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

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

Detailed Description of the Invention

[0001]

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]

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.

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.

(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.

(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.

(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.

(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.

(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.

(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]

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]

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.

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.

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.

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.

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.

(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.

(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.

(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.

(F) Immerse in concentrated sulfuric acid at a temperature of about 30 to 70 ° C., and then wash with water.

(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.

(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.

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.

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.

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.

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.

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.

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.

(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.

(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.

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.

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.

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.

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.

(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).

(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).

(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.

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.

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.

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.

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.

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).

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.

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.

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.

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.

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.

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]

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.

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.

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.

Furthermore, since the silver ion can be maintained at a low concentration, it does not harm plants.

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]

EXAMPLES Examples will be shown below to further clarify the features of the present invention.

The antibacterial and antifungal tests in the examples were carried out as follows.

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.

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.

(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.

I-3. Apparatus used for hydroponic culture (a) A wide-mouthed 1 liter bottle was occasionally stirred slowly with a glass rod.

(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)}.

(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.

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 .

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.

(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).

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.

The manifestation of symptoms in each bottle was as follows.

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.

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.

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.

From the above results, it is clear that the silver-treated cloth according to the present invention exerts an excellent disease control effect.

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.

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.

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.

(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).

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.

The manifestation of symptoms in each bottle was as follows.

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.

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.

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.

From the above results, it is clear that the silver-treated woven fabric according to the present invention exhibits an excellent disease control effect.

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 .

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.

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.

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.

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.

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. .

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.

From the above results, the excellent effect of using the silver-coated fabric according to the present invention is clear.

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.

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.

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.

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.

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.

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.

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.

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.

From the above results, it is apparent that the silver-added polyurethane home shows an excellent disease control effect.

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 .

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.

(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).

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.

The manifestation of symptoms in each bottle was as follows.

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

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.

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.

From the above results, it is clear that the silver-treated woven fabric according to the present invention exhibits an excellent disease control effect.

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 .

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.

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.

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.

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.

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.

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.

From the above results, it is clear that the polyamide fiber cloth subjected to the silver addition treatment has an excellent disease control effect.

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 .

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.

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] 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.

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.

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.

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.

From the above results, it is clear that the polyamide fiber cloth subjected to the silver-adding treatment exhibits an excellent disease-controlling effect.

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.

─────────────────────────────────────────────────── ─── 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)

[Claims] (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. 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. 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.