色しないという利点
をも有する。Therefore, the present invention was completed as a result of intensive research aimed at simultaneously solving the problems of the above-mentioned inorganic compound type antimicrobial agents. That is, the present inventor has found that Ca (OH) 2 and / or
Or Mg (OH) 2, by solid solution Cu 2+ and / or Zn 2+ as an active ingredient, a Cu 2+ and / or Zn 2+, Ca (OH) 2 or Mg (OH) 2
It was found that the compound can be eluted at a level close to that of water, that is, slightly soluble to slightly sparingly soluble, whereby the antimicrobial property can be remarkably improved. Since Ca (OH) 2 and Mg (OH) 2 are solid bases, they have the function of improving the heat resistance and weather resistance of resins and rubbers. The decomposition start temperature of the composite metal hydroxide of the present invention is about 300 ° C.
As described above, the problems of decomposition and foaming of resin and rubber at the processing temperature do not occur. Further, even if the compound of formula (1) in which the concentration of copper ion and zinc ion is suppressed to a considerably low level is used, the toxicity can be further reduced due to the ability to exhibit antimicrobial properties.
Furthermore, they have found that they have advantages such as being non-toxic. The compound of formula (1) containing zinc ion is
It also has the advantage that it has excellent whiteness and does not color the added resin.
【００１２】本発明の式（１）で表される化合物は、本
発明者が発見した新規な化合物であり、特願平３−３６
８１３号および平成３年１１月７日付特許願“複合金属
水酸化物およびその製造方法”に記載されたように、Ｃ
ａ（ＯＨ）2および／またはＭｇ（ＯＨ）2にＣｕ2+およ
び／またはＺｎ2+が固溶した、Ｃａ（ＯＨ）2またはＭ
ｇ（ＯＨ）2と同じ結晶構造を有する化合物であり、粉
末Ｘ線回折によりＣａ（ＯＨ）2、Ｍｇ（ＯＨ）2と殆ど
同じ回折パターンを与える。The compound represented by the formula (1) of the present invention is a novel compound discovered by the present inventor.
No. 813 and the patent application “Composite metal hydroxide and its manufacturing method” dated November 7, 1991, C
Ca (OH) 2 or M in which Cu 2+ and / or Zn 2+ is solid-dissolved in a (OH) 2 and / or Mg (OH) 2.
It is a compound having the same crystal structure as g (OH) 2 and gives almost the same diffraction pattern as Ca (OH) 2 and Mg (OH) 2 by powder X-ray diffraction.
【００１３】式（１）において、ｘの値が０.９を超え
ると式（１）の固溶体が生成しなくなり、また抗微生物
効果も殆ど示さない。ｘの値が０.４を超えるとＣａ
（ＯＨ）2またはＭｇ（ＯＨ）2に固溶しない銅および亜
鉛の塩基性塩、酸化物が副生し易くなるので抗微生物効
果が頭打ちとなるので好ましくない。ｘの値が小さ過ぎ
ると有効成分である銅イオンおよび／または亜鉛イオン
の放出濃度が低くなり本発明の効果不十分となる。また
銅および／または亜鉛の式（１）の化合物中の濃度が高
くなる程、水に対する銅イオンおよび／または亜鉛イオ
ンの放出性が低くなり、抗微生物効果が不十分となる傾
向がある。このため、本発明の抗微生物剤のｘの範囲
は、０.０００１≦ｘ＜０.９、好ましくは０.０００１
≦ｘ＜０.４、さらに好ましくは０.００１≦ｘ≦０.２
である。なお本発明において、副生した銅および亜鉛の
塩基性塩、酸化物、水酸化物を、式（１）の複合金属水
酸化物と混合された状態で抗微生物剤として適用しても
差し支えはない。In the formula (1), when the value of x exceeds 0.9, the solid solution of the formula (1) is not formed, and the antimicrobial effect is hardly exhibited. If the value of x exceeds 0.4, Ca
It is not preferable because basic salts and oxides of copper and zinc that are not solid-dissolved in (OH) 2 or Mg (OH) 2 are likely to be produced as a by-product, and the antimicrobial effect reaches the ceiling. If the value of x is too small, the release concentration of copper ions and / or zinc ions, which are active ingredients, will be low, and the effect of the present invention will be insufficient. In addition, the higher the concentration of copper and / or zinc in the compound of formula (1), the lower the release of copper ions and / or zinc ions to water, and the antimicrobial effect tends to be insufficient. Therefore, the range of x of the antimicrobial agent of the present invention is 0.0001 ≦ x <0.9, preferably 0.0001.
≦ x <0.4, more preferably 0.001 ≦ x ≦ 0.2
Is. In the present invention, the by-produced basic salts, oxides and hydroxides of copper and zinc may be applied as an antimicrobial agent in a state of being mixed with the complex metal hydroxide of the formula (1). Absent.
【００１４】本発明の抗微生物剤の製造方法は、Ｃａ2+
および／またはＭｇ2+と、Ｃｕ2+および／またはＺｎ2+
とを含有する水溶液に、これらカチオンの合計量に対し
てほぼ当量以下のアルカリ性物質を加え、撹拌下に反応
させ、必要に応じ、さらに反応物を約１００〜２００℃
でオートクレーブを用いて水熱処理した後、水洗、脱
水、乾燥、粉砕、分級等の慣用の手段を適宜選択して用
いることにより製造される。樹脂、ゴム中での分散性、
親和性をさらに高めるため、アニオン系界面活性剤、ア
ルミニウム、チタネート系カップリング剤等を用いて、
慣用の方法で表面処理してもよい。The method for producing an antimicrobial agent of the present invention comprises Ca 2+
And / or Mg 2+ and Cu 2+ and / or Zn 2+
To an aqueous solution containing and, an alkaline substance in an amount equal to or less than the total amount of these cations is added and reacted with stirring. If necessary, the reaction product is further heated to about 100 to 200 ° C.
After being hydrothermally treated by using an autoclave in 1, a conventional means such as washing with water, dehydration, drying, pulverization and classification is appropriately selected and used. Dispersibility in resin and rubber,
To further improve the affinity, anionic surfactants, aluminum, titanate coupling agents, etc. are used.
The surface may be treated by a conventional method.
【００１５】本発明の抗微生物剤の利用分野としては、
飲料水、食品、樹脂、ゴム、壁紙、浴室内装材、電線、
床材、シャワーカーテン、発泡ウレタン、ブイロープ、
ビニルシート、農業用フィルム、合成皮革、シーラン
ト、建材、家具、繊維製品、例えば布、テント、靴下、
不織布、塗料、接着剤、木材、竹材、化粧品、プール、
クーリングタワー等、微生物による悪影響を受けるおそ
れのある各種分野を挙げることができる。The fields of application of the antimicrobial agent of the present invention include:
Drinking water, food, resin, rubber, wallpaper, bathroom interior materials, electric wires,
Floor material, shower curtain, urethane foam, buoy rope,
Vinyl sheets, agricultural films, synthetic leather, sealants, building materials, furniture, textile products such as cloth, tents, socks,
Non-woven fabric, paint, adhesive, wood, bamboo, cosmetics, pool,
Examples include various fields that may be adversely affected by microorganisms, such as cooling towers.
【００１６】本発明の抗微生物剤の添加量は、目的物１
００重量部に対して通常０.００１〜５０重量部、好ま
しくは０.００１〜１５重量部、さらに好ましくは０.０
１〜５重量部であるが、用途に応じ適宜選択できる。本
発明の抗微生物剤は、平均２次粒子径約０.１〜１μｍ
の微粒子することができ、しかも約３００℃までの加工
温度でも安定で、さらに紫外線に対しても安定である。
このため、繊維を紡糸する前に混練分散した後紡糸する
ことができる。また樹脂やゴムの加工温度で分解発泡す
るトラブルを生じることなく、良好な分散性を示すの
で、成形品外観のみならず、機械的強度を損なうことも
ない。The addition amount of the antimicrobial agent of the present invention is the same as the target product 1
It is usually 0.001 to 50 parts by weight, preferably 0.001 to 15 parts by weight, and more preferably 0.0 to 100 parts by weight.
It is 1 to 5 parts by weight, but can be appropriately selected depending on the application. The antimicrobial agent of the present invention has an average secondary particle diameter of about 0.1 to 1 μm.
Can be formed into fine particles, and is stable even at a processing temperature up to about 300 ° C., and is also stable against ultraviolet rays.
Therefore, the fibers can be kneaded and dispersed before spinning and then spun. Further, since it exhibits good dispersibility without causing trouble of decomposition and foaming at the processing temperature of resin or rubber, not only the appearance of the molded product but also the mechanical strength is not impaired.
【００１７】本発明の抗微生物剤は、固体塩基であるた
め、酸やハロゲンを中和し、不活性化する働きが、Ｍｇ
（ＯＨ）2やＣａ（ＯＨ）2と同等以上にあるため、樹脂
やゴムの熱安定性、耐候性を改善する。Since the antimicrobial agent of the present invention is a solid base, it has the function of neutralizing and deactivating acid and halogen.
Since it is equal to or more than (OH) 2 and Ca (OH) 2, it improves the thermal stability and weather resistance of resins and rubbers.
【００１８】本発明で用いられる樹脂およびゴムを例示
すると次の通りであるが、これらの樹脂およびゴムに限
定されるものではない。ポリエチレン、エチレンと他の
オレフィンとの共重合体、エチレンと酢酸ビニル、アク
リル酸エチルまたはアクリル酸メチルとの共重合体、ポ
リプロピレン、プロピレンと他のα−オレフィンとの共
重合体、ポリブテン−１、ポリスチレン、スチレンとア
クリロニトリル、エチレンとプロピレンジエンゴムまた
はブタジエンとの共重合体、酢酸ビニル、ポリアクリレ
ート、ポリメタクリレート、ポリウレタン、ポリエステ
ル、ポリエーテル、ポリアミド、ポリ塩化ビニル、塩化
ビニルと酢酸ビニルとの共重合体、ポリ塩化ビニリデン
等の熱可塑性樹脂；フェノール樹脂、メラミン樹脂、エ
ポキシ樹脂、不飽和ポリエステル樹脂、アルキド樹脂等
の熱硬化性樹脂、ＥＰＤＭ、ＳＢＲ、ＮＢＲ、ブチルゴ
ム、イソプレンゴム、クロロスルホン化ポリエチレン等
のゴム。Examples of the resins and rubbers used in the present invention are as follows, but the resins and rubbers are not limited to these. Polyethylene, copolymers of ethylene and other olefins, copolymers of ethylene and vinyl acetate, ethyl acrylate or methyl acrylate, polypropylene, copolymers of propylene and other α-olefins, polybutene-1, Polystyrene, styrene and acrylonitrile, ethylene and propylene diene rubber or butadiene copolymer, vinyl acetate, polyacrylate, polymethacrylate, polyurethane, polyester, polyether, polyamide, polyvinyl chloride, vinyl chloride and vinyl acetate copolymerization Thermoplastic resin such as coalesce, polyvinylidene chloride, etc .; thermosetting resin such as phenol resin, melamine resin, epoxy resin, unsaturated polyester resin, alkyd resin, EPDM, SBR, NBR, butyl rubber, isoprene rubber, chlorosulfonate Rubber such as ethylene.
【００１９】以下実施例により本発明をさらに詳細に説
明する。 実施例１ ２.０モル／リットルのＣａ（ＯＨ）2スラリー５００ミ
リリットルと１.０モル／リットルの硝酸亜鉛水溶液５
０ミリリットルを、予め４０℃の２００ミリリットルの
脱イオン水を入れた容量１リットルのステンレス製容器
に、撹拌下に約２分間で全量加え、その後さらに１０分
間撹拌を継続し反応させた。得られた白色スラリーを脱
水、水洗、乾燥、粉砕した。The present invention will be described in more detail with reference to the following examples. Example 1 500 ml of 2.0 mol / l Ca (OH) 2 slurry and 1.0 mol / l zinc nitrate aqueous solution 5
The total amount of 0 ml was added to a stainless steel container having a capacity of 1 liter, which was previously filled with 200 ml of deionized water at 40 ° C., under stirring for about 2 minutes, and then the reaction was continued by further stirring for 10 minutes. The obtained white slurry was dehydrated, washed with water, dried and pulverized.
【００２０】粉砕物の粉末Ｘ線回折パターンは、僅かに
高角度側にシフトしていることを除き、Ｃａ（ＯＨ）2
の回折パターンと同じであった。キレート滴定法により
化学組成を、超音波で分散処理した後レーザービームを
用いてマイクロトラック法により平均２次粒子径を測定
した。抗菌性テストは、寒天平板培地に任意濃度に調製
した接種用菌液を塗抹して培養した後、菌の発育が阻止
される最低濃度をもって、最小発育阻止濃度とした。こ
の濃度が低い程、抗菌性が高いことを意味する。測定結
果を表１に示す。The powder X-ray diffraction pattern of the ground product was Ca (OH) 2 except that it was slightly shifted to the higher angle side.
The diffraction pattern was the same. The chemical composition was measured by the chelate titration method, and the average secondary particle diameter was measured by the microtrack method using a laser beam after the dispersion treatment with ultrasonic waves. In the antibacterial test, the minimum growth inhibitory concentration was defined as the lowest concentration at which the growth of the bacteria was inhibited after the culture was performed by smearing the agar plate medium with the bacterial solution for inoculation prepared at an arbitrary concentration. The lower the concentration, the higher the antibacterial property. The measurement results are shown in Table 1.
【００２１】実施例２ １.１モル／リットルの塩化カルシウムと０.９モル／リ
ットルの硝酸亜鉛の混合水溶液５００ミリリットルと、
４モル／リットルの水酸化ナトリウム５００ミリリット
ルを、予め４０℃の３００ミリリットルの脱イオン水を
加えた容量２リットルのステンレス製容器に、撹拌下に
約５分間で同時に全量加え、反応させた。反応物を濾
過、水洗、乾燥、粉砕した。Example 2 500 ml of a mixed aqueous solution of 1.1 mol / l calcium chloride and 0.9 mol / l zinc nitrate,
All 500 ml of 4 mol / liter sodium hydroxide was simultaneously added to a stainless steel container having a volume of 2 liter, to which 300 ml of deionized water at 40 ° C. had been added, under stirring for about 5 minutes at the same time. The reaction product was filtered, washed with water, dried and ground.
【００２２】この粉末のＸ線回折パターンは、僅かに高
角度側にシフトした他はＣａ（ＯＨ）2の回折パターン
と同じもの、およびＣａ［Ｚｎ（ＯＨ）3］2・２Ｈ2Ｏ
の回折パターンを示した。測定結果を表１に示す。The X-ray diffraction pattern of this powder was the same as that of Ca (OH) 2 except that it was slightly shifted to the higher angle side, and Ca [Zn (OH) 3 ] 2 .2H 2 O.
The diffraction pattern of The measurement results are shown in Table 1.
【００２３】実施例３ １.９６モル／リットルの塩化カルシウムと０.０４モル
／リットルの塩化亜鉛の混合水溶液５００ミリリットル
と、４モル／リットルの水酸化カリウム５００ミリリッ
トルを、実施例２と同様に操作して粉末を得た。この粉
末のＸ線回折パターンは、僅かに高角度側にシフトした
他はＣａ（ＯＨ）2の回折パターンと同じであった。測
定結果を表１に示す。Example 3 500 ml of a mixed aqueous solution of 1.96 mol / l calcium chloride and 0.04 mol / l zinc chloride and 500 ml of 4 mol / l potassium hydroxide were added in the same manner as in Example 2. Manipulation gave a powder. The X-ray diffraction pattern of this powder was the same as that of Ca (OH) 2 except that it was slightly shifted to the higher angle side. The measurement results are shown in Table 1.
【００２４】実施例４ ２モル／リットルのＣａ（ＯＨ）2スラリー５００ミリ
リットルと、１.０モル／リットルの塩化第２銅水溶液
１５０ミリリットルとを実施例１と同様に操作して、粉
末を得た。この粉末のＸ線回折パターンは、僅かに高角
度側にシフトした他はＣａ（ＯＨ）2の回折パターンと
同じであった。測定結果を表１に示す。Example 4 500 ml of 2 mol / liter Ca (OH) 2 slurry and 150 ml of 1.0 mol / liter cupric chloride aqueous solution were treated in the same manner as in Example 1 to obtain a powder. It was The X-ray diffraction pattern of this powder was the same as that of Ca (OH) 2 except that it was slightly shifted to the higher angle side. The measurement results are shown in Table 1.
【００２５】実施例５ ２モル／リットルのＣａ（ＯＨ）2スラリー５００ミリ
リットルと、１.０モル／リットルの塩化第２銅水溶液
５５０ミリリットルとを、予め３０℃の脱イオン水を入
れ撹拌している容量２リットルの反応槽に、ほぼ同時に
加え、約５分間で全量加えた後、さらに約１０分間撹拌
を継続し反応させた。この後、実施例１と同様に処理し
て粉末を得た。この粉末のＸ線回折パターンは、少し高
角度側にシフトした他はＣａ（ＯＨ）2と同じ回折パタ
ーン、および塩基性塩化銅の回折パターンとを示した。
測定結果を表１に示す。Example 5 500 ml of 2 mol / liter Ca (OH) 2 slurry and 550 ml of 1.0 mol / liter cupric chloride aqueous solution were previously charged with deionized water at 30 ° C. and stirred. Into a reaction tank having a capacity of 2 liters, they were added almost at the same time, and after the total amount was added in about 5 minutes, stirring was continued for about 10 minutes to carry out the reaction. Then, the same treatment as in Example 1 was carried out to obtain a powder. The X-ray diffraction pattern of this powder showed the same diffraction pattern as Ca (OH) 2 except that it was shifted to a slightly higher angle side, and that of basic copper chloride.
The measurement results are shown in Table 1.
【００２６】実施例６ ３.０モル／リットルの塩化マグネシウム水溶液５リッ
トルに撹拌下に２モル／リットルのアンモニア水６００
ミリリットルを入れ、４０℃に保持して５日間反応させ
た。この系に１.０モル／リットルの塩化第２銅水溶液
２０ミリリットルを加え、約３０分間反応させた後、脱
水、水洗し、さらに脱水したケーキ状物を、９０℃に加
熱した５モル／リットルの水酸化ナトリウム水溶液５０
０ミリリットルに撹拌下に加え、約２０分間反応させ
た。反応後、濾過、水洗、乾燥し、ついで篩過した。こ
の粉末は、繊維状外形の結晶で、粉末Ｘ線回折パターン
は僅かに低角度側にシフトした他は、Ｍｇ（ＯＨ）2の
回折パターンと同じであった。測定結果を表１に示す。Example 6 To 5 liters of a 3.0 mol / liter magnesium chloride aqueous solution, 600 mol of 2 mol / liter ammonia water was added with stirring.
After adding milliliter, the mixture was kept at 40 ° C. and reacted for 5 days. To this system, 20 ml of a 1.0 mol / liter cupric chloride aqueous solution was added, reacted for about 30 minutes, dehydrated and washed with water, and the dehydrated cake was heated at 90 ° C. to 5 mol / liter. 50 sodium hydroxide solution
The mixture was added to 0 ml with stirring and reacted for about 20 minutes. After the reaction, the mixture was filtered, washed with water, dried, and then sieved. This powder was a crystal having a fibrous outer shape, and was the same as the diffraction pattern of Mg (OH) 2 except that the powder X-ray diffraction pattern was slightly shifted to the lower angle side. The measurement results are shown in Table 1.
【００２７】実施例７ ０.２モル／リットルの塩化マグネシウムと０.１２モル
／リットルの硝酸亜鉛の混合水溶液５００ミリリットル
と、２.０モル／リットルのＣａ（ＯＨ）2スラリー５０
０ミリリットルとを実施例１と同様に操作して反応さ
せ、粉末を得た。この粉末のＸ線回折パターンは、僅か
に低角度側にシフトした他はＭｇ（ＯＨ）2の回折パタ
ーンと同じであった。測定結果を表１に示す。Example 7 500 ml of a mixed aqueous solution of 0.2 mol / liter magnesium chloride and 0.12 mol / liter zinc nitrate and 2.0 mol / liter Ca (OH) 2 slurry 50
0 ml was reacted in the same manner as in Example 1 to cause a reaction, and a powder was obtained. The X-ray diffraction pattern of this powder was the same as that of Mg (OH) 2 except that it was slightly shifted to the lower angle side. The measurement results are shown in Table 1.
【００２８】比較例１ ０.２モル／リットルの塩化カルシウムと１.８モル／リ
ットルの硝酸亜鉛の混合水溶液５００ミリリットルと、
４モル／リットルの水酸化ナトリウム５００ミリリット
ルとを、実施例２と同様に操作して反応させ、粉末を得
た。この粉末のＸ線回折パターンは、ＺｎＯのみであっ
た。測定結果を表１に示す。Comparative Example 1 500 ml of a mixed aqueous solution of 0.2 mol / liter calcium chloride and 1.8 mol / liter zinc nitrate,
500 ml of 4 mol / liter sodium hydroxide were treated and reacted in the same manner as in Example 2 to obtain a powder. The X-ray diffraction pattern of this powder was only ZnO. The measurement results are shown in Table 1.
【００２９】比較例２、３ 市販の抗菌剤である酸化第１銅（比較例２）と銅担持ホ
ウケイ酸ガラス（比較例３）の測定結果を表１に示す。Comparative Examples 2 and 3 Table 1 shows the measurement results of commercially available antibacterial agents cuprous oxide (Comparative Example 2) and copper-supported borosilicate glass (Comparative Example 3).
【００３０】 表１ 抗微生物剤 平均２次粒子径 抗菌性（％） （μｍ） 大腸菌 黄色ブドウ状球菌 実施例１ Ａ ０.９６ ０.１２５ ０.１ 実施例２ Ｂ １.２８ ０.２５ ０.１ 実施例３ Ｃ ０.８０ ０.１２５ ０.１ 実施例４ Ｄ ０.７２ ０.０５ ０.０５ 実施例５ Ｅ １.９１ ０.２５ ０.１ 実施例６ Ｆ ０.７６ ０.２５ ０.１２５ 実施例７ Ｇ ０.４３ ０.２５ ０.１２５ 比較例１ Ｈ ５.１４ １.０以上 １.０以上 比較例２ Ｃｕ2Ｏ １.６９ １.０以上 １.０以上 比較例３ Ｉ ２５.３ １.０ ０.５ 注：Ａ；Ｃａ0.95Ｚｎ0.05（ＯＨ）2 Ｂ；Ｃａ0.55Ｚｎ0.45（ＯＨ）2・ｍＨ2Ｏ Ｃ；Ｃａ0.98Ｃｕ0.02（ＯＨ）2 Ｄ；Ｃａ0.85Ｃｕ0.15（ＯＨ）2 Ｅ；Ｃａ0.55Ｃｕ0.45（ＯＨ）2-yＣｌy・ｍＨ2Ｏ Ｆ；Ｍｇ0.97Ｃｕ0.03（ＯＨ）2 Ｇ；Ｃａ0.84Ｍｇ0.10Ｚｎ0.06（ＯＨ）2 Ｈ；Ｃａ0.1Ｚｎ0.9Ｏy（ＯＨ）2-2y・ｍＨ2Ｏ Ｉ；ホウケイ酸ガラス−銅系抗菌剤（商品名“イオンピ
ュア”、石塚硝子(株)製） 抗菌性；最小発育阻止濃度Table 1 Antimicrobial Agent Average Secondary Particle Size Antibacterial (%) (Μm) E. coli Staphylococcus aureus Example 1 A 0.96 0.125 0.1 Example 2 B 1.28 0.25 0.1 Example 3 C 0.80 0.125 0.1 Example 4 D 0.72 0.05 0.05 Example 5 E 1.91 0.25 0.1 Example 6 F 0.76 0.25 0.125 Example 7 G 0.43 0.25 0.125 Comparison Example 1 H 5.14 1.0 or higher 1.0 or higher Comparative example 2 Cu 2 O 1.69 1.0 or higher 1.0 or higher Comparative example 3 I 25.3 1.0 0.5 0.5 Note: A; Ca 0.95 Zn 0.05 (OH) 2 B; Ca 0.55 Zn 0.45 (OH) 2 · mH 2 O C; Ca 0.98 Cu 0.02 (OH) 2 D; Ca 0.85 Cu 0.15 (OH) 2 E; Ca 0.55 Cu 0.45 (OH) 2 -y Cl y · mH 2 O F; Mg 0.97 Cu 0.03 (OH) 2 G; Ca 0.84 Mg 0.10 Zn 0.06 (OH) 2 H; Ca 0.1 Zn 0.9 O y (OH) 2-2y · mH 2 O I: Borosilicate glass-copper antibacterial agent (trade name "Ion Pure", manufactured by Ishizuka Glass Co., Ltd.) Antibacterial property: Minimum inhibitory concentration
【００３１】実施例８〜１１ 軟質塩化ビニルのシートを作成するため、下記配合比 ポリ塩化ビニル（平均重合度１３００） １００重量部 フタル酸ジオクチル ５０重量部 Ｂａ／Ｚｎ複合熱安定剤（商品名“ＫＶ６２Ｂ−４”、共同薬品(株)製） ２重量部 エポキシ化大豆油 ２重量部 抗カビ剤 １重量部 で均一に混合後、ロールミルを用いて、１７０℃で３分
間溶融混練した。次いでプレス成形機を用いて、厚さ１
ｍｍのシートに、１７０℃で２分間、２００ｋｇ／ｃｍ
2の圧力で成形したExamples 8 to 11 To prepare a soft vinyl chloride sheet, the following compounding ratio: Polyvinyl chloride (average degree of polymerization: 1300) 100 parts by weight Dioctyl phthalate 50 parts by weight Ba / Zn composite heat stabilizer (trade name " KV62B-4 ″, manufactured by Kyodo Yakuhin Co., Ltd.) 2 parts by weight Epoxidized soybean oil 2 parts by weight Antifungal agent 1 part by weight After uniform mixing, the mixture was melt-kneaded at 170 ° C. for 3 minutes using a roll mill. Then, using a press molding machine, thickness 1
mm sheet, 170kg for 2 minutes, 200kg / cm
Molded at a pressure of 2
【００３２】このシートに青カビを振りかけ、その後の
カビの成育状態を観察した。他方このシートを１９０℃
のオーブンに入れ、黒化するまでの時間を測定した。塩
化ビニルは、熱劣化すると黒化するので、黒化するまで
の時間が長い程熱安定性が優れていることを示す。測定
結果を表２に示す。Blue mold was sprinkled on this sheet, and the growth state of the mold thereafter was observed. On the other hand, this sheet is 190 ℃
It was put in the oven of No. 2 and the time until blackening was measured. Since vinyl chloride turns black when it is thermally deteriorated, the longer the time until blackening is, the better the thermal stability is. The measurement results are shown in Table 2.
【００３３】 表２ 抗カビ剤 熱安定性 抗カビ性評価結果（培養日数） 時間（分） ７ １４ ２１ ２８ 実施例８ Ｊ ７０ ０ ０ ０ ０ 実施例９ Ｋ ６０ ０ ０ ０ ０ 実施例１０ Ｌ ６０ ０ ０ ０ １ 実施例１１ Ｍ ７０ ０ ０ ０ １ 比較例４ 無添加 ４０ ３ ４ ４ ４ 注： Ｊ；Ｃａ0.95Ｚｎ0.05（ＯＨ）2 Ｋ；Ｃａ0.85Ｃｕ0.15（ＯＨ）2 Ｌ；Ｍｇ0.97Ｃｕ0.03（ＯＨ）2 Ｍ；Ｃａ0.84Ｍｇ0.10Ｚｎ0.06（ＯＨ）2 評価方法； ０；カビの発育が認められない １；カビの発育が僅かに認められる ２；カビの発育が少し認められる ３；カビの発育が中程度に認められる ４；カビの発育が激しく認められる。Table 2 Antifungal Agent Thermal Stability Antifungal Evaluation Results (Days of Culture) Time (minutes) 7 14 21 28 Example 8 J 70 0 0 0 0 Example 9 K 60 0 0 0 0 Example 10 L 60 0 0 0 1 Example 11 M 70 0 0 0 1 Comparative Example 4 No addition 40 3 4 4 4 Note: J; Ca 0.95 Zn 0.05 (OH) 2 K; Ca 0.85 Cu 0.15 (OH) 2 L; Mg 0.97 Cu 0.03 (OH) 2 M; Ca 0.84 Mg 0.10 Zn 0.06 (OH) 2 Evaluation method 0; no mold development 1; slight mold growth 2; mild mold growth 3; moderate mold growth 4; severe mold growth
【００３４】[0034]
【発明の効果】本発明によれば、水酸化カルシウムまた
は水酸化マグネシウムに銅イオンおよび／または亜鉛イ
オンを固溶させてなる新規な抗微生物剤が提供される。
本発明の抗微生物剤は、銅イオンおよび／または亜鉛イ
オンを適度の量で放出することにより抗微生物性を発揮
すると共に、樹脂やゴム中に含有させたときに樹脂やゴ
ムの物性を損なわないばかりでなく、これらの耐熱性、
耐候性をむしろ向上させる働きを有する。Industrial Applicability According to the present invention, there is provided a novel antimicrobial agent obtained by solid solution of copper ion and / or zinc ion in calcium hydroxide or magnesium hydroxide.
The antimicrobial agent of the present invention exhibits antimicrobial properties by releasing copper ions and / or zinc ions in an appropriate amount, and does not impair the physical properties of the resin or rubber when incorporated in the resin or rubber. Not only these heat resistance,
It has the function of improving weather resistance.
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成４年１２月４日[Submission date] December 4, 1992
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００７[Correction target item name] 0007
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【０００７】本発明は、 下記式（１） （Ｍ１ ２＋）１−ｘ（Ｍ２ ２＋）ｘ（ＯＨ）２ （１） ［式中、Ｍ１ ２＋はＭｇおよび／またはＣａを、Ｍ２
２＋はＣｕおよび／またはＺｎを示し、ｘは０．０００
１≦ｘ＜０．９、好ましくは０．０００１≦ｘ≦０．
４、さらに好ましくは０．０００１≦ｘ≦０．２の範囲
の数を示す］の複合金属水酸化物を有効成分として含有
する抗微生物剤を提供する。The present invention provides the following formula (1) (M 1 2+ ) 1-x (M 2 2+ ) x (OH) 2 (1) [wherein M 1 2+ represents Mg and / or Ca and M 2
2+ represents Cu and / or Zn, and x is 0.000
1 ≤ x <0.9, preferably 0.0001 ≤ x ≤ 0.
4, more preferably a number in the range of 0.0001 ≦ x ≦ 0.2] is provided as an active ingredient.
【手続補正２】[Procedure Amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１３[Correction target item name] 0013
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１３】式（１）において、ｘの値が０．９以上で
は式（１）の固溶体が生成しなくなり、また抗微生物効
果も殆ど示さない。ｘの値が０．４を超えるとＣａ（Ｏ
Ｈ）２またはＭｇ（ＯＨ）２に固溶しない銅および亜鉛
の塩基性塩、酸化物が副生し易くなるので抗微生物効果
が頭打ちとなるので好ましくない。ｘの値が小さ過ぎる
と有効成分である銅イオンおよび／または亜鉛イオンの
放出濃度が低くなり本発明の効果不十分となる。また銅
および／または亜鉛の式（１）の化合物中の濃度が高く
なる程、水に対する銅イオンおよび／または亜鉛イオン
の放出性が低くなり、抗微生物効果が不十分となる傾向
がある。このため、本発明の抗微生物剤のｘの範囲は、
０．０００１≦ｘ＜０．９、好ましくは０．０００１≦
ｘ≦０．４、さらに好ましくは０．００１≦ｘ≦０．２
である。なお本発明において、副生した銅および亜鉛の
塩基性塩、酸化物、水酸化物を、式（１）の複合金属水
酸化物と混合された状態で抗微生物剤として適用しても
差し支えはない。In the equation (1), when the value of x is 0.9 or more,
No longer produces the solid solution of the formula (1), nor almost indicated antimicrobial efficacy. When the value of x exceeds 0.4, Ca (O
It is not preferable because basic salts and oxides of copper and zinc which are not solid-dissolved in H) 2 or Mg (OH) 2 are likely to be produced as a by-product, and the antimicrobial effect reaches the ceiling. If the value of x is too small, the release concentration of copper ions and / or zinc ions, which are active ingredients, will be low, and the effect of the present invention will be insufficient. In addition, the higher the concentration of copper and / or zinc in the compound of formula (1), the lower the release of copper ions and / or zinc ions to water, and the antimicrobial effect tends to be insufficient. Therefore, the range of x of the antimicrobial agent of the present invention is
0.0001 ≦ x <0.9, preferably 0.0001 ≦
x ≦ 0.4, more preferably 0.001 ≦ x ≦ 0.2
Is. In the present invention, the by-produced basic salts, oxides and hydroxides of copper and zinc may be applied as an antimicrobial agent in a state of being mixed with the complex metal hydroxide of the formula (1). Absent.
Claims (2)
ｕおよび／またはＺｎを示し、ｘは０.０００１≦ｘ＜
０.９の範囲の数を示す］の複合金属水酸化物を有効成
分として含有する抗微生物剤。1. The following formula (1) (M 1 2+ ) 1-x (M 2 2+ ) x (OH) 2 (1) [wherein M 1 2+ is Mg and / or Ca, M 2 2+ is C
u and / or Zn, and x is 0.0001 ≦ x <
The compound has a number in the range of 0.9]] as an active ingredient.
求項１記載の抗微生物剤を０.００１〜５０重量部含有
する抗微生物性樹脂またはゴム組成物。2. An antimicrobial resin or rubber composition containing 0.001 to 50 parts by weight of the antimicrobial agent according to claim 1 with respect to 100 parts by weight of the resin or rubber.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33759491A JP2911282B2 (en) | 1991-11-27 | 1991-11-27 | Antimicrobial agent and antimicrobial resin or rubber composition |
| US07/979,230 US5344636A (en) | 1991-11-27 | 1992-11-20 | Anti-microorganism agent and anti-microorganism resin or rubber composition |
| DE69207734T DE69207734T2 (en) | 1991-11-27 | 1992-11-24 | Anti-microorganism and anti-microbial resin or rubber composition |
| EP92310744A EP0544502B1 (en) | 1991-11-27 | 1992-11-24 | Anti-microorganism agent and anti-microorganism resin or rubber composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33759491A JP2911282B2 (en) | 1991-11-27 | 1991-11-27 | Antimicrobial agent and antimicrobial resin or rubber composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0672816A true JPH0672816A (en) | 1994-03-15 |
| JP2911282B2 JP2911282B2 (en) | 1999-06-23 |
Family
ID=18310121
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33759491A Expired - Fee Related JP2911282B2 (en) | 1991-11-27 | 1991-11-27 | Antimicrobial agent and antimicrobial resin or rubber composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2911282B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999030564A1 (en) * | 1997-12-18 | 1999-06-24 | Kyowa Chemical Industry Co., Ltd. | Algal growth or microbial proliferation inhibitors and use thereof |
| JP2003024424A (en) * | 2001-07-11 | 2003-01-28 | S T Chem Co Ltd | Deodorant composition |
-
1991
- 1991-11-27 JP JP33759491A patent/JP2911282B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999030564A1 (en) * | 1997-12-18 | 1999-06-24 | Kyowa Chemical Industry Co., Ltd. | Algal growth or microbial proliferation inhibitors and use thereof |
| US6297193B1 (en) | 1997-12-18 | 2001-10-02 | Kyowa Chemical Industry Co., Ltd. | Algal growth or microbial proliferation inhibitors and use thereof |
| JP2003024424A (en) * | 2001-07-11 | 2003-01-28 | S T Chem Co Ltd | Deodorant composition |
| JP4685283B2 (en) * | 2001-07-11 | 2011-05-18 | エステー株式会社 | Deodorant composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2911282B2 (en) | 1999-06-23 |
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