JPH07203787A - Material for giving antifungal and antibacterial properties in hydroponic culture, its production and antifungal and antibacterial method in nydroponic culture - Google Patents

Material for giving antifungal and antibacterial properties in hydroponic culture, its production and antifungal and antibacterial method in nydroponic culture

Info

Publication number
JPH07203787A
JPH07203787A JP6004100A JP410094A JPH07203787A JP H07203787 A JPH07203787 A JP H07203787A JP 6004100 A JP6004100 A JP 6004100A JP 410094 A JP410094 A JP 410094A JP H07203787 A JPH07203787 A JP H07203787A
Authority
JP
Japan
Prior art keywords
silver
aqueous solution
treated
culture
solution
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.)
Pending
Application number
JP6004100A
Other languages
Japanese (ja)
Inventor
Haruichiro Eguchi
晴一郎 江口
Takao Washimi
隆男 鷲見
Shikou Chiyou
志宏 趙
Takayuki Yamamoto
貴之 山本
Sonomi Tsubota
園美 坪田
Yoshio Okada
義夫 岡田
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.)
Satosen Co Ltd
Original Assignee
Satosen 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
Application filed by Satosen Co Ltd filed Critical Satosen Co Ltd
Priority to JP6004100A priority Critical patent/JPH07203787A/en
Priority to NL9500096A priority patent/NL9500096A/en
Publication of JPH07203787A publication Critical patent/JPH07203787A/en
Pending legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/36After-treatment
    • C08J9/40Impregnation
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01GHORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G31/00Soilless cultivation, e.g. hydroponics
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16Heavy metals; Compounds thereof
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/07Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
    • D06M11/11Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
    • D06M11/20Halides of elements of Groups 4 or 14 of the Periodic Table, e.g. zirconyl chloride
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/51Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof
    • D06M11/55Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof with sulfur trioxide; with sulfuric acid or thiosulfuric acid or their salts
    • D06M11/56Sulfates or thiosulfates other than of elements of Groups 3 or 13 of the Periodic Table
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/58Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides
    • D06M11/64Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides with nitrogen oxides; with oxyacids of nitrogen or their salts
    • D06M11/65Salts of oxyacids of nitrogen
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/83Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M16/00Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04Polyurethanes

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Environmental Sciences (AREA)
  • Zoology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Pest Control & Pesticides (AREA)
  • Inorganic Chemistry (AREA)
  • Biochemistry (AREA)
  • Agronomy & Crop Science (AREA)
  • Plant Pathology (AREA)
  • Microbiology (AREA)
  • Materials Engineering (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Hydroponics (AREA)

Abstract

PURPOSE:To produce the subject material capable of releasing silver ions in a culture solution and protruding water-cultured crops from fungi or bacteria by carrying silver (oxide) on a textile good or a polyurethane foam support under a supecified condition. CONSTITUTION:A textile good or a polyurethane foam is dipped in an aqueous solution containing SnCl2 and/or SnSO4 and HCl and/or H2SO4, and subsequently washed with water. The treated material is then dipped in an aqueous AgNO3 solution to obtain, e.g. a textile good carrying silver and/or its oxide. The obtained material can release a constant concentration of silver ions into a culture solution and protect hydroponically cultured crops from diseases.

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、水耕栽培作物をかびお
よび/または菌から保護する方法、そのために使用する
抗かび性及び抗菌性付与材料の製造方法、ならびに水耕
栽培における抗かび性及び抗菌性付与材料に関する。
FIELD OF THE INVENTION The present invention relates to a method for protecting a hydroponic crop from mold and / or fungi, a method for producing an antifungal and antibacterial property-imparting material used therefor, and an antifungal property in hydroponics. And an antibacterial property imparting material.

【0002】[0002]

【従来の技術】現在、潅水法による水耕栽培(以下単に
水耕ということがある)によって、大量の生鮮野菜、果
物、花卉類、観葉植物などが栽培され、市販されてい
る。この栽培方法で発生する病害には、各種のものがあ
るが、栽培農家にとって一番厄介な病害は、病原菌によ
る根腐病、細菌類による青枯病、黒斑点病などである。
土壌栽培では、土壌中に多くの微生物が存在するので、
作物に悪影響を及ぼす病原菌および細菌類が作物の根に
到達するまでには微生物との競合があり、また、土壌に
は種々の緩衝作用もある。しかしながら、水耕栽培にお
ける養液にはこの作用が少なく、病害抑止という特性
は、殆ど発揮されない。このため、水耕栽培(潅水法)
では、1株でも発病すると、養液中でかび、菌などが急
速に繁殖して、全体に蔓延する危険度が非常に高い。ま
た、水耕は、土耕よりも菌密度が低くても、発病する割
合も高い。
2. Description of the Related Art At present, a large amount of fresh vegetables, fruits, flowers, foliage plants and the like are cultivated and marketed by hydroponic culture (hereinafter sometimes simply referred to as hydroponic culture) by a watering method. There are various kinds of diseases caused by this cultivation method, but the most troublesome diseases for growers are root rot caused by pathogenic fungi, bacterial wilt caused by bacteria, and black spot disease.
In soil cultivation, since many microorganisms are present in the soil,
There are competitions with microorganisms for pathogenic fungi and bacteria that adversely affect crops to reach the roots of crops, and soil also has various buffering effects. However, the nutrient solution in hydroponics has little of this effect, and the characteristic of disease control is hardly exhibited. Therefore, hydroponics (irrigation method)
However, if even one strain becomes ill, there is a very high risk that fungi and bacteria will rapidly propagate in the nutrient solution and spread throughout the plant. In addition, hydroponics has a higher rate of disease, even if it has a lower bacterial density than soil culture.

【0003】このため、土耕におけると同様に、水耕に
おいても、菌の防除対策が必要である。水耕における防
除対策としては、以下のような方法が考えられる。
Therefore, as in soil cultivation, it is necessary to take measures to control fungi in hydroponics. The following methods can be considered as control measures in hydroponics.

【0004】(1)農薬を添加する方法がある。しかし
ながら、現状では、特に野菜などの食用作物について
は、安全性(即ち、適正使用基準の範囲内での使用)の
点で、使用できないものが殆どであり、実質的な防除対
策とはなり得ない。
(1) There is a method of adding a pesticide. However, at present, most of food crops such as vegetables cannot be used in terms of safety (that is, use within the range of appropriate use standards), and it may be a substantial control measure. Absent.

【0005】(2)キュウリの栽培においては、養液中
に銅繊維を入れ、銅イオン濃度を高めることにより防除
に成功している例がある。しかしながら、作物の種類に
よつては高い銅イオン濃度のため薬害を生じる場合があ
るので、この方法も、一般的に各種栽培作物の菌防除対
策に利用することは難しい。
(2) In the cultivation of cucumber, there is an example of successful control by adding copper fiber to the nutrient solution and increasing the copper ion concentration. However, since a high copper ion concentration may cause chemical damage depending on the type of crop, this method is also generally difficult to be used as a fungus control measure for various cultivated crops.

【0006】(3)紫外線照射ランプを直接養液中に投
入して、紫外線を照射する方法がある。この方法は、非
常に効果的である。しかしながら、水耕養液には、作物
の栄養素として生長に必要な鉄およびマンガンイオン
が、EDTAと錯体(錯体を形成しない場合には、養液
のpHが約6であるため、それぞれの水酸化物として沈
殿する)を形成して、溶解している。ところが、水耕養
液に紫外線を照射すると、それらの錯体は分解して、金
属の水酸化物や酸化物として沈殿する。その結果、作物
の生長栄養素がなくなり、また養液が分解生成物により
赤色を帯びて、それらが植物の根に付着するなどの新た
な問題点を生じる。さらに、紫外線ランプの表面に養液
中のイオン、化合物の酸化物などが付着し、ランプの表
面を曇らせ、紫外線の有効強度が著しく低下して、防除
効果が失われるという欠点もある。
(3) There is a method in which an ultraviolet irradiation lamp is directly put into a nutrient solution to irradiate ultraviolet rays. This method is very effective. However, in the hydroponic solution, iron and manganese ions required for growth as nutrients for crops are complexed with EDTA (when the complex is not formed, the pH of the solution is about 6, so that the respective hydroxides are added). Precipitates) and dissolves. However, when the hydroponic solution is irradiated with ultraviolet rays, those complexes decompose and precipitate as metal hydroxides or oxides. As a result, the growth nutrients of the crops are lost, and the nutrient solution becomes reddish due to the decomposition products, which causes new problems such as adherence to plant roots. Further, there is a drawback that ions in the nutrient solution, oxides of compounds, etc. adhere to the surface of the ultraviolet lamp, and the surface of the lamp becomes cloudy, the effective intensity of ultraviolet rays is significantly reduced, and the control effect is lost.

【0007】(4)オゾンを養液の潅水槽中に吹き込ん
で、溶解させる方法もある。しかしながら、この方法に
おいても、紫外線照射法の場合と同様に、鉄の水酸化物
および酸化物、二酸化マンガンなどが沈殿する。また、
オゾンは酸化電位が高いために、7価のマンガンイオン
の生成も考えられ、これは酸化性が高いので、好ましく
ない。さらに、オゾン発生装置は、高価であるため、栽
培コストが高くなるという欠点がある。
(4) There is also a method in which ozone is blown into a nutrient solution irrigation tank to dissolve it. However, also in this method, hydroxides and oxides of iron, manganese dioxide and the like are precipitated as in the case of the ultraviolet irradiation method. Also,
Since ozone has a high oxidation potential, it is considered that heptane-valent manganese ions are generated, which is not preferable because it has high oxidizability. Further, since the ozone generator is expensive, there is a drawback that the cultivation cost is high.

【0008】(5)一般的に殆どの栽培植物(作物)に
対し利用できる防除剤として、銀イオンがあり、現在の
ところ、硝酸銀の形態で使用されている。しかしなが
ら、硝酸銀は、薬事法で劇薬物に指定されており、この
ような劇薬物を栽培者が直接取扱うことは好ましくな
い。また、栽培者がこれを使用する場合には、その毒性
を認識することなく、通常の農薬と同様に大量に使用す
ることも考えられる。さらに、硝酸銀溶液として微量の
銀イオン濃度(0.05〜0.1ppm程度)に調整し
て使用する必要があるので、常に濃度管理のために液分
析を行う必要があり、高価な分析機器を必要とするとい
う難点もある。即ち、銀イオンは、培養装置、植物の
根、液中の不純物などにより容易に吸着され、且つその
吸着速度が速いので、潅水が水路を一巡して銀イオン添
加位置に循環する時点には、液中の銀イオン濃度は希薄
になっている。従って、植物に対する安全性を考慮し
て、仮に初期銀イオン濃度を0.06ppmとし、以後
ほぼこの濃度を保持しようとすれば、常時分析を行う必
要がある。この様な操作を繰返して行うことは、栽培者
にとっては大きな負担となる。
(5) Generally, as a control agent that can be used for most cultivated plants (crops), there is silver ion, which is currently used in the form of silver nitrate. However, silver nitrate is designated as a powerful drug by the Pharmaceutical Affairs Law, and it is not preferable for a grower to directly handle such a powerful drug. In addition, when the grower uses this, it may be possible to use it in a large amount like an ordinary pesticide without recognizing its toxicity. Furthermore, since it is necessary to adjust the silver ion concentration to a minute amount (about 0.05 to 0.1 ppm) as a silver nitrate solution, it is necessary to always perform liquid analysis for concentration control, and to use expensive analytical equipment. There is also the drawback of needing it. That is, the silver ion is easily adsorbed by the culture device, plant roots, impurities in the liquid, and the like, and its adsorption rate is fast, so at the time when the irrigation circulates the water channel to the silver ion addition position, The silver ion concentration in the liquid is dilute. Therefore, in consideration of plant safety, if the initial silver ion concentration is set to 0.06 ppm and it is attempted to maintain this concentration thereafter, it is necessary to carry out continuous analysis. Repeating such operations imposes a heavy burden on the grower.

【0009】(6)上記の養液への硝酸銀添加に代え
て、硝酸銀水溶液を用いてゼオライトに銀を吸着させた
もの、即ちゼオライト銀の培養液への添加が考えられ
る。しかしながら、この場合には、添加の初期には、銀
イオンが急速に溶出し、それに伴って、鉄イオンおよび
マンガンイオンがゼオライトに吸着されるので、植物に
対する栄養の補給が途絶えるとともに、これらのイオン
によりゼオライト表面が被覆されて、それ以降の銀イオ
ンの溶出が殆ど起こらなくなる問題点がある。
(6) In place of the addition of silver nitrate to the above-mentioned nutrient solution, it is possible to add silver nitrate to an aqueous solution of silver nitrate to adsorb zeolite, that is, addition of zeolite silver to the culture solution. However, in this case, at the initial stage of addition, silver ions are rapidly eluted, and along with this, iron ions and manganese ions are adsorbed on the zeolite, so that the nutrient supply to the plant is interrupted, and at the same time, these ions are lost. However, there is a problem in that the surface of the zeolite is coated with silver and the subsequent elution of silver ions hardly occurs.

【0010】[0010]

【発明が解決しようとする課題】従って、本発明は、植
物病原菌であるかびおよび菌に対する従来の防除方法の
問題点を解消乃至軽減して、低価格で、銀イオンの濃度
管理が容易で、さらに優れた抗かび性および抗菌性を奏
しうる技術を提供することを主な目的とする。
Therefore, the present invention solves or alleviates the problems of the conventional control methods for fungi and fungi which are phytopathogenic fungi, is low in price, and is easy to control the concentration of silver ions. The main purpose of the present invention is to provide a technique capable of exhibiting excellent antifungal properties and antibacterial properties.

【0011】[0011]

【課題を解決するための手段】本発明者は、上記のよう
な従来技術の現状に鑑みて鋭意研究を重ねた結果、特定
の化合物を順次使用する置換メッキの手法を繊維品およ
びポリウレタンフォームに適用して銀を付与する場合に
は、繊維品およびポリウレタンフォーム自体に優れた抗
かび性および抗菌性を付与することできること、この様
な繊維品およびポリウレタンフォームを水耕栽培におけ
る潅水に接触させておく場合には、長期にわたり一定濃
度の銀イオンが潅水中に溶出して、水耕作物の病害発生
を効果的に抑制しうることを見出した。
DISCLOSURE OF THE INVENTION As a result of earnest studies in view of the above-mentioned conventional state of the art, the present inventor has conducted a displacement plating method of sequentially using a specific compound on a fiber product and a polyurethane foam. When applied and imparting silver, it is possible to impart excellent antifungal and antibacterial properties to the fiber product and the polyurethane foam itself, by contacting such fiber product and polyurethane foam with irrigation in hydroponics. It was found that a certain concentration of silver ions can be eluted into the irrigation water for a long period of time to effectively suppress the disease occurrence of hydroponic crops when it is stored.

【0012】即ち、本発明は、下記の水耕栽培における
抗かび性および抗菌性付与材料、その製造方法ならびに
水耕栽培における抗かびおよび抗菌方法を提供するもの
である; 1.(1)繊維品またはポリウレタンフォームからなる
被処理品を塩化錫(II)、および硫酸錫(II)の少
なくとも1種と塩酸および硫酸の少なくとも1種とを含
む水溶液に浸漬し、次いで水洗する工程、および(2)
被処理品を硝酸銀の水溶液に浸漬する工程を備えたこと
を特徴とする水耕栽培における抗かび性及び抗菌性付与
材料の製造方法。
That is, the present invention provides the following material for imparting antifungal and antibacterial properties in hydroponics, a method for producing the same, and an antifungal and antibacterial method in hydroponics; (1) A step of immersing a textile product or an article to be treated composed of polyurethane foam in an aqueous solution containing at least one of tin (II) chloride and tin (II) sulfate and at least one of hydrochloric acid and sulfuric acid, and then washing with water , And (2)
A method for producing an antifungal and antibacterial property-imparting material in hydroponics, comprising a step of immersing an article to be treated in an aqueous solution of silver nitrate.

【0013】2.上記項1の方法で得られた銀および/
またはその酸化物を担持する繊維品またはポリウレタン
フォームからなる水耕栽培における抗かび性及び抗菌性
付与材料。
2. Silver and / or obtained by the method of the above item 1
Alternatively, an antifungal and antibacterial property-imparting material for hydroponic culture comprising a fiber product or a polyurethane foam carrying the oxide thereof.

【0014】3.上記項1の方法で得られた銀および/
またはその酸化物を担持する繊維品またはポリウレタン
フォームを水耕培養液栽培の潅水に接触させることによ
り、銀イオンを溶出させて水耕栽培作物をかびおよび/
または菌から保護する方法。本願発明にいう繊維品と
は、素材としては、パルプ、綿、麻、人絹、羊毛、藁、
い草などの天然繊維材料および各種の高分子系合成繊維
材料を包含する。また、その形態としては、糸、シー
ト、不織布、織布、編み物などのすべての繊維製品を包
含する。これらの繊維材料は、糸の形態で本発明方法に
より処理した後、不織布、織布、編み物などに加工して
もよい。以下においては、特に必要でない限り、これら
を繊維品と総称し、必要な場合にのみ、個別的に示す。
3. Silver and / or obtained by the method of the above item 1
Alternatively, a textile or polyurethane foam carrying the oxide is brought into contact with irrigation for hydroponic culture to elute silver ions and mold and / or mold hydroponic crops.
Or how to protect from fungi. The textiles referred to in the present invention include, as materials, pulp, cotton, hemp, human silk, wool, straw,
It includes natural fiber materials such as rush and various polymer-based synthetic fiber materials. Further, the form includes all fiber products such as yarns, sheets, non-woven fabrics, woven fabrics and knitted fabrics. These fibrous materials may be processed into a non-woven fabric, a woven fabric, a knitted fabric or the like after being treated by the method of the present invention in the form of yarn. In the following, unless otherwise required, these are collectively referred to as fiber products, and are individually shown only when necessary.

【0015】本願発明では、繊維品またはポリウレタン
フォーム(以下特に必要でない限り、繊維品を以て両者
を代表させる)を以下の各工程に供する。
In the present invention, a fiber product or a polyurethane foam (unless otherwise required, the fiber product is representative of both) is subjected to the following steps.

【0016】(1)前処理 まず、前処理として、繊維品が汚れている場合或いは引
き続き行われる処理を阻害するバインダーなどを含んで
いる場合には、これらを除去する。この様な前処理は、
繊維品およびプラスチックスなどの非導電性材料へのメ
ッキ形成に際して採用されている方法に準じて行えばよ
く、特に限定されるものではないが、例えば、材質、汚
れなどに応じて、以下のような方法により行うことがで
きる。
(1) Pretreatment First, as a pretreatment, if the fiber product is soiled or contains a binder or the like that inhibits the subsequent treatment, these are removed. Such pretreatment is
It may be carried out according to the method adopted for forming plating on non-conductive materials such as textiles and plastics, and is not particularly limited. Can be performed by any method.

【0017】(イ)汚れが軽度である場合には、水洗の
みを行うか、或いは市販の食器洗い用乃至洗濯用洗剤の
水溶液に浸漬し、或いはそれらの水溶液中で撹拌した
後、水洗する。
(A) When the stain is light, it is washed only with water, or immersed in an aqueous solution of a commercially available dishwashing or laundry detergent, or stirred in these aqueous solutions and then washed with water.

【0018】(ロ)炭酸ナトリウム2〜30g/l+市
販の食器洗い用洗剤2ml/lの水溶液、(ハ)水酸化
ナトリウム約20g/l+燐酸ナトリウム約20g/l
の水溶液、(ニ)水酸化ナトリウム80〜250g/l
の水溶液、(ホ)メタケイ酸ナトリウム約100g/l
の水溶液などに温度約20〜85℃で浸漬した後、水洗
する。
(B) Sodium carbonate 2 to 30 g / l + commercial dishwashing detergent 2 ml / l aqueous solution, (c) sodium hydroxide about 20 g / l + sodium phosphate about 20 g / l
Aqueous solution of (d) sodium hydroxide 80-250 g / l
Aqueous solution of (e) sodium metasilicate about 100 g / l
After immersing in the aqueous solution of the above at a temperature of about 20 to 85 ° C., it is washed with water.

【0019】(ヘ)濃硫酸に温度約30〜70℃で浸漬
した後、水洗する。
(F) Immerse in concentrated sulfuric acid at a temperature of about 30 to 70 ° C., and then wash with water.

【0020】(ト)無水クロム酸20〜400g/l+
硫酸120〜850ml/lの水溶液に温度40〜75
℃で浸漬した後、水洗する。
(G) Chromic anhydride 20 to 400 g / l +
Aqueous solution of sulfuric acid 120-850 ml / l at temperature 40-75
After soaking at ℃, wash with water.

【0021】(チ)無水クロム酸15〜25g/l+硫
酸800〜910ml/l+燐酸250〜330g/l
の水溶液に温度60〜75℃で浸漬した後、水洗する。
(H) Chromic anhydride 15 to 25 g / l + sulfuric acid 800 to 910 ml / l + phosphoric acid 250 to 330 g / l
After being immersed in the aqueous solution of 60 ° C. to 75 ° C., it is washed with water.

【0022】浸漬時間は、被処理品の材質、汚れの程度
などに応じて適宜選択されるが、通常2〜20分間程度
である。前処理は、必要ならば、同種の水溶液を使用し
て複数回行ってもよく、或いは異なる水溶液を使用して
複数回行ってもよい。
The immersion time is appropriately selected depending on the material of the article to be treated, the degree of contamination, etc., but is usually about 2 to 20 minutes. If necessary, the pretreatment may be performed multiple times using the same kind of aqueous solution, or may be performed multiple times using different aqueous solutions.

【0023】上記の前処理において、アルカリ水溶液或
いは酸水溶液を使用する場合には、被処理品の汚れ除去
乃至脱脂が行われるのみならず、被処理品がエッチング
されるので、次工程における銀の析出が良好に行われ
る。
When an aqueous alkali solution or an aqueous acid solution is used in the above-mentioned pretreatment, not only is the stain removed or degreased on the article to be treated, but also the article to be treated is etched, so that silver in the next step is removed. Deposition is performed well.

【0024】前処理方法は、被処理品に対する銀の密着
性にも関連する。従って、材質と汚れの程度に応じて、
前処理方法を適宜選択することが好ましい。例えば、上
記(イ)の方法は、ポリアミド、ポリウレタンフォー
ム、天然繊維などの処理に適しており、上記(ロ)〜
(ホ)の方法は、綿、ポリエステル、ポリアミド、アク
リル樹脂、ポリウレタンフォームなどの処理に適してお
り、上記(ヘ)の方法は、ポリスチレンの処理に適して
おり、上記(ト)〜(チ)の方法は、ポリエチレン、ポ
リプロピレンなどの処理に適している。
The pretreatment method also relates to the adhesion of silver to the article to be treated. Therefore, depending on the material and the degree of contamination,
It is preferable to appropriately select the pretreatment method. For example, the above method (a) is suitable for treating polyamide, polyurethane foam, natural fiber, etc.
The method (e) is suitable for the treatment of cotton, polyester, polyamide, acrylic resin, polyurethane foam, etc., and the method (f) is suitable for the treatment of polystyrene. This method is suitable for treating polyethylene, polypropylene and the like.

【0025】なお、上記の前処理において、無水クロム
酸含有処理液を使用する場合には、被処理品に吸着され
た6価のクロムイオンを3価のクロムイオンに還元する
ために、例えば、シュウ酸50〜120g/l+硫酸8
0〜120g/lの水溶液或いは酸性亜硫酸ナトリウム
約20g/lの水溶液に温度30〜60℃程度で1〜5
分間程度浸漬した後、水洗することが必要である。
In the above pretreatment, when a chromic anhydride-containing treatment liquid is used, in order to reduce hexavalent chromium ions adsorbed on the article to be treated into trivalent chromium ions, for example, Oxalic acid 50-120 g / l + sulfuric acid 8
1 to 5 in an aqueous solution of 0 to 120 g / l or an aqueous solution of about 20 g / l of acidic sodium sulfite at a temperature of about 30 to 60 ° C.
After soaking for about a minute, it is necessary to wash with water.

【0026】被処理品が天然繊維である場合には、上記
(ロ)〜(ホ)のアルカリ水溶液により処理し、次いで
塩酸或いは硫酸などの酸性水溶液に浸漬した後、次亜塩
素酸ナトリウム、過硫酸ナトリウム、過酸化水素などの
酸化剤の水溶液に浸漬して、漂白することが好ましい。
特に被処理品が藁およびい草或いはそれらを素材とする
製品である場合には、アルカリ度が低い水溶液、例えば
炭酸ナトリウム3〜10g/l程度の水溶液により、前
処理することが好ましい。
When the product to be treated is a natural fiber, it is treated with the alkaline aqueous solution of the above (b) to (e), then immersed in an acidic aqueous solution such as hydrochloric acid or sulfuric acid, and then treated with sodium hypochlorite. Bleaching is preferably performed by immersing in an aqueous solution of an oxidizing agent such as sodium sulfate or hydrogen peroxide.
In particular, when the product to be treated is straw and rush, or products made from them, it is preferable to perform pretreatment with an aqueous solution having a low alkalinity, for example, an aqueous solution of about 3 to 10 g / l sodium carbonate.

【0027】また、繊維品が紙からなる場合には、水に
浸漬すると、崩壊することがある。このため、置換メッ
キ工程における最初の処理液であるSnCl2 などの水
溶液の浸透を妨げるバインダーなどが、紙の内部に存在
しない製品(例えば、濾紙)については、直接SnCl
2 などへの水溶液への浸漬を行ってもよい。但し、紙
製品中にバインダーなどの阻害成分が存在する場合に
は、最終的には繊維品表面には銀が付与されるものの、
内部にまでは銀は十分に析出しない。また、この様な阻
害成分が、SnCl2 などの水溶液に溶出して、処理
液を劣化させることもある。この様な場合には、紙製品
が破損しないように留意しつつ、予め水に0.5〜3時
間程度浸漬しておき、阻害成分を除去しておくことが好
ましい。
When the fiber product is made of paper, it may collapse when immersed in water. Therefore, for a product (for example, filter paper) that does not have a binder or the like that prevents the permeation of an aqueous solution such as SnCl 2 which is the first treatment liquid in the displacement plating step, directly into SnCl 2.
You may dip 2 etc. in the aqueous solution. However, when an inhibitor such as a binder is present in the paper product, although silver is finally added to the surface of the fiber product,
Not enough silver is deposited inside. Further, such an inhibitory component may be eluted in an aqueous solution of SnCl 2 or the like to deteriorate the treatment liquid. In such a case, it is preferable to preliminarily immerse the paper product in water for about 0.5 to 3 hours to remove the inhibitory component, taking care not to damage the paper product.

【0028】(2)錫塩の付与 次いで、上記の前処理を行った後(或いは必要がなけれ
ば行うことなく)、被処理品である繊維品を塩化錫(I
I)および硫酸錫(II)の少なくとも1種と塩酸およ
び硫酸の少なくとも1種とを含む水溶液に浸漬し、次い
で水洗する。前処理後に十分な水洗が行われていない場
合には、これらの錫塩水溶液に前処理液に由来する成分
(例えば、アルカリ成分)が混入して、錫塩水溶液を劣
化させ、錫の水酸化物を析出させることがある。この様
な場合には、被処理品を予め塩酸水溶液(0.1〜5%
程度)、硫酸水溶液(0.1〜5%程度)などに浸漬
し、水洗した後、所定の錫塩の水溶液に浸漬することが
好ましい。浸漬に際しては、被処理物に空気に起因する
と考えられる気泡が付着する場合があるので、その付着
を防止し、均一な錫イオンの吸着を行うために、被処理
物が損傷乃至崩壊しないように留意しつつ、水溶液中で
被処理物を緩やかに動かしたり、水溶液をゆっくり撹拌
することなどが好ましい。錫塩の付与に使用する水溶液
の組成および浸漬条件は、通常以下の通りである。
(2) Application of tin salt Next, after the above-mentioned pretreatment (or without it if not necessary), the fiber product to be treated is treated with tin chloride (I).
It is immersed in an aqueous solution containing at least one of I) and tin (II) sulfate and at least one of hydrochloric acid and sulfuric acid, and then washed with water. If sufficient water washing is not carried out after the pretreatment, a component derived from the pretreatment liquid (for example, an alkaline component) is mixed into these tin salt aqueous solutions to deteriorate the tin salt aqueous solution, and to tin hydroxide. May cause precipitation. In such a case, the product to be treated is previously treated with an aqueous hydrochloric acid solution (0.1-5%).
It is preferable to immerse it in an aqueous solution of a predetermined tin salt after immersing it in an aqueous solution of sulfuric acid (about 0.1% to 5%), washing it with water. At the time of immersion, air bubbles that are considered to be caused by air may adhere to the object to be treated, so in order to prevent the adhesion and to uniformly adsorb tin ions, the object to be treated should not be damaged or collapsed. While paying attention, it is preferable to gently move the object to be treated in the aqueous solution or slowly stir the aqueous solution. The composition of the aqueous solution used for applying the tin salt and the immersion conditions are usually as follows.

【0029】(a)塩化錫(II)を使用する場合;S
nCl2・2H2Oを5〜40g/l程度(錫として2.
6〜21g/l程度)と塩酸および/または硫酸を含む
水溶液に10〜40℃程度で1〜10分間程度浸漬す
る。この様な水溶液は、塩化錫(II)と所定濃度およ
び所定量の塩酸水溶液、硫酸水溶液或いは塩酸−硫酸混
合水溶液とを水に添加することにより、調製できる。
(A) When using tin (II) chloride; S
About 5 to 40 g / l of nCl 2 .2H 2 O (as tin 2.
(About 6 to 21 g / l) and hydrochloric acid and / or sulfuric acid at 10 to 40 ° C. for about 1 to 10 minutes. Such an aqueous solution can be prepared by adding tin (II) chloride and a predetermined concentration and a predetermined amount of a hydrochloric acid aqueous solution, a sulfuric acid aqueous solution or a hydrochloric acid-sulfuric acid mixed aqueous solution to water.

【0030】水溶液中の錫濃度が2.6g/lを下回る
場合には、浸漬時間を長くする必要があり、実用的に不
利となる。一方、被処理物が、ポリウレタンフォームな
どである場合には、多量の水溶液を吸収して、次工程へ
の水溶液の持ち出し量が多くなるため、液の濃度管理が
困難となるので、上限量を21g/l程度とする。水溶
液の温度が低すぎる場合には、浸漬時間が長くなり、不
利となるのに対し、高すぎる場合には、短い浸漬時間で
錫が均一に析出するが、液の耐久性が低下する。
When the tin concentration in the aqueous solution is less than 2.6 g / l, it is necessary to prolong the immersion time, which is practically disadvantageous. On the other hand, when the object to be treated is polyurethane foam or the like, it absorbs a large amount of the aqueous solution and the amount of the aqueous solution taken out to the next step increases, which makes it difficult to control the concentration of the solution. It is about 21 g / l. If the temperature of the aqueous solution is too low, the immersion time will be long, which is disadvantageous. On the other hand, if the temperature is too high, tin will be uniformly deposited in a short immersion time, but the durability of the solution will be reduced.

【0031】水溶液の劣化の原因は、十分には解明され
ていないが、おそらくSn2+イオンがSn4+イオンに酸
化されやすくなり、被処理品に対する吸着性が低下する
ものと思われる。従って、これらの条件を総合的に判断
して、浸漬時の水溶液の温度を10〜40℃とした。下
記(b)および(c)における水溶液の錫濃度および温
度の規定値も、同様の理由により定めた。
Although the cause of the deterioration of the aqueous solution has not been fully clarified, it is considered that Sn 2+ ions are likely to be oxidized to Sn 4+ ions, and the adsorptivity to the article to be treated is lowered. Therefore, by comprehensively judging these conditions, the temperature of the aqueous solution during immersion was set to 10 to 40 ° C. The specified values of tin concentration and temperature of the aqueous solution in the following (b) and (c) were also determined for the same reason.

【0032】塩酸水溶液、硫酸水溶液或いは塩酸−硫酸
混合水溶液の配合量は、(イ)36%塩酸5〜40ml
/l程度、(ロ)98%硫酸1.5〜18ml/l程
度、(ハ)36%塩酸1〜39ml/l+98%硫酸1
〜17ml/l程度である。
The mixing amount of the hydrochloric acid aqueous solution, the sulfuric acid aqueous solution or the hydrochloric acid-sulfuric acid mixed aqueous solution is (a) 5% to 40 ml of 36% hydrochloric acid.
/ L, (b) 98% sulfuric acid 1.5 to 18 ml / l, (c) 36% hydrochloric acid 1 to 39 ml / l + 98% sulfuric acid 1
It is about 17 ml / l.

【0033】但し、上記水溶液が塩素イオンを含まない
(即ち、硫酸イオンのみを含む)場合には、天然繊維お
よびポリアミドについては、錫の析出が良好に行われる
ものの、その他の繊維品については、錫の析出が十分で
ない。その理由は明確ではないが、塩素イオンが存在し
なくても、ポリアミドにおいては、錫がそのC−N結合
のN原子に、また天然繊維においては、錫がセルロース
分子のC原子に吸着されやすいためと考えられる。
However, when the above-mentioned aqueous solution does not contain chlorine ions (that is, it contains only sulfate ions), although tin is deposited satisfactorily for natural fibers and polyamides, for other fiber products, Tin deposition is not sufficient. Although the reason for this is not clear, tin is likely to be adsorbed to the N atom of the C—N bond in the polyamide and tin is adsorbed to the C atom of the cellulose molecule in the natural fiber even in the absence of chlorine ions. It is thought to be because.

【0034】(b)硫酸錫(II)を使用する場合;S
nSO45〜38g/l程度(錫として2.6〜21g
/l程度)と塩酸および/または硫酸とを含む水溶液に
10〜40℃程度で1〜10分間程度浸漬する。この様
な水溶液の調製に使用する塩酸および/または硫酸の配
合量は、上記(a)の塩化錫(II)を使用する場合と
同様である。また、水溶液が塩素イオンを含まない場合
には、ポリアミドおよび天然繊維の処理に限られること
は、やはり上記(a)の場合と同様である。
(B) When using tin (II) sulfate: S
nSO 4 5 to 38 g / l (tin as 2.6 to 21 g
(About 1 / l) and an aqueous solution containing hydrochloric acid and / or sulfuric acid at about 10 to 40 ° C. for about 1 to 10 minutes. The blending amount of hydrochloric acid and / or sulfuric acid used for the preparation of such an aqueous solution is the same as in the case of using tin (II) chloride in (a) above. Further, when the aqueous solution does not contain chlorine ions, the treatment is limited to the polyamide and the natural fiber, as in the case (a).

【0035】(c)塩化錫(II)と硫酸錫(II)と
を使用する場合;両者の合計量が2.6〜21g/l程
度(錫として)となるように調製した水溶液に10〜4
0℃程度で1〜10分間程度浸漬する。この様な水溶液
の調製に使用する塩酸および/または硫酸の配合量は、
上記(a)の塩化錫(II)を使用する場合と同様であ
る。また、水溶液が塩素イオンを含まない場合には、ポ
リアミドおよび天然繊維の処理に限られることは、やは
り上記(a)の場合と同様である。
(C) When tin (II) chloride and tin (II) sulfate are used; 10 to 10 parts by weight of an aqueous solution prepared so that the total amount of both is about 2.6 to 21 g / l (as tin). Four
Immerse at about 0 ° C. for about 1 to 10 minutes. The amount of hydrochloric acid and / or sulfuric acid used to prepare such an aqueous solution is
This is the same as in the case of using tin (II) chloride in (a) above. Further, when the aqueous solution does not contain chlorine ions, the treatment is limited to the polyamide and the natural fiber, as in the case (a).

【0036】(3)銀の付与 次いで、上記の錫塩処理を終えた被処理物を水洗した
後、硝酸銀0.4〜10g/lの水溶液に10〜70℃
で0.4〜15分間程度浸漬する。この浸漬に際して
も、被処理物に細かい気泡が付着することがあるので、
その付着を防止し、銀イオンの均一な吸着を行うため
に、被処理物および/または水溶液を動かすことが好ま
しい。
(3) Addition of silver Next, the object to be treated which has been subjected to the tin salt treatment is washed with water, and then added to an aqueous solution of 0.4 to 10 g / l of silver nitrate at 10 to 70 ° C.
Soak for 0.4 to 15 minutes. Even during this immersion, fine bubbles may adhere to the object to be treated, so
It is preferable to move the object to be treated and / or the aqueous solution in order to prevent the adhesion and to uniformly adsorb silver ions.

【0037】硝酸銀の濃度は、通常1〜2g/lを上回
っても被処理物への銀の析出量は特に増大せず、被処理
物を使用した場合の抗菌性および抗かび性の効果の改善
は期待できない。しかしながら、上記の各種の処理液の
場合と同様に、処理液が厚さの大きい不織布、ポリウレ
タンフォームなどである場合には、多量の処理液を吸収
して、液の持ち出し量が多くなるため、液の濃度管理が
困難となるので、硝酸銀の濃度の上限量を10g/lと
する。一方、硝酸銀濃度が0.3g/l程度の液であっ
ても、液の温度を高めるか或いは浸漬時間を長くする場
合には、銀濃度0.4g/l以上の液を使用する場合と
同様の優れた抗菌性および抗かび性を被処理物に付与す
ることができる。しかしながら、建浴(初めに溶液をつ
くる)時からこの様な低濃度とする場合には、やはり厚
さのある織布、ポリウレタンフォームなどを処理する際
に液の濃度管理が困難となるために、硝酸銀濃度の下限
を0.4g/lとする。硝酸銀含有処理液の適切な温度
は、吸着している錫イオンにより銀イオンが還元される
速度、置換された銀が成長する速度などが大きく関係す
る。従って、硝酸銀濃度、温度および浸漬時間を考慮し
て、例えば、(イ)硝酸銀濃度0.4〜1g/;温度1
0〜30℃;浸漬時間5〜15分間、(ロ)硝酸銀濃度
0.4〜1g/;温度40〜60℃;浸漬時間3〜10
分間、(ハ)硝酸銀濃度3〜10g/;温度20〜35
℃;浸漬時間2〜5分間、(ニ)硝酸銀濃度3〜10g
/;温度40〜60℃;浸漬時間0.5〜4分間などの
組合せを採用することが好ましい。但し、本発明におけ
る銀メッキ条件は、これらの組合せに限定されるもので
はなく、他の条件を採用することもできる。
Even if the concentration of silver nitrate exceeds 1 to 2 g / l, the amount of silver deposited on the object to be treated does not increase particularly, and the antibacterial and antifungal effects when the object to be treated is used are exhibited. No improvement can be expected. However, as in the case of the various treatment liquids described above, when the treatment liquid is a large-thickness non-woven fabric, such as polyurethane foam, since a large amount of the treatment liquid is absorbed and the carry-out amount of the liquid increases, Since it is difficult to control the concentration of the liquid, the upper limit of the concentration of silver nitrate is set to 10 g / l. On the other hand, even if the liquid has a silver nitrate concentration of about 0.3 g / l, when raising the temperature of the liquid or prolonging the immersion time, the same as when using a liquid having a silver concentration of 0.4 g / l or more. The excellent antibacterial and antifungal properties of can be imparted to the object to be treated. However, if such a low concentration is used from the time of building the bath (making the solution at the beginning), it will be difficult to control the concentration of the liquid when processing thick woven fabric, polyurethane foam, etc. The lower limit of the silver nitrate concentration is 0.4 g / l. The appropriate temperature of the processing solution containing silver nitrate is greatly related to the rate at which silver ions are reduced by adsorbed tin ions and the rate at which substituted silver grows. Therefore, considering the silver nitrate concentration, temperature and immersion time, for example, (a) silver nitrate concentration 0.4 to 1 g /; temperature 1
0-30 ° C; immersion time 5-15 minutes, (b) silver nitrate concentration 0.4-1 g /; temperature 40-60 ° C; immersion time 3-10
Min., (C) silver nitrate concentration 3 to 10 g /; temperature 20 to 35
C .; immersion time 2 to 5 minutes, (d) silver nitrate concentration 3 to 10 g
It is preferable to employ a combination such as /; temperature 40 to 60 ° C .; immersion time 0.5 to 4 minutes. However, the silver plating conditions in the present invention are not limited to these combinations, and other conditions can be adopted.

【0038】硝酸銀水溶液による処理を終えた被処理物
は、水洗され、必要ならば乾燥されて、所望の水耕栽培
における抗かび性および抗菌性付与材料が得られる。
The object to be treated, which has been treated with the aqueous silver nitrate solution, is washed with water and, if necessary, dried to obtain the desired antifungal and antibacterial property-imparting material for hydroponics.

【0039】なお、抗かび性および抗菌性付与材料を使
用する場所(水耕栽培圃場)が上記の銀付与処理を行っ
た場所に近い場合には、上記の乾燥を行うことなく、そ
のまま圃場で使用することができる。
When the place where the antifungal and antibacterial property-imparting material is used (hydroponics field) is close to the place where the above-mentioned silver application process is performed, the above-mentioned drying is not performed and the field is used as it is. Can be used.

【0040】また、銀の付着量を増大させる必要がある
場合には、被処理物に対する錫塩の付与および銀の付与
操作を必要な回数行えばよい。この際、銀の付与を終え
た被処理物は、乾燥することなく、そのまま錫塩の付与
に供することができる。
When it is necessary to increase the amount of silver deposited, the tin salt application and silver application operations to the object to be treated may be performed as many times as necessary. At this time, the object to be treated after the addition of silver can be directly applied to the tin salt without being dried.

【0041】本発明による抗かび性および抗菌性付与材
料は、銀の酸化物と考えられる化合物(但し、本明細書
においては、単に銀と記載する場合がある)で被覆され
ている。
The antifungal and antibacterial property-imparting material according to the present invention is coated with a compound that is considered to be an oxide of silver (however, it may be simply referred to herein as silver).

【0042】銀の酸化物は、繊維品に高度で且つ持続性
に優れた抗かび性および抗菌性を付与し、ひいては水耕
栽培圃場における養液と接触する作物の病害を効果的に
抑制する。上記で得られた繊維品にどの程度の量の銀が
付与されているかは、繊維品の構造および性質上、明確
に算出することはできない。このため、繊維品中で最も
銀が付着しにくいポリエステルに対する銀付与量の目安
と銀付与工程の繰り返しによる付与量の変化について検
討した。即ち、ポリエステルの短繊維について、上記の
方法で各種の組成および条件で銀を付与した後、硝酸に
溶解させ、原子吸光度分析法により定量分析したとこ
ろ、平均約0.0003mg/cm2であった。従っ
て、この量以上の銀が被覆されていれば、抗かび性およ
び抗菌性付与材料として有用であると推測される。ま
た、前述のようにして、被処理物に対する銀付与工程を
2回繰り返したところ、銀の付与量は、1回処理した場
合の1.5〜2倍であった。さらに、被処理物に対する
銀付与工程を2回繰り返したところ、銀の付与量は、銀
の付与量は、1回処理した場合の2.3〜3.3倍に達
していた。
The silver oxide imparts a high degree and long-lasting antifungal and antibacterial properties to the fiber product, and effectively suppresses the diseases of the crops which come into contact with the nutrient solution in the hydroponics field. . The amount of silver added to the fiber product obtained above cannot be clearly calculated from the structure and properties of the fiber product. Therefore, the standard of the amount of silver applied to polyester, which is the most difficult to attach silver in the fiber product, and the change in the amount of silver applied by repeating the silver applying step were examined. That is, when short fibers of polyester were applied with silver in various compositions and conditions by the above method, dissolved in nitric acid, and quantitatively analyzed by atomic absorption spectrometry, the average was about 0.0003 mg / cm 2 . . Therefore, it is presumed that if it is coated with silver in this amount or more, it is useful as a material imparting antifungal and antibacterial properties. Further, as described above, when the step of applying silver to the object to be treated was repeated twice, the amount of silver applied was 1.5 to 2 times that in the case of performing the treatment once. Further, when the step of applying silver to the object to be processed was repeated twice, the applied amount of silver reached 2.3 to 3.3 times the applied amount of silver as compared with the case where the treatment was performed once.

【0043】なお、繊維品に付与された銀の化学状態お
よびその組成についての詳細は不明であるが、X線光電
分光分析の結果からは、銀は金属の状態ではなく酸化し
ている化学状態にあると考えられる。理論的には、吸着
した錫イオンにより銀イオンが金属銀に還元されると考
えられる。
Although the details of the chemical state of silver applied to the textile and its composition are unknown, the results of X-ray photoelectron spectroscopy show that silver is not in a metallic state but in a oxidized chemical state. It is believed to be in. Theoretically, it is considered that the adsorbed tin ions reduce silver ions to metallic silver.

【0044】 Sn2++2Ag2+ → Sn4++2Ag0 しかしながら、付与される銀の成長速度が遅く、またそ
の厚さが非常に薄いため、溶液中および測定までの大気
中での放置により、一旦析出した金属銀が酸化している
ものと推定される。なお、繊維品を肉眼で観察した限り
では、銀は、灰黒色、茶褐色などの色を呈していた。
Sn 2+ + 2Ag 2+ → Sn 4+ + 2Ag 0 However, since the growth rate of the applied silver is slow and the thickness thereof is very thin, it may be left in the solution and in the atmosphere until the measurement. It is presumed that the metallic silver once deposited is oxidized. As long as the fiber product was observed with the naked eye, silver exhibited colors such as gray black and brown.

【0045】本発明による抗かび性および抗菌性付与材
料は、水耕栽培養液に接触させる(例えば、潅水糟に浸
漬する)ことにより、銀イオンを溶出させて水耕栽培作
物をかびおよび/または菌から保護する。潅水糟に浸漬
する抗かび性および抗菌性付与材料の寸法乃至量は、溶
液中に銀イオン濃度が0.003〜0.8ppmとなる
様にすればよい。水耕栽培に際しての他の条件(養液の
組成、温度、対流条件など)は、従来技術のそれらと同
様であって良い。
The antifungal and antibacterial property-imparting material according to the present invention is contacted with a hydroponic culture nutrient solution (for example, immersed in an irrigation tank) to elute silver ions to mold and / or mold hydroponic crops. Or protect from fungi. The size and amount of the antifungal and antibacterial property-imparting material dipped in the irrigation bath may be such that the concentration of silver ions in the solution is 0.003 to 0.8 ppm. Other conditions for hydroponics (composition of nutrient solution, temperature, convection conditions, etc.) may be the same as those of the prior art.

【0046】本発明により、水耕栽培作物の病害抑制に
顕著な効果が達成されるのは、以下のような理由による
ものと推測される。即ち、水耕栽培養液中に溶出した銀
の酸化物が、植物病原菌、養液の浮遊化合物などと反応
して、それよりも低級の酸化物に還元される際に、下記
に示す様に、活性の強い酸素を放出するものと考えられ
る。
The reason why the present invention achieves a remarkable effect on the disease control of hydroponic crops is presumed to be due to the following reasons. That is, the oxide of silver eluted in the hydroponic nutrient solution reacts with plant pathogenic bacteria, floating compounds of the nutrient solution, etc., and when it is reduced to a lower oxide, as shown below. , Which is thought to release highly active oxygen.

【0047】2AgO→ Ag2O+1/2O2 上記の反応において、安定な酸素分子になる前の活性な
酸素、即ち、原子状の酸素によって、防かび乃至防菌効
果が達成されることが考えられる。一方、上記式におけ
るAg2Oは、養液中のO2、OH-イオンなどにより酸
化され、再びAgOになることが考えられ、この銀酸化
物の自己酸化−還元も、低濃度の銀イオンによる防かび
乃至防菌効果に寄与しているものと考えられる。その結
果、本発明においても、銀を付与された繊維品を液中に
浸漬することにより、銀イオンの溶解ロスは避けられな
いが、仮に銀イオンの溶出がなくなったしても、微量の
銀が残存している限り、防除効果が発揮される。
2AgO → Ag 2 O + 1 / 2O 2 In the above reaction, it is considered that active oxygen before forming stable oxygen molecule, that is, atomic oxygen, achieves antifungal or antibacterial effect. . On the other hand, Ag 2 O in the above formula is considered to be oxidized again by O 2 , OH ions and the like in the nutrient solution to become AgO again. It is considered that this contributes to the antifungal or antibacterial effect. As a result, also in the present invention, by immersing the fiber product provided with silver in the liquid, dissolution loss of silver ions is unavoidable, but even if the elution of silver ions is stopped, a trace amount of silver is lost. As long as remains, the control effect is exerted.

【0048】[0048]

【発明の効果】本発明による抗かび性および抗菌性付与
材料を水耕栽培の養液に浸漬して使用する場合には、そ
の面積に比例して、浸漬開始から約2日間程度は、銀イ
オン濃度がほぼ直線的に増大し、その後はほぼ一定とな
る。
INDUSTRIAL APPLICABILITY When the antifungal and antibacterial property-imparting material according to the present invention is used by immersing it in a nutrient solution for hydroponics, silver is used for about 2 days in proportion to its area. The ion concentration increases almost linearly and then becomes almost constant.

【0049】従って、 本発明によれば、銀で被覆され
た繊維品の面積と養液量との割合を調整することによ
り、持続的に一定量の銀イオンを養液中に溶出させるこ
とが可能となり、水耕栽培される作物の病害を持続的に
且つ効果的に抑制することができる。
Therefore, according to the present invention, a certain amount of silver ions can be continuously eluted into the nutrient solution by adjusting the ratio of the area of the fiber product coated with silver and the amount of the nutrient solution. It becomes possible and the disease of the hydroponically grown crop can be suppressed continuously and effectively.

【0050】また、有害な硝酸銀を添加使用する従来技
術と異なり、安全性が高く、且つ銀イオン濃度の測定の
ための高価な装置を必要とはしない。
Also, unlike the prior art in which harmful silver nitrate is added and used, it is not necessary to have an expensive device with high safety and for measuring the silver ion concentration.

【0051】さらに、銀イオンを低濃度に維持すること
ができるので、植物に害を与えることもない。
Furthermore, since the silver ion can be maintained at a low concentration, it does not harm plants.

【0052】本発明は、植物の根を介して発生するかび
類による病害(根腐病、萎ちょう病、つる割れ病など)
および菌類による病害(青枯病、黒斑点病など)の予防
および防除に極めて有用である。
The present invention relates to diseases caused by molds which occur through the roots of plants (root rot, wilt, vine cracking, etc.).
It is also extremely useful for the prevention and control of diseases caused by fungi (blight wilt, black spot, etc.).

【0053】[0053]

【実施例】以下に実施例を示し、本発明の特徴とすると
ころをより一層明らかにする。
EXAMPLES Examples will be shown below to further clarify the features of the present invention.

【0054】なお、実施例における抗菌性試験および抗
かび性試験は、以下の様にして行った。
The antibacterial and antifungal tests in the examples were carried out as follows.

【0055】I. 植物病原菌の防除試験 I−1.供試病原菌 病原菌としては、根腐病の原因となる水生菌(かび類)
のPythium butleriSUBRAMNIAM(IFO 31214)菌およ
びキュウリ、メロンなどのつる割れ病の原因となるFusa
rium oxysporum f.sp.cucumerium菌ならびに青枯病の原
因となる細菌のPseudomonas solanacearum菌(農林水産
省農業資源研究所で登録番号No.03-01525)を使用し
た。
I. Pest control fungus control test I-1. Test pathogens As pathogens, aquatic fungi (molds) that cause root rot
Of Pythium butleri SUBRAMNIAM (IFO 31214) and Fusa causing vine cracking diseases such as cucumber and melon
The rium oxysporum f.sp.cucumerium fungus and Pseudomonas solanacearum fungus (a registration number No. 03-01525 at the Ministry of Agriculture, Forestry and Fisheries National Institute for Agricultural Resources) were used.

【0056】I−2.発病試験法 (a)試験に用いた水耕培養液の液組成濃度は硝酸カル
シウム0.95g/l、 硝酸カリウム0.81g/
l、硫酸マグネシウム0.5g/l、リン酸第一アンモ
ニウム0.155g/l、硫酸第一鉄0.08g/l、
硫酸マンガン0.07g/l、EDTA0.08g/l
を基本液組成濃度とし、その基本組成濃度の1/2およ
び2/3の濃度に調整した。なお、硫酸第一鉄および硫
酸マンガンは、一旦EDTAに溶解した後、添加混合し
た。いずれの濃度においても、水酸化カリウム水溶液に
より、pHは、約6に調整した。
I-2. Disease test method (a) The liquid composition concentration of the hydroponic culture solution used in the test is calcium nitrate 0.95 g / l, potassium nitrate 0.81 g /
1, magnesium sulfate 0.5 g / l, ferrous ammonium phosphate 0.155 g / l, ferrous sulfate 0.08 g / l,
Manganese sulfate 0.07 g / l, EDTA 0.08 g / l
Was used as the basic liquid composition concentration, and the concentrations were adjusted to 1/2 and 2/3 of the basic composition concentration. The ferrous sulfate and manganese sulfate were once dissolved in EDTA and then added and mixed. At any concentration, the pH was adjusted to about 6 with an aqueous potassium hydroxide solution.

【0057】(b)水耕培養液中のかびおよび細菌の濃
度は、約103個/mlとになるように接種し、発病性
について調べた。
(B) The fungi and bacteria in the hydroponic culture solution were inoculated so that the concentration thereof was about 10 3 cells / ml, and the pathogenicity was examined.

【0058】I−3.水耕培養に用いた装置 (a)広口の1l瓶で、ガラス棒により時々ゆっくりと
攪拌した。
I-3. Apparatus used for hydroponic culture (a) A wide-mouthed 1 liter bottle was occasionally stirred slowly with a glass rod.

【0059】(b)培養液が循環できる装置{(溜槽5
0cm×50cm×深さ約50cmに循環ポンプを設置
し、30〜300l/hで水路へ循環)および水路(植
物を育成する部分は、幅約22cm×深さ約23cm×
長さ約200cmで、中間を仕切ることもできる)}を
用いた。
(B) Device for circulating the culture solution {(reservoir 5
A circulation pump is installed at 0 cm x 50 cm x depth of about 50 cm, and circulates to the waterway at 30 to 300 l / h) and a waterway (the part for growing plants is about 22 cm wide x 23 cm deep).
The length is about 200 cm, and the middle can be partitioned)}.

【0060】(c)前記(b)の水路にネット状のプラ
スチック板、穴があいた発泡スチロールを置き、その上
で薄膜法での栽培ができるようにした。
(C) A net-shaped plastic plate and Styrofoam with holes were placed in the water channel of (b) above, and cultivation by the thin film method was made possible on it.

【0061】実施例1 綿繊維100%からなる厚さ約0.35mmの織物を水
酸化ナトリウム170g/lの水溶液(温度60〜68
℃)に45分間浸漬し、時々ゆっくりかき混ぜて汚れを
除去した後、よく水洗して6%塩酸水溶液に浸浸し、さ
らによく水洗した。次いで、SnCl2・2H20約20
g/lと濃塩酸(HCl)約15ml/lとの混合水溶
液(温度約22℃)に約5分間浸漬し、ゆっくりかき混
ぜた後、よく水洗し、次にAgNO3約2g/lの水溶
液(温度約51℃)に約5分間浸漬し、ゆっくりかき混
ぜ、よく水洗した。得られた銀付与織物の一部を次亜塩
素酸ナトリウム水溶液に浸漬して、銀およびその酸化物
を溶解し、銀としての付着量を算出すると、1m2当た
り約1.5gであった。
Example 1 A woven fabric made of 100% cotton fiber and having a thickness of about 0.35 mm was used as an aqueous solution of 170 g / l of sodium hydroxide (temperature: 60 to 68).
(45 ° C.) for 45 minutes, stirring gently occasionally to remove stains, thoroughly rinsing with water, immersing in 6% hydrochloric acid aqueous solution, and further rinsing with water. Then, SnCl 2 · 2H 2 0 about 20
Immerse in a mixed aqueous solution of g / l and concentrated hydrochloric acid (HCl) of about 15 ml / l for about 5 minutes, stir slowly, wash well, and then wash with water of AgNO 3 about 2 g / l ( It was immersed in a temperature of about 51 ° C.) for about 5 minutes, stirred slowly, and thoroughly washed with water. A part of the obtained silver-provided woven fabric was dipped in an aqueous solution of sodium hypochlorite to dissolve silver and its oxide, and the adhesion amount as silver was calculated to be about 1.5 g per 1 m 2 .

【0062】前記Iー3.(a)項の1l用瓶を20個
用意し、そのなかの15個に培養液の基本液とPythium
butleri SUBRAMNIAM菌が培養液の1ml当たり約103
個となる様に接種し、全体の量を調整してそれぞれ1l
とした。これら15個の瓶を以下の3つの群に分けた。
I-3. Prepare 20 bottles for 1 liter as described in (a), 15 of which are the basic solution of the culture solution and Pythium.
butleri SUBRAMNIAM bacteria is about 10 3 per 1 ml of culture solution.
Inoculate so that it will be individual, adjust the total amount and each 1 liter
And These 15 bottles were divided into the following 3 groups.

【0063】(イ)5個には上記で製造した銀処理布を
約50cm2/lの割合で入れ、(ロ)5個には銀処理
していない布を約50cm2/lの割合で入れ、(ハ)
5個には何にも入れなかった。また、残りの5個の瓶に
は、培養液の基本液を1lのみ入れた(菌は接種してい
ない)。
(B) The silver-treated cloth produced above was put in 5 pieces at a ratio of about 50 cm 2 / l, and (b) 5 pieces of unsilvered cloth were put in a ratio of about 50 cm 2 / l. Put, (C)
I didn't put anything in the five. The remaining 5 bottles contained only 1 liter of the basic solution of the culture solution (the bacteria were not inoculated).

【0064】上記の各瓶を18〜25℃で1日間保持し
た後、それぞれにホウレンソウ苗(草丈約13cm)を
移植した。
Each of the above bottles was kept at 18 to 25 ° C. for 1 day, and then spinach seedlings (plant height of about 13 cm) were transplanted to each.

【0065】各瓶における病徴発現は、以下の通りであ
った。
The manifestation of symptoms in each bottle was as follows.

【0066】菌が接種してあり、銀処理布を入れないも
のは、移植から1日でホウレンソウがしおれ始め、2日
目には根がぬるぬるし、4〜5日目で完全にしおれて、
枯れた。
For those inoculated with the bacteria and without the silver-treated cloth, the spinach started wilting one day after transplanting, the roots became slimy on the second day, and completely wilted on the fourth to fifth days.
Dead.

【0067】これに比して、菌が接種してあり且つ銀処
理布を入れたものは、菌を接種していないものと同じ生
育状態を示した。また、15日間経過後、新しいホウレ
ンソウの苗(草丈約15cm)に取り替え、15日間経
過後に再び新しいホウレンソウの苗(草丈約14cm)
に取り替え、この繰返しを7サイクル実施したが、生育
は健全であった。なお、この期間においては、培養液の
濃度分析を行い、不足成分を適宜補うとともに、過剰分
は銀付与布を培養液から引き上げて調整した。
In contrast, those inoculated with the fungus and containing the silver-treated cloth showed the same growth state as those not inoculated with the fungus. In addition, after 15 days, it is replaced with a new spinach seedling (plant height of about 15 cm), and after 15 days, new spinach seedling (plant height of about 14 cm) is replaced.
This was repeated for 7 cycles, but the growth was sound. During this period, the concentration of the culture broth was analyzed to appropriately supplement the deficient components, and the excess was adjusted by pulling up the silver-applied cloth from the culture broth.

【0068】なお、菌を接種しない場合には、4サイク
ル目から3個の瓶でホウレンソウがしおれ始め、日数の
経過とともに枯れた。これは、恐らくいずれかの種類の
菌がその瓶中に侵入し、増殖したものと考えられる。
When the bacteria were not inoculated, spinach began to wilt from the 3rd bottle in the 4th cycle and died with the passage of days. This is probably due to the infestation of any type of fungus into the bottle and growth.

【0069】以上の結果から、本発明による銀処理布
は、優れた病害抑制効果を発揮することが明らかであ
る。
From the above results, it is clear that the silver-treated cloth according to the present invention exerts an excellent disease control effect.

【0070】実施例2 綿繊維100%からなる厚さ約0.35mmの織物を水
酸化ナトリウム100g/lの水溶液(温度60〜68
℃)に45分間浸漬し、時々ゆっくりかき混ぜて汚れを
除去した後、よく水洗し、3%塩酸水溶液に浸浸し、よ
く水洗し、次亜塩素酸ナトリウムの3%水溶液に20分
浸漬し、よく水洗した。次いで、織物を1%硫酸水溶液
に浸漬し、よく水洗し、酸性亜硫酸ナトリウム5%水溶
液に20分間浸漬した後、よく水洗した。
Example 2 A woven fabric made of 100% cotton fiber and having a thickness of about 0.35 mm was treated with an aqueous solution of 100 g / l of sodium hydroxide (temperature: 60 to 68).
C.) for 45 minutes, and occasionally stirring gently to remove stains, then wash thoroughly with water, soak in 3% aqueous hydrochloric acid solution, then wash well with water, and soak in 3% aqueous solution of sodium hypochlorite for 20 minutes, Washed with water. Then, the woven fabric was dipped in a 1% aqueous solution of sulfuric acid, thoroughly washed with water, dipped in a 5% aqueous solution of sodium acid sulfite for 20 minutes, and then thoroughly washed with water.

【0071】次いで、SnCl2・2H20約20g/l
と濃塩酸(HCl)約15ml/lの混合水溶液(温度
約22℃)に約5分間浸漬し、ゆっくりかき混ぜた後、
よく水洗し、AgNO3約1g/lの水溶液(温度約5
1℃)に約5分間浸漬し、ゆっくりかき混ぜた後、水洗
した。銀を付与した織物の一部を次亜塩素酸ナトリウム
水溶液に浸漬し、銀およびその酸化物を溶解させて、銀
としての付着量を算出すると、1m2当たり約1.7g
であった。
Then, SnCl 2 .2H 2 0 about 20 g / l
And 15 ml / l of concentrated hydrochloric acid (HCl) in a mixed aqueous solution (temperature of about 22 ° C.) for about 5 minutes, and after gently stirring,
Wash thoroughly with water, and then use an aqueous solution of about 1 g / l AgNO 3 (temperature about 5
It was immersed in 1 ° C.) for about 5 minutes, stirred slowly, and washed with water. A part of the woven fabric to which silver is applied is dipped in an aqueous solution of sodium hypochlorite to dissolve silver and its oxide, and the adhesion amount as silver is calculated to be about 1.7 g per 1 m 2.
Met.

【0072】前記Iー3.(a)項の1l用瓶を20個
用意し、そのなかの15個に培養液の基本液とPythium
butleri SUBRAMNIAM菌が培養液の1ml当たり約103
個となる様に接種し、全体の量を調整してそれぞれ1l
とした。これら15個の瓶を以下の3つの群に分けた。
The above I-3. Prepare 20 bottles for 1 liter as described in (a), 15 of which are the basic solution of the culture solution and Pythium.
butleri SUBRAMNIAM bacteria is about 10 3 per 1 ml of culture solution.
Inoculate so that it will be individual, adjust the total amount and each 1 liter
And These 15 bottles were divided into the following 3 groups.

【0073】(イ)5個には上記で製造した銀処理織物
を約50cm2/lの割合で入れ、(ロ)5個には銀処
理していない織物を約50cm2/lの割合で入れ、
(ハ)5個には何にも入れなかった。また、残りの5個
の瓶には、培養液の基本液を1lのみ入れた(菌は接種
していない)。
(B) The silver-treated fabric produced above was put in 5 pieces at a rate of about 50 cm 2 / l, and (b) 5 pieces of the untreated silver sheet were put in a rate of about 50 cm 2 / l. Get in,
(C) I couldn't put anything in the 5 pieces. The remaining 5 bottles contained only 1 liter of the basic solution of the culture solution (the bacteria were not inoculated).

【0074】上記の各瓶を18〜25℃で1日間保持し
た後、それぞれにホウレンソウ苗(草丈約14cm)を
移植した。
Each of the above bottles was kept at 18 to 25 ° C. for 1 day, and then spinach seedlings (plant height: about 14 cm) were transplanted to each.

【0075】各瓶における病徴発現は、以下の通りであ
った。
The manifestation of symptoms in each bottle was as follows.

【0076】菌が接種してあり、銀処理布を入れないも
のは、移植から1日でしおれ始め、3日目には根がぬる
ぬるし、4〜5日目には完全にしおれて、枯れるものも
あった。
Those which had been inoculated with the bacteria and did not contain the silver-treated cloth began to wilt one day after transplantation, and the roots became slimy on the third day and completely wilted and died on the fourth to fifth days. There were things.

【0077】これに比して、菌が接種してあり且つ銀処
理織物を入れたものは、菌を接種していないものと同じ
生育状態を示した。
In contrast, those inoculated with the fungus and containing the silver-treated fabric showed the same growth condition as those not inoculated with the fungus.

【0078】なお、菌を接種しない場合には、9日目頃
から2個の瓶でホウレンソウがしおれ始め、日数の経過
とともに完全に枯れた。これは、恐らくいずれかの種類
の菌がその瓶中に侵入し、増殖したものと考えられる。
When the bacteria were not inoculated, the spinach began to wilt in two bottles from the 9th day, and the spinach completely died with the passage of days. This is probably due to the infestation of any type of fungus into the bottle and growth.

【0079】以上の結果から、本発明による銀処理織物
は、優れた病害抑制効果を発揮することが明らかであ
る。
From the above results, it is clear that the silver-treated woven fabric according to the present invention exhibits an excellent disease control effect.

【0080】実施例3 ポリアミド繊維100%からなる厚さ約0.2mmの織
物を水酸化ナトリウム170g/lの水溶液(温度60
〜68℃)に45分間浸漬し、時々ゆっくりかき混ぜて
汚れを除去した後、よく水洗し、6%塩酸水溶液に浸浸
し、再度よく水洗した。次いで、この織物をSnCl2
・2H20約20g/lと濃塩酸(HCl)約15ml
/lの混合水溶液(温度約22℃)に約5分間浸漬して
ゆっくりかき混ぜた後、よく水洗し、次いでAgNO3
約2g/lの水溶液(温度約51℃)に約5分間浸漬
し、ゆっくりかき混ぜた後、水洗した。この様にして銀
を付与した織物の一部を次亜塩素酸ナトリウム水溶液に
浸漬し、銀およびその酸化物を溶解させて銀としての付
着量を算出すると、1m2当たり約2gであった。
Example 3 A woven fabric made of 100% polyamide fiber and having a thickness of about 0.2 mm was treated with an aqueous solution of 170 g / l of sodium hydroxide (at a temperature of 60).
The mixture was immersed in (-68 ° C.) for 45 minutes, and occasionally stirred gently to remove stains, washed thoroughly with water, immersed in a 6% hydrochloric acid aqueous solution, and again washed thoroughly with water. The fabric is then SnCl 2
・ 2H 2 0 about 20g / l and concentrated hydrochloric acid (HCl) about 15ml
/ L mixed aqueous solution (Temperature: about 22 ° C) for about 5 minutes, stir slowly, wash well, then AgNO 3
It was immersed in an aqueous solution of about 2 g / l (temperature of about 51 ° C.) for about 5 minutes, gently stirred, and then washed with water. A part of the woven fabric thus provided with silver was immersed in an aqueous solution of sodium hypochlorite to dissolve silver and its oxide, and the amount of adhesion as silver was calculated to be about 2 g per 1 m 2 .

【0081】前記Iー3.(c)項の装置を使用して、
水耕栽培を行った。即ち、この装置の液溜槽に上記で銀
付与処理した織物を約50cm2/lの割合で入れた
後、培養液の基本液1lとPythium butleri SUBRAMNIAM
菌が培養液の1ml中に約103個の割合となる様に接
種し、18〜24℃に1日間保持した。次いで、予めポ
リウレタンホーム上に薄膜法で栽培してあるミツバ(草
丈約7cm)の7株を水路のプラスチック板(ネット
状)の上に置き、移植した。対流の流速は約60l/h
で行った。
The above I-3. Using the device of (c),
Hydroponics was performed. That is, after putting the above-mentioned silver-added woven fabric at a ratio of about 50 cm 2 / l into the liquid storage tank of this device, 1 liter of the basic liquid of the culture liquid and Pythium butleri SUBRAMNIAM
The bacteria were inoculated at a ratio of about 10 3 per 1 ml of the culture broth and kept at 18 to 24 ° C for 1 day. Then, 7 strains of honeywort (plant height of about 7 cm) that had been cultivated on the polyurethane home in advance by the thin film method were placed on the plastic plate (net shape) of the waterway and transplanted. Convection flow rate is about 60 l / h
I went there.

【0082】一方、銀付与処理しないポリアミド織物を
用いて、同様の移植試験を行った。即ち、織物を装置の
液溜槽中に約50cm2/lの割合で入れた後、培養液
の基本液1lとPythium butleri SUBRAMNIAM菌が培養液
1ml当たり約103個の割合になる様に接種し、18
〜24℃に1日間保持した。次いで、予めポリウレタン
ホーム上に薄膜法で栽培してあるミツバ(草丈約7c
m)7株を水路のプラスチック板(ネット状)の上に置
き、移植した。
On the other hand, a similar transplantation test was conducted using a polyamide woven fabric which was not subjected to silver addition treatment. That is, after putting the fabric into the liquid storage tank of the apparatus at a ratio of about 50 cm 2 / l, inoculate 1 l of the culture solution basic solution and Pythium butleri SUBRAMNIAM bacteria at a rate of about 10 3 per 1 ml of the culture solution. , 18
Hold at -24 ° C for 1 day. Next, honeywort (plant height approx.
m) 7 strains were placed on a plastic plate (net-like) in a waterway and transplanted.

【0083】また、菌を接種せず且つ銀付与織物を入れ
ないものについても、同様にミツバ7株を移植した。
In addition, 7 strains of Mitsuba were transplanted in the same manner to those in which the fungus was not inoculated and the silver-coated fabric was not inserted.

【0084】銀付与処理織物を入れない場合には、2日
でしおれ始め、3日目には根がぬるぬるし、4〜5日目
では完全にしおれて枯れた。
When the silver-applied fabric was not added, it started wilting in 2 days, and the roots were slimy on the 3rd day, and completely wilted and died on the 4th to 5th days.

【0085】これに比して、銀付与処理した織物を入れ
た場合には、菌を接種していないものと同じ生育状態を
示した。また、15日間経過後、新しいミツバの苗(草
丈約6cm)に取り替え、15日間経過後に再び新しい
ミツバの苗(草丈約5cm)に取り替え、この繰り返し
を7サイクル行っても生育は健全であった。
On the other hand, when the woven fabric treated with silver was added, the same growth condition as that in which the fungus was not inoculated was exhibited. After 15 days, the seedlings were replaced with new honeybee seedlings (plant height of about 6 cm), and after 15 days, they were replaced with new honeybee seedlings (plant height of about 5 cm), and the growth was healthy even after repeating 7 cycles. .

【0086】また、菌を接種していないものは、4サイ
クル目で7株ともにしおれ始め、日数の経過とともに枯
れた。これは、恐らくいずれかの種類の菌が、培養装置
内に侵入し、増殖したものと考えられる。
In addition, all the 7 strains that had not been inoculated with the bacteria began to wither at the 4th cycle, and died with the passage of days. This is probably because some kind of bacteria invaded the culture device and grew.

【0087】以上の結果から、本発明による銀付与織物
をの使用による優れた効果が明らかである。
From the above results, the excellent effect of using the silver-coated fabric according to the present invention is clear.

【0088】実施例4 ポリウレタンフォーム(厚さ約3mm)を水酸化ナトリ
ウム150g/lの水溶液(温度60〜70℃)に40
分間浸漬しつつ時々ゆっくりかき混ぜて、汚れを除去し
た後、よく水洗し、6%塩酸水溶液に浸浸し、よく水洗
した。次いで、SnCl2・2H20約20g/lと濃塩
酸(HCl)約15ml/lの混合水溶液(温度約22
℃)に約5分間浸漬し、ゆっくりかき混ぜた後、よく水
洗した。
Example 4 Polyurethane foam (thickness: about 3 mm) was added to an aqueous solution of sodium hydroxide 150 g / l (temperature: 60 to 70 ° C.) to give 40 parts.
After dipping for a minute, occasionally stirring gently to remove dirt, followed by thorough washing with water, dipping in a 6% aqueous hydrochloric acid solution, and thorough washing with water. Then, a mixed aqueous solution of SnCl 2 · 2H 2 0 about 20 g / l and concentrated hydrochloric acid (HCl) about 15 ml / l (temperature about 22
C.) for about 5 minutes, slowly stirred, and then thoroughly washed with water.

【0089】次いで、上記の処理を行ったポリウレタン
フォームをAgNO3約2g/lの水溶液(温度約51
℃)に約5分間浸漬しつつゆっくりかき混ぜた後、水洗
し、乾燥した。この様にして得られた銀付与ポリウレタ
ンフォームの一部を次亜塩素酸ナトリウム水溶液に浸漬
し、銀およびその酸化物を溶解して、銀としての付着量
を算出すると、1m2当たり約1.8gであった。
Then, the polyurethane foam treated as described above was treated with an aqueous solution of about 2 g / l of AgNO 3 (at a temperature of about 51
C.) for about 5 minutes while slowly stirring, washing with water and drying. A portion of silver applied polyurethane foams obtained in this manner was immersed in an aqueous solution of sodium hypochlorite, by dissolving the silver and oxides thereof, calculating the adhesion amount of silver, about per 1 m 2 1. It was 8 g.

【0090】前記Iー3.(b)項の装置を使用して、
水耕栽培を行った。即ち、装置の溜槽に上記の処理によ
り得られた銀付与ポリウレタンフォームを約50cm2
/lの割合で入れた後、培養液の基本液1lとPythium
butleri SUBRAMNIAM菌が培養液1ml当たり約103
の割合となる様に接種し、18〜24℃に1日間保持し
た後、キュウリの苗(草丈約16cm)4株を水路の発
泡スチロール部分(穴があけてある)に移植した。対流
の流速は約60/hで行った。
The above I-3. Using the device of (b),
Hydroponics was performed. That is, about 50 cm 2 of the silver-added polyurethane foam obtained by the above treatment was placed in the reservoir of the apparatus.
1 liter of culture solution and 1 liter of Pythium
After inoculating butleri SUBRAMNIAM bacteria at a rate of about 10 3 per 1 ml of the culture solution and holding at 18 to 24 ° C for 1 day, 4 cucumber seedlings (plant height about 16 cm) were placed on the styrofoam part of the waterway (holes Have been opened). The flow rate of convection was about 60 / h.

【0091】一方、銀付与処理しないポリウレタンフォ
ームについても同様の操作を行った。即ち、装置の溜槽
に銀を付与していないポリウレタンフォームを約50c
2/lの割合で入れた後、培養液の基本液1lとPythi
um butleri SUBRAMNIAM菌が培養液1ml当たり約103
個の割合となる様に接種し、18〜24℃に1日間保持
した後、キュウリの苗(草丈約16cm)4株を水路の
発泡スチロール部分(穴があけてある)に移植した。
On the other hand, the same operation was carried out for a polyurethane foam which was not subjected to silver addition treatment. That is, about 50c of polyurethane foam without silver added to the reservoir of the device
After adding at a ratio of m 2 / l, 1 liter of the basic solution of the culture solution and Pythi
um butleri SUBRAMNIAM bacteria is about 10 3 per 1 ml of culture solution.
The seeds were inoculated in such a manner that they would be in the ratio of 1 and kept at 18 to 24 ° C. for 1 day, and then 4 cucumber seedlings (plant height of about 16 cm) were transplanted to the styrofoam part (with holes) of the water channel.

【0092】また、菌を接種せず且つ銀付与ポリウレタ
ンフォームをも入れないものについて、同様に4株につ
いて行った。
Further, the same test was carried out for 4 strains in which the fungus was not inoculated and the silver-added polyurethane foam was not added.

【0093】銀付与したポリウレタンフォームを入れな
い場合には、キュウリは、2日でしおれ始め、3日目に
は根がぬるぬるし、4〜5日目で完全にしおれて枯れ
た。
When the polyurethane foam with silver added was not added, the cucumber started to wilt on the 2nd day, the roots were slimy on the 3rd day, and completely wilted and died on the 4th to 5th days.

【0094】これに比して、銀付与処理したポリウレタ
ンフォームを入れた場合には、菌を接種していないもの
と同様の生育状態を示し、また、他の菌による病日疫徴
もなく、収穫は順当であった。
On the other hand, when the polyurethane foam treated with silver was added, it showed the same growth condition as that in which the bacteria were not inoculated, and there was no sickness epidemic due to other bacteria. The harvest was all right.

【0095】一方、菌を接種していないものは、収穫期
に入って、突如として4株とも根が腐敗し、枯れた。こ
れは、キュウリが何らかの菌に侵されたたものと考えら
れる。
On the other hand, the roots of all the 4 strains that had not been inoculated with the fungus suddenly rotted and died at the beginning of the harvesting season. This is probably because the cucumber was infested with some fungus.

【0096】以上の結果から、銀付与処理を行ったポリ
ウレタンホームは、優れた病害抑制効果を示すことが明
らかである。
From the above results, it is apparent that the silver-added polyurethane home shows an excellent disease control effect.

【0097】実施例5 綿繊維100%からなる厚さ約0.35mmの織物を水
酸化ナトリウム170g/lの水溶液(温度60〜68
℃)に45分間浸漬しつつ時々ゆっくりかき混ぜて汚れ
を除去した後、よく水洗し、6%塩酸水溶液に浸浸し、
再度よく水洗した。次いで、上記の織物をSnCl2
2H20約20g/lと濃塩酸(HCl)約15ml/
lの混合水溶液(温度約22℃)に約5分間浸漬し、ゆ
っくりかき混ぜた後、よく水洗した。次いで、上記の織
物をAgNO3約2g/lの水溶液(温度約51℃)に
約5分間浸漬してゆっくりかき混ぜた後、水洗した。得
られた銀付与織物の一部を次亜塩素酸ナトリウム水溶液
に浸漬し、銀およびその酸化物を溶解させて、銀として
の付着量を算出すると、1m2当たり約1.5gであっ
た。
Example 5 A woven fabric made of 100% cotton fiber and having a thickness of about 0.35 mm was used as an aqueous solution of 170 g / l of sodium hydroxide (temperature: 60 to 68).
℃) for 45 minutes while stirring occasionally to remove dirt, rinse well with water, and soak in 6% hydrochloric acid aqueous solution.
It was washed well again with water. Then, the above woven fabric is SnCl 2 ·.
2H 2 0 about 20 g / l and concentrated hydrochloric acid (HCl) about 15 ml /
It was immersed in a mixed aqueous solution of 1 (temperature: about 22 ° C.) for about 5 minutes, stirred slowly, and then thoroughly washed with water. Next, the above woven fabric was immersed in an aqueous solution of AgNO 3 of about 2 g / l (temperature of about 51 ° C.) for about 5 minutes, stirred gently, and then washed with water. A part of the obtained silver-coated woven fabric was dipped in an aqueous solution of sodium hypochlorite to dissolve silver and its oxide, and the adhesion amount as silver was calculated to be about 1.5 g per 1 m 2 .

【0098】前記Iー3.(a)項の1l用瓶を20個
用意し、そのなかの15個に培養液の基本液1lとPseu
domonas solancearum菌が培養液1ml当たり約103
の割合となる様に接種し、全体の量を調整してそれぞれ
1lとした。これら15個の瓶を以下の3つの群に分け
た。
The above I-3. Prepare 20 bottles for 1 liter in (a), 15 of which will be 1 liter of the basic solution of culture medium and Pseu.
The domonas solancearum bacterium was inoculated at a rate of about 10 3 per 1 ml of the culture solution, and the total amount was adjusted to 1 liter. These 15 bottles were divided into the following 3 groups.

【0099】(イ)5個には上記で製造した銀処理織物
を約50cm2/lの割合で入れ、(ロ)5個には銀処
理していない織物を約50cm2/lの割合で入れ、
(ハ)5個には何にも入れなかった。また、残りの5個
の瓶には、培養液の基本液を1lのみ入れた(菌は接種
していない)。
(A) The silver-treated fabric produced above was put in 5 pieces at a ratio of about 50 cm 2 / l, and (b) 5 the non-silver-treated cloth was put in about 50 cm 2 / l. Get in,
(C) I couldn't put anything in the 5 pieces. The remaining 5 bottles contained only 1 liter of the basic solution of the culture solution (the bacteria were not inoculated).

【0100】上記の各瓶を18〜25℃で1日間保持し
た後、それぞれにホウレンソウ苗(草丈約14cm)を
移植した。
Each of the above bottles was kept at 18 to 25 ° C. for 1 day, and then spinach seedlings (plant height of about 14 cm) were transplanted to each.

【0101】各瓶における病徴発現は、以下の通りであ
った。
The manifestation of symptoms in each bottle was as follows.

【0102】菌が接種してあり、銀処理布を入れないも
のは、移植から3日でしおれ始め、4日目には根がぬる
ぬるし、4〜5日目には完全にしおれて、枯れた。
Those which had been inoculated with the bacteria and did not contain the silver-treated cloth began to wilt 3 days after the transplantation, and the roots became slimy on the 4th day, and completely wilted on the 4th to 5th days and died. It was

【0103】これに比して、菌が接種してあり且つ銀処
理織物を入れたものは、菌を接種していないものと同じ
生育状態を示した。また、15日間経過後、新しいホウ
レンソウ苗(草丈約15cm)に取り替え、15日間経
過後に再び新しいホウレンソウ苗(草丈約14cm)に
取り替え、この繰り返しを7サイクル行っても、生育は
健全であった。なお、この期間においては、培養液の濃
度分析を行い、不足成分を適宜補った。
In contrast, those inoculated with the fungus and containing the silver-treated fabric showed the same growth condition as those not inoculated with the fungus. After 15 days, new spinach seedlings (plant height: about 15 cm) were replaced, and after 15 days, new spinach seedlings (plant height: about 14 cm) were replaced again. Even after repeating 7 cycles, the growth was healthy. During this period, the concentration of the culture broth was analyzed to appropriately supplement the deficient components.

【0104】なお、菌を接種せず且つ銀処理織物を入れ
ない場合には、5サイクル頃から3個の瓶でホウレンソ
ウがしおれ始め、日数の経過とともに完全に枯れた。こ
れは、いずれかの種類の菌がその瓶中に侵入し、増殖し
たものと考えられる。
When the fungus was not inoculated and the silver-treated fabric was not added, spinach began to wilt in three bottles from about 5 cycles and completely died as the number of days passed. It is thought that this is because bacteria of either type entered the bottle and proliferated.

【0105】以上の結果から、本発明による銀処理織物
は、優れた病害抑制効果を発揮することが明らかであ
る。
From the above results, it is clear that the silver-treated woven fabric according to the present invention exhibits an excellent disease control effect.

【0106】実施例6 ポリアミド繊維布(厚さ約0.2mm)を水酸化ナトリ
ウム150g/lの水溶液(温度60〜70℃)に40
分間浸漬し、時々ゆっくりかき混ぜて、汚れを除去した
後、よく水洗し、6%塩酸水溶液に浸浸し、再度よく水
洗した。次いで、SnCl2・2H20約20g/lと濃
塩酸(HCl)約15ml/lの混合水溶液(温度約2
2℃)に約5分間浸漬し、ゆっくりかき混ぜた後、よく
水洗し、次にAgNO3約2g/lの水溶液(温度約5
1℃)に約5分間浸漬しつつゆっくりかき混ぜ、水洗
し、乾燥した。得られた銀付与ポリアミド繊維布の一部
を次亜塩素酸ナトリウム水溶液に浸漬し、銀およびその
酸化物を溶解して、銀としての付着量を算出すると、1
2当たり約1.7gであった。
Example 6 Polyamide fiber cloth (thickness: about 0.2 mm) was added to an aqueous solution of sodium hydroxide 150 g / l (temperature: 60 to 70 ° C.) to give 40 parts.
After soaking for a minute and occasionally stirring gently to remove stains, it was thoroughly rinsed with water, immersed in a 6% aqueous hydrochloric acid solution, and again thoroughly rinsed with water. Then, a mixed aqueous solution of about 20 g / l of SnCl 2 · 2H 2 0 and about 15 ml / l of concentrated hydrochloric acid (HCl) (temperature of about 2
2 ° C) for about 5 minutes, slowly stir, then wash thoroughly with water, and then about 2 g / l of AgNO 3 in water (temperature about 5
The mixture was slowly stirred while being immersed in (1 ° C) for about 5 minutes, washed with water, and dried. A part of the obtained silver-added polyamide fiber cloth is dipped in an aqueous solution of sodium hypochlorite to dissolve silver and its oxide, and the adhesion amount as silver is calculated as 1
It was about 1.7 g per m 2 .

【0107】前記Iー3.(b)項の装置を使用して、
水耕栽培を行った。即ち、装置の溜槽に上記の処理によ
り得られた銀付与ポリアミド繊維布を約50cm2/l
の割合で入れた後、培養液の基本液1lとPseudomonas
solancearum菌が培養液1ml当たり約103個の割合と
なる様に接種し、18〜24℃に1日間保持した後、キ
ュウリの苗(草丈約16cm)4株を水路の発泡スチロ
ール部分(穴があけてある)に移植した。対流の流速は
約60/hで行った。
The above I-3. Using the device of (b),
Hydroponics was performed. That is, about 50 cm 2 / l of the silver-added polyamide fiber cloth obtained by the above treatment was placed in the reservoir of the apparatus.
1 liter of culture medium and Pseudomonas
After inoculating solancearum fungus at a rate of about 10 3 per 1 ml of the culture solution and holding at 18 to 24 ° C for 1 day, 4 cucumber seedlings (plant height about 16 cm) 4 strains were used for the styrofoam part of the waterway (open holes). Have been transplanted to. The flow rate of convection was about 60 / h.

【0108】一方、銀付与処理しないポリアミド繊維布
についても同様の操作を行った。即ち、装置の溜槽に銀
を付与していないポリアミド繊維布を約50cm2/l
の割合で入れた後、培養液の基本液1lとPseudomonas
solancearum菌が培養液1ml当たり約103個の割合と
なる様に接種し、18〜24℃に1日間保持した後、キ
ュウリの苗(草丈約16cm)4株を水路の発泡スチロ
ール部分(穴があけてある)に移植した。
On the other hand, the same operation was performed on the polyamide fiber cloth which was not subjected to the silver addition treatment. That is, about 50 cm 2 / l of polyamide fiber cloth without silver added to the tank of the device
1 liter of culture medium and Pseudomonas
After inoculating solancearum fungus at a rate of about 10 3 per 1 ml of the culture solution and holding at 18 to 24 ° C for 1 day, 4 cucumber seedlings (plant height about 16 cm) 4 strains were used for the styrofoam part of the waterway (open holes). Have been transplanted to.

【0109】また、菌を接種せず且つ銀付与ポリアミド
繊維布をも入れないものについて、同様に4株について
行った。
The same test was carried out for 4 strains in which the fungus was not inoculated and the silver-added polyamide fiber cloth was not added.

【0110】銀付与したポリアミド繊維布を入れない場
合には、キュウリは、2日でしおれ始め、4〜5日目で
完全にしおれて枯れた。
When the silver-added polyamide fiber cloth was not added, the cucumber started to wither in 2 days and completely withered and withered in 4 to 5 days.

【0111】これに比して、銀付与処理したポリアミド
繊維を入れた場合には、菌を接種していないものと同様
の生育状態を示し、また、他の菌による病日疫徴もな
く、収穫は順当であった。
In contrast, when the silver-added polyamide fiber was added, the same growth state as that in which the fungus was not inoculated was exhibited, and there was no morbid epidemic due to other fungus. The harvest was all right.

【0112】一方、菌を接種していないものは、収穫期
に入って、突如として4株とも根が腐敗し、枯れた。こ
れは、キュウリが何らかの菌に侵されたものと考えられ
る。
On the other hand, the roots of all the 4 strains that had not been inoculated with the fungus suddenly rotted and died during the harvest season. This is probably because the cucumber was invaded by some fungus.

【0113】以上の結果から、銀付与処理を行ったポリ
アミド繊維布は、優れた病害抑制効果を示すことが明ら
かである。
From the above results, it is clear that the polyamide fiber cloth subjected to the silver addition treatment has an excellent disease control effect.

【0114】実施例7 ポリアミド繊維布(厚さ約0.2mm)を水酸化ナトリ
ウム170g/lの水溶液(温度60〜68℃)に40
分間浸漬し、時々ゆっくりかき混ぜて、汚れを除去した
後、よく水洗し、6%塩酸水溶液に浸浸し、再度よく水
洗した。次いで、SnCl2・2H20約20g/lと濃
塩酸(HCl)約15ml/lの混合水溶液(温度約2
2℃)に約5分間浸漬し、ゆっくりかき混ぜた後、よく
水洗し、次にAgNO3約2g/lの水溶液(温度約5
1℃)に約5分間浸漬しつつゆっくりかき混ぜ、水洗
し、乾燥した。得られた銀付与ポリアミド繊維布の一部
を次亜塩素酸ナトリウム水溶液に浸漬し、銀およびその
酸化物を溶解して、銀としての付着量を算出すると、1
2当たり約2gであった。
Example 7 A polyamide fiber cloth (thickness: about 0.2 mm) was added to an aqueous solution of 170 g / l of sodium hydroxide (temperature: 60 to 68 ° C.) to give 40 parts.
After soaking for a minute and occasionally stirring gently to remove stains, it was thoroughly rinsed with water, immersed in a 6% aqueous hydrochloric acid solution, and again thoroughly rinsed with water. Then, a mixed aqueous solution of about 20 g / l of SnCl 2 · 2H 2 0 and about 15 ml / l of concentrated hydrochloric acid (HCl) (temperature of about 2
2 ° C) for about 5 minutes, slowly stir, then wash thoroughly with water, and then about 2 g / l of AgNO 3 in water (temperature about 5
The mixture was slowly stirred while being immersed in (1 ° C) for about 5 minutes, washed with water, and dried. A part of the obtained silver-added polyamide fiber cloth is dipped in an aqueous solution of sodium hypochlorite to dissolve silver and its oxide, and the adhesion amount as silver is calculated as 1
It was about 2 g per m 2 .

【0115】前記Iー3.(b)項の装置を使用して、
水耕栽培を行った。即ち、装置の溜槽に上記の処理によ
り得られた銀付与ポリアミド繊維布を約50cm2/l
の割合で入れた後、培養液の基本液1lとFusarium oxy
sporum f.sp.cucumerium菌が培養液1ml当たり約10
3個の割合となる様に接種し、18〜24℃に1日間保
持した後、キュウリの苗(草丈約17cm)4株を水路
の発泡スチロール部分(穴があけてある)に移植した。
対流の流速は約60/hで行った。
The above I-3. Using the device of (b),
Hydroponics was performed. That is, about 50 cm 2 / l of the silver-added polyamide fiber cloth obtained by the above treatment was placed in the reservoir of the apparatus.
1 liter of culture solution and Fusarium oxy
About 10 sporum f.sp.cucumerium per 1 ml culture
After inoculating so as to have a ratio of 3 plants and maintaining the temperature at 18 to 24 ° C. for 1 day, 4 cucumber seedlings (plant height: about 17 cm) were transplanted to the styrofoam portion (with holes) of the water channel.
The flow rate of convection was about 60 / h.

【0116】一方、銀付与処理しないポリアミド繊維布
についても同様の操作を行った。即ち、装置の溜槽に銀
を付与していないポリアミド繊維布を約50cm2/l
の割合で入れた後、培養液の基本液1lとFusarium oxy
sporum f.sp.cucumerium菌が培養液1ml当たり約10
3個の割合となる様に接種し、18〜24℃に1日間保
持した後、キュウリの苗(草丈約17cm)4株を水路
の発泡スチロール部分(穴があけてある)に移植した。
On the other hand, the same operation was performed on the polyamide fiber cloth which was not subjected to the silver addition treatment. That is, about 50 cm 2 / l of polyamide fiber cloth without silver added to the tank of the device
1 liter of culture solution and Fusarium oxy
About 10 sporum f.sp.cucumerium per 1 ml culture
After inoculating so as to have a ratio of 3 plants and maintaining the temperature at 18 to 24 ° C. for 1 day, 4 cucumber seedlings (plant height: about 17 cm) were transplanted to the styrofoam portion (with holes) of the water channel.

【0117】また、菌を接種せず且つ銀付与ポリアミド
繊維布をも入れないものについて、同様に4株について
行った。
[0117] In addition, the same test was carried out for 4 strains in which the fungus was not inoculated and the silver-added polyamide fiber cloth was not added.

【0118】銀付与したポリアミド繊維布を入れない場
合には、キュウリは、7日目につるが割れ始め、10日
目頃からしおれ始め、14日目で完全に枯れた。
When the polyamide fiber cloth to which silver was added was not added, the vine started to crack on the 7th day, began to wilt about the 10th day, and completely died on the 14th day.

【0119】これに比して、銀付与処理したポリアミド
繊維を入れた場合には、生育状態は順調で、また、他の
菌による病日疫徴もなく、収穫は順調であった。
In contrast, when the silver-added polyamide fiber was added, the growth condition was good, and there was no illness symptom due to other fungi, and the harvest was good.

【0120】一方、菌を接種していないものは、30日
目頃に1株につる割れ病が発生した。その後3日目に
は、他の3株にもつる割れ病が発生した。これは、おそ
らく伝染性があるFusarium oxysporum f.sp.cucumerium
菌を近くで取り扱っていたために、これに伝染したため
と考えられる。
On the other hand, in the case where the fungus was not inoculated, a vine cracking disease occurred in one strain around the 30th day. On the third day after that, cracking diseases involving the other three strains occurred. This is probably contagious Fusarium oxysporum f.sp.cucumerium
It is considered that the bacteria were transmitted nearby because they were handled by them.

【0121】以上の結果から、銀付与処理を行ったポリ
アミド繊維布は、優れた病害抑制効果を示すことが明ら
かである。
From the above results, it is clear that the polyamide fiber cloth subjected to the silver-adding treatment exhibits an excellent disease-controlling effect.

【0122】試験例 以上の各実施例で得られた各作物を乾燥し、細かく砕
き、それぞれの100gを採取して、次亜塩素酸ナトリ
ウム水溶液1lに3日間浸漬した後、溶出する銀イオン
濃度を原子吸光法により分析したところ、銀イオン濃度
は、検出限界以下であった。
Test Example Each of the crops obtained in each of the above examples was dried, crushed finely, 100 g of each was sampled, and immersed in 1 liter of an aqueous solution of sodium hypochlorite for 3 days. Was analyzed by atomic absorption spectrometry, the silver ion concentration was below the detection limit.

───────────────────────────────────────────────────── 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 // D06M 101:06 101:34 (72)発明者 坪田 園美 大阪府大阪市西成区花園南1−3−7 (72)発明者 岡田 義夫 兵庫県宝塚市御殿山3−10−13─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification number Reference number within the agency FI technical display location // D06M 101: 06 101: 34 (72) Inventor Sonomi Tsubota 1 Hanazono Minami, Nishinari-ku, Osaka-shi, Osaka -3-7 (72) Inventor Yoshio Okada 3-10-13 Gotenyama, Takarazuka City, Hyogo Prefecture

Claims (3)

【特許請求の範囲】[Claims] 【請求項1】(1)繊維品またはポリウレタンフォーム
からなる被処理品を塩化錫(II)および硫酸錫(I
I)の少なくとも1種と塩酸および硫酸の少なくとも1
種とを含む水溶液に浸漬し、次いで水洗する工程、およ
び(2)被処理品を硝酸銀の水溶液に浸漬する工程を備
えたことを特徴とする水耕栽培における抗かび性及び抗
菌性付与材料の製造方法。
(1) An article to be treated composed of a fiber article or a polyurethane foam is treated with tin (II) chloride and tin sulfate (I).
At least one of I) and at least one of hydrochloric acid and sulfuric acid
A material for imparting antifungal and antibacterial properties in hydroponics, which comprises a step of immersing in an aqueous solution containing seeds and then washing with water, and (2) a step of immersing the article to be treated in an aqueous solution of silver nitrate. Production method.
【請求項2】請求項1の方法で得られた銀および/また
はその酸化物を担持する繊維品またはポリウレタンフォ
ームからなる水耕栽培における抗かび性及び抗菌性付与
材料。
2. A material for imparting antifungal and antibacterial properties in hydroponics comprising a fiber product or a polyurethane foam carrying silver and / or its oxide obtained by the method of claim 1.
【請求項3】請求項1の方法で得られた銀および/また
はその酸化物を担持する繊維品またはポリウレタンフォ
ームを水耕培養液栽培の潅水に接触させることにより、
銀イオンを溶出させて水耕栽培作物をかびおよび/また
は菌から保護する方法。
3. A silver or / and its oxide-supporting fiber product or polyurethane foam obtained by the method of claim 1 is brought into contact with irrigation for hydroponic culture.
A method of eluting silver ions to protect hydroponic crops from mold and / or fungi.
JP6004100A 1994-01-19 1994-01-19 Material for giving antifungal and antibacterial properties in hydroponic culture, its production and antifungal and antibacterial method in nydroponic culture Pending JPH07203787A (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP6004100A JPH07203787A (en) 1994-01-19 1994-01-19 Material for giving antifungal and antibacterial properties in hydroponic culture, its production and antifungal and antibacterial method in nydroponic culture
NL9500096A NL9500096A (en) 1994-01-19 1995-01-19 Method for preparing a fungicidal / bactericidal material for hydroponic use, material thus obtained and method for protecting crops against fungi and / or bacteria in hydroponic.

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP6004100A JPH07203787A (en) 1994-01-19 1994-01-19 Material for giving antifungal and antibacterial properties in hydroponic culture, its production and antifungal and antibacterial method in nydroponic culture

Publications (1)

Publication Number Publication Date
JPH07203787A true JPH07203787A (en) 1995-08-08

Family

ID=11575379

Family Applications (1)

Application Number Title Priority Date Filing Date
JP6004100A Pending JPH07203787A (en) 1994-01-19 1994-01-19 Material for giving antifungal and antibacterial properties in hydroponic culture, its production and antifungal and antibacterial method in nydroponic culture

Country Status (2)

Country Link
JP (1) JPH07203787A (en)
NL (1) NL9500096A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001072642A1 (en) * 2000-03-31 2001-10-04 Jeon In Soo Silver ion-containing solution and use thereof
CN103643521A (en) * 2013-12-02 2014-03-19 常熟市新蕾针织有限公司 Preparation method of antibacterial ultraviolet-resistant textile
JP2021041371A (en) * 2019-09-13 2021-03-18 株式会社キャスティングイン Manufacturing method for silver-supported objects

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9713023D0 (en) * 1997-06-20 1997-08-27 Reckitt & Colmann Prod Ltd Improvements in or relating to the cleansing of surfaces

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8819205D0 (en) * 1988-08-12 1988-09-14 Pilkington Plc Wool puller
JPH0353825A (en) * 1989-07-21 1991-03-07 Shinagawa Nenryo Kk Medium for water culture
JPH03180125A (en) * 1989-12-07 1991-08-06 Mikado Kako Kk Film for nutrious solution culture
JP3273269B2 (en) * 1993-02-17 2002-04-08 株式会社サトーセン Method for imparting antibacterial and antifungal properties to textiles
JP3475254B2 (en) * 1993-03-01 2003-12-08 株式会社サトーセン Method for imparting antibacterial and antifungal properties to polyurethane foam

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001072642A1 (en) * 2000-03-31 2001-10-04 Jeon In Soo Silver ion-containing solution and use thereof
CN103643521A (en) * 2013-12-02 2014-03-19 常熟市新蕾针织有限公司 Preparation method of antibacterial ultraviolet-resistant textile
JP2021041371A (en) * 2019-09-13 2021-03-18 株式会社キャスティングイン Manufacturing method for silver-supported objects

Also Published As

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