JPS5920209A - Improved germicidal composition - Google Patents

Abstract

PURPOSE:A germicidal composition, prepared by microencapsulating a substance containing a basic copper chloride, basic copper sulfate, cupric hydroxide, copper 8-quinolinol copper, etc. with a water-insoluble high polymer, and capable of controlling the dissolution on leaves and giving a residual effect. CONSTITUTION:A stabilized germicidal composition prepared by microencapsulating a substance containing one type selected from basic copper chloride, basic copper sulfate, cupric hydroxide, basic copper carbonate, copper sulfate and 8-quinolinol copper with a water-insoluble high polymer. The resultant composition is capable of controlling the dissolution on leaves, and the phytotoxicity can be reduced. The residual effect is imparted thereto, and an additive, e.g. calcium carbonate or calcium hydroxide, need not be added. Crops are not contaminated. The mixing and formulating with another agricultural chemical decomposable with the above-mentioned additive is possible. The microencapsulation is carried out by dispersing the copper compound in a dilute aqueous solution of two colloidal substances, e.g. gelatin-gum arabic, etc., having opposite electric charges.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides basic copper chloride, basic copper sulfate, basic copper carbonate, cupric hydroxide, sulfuric acid and 8- Quinolitool copper (referred to as oxine copper) (hereinafter referred to as "copper compound")
This invention relates to an improved disinfectant composition comprising a substance containing one selected from the following as an active ingredient.

Copper compounds have been used as fungicides for a long time, and there are many types, including Bordeaux liquid, basic copper chloride,
There are powder preparations containing basic copper sulfate, basic copper carbonate, or cupric hydroxide, and oxine copper, which has copper ions chelated to oxine, is also used as a single agent or as a mixture.

Copperized substances sprayed on plants are eluted as copper ions by rain and dew, air, plant secretions, and organic acids from pathogenic bacteria, and are adsorbed to the surface of pathogenic bacteria, where the chitin that forms the cell membrane becomes a protein enzyme. The antibacterial properties of copper compounds are non-selective and can be applied to a wide range of disease fields due to their ability to inhibit the system.

Therefore, the higher the concentration of copper ions in Yuzant, the higher the effectiveness, but the possibility of causing chemical damage to crops also increases, so in actual application situations, it is not recommended to add calcium hydroxide, calcium carbonate, etc. many. Although calcium hydroxide and calcium carbonate are still added to prevent drug damage in formulations, a major problem is that it is not possible to formulate mixtures with pesticide active ingredients that can be broken down by such additives. It has become.

As a result of intensive studies aimed at reducing the chemical toxicity of copper compounds and solving the disadvantages of formulations, the present inventors have solved these disadvantages by microencapsulating copper compounds with water-insoluble polymer compounds. I found out that it is possible. 1 more
In addition to the effect of reducing drug damage, various advantages described below can be obtained. That is, the effects when microencapsulated copper compounds are applied to crops are as follows.

(1) It was possible to control the elution of copper ions in the leaves, reducing chemical damage.

(2) The residual effect was confirmed.

(3) Concomitant use with additives such as calcium carbonate and calcium hydroxide was avoided, eliminating crop contamination.

(4) It has become possible to formulate mixed formulations with active pesticide ingredients such as kasugamycin (generic name) and cabp> (generic name) that are decomposed by these additives.

Any commonly used method can be used to microencapsulate the copper compound. For example, (1
) complex coacervation method, (2) in-liquid drying method, (3) interfacial polymerization method, and (4) suffled drawing method, but are not limited to these methods.

The complex coacervation method and submerged drying method used in the present invention will be explained below.

The complex coacervation method consists of two colloidal substances with opposite charges, such as positively charged colloidal substances (polycationic colloids) such as gelatin (natural or modified), casein, albumin, fibrinogen, and hemoglobin, and gum arabic, carboxylic acid, etc. When mixed with a dilute aqueous solution of negatively charged colloidal substances (polycationic colloids) such as methylcellulose, %fi, ), laggant gum, and cellulose phthalate, phase separation occurs due to electrical interaction. It is a method that utilizes the phenomenon,
When a copper compound is dispersed in this mixed colloid, the phase fraction is 1v.
The concentrated coro-f-do phase caused by fG sticks around the copper compound particles, making it possible to encapsulate them.

Q-K simple process of complex coacervation method
052 To clarify, (1) a step of dispersing the can compound in an aqueous solution of an aqueous colloid (first colloid) that can be ionized in water (dispersion step); After mixing an aqueous solution of a hydrophilic colloid (second colloid) with a charge into the dispersion liquid of (1), water is added or the pH is adjusted to cause coacervation and the composite colloid sticks around individual particles. (3) Step of cooling and gelling the coacervate (gelling step); (4) Adjusting the pH to an alkaline side in the presence of a curing agent, or There are steps such as adding a curing agent after adjusting the curing agent to be alkaline, or adding a curing agent and an alkali simultaneously (pre-curing treatment step).

In the coacervation step shown in (2) above, the ratio of the first colloid to the second colloid varies depending on the electrical properties of each substance, but in the gelatin-gum arabic system it is 1:
A weight l=ratio of 1 is optimal. The concentration of the mixed colloid of the first colloid and the second colloid must be a dilute solution, and the appropriate concentration for 1 degree is 4 times)? L% or less. In addition, pH adjustment can be done with 'K (acid or inorganic acid), but acetic acid is most suitable in the -viradine-arabic acid system.When using 1 liter of acetic acid,
% or less dilute solutions are used. In the pre-hardening treatment step shown in (4), since the film of the microcapsules produced in steps (1) to (filter) is water-soluble, a curing agent is used to make this film insoluble. Hardening agents include formaldehyde, chromic acid, tannic acid, innic acid, and glutaraldehyde, but formamide 1! Alternatively, glutaraldehyde is suitable.

After 20 steps, the microcapsules are filtered and centrifuged.
e1f, +q゛ (Can be recovered by fog drying, etc.)

This method is suitable for the following (in-liquid) drying method and for microencapsulation of aqueous solutions. First, the boiling point is low, steam 11
Wall material po IJ-v- in a solvent that has a large circle and does not mix with water.
A w10 type emulsion is obtained by dissolving an aqueous solution of the core substance in this solvent. Further, the above emulsion is dispersed in an aqueous solution containing a protective colloid as a dispersion medium for capsules to obtain a W10/W type composite emulsion, and a polymer solvent is extracted from this system by heating, vacuum, solvent extraction, etc. This method is used to obtain microcapsules by drying.

Ethylcellulose, polystyrene, and wall material polymers
Examples include silicone derivatives, chlorinated rubber, 11 yen') carbonate, polyvinyl chloride, polyvinyl acetate, polyvinylidene chloride, polyacrylic acid ester, cellulose acetate, maleic acid resin, and the like. Examples of the solvent include 4J carbon, methylene chloride, and benzene. Further, gelatin, starch, gum arabic, polyvinyl alcohol, etc. can be used as a dispersion medium.

Next, the production of microcapsules containing a copper compound will be specifically explained using cleaning as an example. Step 1 Complex coacervation method using Zeddidine-Azibia gum system Basic chloride f1110v is added to a 10% gelatin aqueous solution. 60
me vc 9 defeats, then 10 more) Add Labia Gum 00me, keep at 40℃±1℃, and boil in warm water (4
0'C) 880m1! Add. Next, add 2.5% acetic acid aqueous solution and adjust the pH of solution C to 4.1. Cool this solution to 5°C, and add 37 cypolmarine aqueous solution to 1.
Add mi, drop a 2.5% aqueous sodium carbonate solution, and adjust the plI of the liquid to 8.5. Next, the liquid temperature is increased to 5LI'C at a rate of 1°C/min. This liquid was separated using a centrifugal strainer, and the collected precipitate was dried to obtain microcapsules of basic copper chloride 902.

Other copper compounds were also produced in the same manner.

Production Example 2 In-liquid drying method using polystyrene-methylene chloride system An aqueous solution in which 4t of copper sulfate was dissolved in 20f of a 1% gelatin solution was emulsified in 60f of a 10% polystyrene-methylene chloride solution to obtain a W10 type emulsion, and further K. A homomixer is used to emulsify the mixture in 800 mε of an aqueous solution of 1tigelatin to obtain a w10/w type composite emulsion. Without stirring the system, the liquid temperature was raised to 57°C, and methylene chloride was distilled off over about 2 hours. The aqueous solution containing the polystyrene capsules was separated using a centrifuge, and the precipitate was dried to obtain the capsules. The particle size of the microencapsulated copper compound used in the present invention is 200 microns or less, preferably 1 to 50 microns.

In order to formulate the microcapsules produced as described above, a suitable carrier such as clay, talc, bentonite, diatomaceous earth, white carbon, etc. and auxiliary agents such as wetting agents, dispersants, anti-settling agents, and flow improvers are used. Wettable powders, powders, flow dusts, suspensions, etc. are obtained by mixing agents.

Examples are given below to specifically explain the present invention, but the present invention is not limited thereto. In the examples, all parts refer to heavy Yλ parts.

Example 1 Wettable powder basic chloride steel microcapsules (57% as metal steel)
) 8aOl, alkylbenzenesulfonic acid sorter 2
．． 0 parts, 3.0 parts of lignin sulfonic acid sorter, and 8.0 parts of clay are mixed and ground to obtain a wettable powder containing 50% of metallic copper.

Example 2 Water No. 11 agent Cupric hydroxide microcapsules (64.8 as metal copper)
%) ao, sQL alkylbenzene cisphone f-year old soda 2.0 parts, lignin sulfonic acid sodium 3.0f1b and clay 14.8 parts were mixed and ground to produce 52% metal steel.
% is obtained.

Example 3 Wettable powder: 55.9 parts of oxine copper microcapsules, 2.0 parts of sodium alkylbenzenesulfonate, 3.0 parts of lignin sulfonic acid sorghum, and 39.1 parts of clay were mixed and ground to contain 50 parts of oxine copper. Obtain an irrigation agent.

Example 4 Wettable powder basic copper sulfate microcapsules (50.8% as metallic copper)
%) 6311S, sodium alkylbenzenesulfonate 2
1 part, 3 parts of sodium ligninsulfonate, and 32 parts of clay are mixed and ground to obtain a wettable powder containing 52% of metallic copper.

Example 5 Wettable powder basic copper carbonate microcapsules (50.2% as metallic copper)
g6) 89.7 parts, 2 parts of sodium alkylbenzenesulfonate, 3 parts of sodium ligninsulfonate, and 5 parts of clay
．． Mix 3 parts 1>) 45% as crushed metal copper 1
° Obtain a hydrating agent.

Example 6 Powder basic υ flat copper micro hill (same as metal)
15 (], 8 candy) 11.9 parts, PAP (・proboscis 3!
0.5 part of (Ii property improver) and 87.6 parts of clay were mixed and ground to obtain a powder containing hard powder as Kinichido.

Example 7 Powder over the agent: 1 fortune (beef
Same as -cs 7.0%) 10.6 parts, pAp (
Physical property improver) [1.5 parts and 88.9 parts of clay are mixed and ground to obtain a powder containing 6 parts as metal steel.

Example 8 Powder Basic copper carbonate microcapsules (metal)
(including Article 2) 12.0 parts, PAP (physical property improver)
Mix and grind 05 parts and 87.5 parts of clay to obtain gold 1-4.
A powder containing 6% as copper is obtained.

Example 970 - Dust agent basic chloride steel micro force press I as a metal steel 57.
0%) and 29.8 parts of white carbon are mixed and pulverized to obtain flow dust containing 40 Ti as gold and copper.

Example 1070 - Dust agent basic copper sulfate microcapsules (50.8 as gold 4 copper)
%) and 41 parts of point carbon are mixed and ground to obtain a 70-dust agent containing 30% as metallic copper.

Example 11 The mixed wettable powder residue was 5.0 parts of mycin hydrochloride, 79 parts of basic copper chloride microcapsules (57.0% as metal steel), 2 parts of sodium alkynodibenzenesulfonate, and 3 parts of sodium ligninsulfonate. and 11 parts of clay are mixed and ground to obtain a mixed wettable powder.

Comparative examples were prepared by substituting a non-microencapsulated copper compound for the microencapsulated copper compound 1, which is the active ingredient in each example. Phytotoxicity test for 4,000 kg of fully ripened young manure per 10 ares and chemical fertilizers (N 1 fl, P 14% and Ni 8) 100 to 9
Chinese cabbage (cultivar: Nozaki hybrid Harumaki No. 1) at the 5-leaf stage, which had been grown in a vinyl pot with a diameter of 9 cm, was planted in a field that had been applied as a starter fertilizer (plant spacing: 75 crn, plant spacing: 45 on).

40 days after planting, from the beginning of flowering, twice at 7-plant intervals (Tewadari irrigation agent: 500ml diluted with 500 ppm per plant)
using a hand spreader, and powder at 6 per 10 ares.
An amount equivalent to Kg was sprayed using a midget duster.

In addition, the powder dispersion device should not be used with C′-
On the day of spraying and in the evening one day later, water was lightly sprayed using a hand sprayer.

The test Chinese cabbage was covered with flow dust in a 1.5 m x 1.5 m x 1.5 m vibrator tent, and an amount equivalent to 5,001 ml per 10 ares was applied through the opening using a midget duster after sunset, and left overnight.

The drug damage investigation was conducted 10 days after the final chemical spraying, and the degree of drug damage was calculated using the following formula according to the following drug damage investigation criteria.

This test was conducted in five consecutive trials with six plants in each district, and the average value was calculated. The results are shown in Table 1.

Drug damage investigation criteria 0 No drug damage 1 Slight perspective symptoms are observed on the lower leaves of Chinese cabbage (1
(Less than 5% of all plants) 3 Warm spot symptoms are observed in 5% or more of all Chinese cabbage plants but less than 25% of all 41 Chinese cabbage plants 5 25% or more of all 41 Hansa plants less than 50% Ktak
7 Severe symptoms were observed in 50 or more of the 41 plants of No. 1. Table 1 Test drugs Copper compounds Chemical damage example 1 (water use agent) Basic copper chloride microcapsule
4.2tt 2(p) Cupric hydroxide 〃5
．． .

tt 3(p) Oxine copper
4.1p 4(p) Basic copper sulfate 〃4
．． 5tt 5(p) Basic copper carbonate 〃4.
81 6 (powder) basic copper sulfate 〃5.5tt
7(s) Cupric hydroxide 〃5.2//8
(// ) Basic copper carbonate 〃4.9〃 9(
Flow dust agent) Basic copper chloride 〃5.1 Comparative example 1 (
Irrigation agent) Basic copper chloride 5o, 8tt
2(tt) cupric hydroxide
51゜2tt 3(tt) Oxine copper
49.5tt 4(tt) Basic copper sulfate 50.2tt 5(tt
) Basic carbonate steel 55,1 6
(Powder) Base +1 (+'+ie acid'M62.5tt
7(tt) cupric hydroxide
67.8〃 8(//) Basic copper carbonate
66.3〃 9 (Floataste agent) Basic copper chloride 6
2.8■・(:Experiment f112 Direct test of citrus canker control effect of microencapsulated copper agent Then, uniform extraction of new leaves was promoted in the room.When the new leaves had grown to about % of the adult leaves, at 11CI'!', the specified e of the hydrating agent shown in Table 2 was applied.
The J degree diluted solution was thoroughly spread on the front and back surfaces of the leaves. After spraying, phase change U is treated in a greenhouse, and from 4 days after spraying, artificial rainfall treatment (Ugetsu intensity 20 mm/1 hour) for 2 hours at 5th intervals is performed 4 times in 4H1°. 5 days after spraying potato powder and 25 days after
After a few days, the tangerine canker bacterium (Xanthomonas silli, Xanthr+monas cJ, tri) @
Turbid liquid (bacteria (4 degrees 10711 m/me) IiC
40D Metsu'/Yuno:/J-Borangum all 1 of 5
Added as a reward, use it as a divine source, and use a spray gun to apply a pressure of 2'l'g/cm2 to the surface of the leaves in Summer 1''!
ii↓ side was inoculated with blowing. J concubine (1p, 41 to 41+1) was kept in a room at 28℃ for 2 days, and then kept in a warm room. 20 days after inoculation, 50 leaves were randomly extracted per pot. The number of lesions per leaf was investigated, and the control value (sub) was calculated using the following formula. The results are shown in Table 2.

Table 2 Example 1 (Basic copper chloride) 300 95 90
98 92// 5[]
0 100 98 100 98 2 (cupric hydroxide) 300 98 92 100 95/'
500 100 98
100 99〃 3 (Basic copper sulfate) 00 9
5 91 97 93”
500 100 100 100 96 Comparative example 1 (basic copper chloride) 300 38 29 45
41# 500 42 35
53 52〃 2 (Copper hydroxide) 300 3
9 30 48 43//
500 45 41 55 51s 3 (basic sulfuric acid m) 300 35! 10 48
40// 500 40
37 54 49 Test Example 3 Test of the effect of microcapsule copper agent on tomato late blight control A sufficient amount of a dilute solution of a predetermined concentration of the hydrating agent was sprayed at the 5th leaf stage of tomatoes (cultivar Pontilosa) cultivated in soil in pots with a diameter of 9αn. Also, powder is 1.5 K9 t per 10 ares.
Only 5. A dose equivalent to OKg was sprayed.

Tomatoes after spraying with chemicals are managed outdoors, and 10 days after spraying, they are infected with late blight fungus (Phytophtreinfestans, I").
Preliminary migration test of hytophthOra 1nfestans) A direct suspension was inoculated by spraying onto the front and back surfaces of tomato leaves.

After inoculation, the tomatoes were stored in a dark box at 20°C and a relative humidity of 100°C, and after 3 days, the area rate of tomato late blight spots on the first to fourth true leaves of the tomatoes was investigated, and the control value was calculated using the following formula. eaves,
I put it out. The results are shown in Table 6.

Table 3 Test Example 4 Kasugamycin decomposition prevention test of a mixture of microencapsulated copper compound and kascamycin A hydrating agent 50f having the composition shown in Table 3 was applied at 100 m/! Yong M
After storing the sample in a glass bottle for 30 days and 60 days (40° C.) in a thermostatic chamber, the decomposition rate (sub) of kasugamycin was determined using the following formula. The analytical value of kasugamycin was determined by bioassay method. The results are shown in Table 4.

×100 Table 4 Oxine copper microcapsules -5'0.3
- -Basic copper chloride -176
・9 - Oxine copper ---49,
5 Kasugamycin 5.0 5.0
5.0 5.0 Sodium lignin sulfonate
Ro, 0 3.0 Ro, 0 3.
0 clay 11.0 39.7 13.1
40.5 total 100. [l 100.01DL1
．． 01 (10,0 force sugamycin M rate)

Claims (1)

[Claims] One type selected from basic steel chloride, basic copper sulfate, basic copper carbonate, cupric hydroxide, copper sulfate, and 8-quinolite copper is used as an active ingredient by microencapsulation obtained with a water-insoluble polymer compound. An improved disinfectant composition characterized in that the substance contained therein is encapsulated.