JPS6157504A - Release speed control medicine and use - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to controlled release rate formulations and their uses.

In rice cultivation, controlling blast disease is extremely beneficial economically. Tricyclazole, beaten, 5-methyl-
1,2,4-triazolo(3,4-b) benzothiazole is used in the blast fungus P 1ric, which is the pathogen of rice blast.
ularia oryzae) (U.S. Pat. No. 4,064,261).

The present invention provides a controlled release rate formulation containing 1-lycyclazole and its uses.

The formulation according to the invention can be applied to rice growing areas and provides a long-term release of the active substance tricyclazole, which is superior to conventional formulations known in the art. Traditionally commercially available tricyclazole formulations such as aqueous suspensions, granules and wettable powders release the active substance rapidly when applied to the soil, providing the necessary protection for rice plants through the sweet potato stage. During this period, rice cannot be protected.

Furthermore, conventional formulations release high concentrations of active substances rapidly, which may damage rice seedlings. In contrast, the controlled release rate formulation of the present invention overcomes these drawbacks of conventional formulations by releasing J.lycyclazole over a long period of time without the risk of high active substance concentration at the initial stage of application. be. Therefore, the formulation according to the present invention is advantageous over existing tricyclazole formulations in that it can reduce phytotoxicity to rice seedlings.

Furthermore, the release rate control i! according to the present invention! Preparation No. 11 does not require frequent application of active substances during the sweet mochi disease stage;
This is extremely advantageous for rice farmers as it saves time and money.

The present invention uses tricyclazole and a minimum film formation temperature of 100%.
℃ or less and a polymer having a water absorption rate in the range of 5 to 500%.

As used herein, the term "polymer" refers to both homopolymers and copolymers.

The average molecular size of the polymer used in the release rate controlled preparation according to the present invention is about 500 to 3,000°, and preferably about i,ooo to 1,00o,ooo.

Furthermore, the polymer used in the formulation according to the invention is 100
It is necessary to have a minimum film formation temperature of 'C or less. The minimum film forming temperature is measured with a normal film forming temperature measuring device. For formulations with insufficient polymer film formation, the release of tricyclazole is not reproducible (and the release control is also insufficient.
Due to the formulation process, it is desirable to form a film under drying conditions.
Even if film formation is insufficient under rough drying conditions, it is desirable to form a film by heating within a range that does not adversely affect tricyclazole.

Moreover, the polymer used in the present invention is JISK720
Water absorption rate after 24 hours measured based on 9 is 5-50
It is necessary that the range is 0%. When the water absorption rate is less than 5%, the release of tricyclazole is slow, and a formulation with a high concentration of tricyclazole is required to achieve a concentration that exhibits medicinal efficacy. Furthermore, most of the tricyclazole used tends not to be released, making it difficult to utilize the tricyclazole effectively. On the other hand, with polymers that exhibit a water absorption rate of over 500%, tricyclazole is released too quickly and a sufficient sustained release effect cannot be achieved, and the test piece used to measure the water absorption rate may be dissolved or redispersed in water and the water absorption rate may increase. Polymers that cannot be measured are also undesirable because tricyclazole is released too quickly. As described above, the release rate controlled formulation according to the present invention uses a polymer having a minimum film formation temperature of 100°C or less and a water absorption rate measured based on JIs K7209 in the range of 5 to 500%. However, as long as this condition is satisfied, the polymer may be linear, crosslinked, or cross-linked with metal ions. It is particularly preferable that these polymers be obtained in the form of an aqueous emulsion or aqueous solution because they are easy to handle in the formulation process.
It is not particularly limited to these.

Next, some representative emulsions of the polymers used in the present invention are illustrated.

Acrylics and lujons include Acryset 'EMN-10X and Acryset' EM manufactured by Nippon Shokubai Chemical Industry Co., Ltd.
N-20X, Acryset [phase] EMN-30X, and the like. Examples of the ethylene/vinyl acetate copolymer emulsion include Sumikaflex@400 and Sumikaflex@500 manufactured by Sumitomo Chemical Co., Ltd. As a vinylidene chloride emulsion, Furehalon from Prefectural Chemicals ■Do
, Fleharon OAO, etc. Examples of the polyolefin emulsion include Chemivar 0he-100 and Chemivar@S-100 manufactured by Mitsui Petrochemical Industries. In addition, as styrene-maleic acid water-soluble resins, SMA■2625Δ and SMA manufactured by Alco Chemical Co., Ltd.
Examples include @17352.

In the present invention, tricyclazole and the polymer are preferably formulated with a suitable agriculturally acceptable carrier. Such carriers may be adsorptive or absorbent. Typical carriers include limestone, sand, gypsum, crushed volcanic rock, montmorite, attapal resin,
This includes clays such as phosphorus, ball clay, talc, fertilizer, soybean flour, and agricultural products such as coarsely ground corn cobs and rice husks. Among these, attabulgyrate clay & 5 and rice husk powder are preferred. In addition, when granulating by extrusion method, ball clay is preferable. However, it is advantageous that the carrier can be selectively selected due to availability and cost.

The concentrations of tricyclazole and polymer in the formulations of the present invention do not have to be critical, as long as there is an effective concentration of the polymer to control and delay the release of tricyclazole to surrounding areas. Generally, the higher the concentration of polymer in the agent, the slower the rate of release of tricyclazole into the surrounding medium. The preferred concentration also varies depending on whether the formulation contains only tricyclazole and the polymer, or whether it also contains an agriculturally acceptable carrier. Usually, in the case of a preparation that does not contain 1 g of tricyclazole and consists only of tricyclazole and a polymer, tricyclazole is added in an amount of about 0.1 to about 75 weight (%) (these values and the following numbers 1iTi L, L). 9-25 to about 95% of the polymer.

It is desirable to contain 5% by weight. Of these, tricyclazole is in the range of about 50 fff (%) and polymer is in the range of about 50 to about 99 fff (%).
Usually, in the case of a antifungal agent consisting of three or more components, tricyclazole is added to about 0.1 to about 30 mol of chloride (
%), about 10 to 60 mm (%) of polymer, about 20 to about 89.9 weight (%) of d3 and 1 q of agriculturally acceptable carrier.
It is desirable to contain.

Among them, 1-linkrazole is about 1 to about 201 (%)
Preferably, the polymer is in the range of about 20 to about 60 weight percent, and the carrier is in the range of about 2 Q to about 79 weight percent.

Novel release rate flill fill according to the present invention! F
! The l agent can be produced by the following method. The active substance (preferably finely divided) is placed in an aqueous emulsion or solution of the polymer to form a slurry. Fine particles of the active substance '1'1 can be easily pulverized using any of the well-known techniques such as powdering within a fluid energy crushing threshold within a few seconds. The particle size of tricyclazole in Run 1 of J21i was 99.9% 326
J is so sad that it passes through the mesh sieve. The mixture of active substance and aqueous emulsion or solution may then be combined with a suitable agriculturally acceptable carrier and mixed until homogeneous. In order to obtain a dry rate controlled gII formulation suitable for application to control diseases of i!I! It is usually necessary to dry the prepared preparations, such as granules, by heating or heating.

The slurry of polymer and tricyclazole is preferably added to the carrier with stirring. This can be easily done using known methods and equipment.

However, it is also possible to add a carrier to the tricyclazole/polymer mixture. Suitable mixers that can be used for such agitation include Coach 5f Nguban mixer, cement mixer, etc.
Mixer, 1 obart mixer, mini tumbler
mixers, ribbon blenders, or any similar "1-Tally" type appliances; this mixing is usually carried out at ambient temperature;

Polymer,] lycyclazole and, if necessary,
After thoroughly mixing the carrier until it becomes uniform, it is preferable to dry and toss it under heating or heating in order to promote agglomeration between the polymers and form a continuous IC polymer coating. The temperature varies depending on the minimum film forming temperature of the polymer used, but is usually about 5 to 180°C, preferably in the range of 30 to 125°C.The type of drying equipment is m
IR selected randomly from among the instruments well known to the engineer.
You can do it. Typical dryers include rotary set dryers and 92 dryers used under normal pressure or reduced pressure.
There is this type. Depending on the polymer, the formulation may be
May be dried underneath.

Alternatively, the polymer, tricyclazole and a suitable carrier may be homogeneously mixed as described in 1111,
It may be subsequently dried to form pellets or granules. The technique of extrusion is well known. For this embodiment, it is important to use a suitable material for extrusion. Ball-type clays are generally preferred. However, the precise definition of clay is is not important, and may be appropriately selected from those that are easy to handle.

When using one carrier in which it is difficult to disperse the aqueous medium r',
It is desirable to use a suitable surfactant. The type of surfactant used is selected depending on the nature of the ingredients in the composition and the ability of the active agent to disperse the composition in water. For example, when rice husk is used as a carrier, a surfactant is required to facilitate dispersion of the composition in water. Suitable surfactants are dry and may be nonionic, anionic or cationic.

Anionic surfactants include, for example, sodium alkyl or aryl sulfonates or sulfonic acids, cardim alkylaryl sulfonates, and alkyl alcohol esters of phosphoric acid. Nonionic surfactants include ethoxylated alkylphenols, l-thyl 11 jJ3 and alcohols, sorbitan esters, and ethoxylated sorbitan esters and alcohols.
, and ethers.

Emulsifiers and additives (6 interfaces) Can be used as emulsifying agents. Commercially, do you need at least 40? L-forming agents are mainly anionic and nonionic agents. The proportion of surfactants in the formulation (J, usually about 0.01-.5% based on dry weight).

It is believed that the formulation of the present invention exerts its action by the active ingredient diffusing into the surrounding water medium through the specific polymeric matrix used in the present invention. However, the exact mechanism of action of the controlled release formulation according to the present invention is unknown, and the formulation according to the present invention is not limited to a specific mode of action.

The formulation according to the present invention is preferably applied to rice growing areas using conventional methods. The controlled release rate 211 formulation can be applied by the method of dispensing C1 using mechanical equipment or simply by hand. (Measuring devices include metered applicators that can precisely measure and apply granular compositions to the soil surface. The person operating the applicator implements the desired application method. Care should be taken to apply the appropriate m of the drug per unit area and to apply the foot evenly to the rice field requiring treatment, so that a drug application rate of .

The preparation of the present invention is preferably applied to the soil of a standard flat transplanting box (seedling box) in which rice seedlings are raised, but it can also be administered to a flooded rice paddy field.

In order to ensure optimum control of blast disease when applying the controlled release formulation of the present invention to the soil in a transplant box during seedling raising, it is important to transplant the seedlings using a transplanting machine. If mechanical transplantation is not possible, a method should be adopted in which all of the soil attached to the roots is transferred to the rice field into which the seedlings will be transplanted.

As a result, tricyclazole, which is contained in the soil attached to the roots of transplanted seedlings, invades the body of the rice plant and continuously controls rice blight throughout the growing season.

EXAMPLES The present invention will be described in detail below with reference to Examples. These examples are in no way intended to limit the invention, nor should they be construed as such.

Example 1 Foundry Hill Cream Clay (ball clay supplied by Spinks Clay Co., Paris Tennessee, hereafter referred to as FHC clay>760 (l), air-pulverized tricyclazole 40 (l) and Acryset@EMN- 20X
(Acrylic emulsion, manufactured by Nippon Shokubai Chemical Co., Ltd.)
Added to the mixed slurry with 425g and mixed in a mixer. After 10 minutes, the mixture was extruded through an experimental pellet mill equipped with a 5 mm thick die to form granules with a diameter of 2 mm and a length of 3 to 7 mm. The crushed granules were dried at 40° C. for 24 hours. Table 1 shows the minimum film forming temperature and water absorption rate of Acryset ■EMN-20X.

Examples 2-9. Comparative Examples 1 to 3 Granules of Examples 2 to 9 and Comparative Examples 1 to 3 were prepared using the polymers shown in Table 1 and the compositions shown in Table 2 in the same manner as in Example 1. However, in Examples 4 and 8, after completing the same procedure as in Example 1, heat treatment was performed in a hot air dryer at 100''C for 2 hours.

Table 1 No. Polymer packaging
Temperature Minimum film formation Water absorption rate Product number
Company name (%) Temperature (℃) (%) (”
1 1 Acryset “EMN-20X $1 per day
47 17.5 53 (Acrylic emulsion) Chemical engineering numakki 2 Acryset @EMN-3
0X Nippon Shokubai 50 0 or less 134
(Acrylic emulsion) Kagaku 1 pear ■ 3 Sumikaflex Φ400 Sumitomo Chemical ■ 5501
4 (ethylene-vinyl acetate copolymer emulsion) 4 Chemivar @5-too Mitsui Oil
27 90 6.5 (polyolefin type
Chemistry ■ Emulsion) 5 Flehalon ΦDOA Chemistry by prefecture ■
50-5214+9 (vinylidene chloride emulsion) 6 SMAΦ2625A 7/l/:
I Chemical 200 GG (Styrene-
Maleic acid type ((water-soluble resin) 7 Finetex 650 Dainippon Ink Q
ld 30 6.5 18M (polyester emulsion) 8 Kuraray Bobal 205 Kura Su
20 0 Dissolution (Polyvinyl Alcohol) 9 Carboxymethyl Kishida Chemical tel
+ 0 Dissolved cellulose natoki
An MFT measuring device manufactured by Nippon Rigaku Kogyo Co., Ltd. was used to measure the minimum film formation temperature of the salt (Note 1).

(Note 2) Water absorption rate Measured based on JIS K7209.

Preparation of test piece An aqueous emulsion or aqueous solution of the polymer was cast onto a Teflon plate so that the dry film thickness was 1 mm, and dried for two days and nights. After that, it was placed in a constant temperature bath at 50℃ for 24 hours.
Dry for an hour.

(For Chemivar S-100, after leaving it for one day and night,
It was dried for 2 hours in a constant temperature bath at ℃. ) Measurement of water absorption A test piece of 50 mm x 5 Q mm was cut out and immersed in distilled water kept at 25° C. for 24 hours, and then calculated from the following formula.

Water absorption rate -E (W2-W3)/W+ ] X100
(%)W+:12iI! Weight of test piece before immersion W2: Weight of test piece after immersion W3: Dry weight after immersion Example Polymer Support Tricyclazole Polymer Pt1%)'-・% 1 Acryset @ FHCIC Clay 420EMN-20X 2 Acryset FHCIC Clay 420EMN-30X 3 Sumikaflex@400 FHCIC clay 4 204 Chemivar Φ3-1
00 FHCIC clay 4205 Flehalon DOA Fl-IC clay 410
6 7 Criset 0 Crushed rice husks
8306MN-20X 7 Sumikaflex”400 Crushed rice husks
8308 Chemivar @S-100wa)伜Rice Husk 8 309 SMA”2
625A FHCIC clay 420 ammonium salt comparative example 1 Finetex Φ650 F IC clay 420 ratio example 2 Kuraray Bobal 205
FHCIC clay 4 20 comparative example 3
Carboxymethyl cell Fl-IC clay
410-Lunatrim Salt Example 10 Tricyclazole sustained-release granules were sprayed on the surface of a 1i3 portion of a 28 x 58 x 3 cm hand box (seedling box) in which 18-day-old rice seedlings were raised. Granules contain the active ingredient approximately 4
% or 8%.

Each hand box was treated with a total application of 1.5, 3.0 and 6.0 g of active ingredient. After 24 hours at tJ8, seedlings from each section were transplanted into 1 quart, 4 inch diameter flooded plastic pots without drainage holes and filled with non-sterile soil. After transplanting from hand box to flooded container, 1463
and on the 23rd day, the loss III statement was graded. 23 of transplants
After a few days, the seedlings are infected with blast disease
aria 0ry7ae) and cultured for 48 hours at 70'F (21°C) in a humidity chamber.

Seven days after inoculation, the blast disease expression rate (%) of the seedlings was recorded.

Similar experiments were conducted using sustained release granules not containing tricyclazole (blank test granules) and water (control). A tricyclazole formulation of 75WP (a hydrating powder containing 75% by weight of active substance) was also tested for comparison. The degree of damage to the crop in comparison with the untreated 3J crop was graded from O to 10 according to the following scale: o - no damage 1 to 3 = slight damage 4 to 6 = moderate damage 7 to 9 = simple The results of this test are based on the average value of the three trials.
14. 23F Power Scream Martyr 1
G, 0 4,3 3.7
f) 3.02.3 1.7 0 +,,'+ 0.3 0.3
0.72 G, 0
4.7 4.3 03.0
2.7 2.0 0i, 5
1,3 0.7 0.033
G, OS, 7 4.7 0
3.0 2.7 2.3
01.5 +, 7 0,7
0.74 6.0
4,7 3.3 0.73.0
．． 3. OO,72,31,51,008,7 56,0G,0 4,7 03.0
4,3 3゜00L5
2,3 +,7 0.036
6.0 4.0 2.7
03.0 2,7 L3
0.03+, 5 0.7
0.3 0.7 Tricycla 6.
0 8.3 7.7 0
Sol 3.0 6.
7 (i, 0 0 hydrating agent
1.5 3,3 3.0
1.7 Comparative Example 11 G, 0
7.7 7.3 03.0
6.3 6.0 01.53.
7 3.3 0.7 Comparative example 2
(i, 0 7.0 6,7
03.0 5.7 13
．． 0 0,031.5 3.
0 2.7 1.4 It is clear from the above experiments that the typical release rate controlled formulation according to the present invention causes less damage to plants than currently commercially available formulations, and is more effective against rice potatoes. It is effective in controlling leprosy.

Experiments were also conducted to demonstrate the sustained release properties of the formulation of the invention. The method used to prove these properties is as follows. At room temperature, 3 Jl of deionized water was placed in the beaker. Next, in this water, when all the tricyclazole in the granules is eluted, Ha is 20 ppm.
The sustained release formulation to be tested was added such that the total amount of active substance corresponded to 60mc+. Sample water was taken from the beaker at various time intervals after addition, and the concentration of the active substance contained in the sample was determined.

For comparison, a 75% hydrating agent was also investigated. The results are shown in Table 4 in ppm.

This study demonstrates that the controlled III formulation of the present invention provides a sustained release of the active substance over an extended period of time, especially when compared to tricyclazole wettable powders that release the active substance rapidly (within 1 hour). It is something to do.

Patent Applicant: Eli Lilly & Company Agent: Patent Attorney: Qing Bai Bao and 1 other person Procedural Amendment July 29, 1985 1. Indication of the Case 1980 Patent Application No. 179156 52. Release of the title of the invention Rate-controlling preparations and their uses 3, and their relationship to the amendr case Patent applicant address: 307 East Mazzucati Street, Indianapolis, Indiana, U.S.A. Name: Eli Lilly & Company 1, Agent address: Osaka, Osaka Prefecture 7, Honmachi Building, 2-10 Honmachi, Higashi-ku, Ichi.
hli positive content 1. Amendment to the Scope of Claims As shown in the appendix 2, Amendment to the Detailed Description of the Invention column 1) "There is" written in page i9, line 12 is amended as follows.

"In that case, it is desirable to perform the drying process at a temperature higher than the minimum film forming temperature of the polymer, and more preferably to perform the drying process at a temperature 10°C or more higher than the minimum film forming temperature." 2) On page 10, lines 8 to 10, "Usually, the drying device's It is more preferable that the temperature is 10°C or more higher than the minimum film forming temperature, and is usually in the range of about 5 to 180°C, preferably 30 to 125°C.Of course, after drying at a temperature lower than the minimum film forming temperature, Drying may be further performed at a temperature higher than the film forming temperature, preferably 10° C. or higher.

What is the type of drying device?''

3) Page 1 O, line 14, line 5, “Polymer (by this means,
``If it is lower than the polymer's hardness or perforation, it is expressed as ``.

Above 2, scope of claims! , trinocrazole, and a polymer having a minimum film formation temperature of 100° C. or lower and a water absorption rate of 5 to 500%.

2. The formulation according to item 1, comprising trisocrazole and the polymer, together with an agriculturally acceptable carrier as an additional ingredient, formed into granules.

3. Item 1~ where the polymer is in the form of an aqueous emulsion
The formulation according to any of paragraph 2.

The formulation described in.

i. The granule according to item 2, wherein the carrier is clay.

i. The granule according to item 2, wherein the carrier is rice husk.

L, in the second term where the carrier is limestone, iL! The granules listed above.

A method for protecting rice from rice blast by applying the release rate controlled preparation according to any one of Items 1 to 3 to a rice growing area.

Claims (1)

[Scope of Claims] 1. A release rate controlled preparation containing tricyclazole and a polymer having a minimum film formation temperature of 100°C or less and a water absorption rate in the range of 5 to 500%. 2. The formulation according to item 1, wherein tricyclazole and the polymer are formed into granules together with an agriculturally acceptable carrier as an additional ingredient. 3. Item 1~ where the polymer is in the form of an aqueous emulsion
The formulation according to any of paragraph 2. 4. The granule according to item 2, wherein the carrier is clay. 5. The granule according to item 2, wherein the carrier is rice husk. 6. The granule according to item 2, wherein the carrier is limestone. 7. A method for protecting rice from rice blast by applying the release rate controlled preparation according to any one of items 1 to 6 to a rice growing area.