JPH05105609A - Germicide - Google Patents

Germicide

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Publication number
JPH05105609A
JPH05105609A JP3296438A JP29643891A JPH05105609A JP H05105609 A JPH05105609 A JP H05105609A JP 3296438 A JP3296438 A JP 3296438A JP 29643891 A JP29643891 A JP 29643891A JP H05105609 A JPH05105609 A JP H05105609A
Authority
JP
Japan
Prior art keywords
silver
carrier
resistance
silver ion
antibiotics
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.)
Granted
Application number
JP3296438A
Other languages
Japanese (ja)
Other versions
JP3197308B2 (en
Inventor
Tatsuo Yamamoto
達雄 山本
Shinji Uchida
眞志 内田
Ichiro Nakayama
一郎 中山
Yasuo Kurihara
靖夫 栗原
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SHINANEN ZEOMITSUKU KK
Shinagawa Fuel Co Ltd
Original Assignee
SHINANEN ZEOMITSUKU KK
Shinagawa Fuel Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
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Application filed by SHINANEN ZEOMITSUKU KK, Shinagawa Fuel Co Ltd filed Critical SHINANEN ZEOMITSUKU KK
Priority to JP29643891A priority Critical patent/JP3197308B2/en
Publication of JPH05105609A publication Critical patent/JPH05105609A/en
Application granted granted Critical
Publication of JP3197308B2 publication Critical patent/JP3197308B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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  • Apparatus For Disinfection Or Sterilisation (AREA)
  • Medicinal Preparation (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

PURPOSE:To obtain a germicide showing disinfecting effects on methicilin- resistant Staphylococcus aureus (MRSA) having acquired resistance against antibiotics such as methicilin with a small amount free from acquisition of resistance. CONSTITUTION:A germicide against microorganisms readily acquiring resistance to antibiotics, comprising a silver ion and a carrier such as zirconium phosphate stably retaining the silver ion. Content of the silver ion, for example, is 0.2-20wt.%. The carrier favorably has >=0.2, preferably >=15 silver stability coefficient KAg in order to stably retain silver ion.

Description

【発明の詳細な説明】Detailed Description of the Invention

【0001】[0001]

【産業上の利用分野】本発明は銀系殺菌剤に関するもの
であって、さらに詳しくは、抗生物質に対して耐性を獲
得しやすい微生物用の殺菌剤に関するものである。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver-based bactericide, and more particularly to a bactericide for microorganisms which easily acquire resistance to antibiotics.

【0002】[0002]

【従来の技術】近年、抗菌剤・殺菌剤の有効成分として
無機物質が注目されている。無機系薬剤は一般に従来よ
り知られている有機系薬剤に比べて、耐熱性、耐水性に
優れた材料であり、種々の物質が提案されている。例え
ば、ヨウ素イオン(特開昭62−43431号)、銅塩
(特開平1−104390号)、銀担持活性炭(特開昭
49−61950号)、銀成分含有ガラス(特開昭63
−307807号)、抗菌性ゼオライト(特開昭60−
181002号)がある。
2. Description of the Related Art In recent years, inorganic substances have attracted attention as active ingredients of antibacterial agents and bactericides. Inorganic drugs are materials that are more excellent in heat resistance and water resistance than conventionally known organic drugs, and various substances have been proposed. For example, iodine ion (JP-A-62-43431), copper salt (JP-A-1-104390), silver-supported activated carbon (JP-A-49-61950), silver component-containing glass (JP-A-63).
No. 307807), antibacterial zeolite (JP-A-60-
181002).

【0003】[0003]

【発明が解決しようとする課題】最近、合成ペニシリン
の一種であるメチシリンをはじめ多くの抗生物質薬剤に
対して耐性を獲得した黄色ブドウ球菌(methici
llin resistant Staphylocc
us aureus;以下MRSAと言う)が世界的に
流行しその消毒剤・殺菌剤の開発が望まれている。
Recently, Staphylococcus aureus has acquired resistance to many antibiotic drugs including methicillin, which is a kind of synthetic penicillin.
llin Resistant Staphylocc
us aureus; hereinafter referred to as MRSA) has spread worldwide, and the development of disinfectants and bactericides thereof is desired.

【0004】MRSAはグラム陽性菌の一種であり、そ
の菌の産生する毒素によって食中毒の症状を発する。そ
のため、その感染防止が特に問題視されている。MRS
Aの感染防止には、特に院内感染によるものが多いこと
から、患者、医療従事者、医療器械は勿論のこと、床、
壁や空調といった病院環境全体の消毒及び殺菌が必要と
される。しかし、これまで耐性獲得がなく、かつ消毒・
殺菌効果が持続する薬剤は見い出されていなかった。
MRSA is a type of Gram-positive bacterium, and the toxins produced by the bacterium cause symptoms of food poisoning. Therefore, prevention of the infection is regarded as a particular problem. MRS
Infection control of A is often due to nosocomial infections, so not only patients, medical personnel, and medical equipment, but also floors,
Disinfection and sterilization of the entire hospital environment such as walls and air conditioning is required. However, until now there has been no acquisition of resistance and disinfection /
No drug has been found to have a sustained bactericidal effect.

【0005】上記MRSA以外にも抗生物質に対する耐
性を獲得しやすく、抗生物質によって殺菌できない微生
物がある。
In addition to the MRSA mentioned above, there are microorganisms which easily acquire resistance to antibiotics and cannot be killed by antibiotics.

【0006】そこで本発明の目的は、耐性獲得せず、か
つ極く少量で殺菌効果を発揮し持続性にも優れた殺菌剤
を提供することにある。
Therefore, an object of the present invention is to provide a bactericide which does not acquire resistance, exhibits a bactericidal effect even in an extremely small amount, and is excellent in durability.

【0007】[0007]

【課題を解決するための手段】本発明者等は上記課題に
鑑みて、各種の抗菌・殺菌薬剤に関して耐性獲得性試験
及び殺菌効果持続試験を行った。その結果、有効成分と
して銀イオンを用い、かつ銀イオンを担持体に安定に保
持させることで、本発明の目的を達成できることを見い
出した。
In view of the above problems, the present inventors have conducted resistance acquisition test and bactericidal effect duration test for various antibacterial and bactericidal agents. As a result, it has been found that the object of the present invention can be achieved by using silver ions as an active ingredient and stably holding the silver ions on the carrier.

【0008】本発明は、銀イオン及び該銀イオンを安定
して保持する担持体からなることを特徴とする抗生物質
に対して耐性を獲得しやすい微生物用殺菌剤に関する。
The present invention relates to a bactericidal agent for microorganisms which easily acquires resistance to antibiotics, which is characterized by comprising silver ions and a carrier which stably holds the silver ions.

【0009】以下本発明について説明する。本発明にお
いて有効成分である銀イオンはその担持体に安定して担
持されることが必要である。ここで安定に保持されると
は、熱(例えば温度200℃以下)、水(例えば湿度1
0〜100%)による影響がなく常にイオンの状態であ
り、金属や酸化物等の非イオン状態に変化しないことを
意味する。
The present invention will be described below. In the present invention, it is necessary that the active ingredient, silver ions, be stably supported on the carrier. Here, being stably held means that heat (for example, a temperature of 200 ° C. or lower), water (for example, humidity 1
(0 to 100%), it is always in an ionic state without any influence and does not change to a nonionic state such as a metal or an oxide.

【0010】担持体が銀イオンを保持する安定性は、担
持体の銀安定度係数により表すことができる。イオン交
換体(担持体)Rにおける銀安定度係数KAgは、ナトリ
ウム(Na)イオン等と銀(Ag)イオンとのイオン交
換反応R・Na+Ag+ ←→R・Ag+Na+ において
平衡に達している時、下記の式により定義する。 KAg=〔イオン交換体中の銀濃度(R・Ag)〕/〔溶
液中の銀濃度(Ag+ )〕
The stability of the carrier for holding silver ions can be expressed by the silver stability coefficient of the carrier. The silver stability coefficient K Ag in the ion exchanger (support) R reaches equilibrium in the ion exchange reaction R · Na + Ag + ← → R · Ag + Na + between sodium (Na) ions and silver (Ag) ions. Then, it is defined by the following formula. K Ag = [silver concentration in ion exchanger (R · Ag)] / [silver concentration in solution (Ag + )]

【0011】銀安定度係数は、ナトリウムイオンと銀イ
オンを等モル存在させた溶液中にイオン交換体(担持
体)を加えて、室温下攪拌して平衡に達していることを
堪忍後、イオン交換体(担持体)相と溶液相の銀濃度を
測定して得られる。
The silver stability coefficient is determined by adding an ion exchanger (supporting material) to a solution in which sodium ions and silver ions are present in equimolar amounts and stirring at room temperature to reach equilibrium. It is obtained by measuring the silver concentrations of the exchanger (support) phase and the solution phase.

【0012】本発明に用いる銀イオンを安定して保持す
る担持体は、一定量の銀イオンを長時間安定して水等の
媒液に供給できるという観点から上記銀安定度係数KAg
が、0.2以上、好ましくは15以上、より好ましくは
50以上であることが適当である。
The carrier for stably holding silver ions used in the present invention has the above-mentioned silver stability coefficient K Ag from the viewpoint that a certain amount of silver ions can be stably supplied to a liquid medium such as water for a long time.
Is 0.2 or more, preferably 15 or more, more preferably 50 or more.

【0013】本発明において銀イオンを安定して保持す
る担持体は、例えばリン酸ジルコニウム(Zr(HPO42
・nH2O)、チタン酸カリウム(K2Ti2O5 )、ウラン酸カ
リウム(K2U2O7)、バナジン酸カリウム(KV2O8)、ニオ
ブ酸カリウム(KNbO8)、タングステン酸ナトリウム(Na
2W4O13) 、モリブデン酸マグネシウム(Mg2Mo2O7) 等の
酸素酸塩、ペンタホウ酸塩(Ca2(B5O9) (OH))、グラフ
ァイト(C)、結晶性アルミノケイ酸塩(xR2O・AL2O3
・ySiO2)、結晶性リン酸アルミニウム(xR2O・Al2O3
yP2O5)、ヘキサシアノ鉄酸塩(R[Fe(CN)6]) 、セピオラ
イト(Mg8Si12O30(OH)4(H2O)4)、モンモリロナイト(xR
(Al.Mg)Si4O10(OH)2)等のゼオライト様物質、βーアル
ミナ(Al2O3)、含水酸化チタン(TiO4・nH2O)、ヒドロ
キシアパタイト(Ca2(PO4)(OH)・nH2O)等の含水酸化物
やスルホン基、カルボキシル基、フェノール性水酸基、
アミノ基、第4級アンモニウム基含有のイオン交換樹脂
を挙げることができる。このうち銀イオンを安定して多
量に保持できる点よりリン酸ジルコニウム、チタン酸カ
リウム、Si/Al比10以下の結晶性アルミノケイ酸
塩、P/Al比10以下の結晶性リン酸アルミニウムが
より好ましい。
In the present invention, a carrier that stably holds silver ions is, for example, zirconium phosphate (Zr (HPO 4 ) 2
・ NH 2 O), potassium titanate (K 2 Ti 2 O 5 ), potassium uranate (K 2 U 2 O 7 ), potassium vanadate (KV 2 O 8 ), potassium niobate (KNbO 8 ), tungstic acid Sodium (Na
2 W 4 O 13 ), oxyacid salts such as magnesium molybdate (Mg 2 Mo 2 O 7 ), pentaborate (Ca 2 (B 5 O 9 ) (OH)), graphite (C), crystalline aluminosilicate Salt (xR 2 O ・ AL 2 O 3
・ YSiO 2 ), crystalline aluminum phosphate (xR 2 O ・ Al 2 O 3
yP 2 O 5 ), hexacyanoferrate (R [Fe (CN) 6 ]), sepiolite (Mg 8 Si 12 O 30 (OH) 4 (H 2 O) 4 ), montmorillonite (xR
Zeolite-like substances such as (Al.Mg) Si 4 O 10 (OH) 2 ), β-alumina (Al 2 O 3 ), hydrous titanium oxide (TiO 4 · nH 2 O), hydroxyapatite (Ca 2 (PO 4 )) (OH) ・ nH 2 O) and other hydrous oxides, sulfone groups, carboxyl groups, phenolic hydroxyl groups,
An ion exchange resin containing an amino group and a quaternary ammonium group can be mentioned. Among these, zirconium phosphate, potassium titanate, crystalline aluminosilicate having a Si / Al ratio of 10 or less, and crystalline aluminum phosphate having a P / Al ratio of 10 or less are more preferable from the viewpoint of stably retaining a large amount of silver ions. ..

【0014】本発明における銀イオン担持体に含まれる
銀イオンは0.2〜20重量%、より好ましくは0.5
〜15重量%であることが殺菌効果の点より良い。
The silver ion carrier in the present invention contains silver ion in an amount of 0.2 to 20% by weight, more preferably 0.5.
From the viewpoint of the bactericidal effect, it is preferable to be 15% by weight.

【0015】本発明の殺菌剤は、水に対する銀イオンの
溶出量が24時間当たり、0.005mg/l以上であ
ることが殺菌持続性の観点より好ましい。また該担持体
の粒子径は0.2〜15μmとすることが、少量で効果
的に有効性を発揮できるという観点から好ましい。
In the bactericide of the present invention, it is preferable that the elution amount of silver ion in water is 0.005 mg / l or more per 24 hours from the viewpoint of sterilization sustainability. Further, it is preferable that the particle size of the carrier is 0.2 to 15 μm from the viewpoint that the effectiveness can be effectively exhibited even with a small amount.

【0016】本発明の殺菌剤は溶解性の高い銀化合物の
溶液に担持体粉末を加えて攪拌することによって得るこ
とができる。使用できる銀化合物としては硝酸銀、硫酸
銀、過塩素酸銀、酢酸銀、ジアンミン銀硝酸塩、ジアン
ミン硫酸塩等を挙げることができる。攪拌は10〜80
℃、好ましくは40〜60℃で1〜50時間、好ましく
は10〜24時間バッチ式又は連続式によって行うこと
ができる。攪拌終了後、担持体を充分水洗したのち60
〜170℃で乾燥する。
The bactericide of the present invention can be obtained by adding a carrier powder to a solution of a highly soluble silver compound and stirring the mixture. Examples of silver compounds that can be used include silver nitrate, silver sulfate, silver perchlorate, silver acetate, diammine silver nitrate, and diammine sulfate. Agitation 10-80
It can be carried out at a temperature of 0 ° C., preferably 40 to 60 ° C. for 1 to 50 hours, preferably 10 to 24 hours, by a batch system or a continuous system. After the stirring is completed, the carrier is thoroughly washed with water and then 60
Dry at ~ 170 ° C.

【0017】本発明の殺菌剤の形態は通常粉体である
が、これを二次加工することもできる。即ち、サスペン
ション、粒状体、抄紙体、ペレット体、シート、フィル
ム等の成型体、スプレー、多孔質体、繊維体の形態とす
ることができる。さらにそれらを不織布、発砲シート、
紙、プラスチック、無機質板などに加工することもでき
る。
The bactericide of the present invention is usually in the form of powder, but it can be subjected to secondary processing. That is, it may be in the form of a suspension, a granular body, a papermaking body, a pellet body, a molded body such as a sheet or a film, a spray, a porous body or a fibrous body. Furthermore, they are made of non-woven fabric, foam sheet,
It can also be processed into paper, plastic, inorganic plates and the like.

【0018】本発明の殺菌剤にはMRSAや細菌(グラ
ム陰性菌、例えばシュードモナス属、ナイセリア属、ア
シネトバクター属の細菌)、酵母、かびや藻類等広範囲
の抗生物質に対して耐性を獲得しやすい微生物の繁殖を
抑制することが望まれる各種分野に使用できる。例えば
医療分野、農林水産分野、化粧品分野、食品加工分野、
繊維衣料分野、寝装分野、建材分野、船舶分野、電子工
業分野、水処理分野等を挙げることができる。医療分野
には医薬品、手術用具、ばんそう膏、医療廃棄物容器、
リネン類等に使用するのが好ましい。
The bactericide of the present invention is a microorganism which easily acquires resistance to a wide range of antibiotics such as MRSA and bacteria (Gram-negative bacteria such as Pseudomonas, Neisseria, Acinetobacter), yeast, fungi and algae. It can be used in various fields in which it is desired to suppress the reproduction of the. For example, medical field, agriculture, forestry and fisheries field, cosmetics field, food processing field,
Examples include the field of textile clothing, the field of bedding, the field of building materials, the field of ships, the field of electronics industry, and the field of water treatment. In the medical field, medicines, surgical tools, bandages, medical waste containers,
It is preferably used for linens and the like.

【0019】[0019]

【発明の効果】本発明の殺菌剤は、MRSAをはじめ細
菌、酵母、かびや藻類等広範囲の微生物に対して耐性獲
得することなく、その繁殖を抑制することができ、各種
分野の殺菌剤として利用することができる。
INDUSTRIAL APPLICABILITY The bactericide of the present invention can suppress the reproduction of MRSA and a wide range of microorganisms such as bacteria, yeasts, molds and algae without acquiring resistance, and is useful as a bactericide in various fields. Can be used.

【0020】[0020]

【実施例】以下本発明を実施例により説明する。EXAMPLES The present invention will be described below with reference to examples.

【0021】実施例(殺菌剤の調製) 各種のイオン担持体として、リン酸ジルコニウム(Zr(H
PO4)2・nH2O) 、リン酸チタニウム(Ti(HPO4)3)、チタ
ン酸カリウム(K2Ti2O5)、ウラン酸カリウム(K2U2O7)
、バナジン酸カリウム(KV2O8)、ニオブ酸カリウム(K
NbO8)、タングステン酸ナトリウム(Na2W4O13) 、モル
ブデン酸マグネシウム(Mg2Mo2O7) 、ペンタホウ酸塩
(Ca2(B5O9)(OH))、結晶性アルミノケイ酸塩(xR2O ・Al
2O3 ・ySiO2)、結晶性リン酸アルミニウム(xR2O・Al2O
3 ・yP2O5)、ヘキサシアノ鉄酸塩(R[Fe(CN)6]) 、セピ
オライト(Mg8Si12O30(OH)4(H2O)4)、モンモリロナイト
(xR(Al 、Mg)Si4O10(OH)2)、βーアルミナ(Al2O3)、
含水酸化チタン(TiO4・nH2O)、ヒドロキシアパタイト
(Ca2(PO4)(OH)・nH2O)スルホン基含有陽イオン交換樹
脂を用い、これらを0.05N硝酸銀水溶液に入れ40
℃、15時間攪拌混合することにより本発明の銀イオン
担持殺菌剤を得た。各サンプルに含有される銀イオンの
量、各担持体の粒子径及び担持体の銀安定度係数を表1
に示す。
Example (Preparation of bactericide) As various ion carriers, zirconium phosphate (Zr (H
PO 4 ) 2・ nH 2 O), titanium phosphate (Ti (HPO 4 ) 3 ), potassium titanate (K 2 Ti 2 O 5 ), potassium uranate (K 2 U 2 O 7 ).
, Potassium vanadate (KV 2 O 8 ), potassium niobate (K
NbO 8 ), sodium tungstate (Na 2 W 4 O 13 ), magnesium morbuteneate (Mg 2 Mo 2 O 7 ), pentaborate (Ca 2 (B 5 O 9 ) (OH)), crystalline aluminosilicate (xR 2 O ・ Al
2 O 3・ ySiO 2 ), crystalline aluminum phosphate (xR 2 O ・ Al 2 O
3・ yP 2 O 5 ), hexacyanoferrate (R [Fe (CN) 6 ]), sepiolite (Mg 8 Si 12 O 30 (OH) 4 (H 2 O) 4 ), montmorillonite (xR (Al, Mg ) Si 4 O 10 (OH) 2 ), β-alumina (Al 2 O 3 ),
Hydrous titanium oxide (TiO 4 · nH 2 O), hydroxyapatite (Ca 2 (PO 4 ) (OH) · nH 2 O) Sulfonate-containing cation exchange resin was used.
The silver ion-supported bactericide of the present invention was obtained by stirring and mixing at 15 ° C. for 15 hours. Table 1 shows the amount of silver ions contained in each sample, the particle size of each carrier and the silver stability coefficient of the carrier.
Shown in.

【0022】[0022]

【表1】 [Table 1]

【0023】試験例1(耐性獲得試験) 実施例で得た種々の殺菌剤についてMRSAに対する耐
性獲得試験を実施した。試験方法は、任意濃度に各殺菌
剤を添加したMH液体培地にMRSAの菌液を接種培養
後、発育が阻止させた最低濃度を持って殺菌剤の最小発
育阻止濃度(MIC)とした。この際、菌の発育が見ら
れた最高濃度の培養液を接種用菌液として用い、同様の
試験を10回繰り返し最小発育濃度が高くなる(耐性を
獲得する)かどうかを測定した。結果を表2及び3に示
す。
Test Example 1 (Resistance Acquisition Test) MRSA resistance acquisition tests were carried out on the various fungicides obtained in the examples. The test method was as follows: The minimum inhibitory concentration (MIC) of the bactericide was defined as the minimum concentration at which the growth was inhibited after inoculating and culturing the MH liquid medium in which the bactericide was added at an arbitrary concentration. At this time, a culture solution with the highest concentration in which the growth of the bacteria was observed was used as a bacterial solution for inoculation, and the same test was repeated 10 times to determine whether the minimum growth concentration was high (acquiring resistance). The results are shown in Tables 2 and 3.

【0024】[0024]

【表2】 [Table 2]

【0025】[0025]

【表3】 [Table 3]

【0026】試験例2(殺菌持続試験) 各殺菌剤の殺菌持続性を測定するため、湿度95%の状
態で50時間放置した後の銀イオンの状態変化の有無を
X線回折分析と目視による変色を観察することにより調
べた。また殺菌性を調べるために上記最小発育阻止濃度
(MIC)を1回測定した。結果を表4に示す。
Test Example 2 (Sterilization Persistence Test) In order to measure the sterilization persistence of each disinfectant, the presence or absence of a change in the state of silver ions after being left for 50 hours at a humidity of 95% was determined by X-ray diffraction analysis and visual inspection. It was examined by observing the discoloration. The minimum inhibitory concentration (MIC) was measured once in order to examine the bactericidal property. The results are shown in Table 4.

【0027】[0027]

【表4】 [Table 4]

───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 FI 技術表示箇所 A61L 2/16 A 7108−4C // A61K 33/38 ADZ 8314−4C (72)発明者 中山 一郎 愛知県知多市西巽が丘2丁目9番5号 (72)発明者 栗原 靖夫 愛知県名古屋市瑞穂区豊岡通3丁目35番地─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification number Office reference number FI technical display location A61L 2/16 A 7108-4C // A61K 33/38 ADZ 8314-4C (72) Inventor Ichiro Nakayama 2-9-5 Nishitatsugaoka, Chita-shi, Aichi (72) Inventor Yasuo Kurihara 3-35, Toyooka-dori, Mizuho-ku, Nagoya-shi, Aichi

Claims (3)

【特許請求の範囲】[Claims] 【請求項1】 銀イオン及び該銀イオンを安定して保持
する担持体からなることを特徴とする抗生物質に対して
耐性を獲得しやすい微生物用殺菌剤。
1. A bactericidal agent for microorganisms which easily acquires resistance to an antibiotic, characterized by comprising silver ions and a carrier that stably holds the silver ions.
【請求項2】 銀イオンの含有量が0.2〜20重量%
である請求項1記載の殺菌剤。
2. The silver ion content is 0.2 to 20% by weight.
The disinfectant according to claim 1, which is
【請求項3】 抗生物質に対して耐性を獲得しやすい微
生物が黄色ブドウ球菌である請求項1記載の殺菌剤。
3. The fungicide according to claim 1, wherein the microorganism that easily acquires resistance to an antibiotic is Staphylococcus aureus.
JP29643891A 1991-10-16 1991-10-16 Fungicide Expired - Fee Related JP3197308B2 (en)

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US7407899B2 (en) * 2003-01-10 2008-08-05 Milliken & Company Textile substrates having layered finish structure for improving liquid repellency and stain release
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995014484A1 (en) * 1993-11-26 1995-06-01 Kimurakogyo Co., Ltd. In vivo free-radical generator
JPH07330532A (en) * 1994-06-06 1995-12-19 Shiken:Kk Dental material composition
US7407899B2 (en) * 2003-01-10 2008-08-05 Milliken & Company Textile substrates having layered finish structure for improving liquid repellency and stain release
WO2005037296A1 (en) * 2003-10-16 2005-04-28 Toagosei Co., Ltd. Anti-coronavirus agent
WO2008155966A1 (en) * 2007-06-18 2008-12-24 Big Bio Co., Ltd. Molded cement product and method of producing the same
JP2008308390A (en) * 2007-06-18 2008-12-25 Big Bio:Kk Cement formed body and method for producing the same
JP2011041874A (en) * 2009-08-19 2011-03-03 Japan Organo Co Ltd Water treatment device for fuel cell
JP2011231052A (en) * 2010-04-28 2011-11-17 Kracie Home Products Ltd Skin care external preparation composition

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