JP2969316B2 - Sterilization materials using metal ions and zeolite compounds - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a bactericidal material mainly composed of a metal ion such as copper and a zeolite compound, which is suitable mainly as an agricultural chemical.

[0002]

2. Description of the Related Art Conventionally, zeolites, whether natural zeolites or artificial zeolites, are used alone as soil conditioners by utilizing their properties such as adsorption and fertilizing power and ion exchange capacity, or mixed or administered with fertilizers and pesticides. It has been known that it is used for a great effect. Copper is present in animals and plants as a trace component or in soil, but copper chelate oxine copper is used to inhibit the SH group of enzymes in the organisms of fungi and molds. Is known, and SH inhibition by a 1: 1 chelate in vivo has been reported. Further, the antibacterial property, activity imparting property, growth promoting property and the like of chitosan for plants are known, for example, from Japanese Patent Publication No. 2-500796.

[0003]

However, since pesticide materials using copper are almost water-based materials, it is difficult to immobilize copper ions, and when administered to soil, they run down to the groundwater system and cause secondary contamination of the water system. Was a problem. In addition, chitosan, which is generally known in the past, has a high molecular weight and therefore has poor absorption and affinity for plants and has little effect on administration. There is a disadvantage that the desired application effect cannot be obtained. An object of the present invention is to provide an agricultural chemical material that solves these problems.

[0004]

The material of the present invention for solving the above-mentioned problems is, first, a low-grade material containing zeolite as a carrier.
Copper ion as an immobilizing material for molecular weight chitosan
Is characterized by being complexed or bonded with a compound . Second , when the molecular weight of chitosan is 320 or more and 28,
It has a molecular weight of 000 or less. Third
In addition, copper chloride is added in a weight ratio of 0.1 to chitosan having a reduced molecular weight.
It is characterized by being reacted or complexed at a rate of 1 to 1% .

[0005]

[Action] Zeolite has fertilizing ability and has soil improving effect. This is due to the fact that zeolite has ion exchange and adsorption ability, and N, P,
It is caused by adsorbing K, Mn, and Fe. These substances are ionizable substances of II valence and III valence, and it is considered that metal ions such as copper also become I valence and II valence ionized substances, so that they bind to zeolite.

It is also presumed that the amino group of chitosan also binds. Since these complexes of copper and chitosan are complexes with carboxyl groups, a complex reaction between chitosan and a metal such as copper is carried out in a basic environment. The bond between the amino group of chitosan and the zeolite is due to the bond between the free amino group of chitosan on the acidic side of the solvent.

[0007] On the other hand, chitosan alone has antibacterial activity per 7 sugars per D-glucosamine, but antifungals having a reduced molecular weight of 48,000 or less also have antibacterial activity. In particular, low molecular weight chitosan is C-
It has an amino group at position 2 and has a structure similar to kanamycins as an antibiotic, acts on prokaryotic 16s ribosomal RNA, specifically inhibits ribosome translation, and is a group 2 intron known as one of ribozymes. 5 '
It acts on guanosine, which works to release exons on the side, and inhibits brushing.
It is thought that it works by recognizing the higher-order structure of s-ribosomal RNA, and this is expected as an inhibitory effect on the growth of fungi and fungi.

[0008] Low molecular weight chitosan is obtained by binding a free amino group in the molecule of chitosan to a carboxyl group and a hydroxyl group of a constituent polysaccharide for fungi, molds and insects having chitin as a structural substance. Is considered
Thus fungi and fungi, feedback phenomenon of biological building materials constituting sugar chains of insects is expressed and Ru to induce low molecular weight proteoglycans shell surface.

Since humans, animals and plants do not have chitin, they are harmless and are presumed to work specifically on those having chitin as a bio-building substance such as fungi, molds and insects.

[0010]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail by way of example. First, in the present invention, a chitooligosaccharide, 2.5-anhydromannose,
Using low molecular weight chitosan as a medium, copper ions are complexed or bound to the functional groups of chitosan, these are immobilized, and copper ions are gradually dissociated by soil pH and organic acids secreted by plants.

[0011] The fungi and molds that have taken up these copper ions inhibit the synthesis pathway of citrate production from acetic acid in the living body, thereby inhibiting their growth. And as the zeolite used as agrochemical materials, clinoptilolite (from Akita), mordenite (from Shimane) or artificial zeolite, etc.
These are crushed and classified to a particle size that can be easily applied according to the intended use of the target material, washed with pure water, heat-dried after removing stenosis, and used as chitooligosaccharide, 2.5-anne. Hydromannose and low molecular weight chitosan are adjusted to pH 8.5 using an aqueous solution having a weight concentration of 0.01 to 5%.

Metal elements classified as 1B such as copper sulfate, basic copper sulfate, basic calcium sulfate-producing calcium, basic copper chloride, cupric hydroxide, basic copper carbonate, copper zinc oxide, silver, etc. And related compounds, metal elements classified as 6A such as chromium, and metalloids classified as 3B such as boron, boric acid, perboric acid, and aluminum are used alone or in all inorganic acids or organic acids. PH 5 to 5
An aqueous solution of 6.5 is mixed with the above-mentioned aqueous solution of zeolite and chitosan and reacted at room temperature. Of the above, the complex or bond of zeolite with copper gives a green or blue color, confirming that these compounds have been formed.
The zeolite complex compound in these solutions is taken out and immersed in alcohols or ethers. In this case, the amount is preferably equal to or more than the amount of the zeolite complexed with copper, and moisture adhering to these complex substances and to the carrier is removed and dried.

[0013] Chitosan has affinity for living organisms, and high-electrolyte ones having a molecular weight of about 15 to 50,000 are commercially available. These products are used for enzymes such as chitinase and chitosanase, inorganic and inorganic substances. Reduce the molecular weight with an organic solvent,
Cut molecular chains to a size that can penetrate cell walls and cell membranes,
The functional group present in the molecule has a sustained release property by complexing or bonding a copper ion to an arbitrary functional group of an amino group at the C-2 position, a hydroxyl group at the C-3 position, and a carboxyl group at the C-5 position. This is to cause SH group inhibition of the microorganism organism. Copper is present as a trace component in plant and animal organisms,
In addition, they are present in the soil, but inhibit SH enzymes when they are taken into living organisms such as fungi and molds.

More specifically, 300 ml of cryptotyrolite zeolite is stirred and permeated with 900 ml of pure water to remove stenosis, dried at 120 ° C. for 3 hours, and stored on silica gel. 300 ml of cryptotyrolite zeolite,
22.5 grams of molecular weight 320 per 450 ml of pure water
Above 28,000 or less low molecular weight chitosan and / or 2.5-anhydromannose or a heterosaccharide of chitooligosaccharide was mixed to a concentration of 5%, and the mixture was allowed to stand at room temperature for 2 hours.
At this time, the pH of the solution was 7.2, and the solution was pale red.
To this solution, 90 mg of cupric chloride was added, and when the pH was adjusted to 6.5, the reaction color changed from blue to green, confirming that the complex-bonding reaction had proceeded. Next, in order to stabilize the pH, the pH was adjusted to 5.5 using 1N HCl, and the mixture was stabilized overnight at room temperature.

In this embodiment, the cryptotyrolite zeolite changes its color from white to green, and complexation or bonding is recognized. Therefore, the solution is completely removed and immersed in 900 ml of ethanol to completely remove water. Removal and drying were promoted. The chitosan in the present example is
In addition to those disclosed in JP-A-2-41031 and JP-A-5-65302, those obtained by the methods described in JP-A-1-104158 and JP-A-2-152904 can be used.

Next, Table 1 shows the results of antibacterial experiments on various pathogenic bacteria using the pesticidal material described in claim 2. The bacterial names (strains), bacterial classifications, (a) disease names and pathogenic bacteria adhering entities, and (b) bacterial collection or storage locations of the specimens A to D in this experiment are as follows. A. Rhizoctonia solani [Rhizoctonia
solani, AG-2-2] (A) Large patch (Korai turf) (B) Fuji International Country Club (Shizuoka) Resonectonia Solani [Same as above] (I) Large patch (Korai turf) (B) Hisayama Country Club (Fukuoka) R. solutonia solani [AG-1 (1A)] (a) Brown patch (bent grass) (b) Kansai Green Research Institute D. Carbularia ship
p) * This is a fungus that does not have a spore shape and has the highest pathogenicity in inoculation tests. (A) Leaf blight (Korai turf) (B) Preserved by East Japan Green Research Institute Carburaria Ship (a) Leaf blight (Korai turf) (b) Daitakarazuka Country Club (Hyogo) The culture medium and culture conditions for the above strains are as follows. (Medium) Control (Basic medium) pH5 Malt extract 20g, Peptone 1g, Glucose 20g, Distilled water 1L Harden the basal medium in a petri dish, then sprinkle 0.2g and 2g of sterilized material on it, and further thinly Harden the basal medium (to the extent that the material and the pathogen can come into contact). (Culture) A colony is extracted from the pre-cultured plate with a cork borer of 5 mm in diameter and placed at the center of the test plate. The cells were cultured at 25 ° C. until the colonies grew sufficiently.

[0017]

[Table 1]

In addition to the above experiment, a two-nucleated Rhizoctonia (Ce) associated with spring baldness of codgrass turf collected from different places.
ratobasidium cornigerum, A
Culture experiments were performed under the same conditions for GQ), but no spores were formed and culture was not possible.

As apparent from Table 1 above, the material 0.2
In g, there is a part or variation where the result is insufficient, but 2
g shows sufficient antibacterial properties.

[0020]

In the material of the present invention constituted as described above, metal ions such as copper are a kind of digestive toxin for fungi and molds, and when taken into a living body, these F ions are produced.
It acts on e2 ⁺ -dependent enzyme aconitase to block the progress of the TCA cycle, thereby inhibiting the growth of fungi and fungi.

On the other hand, zeolite generally disintegrates in about two years when sprinkled on soil and collapses, losing active groups.
It has strong fertilizing power and is useful as agricultural material. Dissociated chitosan and copper ions are gradually decomposed into soil, metal ionized products such as copper are ingested as trace elements of plants, and chitosan is decomposed and ingested by actinomycetes and is also ingested as physiological sugars of plants. There is no persistence inside.

Zeolite having these functions acts as a soil admixture for plant cultivation and acts on bacteriostatic fungi and molds.
It is useful as other soils, such as soil for rice seedling boxes, soil for grass, pot soil for plantins, soil for continuous crop control in house cultivation, soil for fungus control for seedling cultivation, etc. It can also be used as a material for fungi, fungicides and deodorants.

──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-4-360806 (JP, A) JP-A-4-69304 (JP, A) JP-A-3-120204 (JP, A) JP-A-5-205 279222 (JP, A) JP-A-4-198111 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) A01N 59/16-59/20 A01N 63/00 A01N 43/16

Claims (3)

(57) [Claims] 1. A low molecular weight chito using zeolite as a carrier.
Complexing copper ionized material with copper as immobilizing material in sun
Or a germicidal material using a metal ion and a zeolite compound combined. 2. A low-molecular-weight chitosan having a molecular weight of 320 to 28,
The sterilizing material according to claim 1, which has a molecular weight of not more than 000 . 3. The method according to claim 1, wherein copper chloride is used in weight against chitosan having a reduced molecular weight.
A reaction or complex formed at a ratio of 0.1 to 1% by weight
A disinfecting material comprising the metal ion of claim 1 and a zeolite compound.