Coated granular pesticide method for producing the same and applications thereof

A coated granular pesticide comprising a granular pesticide for use on plants which comprises at least one hardly water-soluble active ingredient and at least one water-swelling substance, and a thermoplastic resin-based film which covers the surface of the granular pesticide; a method for producing the same; and applications thereof. A surfactant, inorganic powder insoluble or hardly soluble in water, water-absorbing and/or water-soluble polymer fine powder, a thermosetting resin, or a biodegradable polymer insoluble or hardly soluble in water, or a combination thereof may be incorporated into the film. The coated granular pesticide can externally release the hardly water-soluble active ingredient due to the combined effects of the thermoplastic resin as the film-forming component and the water-swelling component as the core component whereby the water-swelling substance absorbs the water present in the exterior of the coated granular pesticide, which gradually penetrates into the granule through the coating film.

TECHNICAL FIELD 
The present invention relates to a timed-release type or controlled release 
type pesticide. More specifically, the present invention pertains to a 
coated granular pesticide comprising a granular pesticide which comprises 
a hardly water-soluble active ingredient and a water-swelling substance 
and whose surface is covered with a film-foaming material comprising a 
thermoplastic resin as a principal component, a method for producing the 
same and a method for using the coated granular pesticide. 
BACKGROUND ART 
The use of insecticides, fungicides or herbicides has been indispensable to 
the cultivation of field crops. When applying a pesticide, it is 
preferably applied in a large amount at a time from the viewpoint of the 
reduction of labor required for the application thereof, but such 
application suffers from various problems such that crops and human bodies 
are damaged by such a high concentration of the active ingredient, that 
the active ingredient is lost through washing away and that the duration 
of the efficacy thereof is correspondingly reduced. 
In case of the crops which require the transplantation of the seedling such 
as those represented by paddy rice, they are damaged upon transplantation, 
for instance, by cutting of hair-roots and breakage of the seedlings. 
Moreover, the seedlings after the transplantation are in an unstable state 
till complete rooting thereof because of the great difference between the 
environmental conditions of nursery beds and final fields. For this 
reason, the application of a pesticide possessing a herbicidal action at 
this stage may bring about hypotrophy and withering of seedlings due to 
its phytotoxity. 
If a pesticide such as a herbicide may be applied to seedlings when 
transplanting the seedlings, the labor required for farm working can 
effectively be reduced. In case of paddy rice, however, any herbicide can 
be applied thereto only after the complete rooting of the seedlings, i.e., 
after the lapse of about one week from the transplanting the seedlings, 
under the existing circumstances. 
There have been known a variety of sustained release pesticides which are 
developed for eliminating such drawbacks and are so designed that active 
ingredients are gradually released from those applied to fields. 
Japanese Patent Laid-Open Publication (JP-A) 286602/1990 discloses a 
granular controlled release pesticide which comprises mineral particles 
impregnated with a liquid active ingredient and hydrophobic fine particles 
which cover the surface of the mineral granules. However, the controlled 
release pesticide initiates the release of the active ingredient thereof 
immediately after the application thereof to fields and accordingly, it is 
not suitably applied to fields during the transplantation of seedlings. 
Japanese Examined Patent Publication (JP-B) 5002/1989 discloses a sustained 
release pesticide which comprises a water-soluble or volatile active 
ingredient covered with a thermoplastic resin. In the controlled release 
pesticide, the active ingredient is released through the thermoplastic 
resin film. Therefore, this technique is suitable for water-soluble or 
volatile active ingredients, but it is difficult to apply the technique to 
hardly water soluble active ingredients. In general, most of the active 
ingredients used in herbicides are hardly soluble in water and if these 
active ingredients are covered with the films disclosed in JP-B 5002/1989, 
the resulting pesticide suffers from such problems that a desired 
herbicidal effect cannot be expected because of its extremely low release 
rate and that the active ingredient remains in the soil even after the 
harvesting of crops to thus cause contamination of the soil therewith. 
JP-A 9304/1994 and JP-A 72805/1994 disclose timed-release, controlled 
release type pesticides, in which a part of the coating film is dissolved, 
after the application thereof to fields, to form openings through which 
the active ingredient is released. Moreover, JP-A 9303/1994 and JP-A 
80514/1994 also disclose timed-release, controlled release type 
pesticides, in which the active ingredient is released through cracks 
formed, after the application thereof to fields, on a part of the coating 
film. In these timed-release, controlled release type pesticides, however, 
the timed-release characteristics are achieved by the use of a coating 
film having a double layered structure and the method for the production 
thereof requires complicated steps and the resulting product is expensive. 
Moreover, since the active ingredient is released through small openings 
or cracks formed on the film, the release rate thereof is show and thus it 
is difficult to apply these techniques to hardly water-soluble active 
ingredients. 
The present invention intends to eliminate the foregoing drawbacks 
associated with the existing controlled release pesticides and 
accordingly, it is an object of the present invention to provide a coated 
granular pesticide which does not release any active ingredient 
immediately after the application thereof to fields and initiates the 
release of the active ingredient after the lapse of a desired period of 
time and which can complete the release of the active ingredient during 
the cultivation period, in particular, those effectively applied to hardly 
water-soluble active ingredients. It is another object of the present 
invention to provide a method for producing the same and a method for 
using the same. 
DISCLOSURE OF THE INVENTION 
The inventors have conducted extensive studies in order to accomplish the 
foregoing objects, and have found out that the desired objects can be 
achieved by a coated granular pesticide which comprises a granular 
pesticide comprising a hardly water-soluble active ingredient and a 
water-swelling substance, whose surface is coated with a film mainly 
comprising a thermoplastic resin. On the basis of this finding, the 
present invention has been completed. 
As the thermoplastic resin of the coating film, it is preferred to use at 
least one polymer selected from the group consisting of olefinic polymers 
and olefinic copolymers comprising an olefin as a major monomer. 
The coating film preferably comprises not more than 15% by weight of an 
ethylene/vinyl acetate copolymer. It is also preferred that the coating 
film comprises a surfactant, an powdery inorganic substance insoluble or 
hardly soluble in water, a water-absorbing and/or water-soluble fine 
polymer powder, a thermosetting resin or a biodegradable polymer insoluble 
or hardly soluble in water, which may be used alone or in any combination.

1 spouting column; 
2 opening for introducing granules; 
3 outlet for exhaust gas; 
4 spray nozzle; 
5 granular pesticide; 
6 pump; 
7 opening for withdrawal; 
8 heat exchanger; 
9 orifice flowmeter; 
10 blower; 
11 dissolution tank; 
12 mixed solution of film-forming materials; 
T.sub.1 temperature of flowing gas; 
T.sub.2 temperature of granular pesticide; 
T.sub.3 temperature of exhaust gas; 
SL steam 
BEST MODE FOR CARRYING OUT THE INVENTION 
The present invention will hereinafter be described in more detail. 
The coated granular pesticide according to the present invention is a 
timed-release, sustained release type coated granular pesticide which does 
not release externally the hardly water-soluble active ingredient included 
in the granular pesticide within a predetermined period of time till the 
coating film is disintegrated, but the active ingredient is gradually and 
externally released after once the disintegration of the film is 
initiated. 
More specifically, in the coated granular pesticide according to the 
present invention, water present in the external environment penetrates 
into the inside of the coated granular pesticide through the coating film, 
where the water-swelling substance gradually absorbs the water to swell 
and grow its volume, thereby applying increasing stress to the coating 
film. When the stress due to the swelling exceeds the threshold stress of 
the coating film, cracks are formed on the film, through which water 
rapidly enters into the coated pesticide to accelerate the swelling of the 
water-swelling substance and thus to grow the cracks thereby rapidly 
disintegrating the coating film. Consequently, the hardly water-soluble 
active ingredient included in the granular pesticide comes in close 
contact with a large amount of water and as a result, the release of the 
hardly water-soluble active ingredient is initiated. 
Photographs illustrating the breakage of the film of the coated granular 
pesticide according to the present invention are shown in FIG. 1. More 
specifically, FIG. 1-A and FIG. 1-B are photographs showing the coated 
granular pesticide 1 prior to and after the breakage of the coating film. 
The present invention makes it possible to control the time required for 
the disintegration of the film and the initiation of the release of the 
hardly water-soluble active ingredient after the application of the coated 
granular pesticide (hereinafter referred to as "film-disintegration 
time"). To this end, it is important to take into consideration the 
moisture permeability of the film, the critical strength of the film and 
the swelling ability of the granular pesticide. 
The moisture permeability of the film is greatly affected by the 
film-forming components, namely the thermoplastic resin used as a 
principal ingredient for the film and other components optionally 
incorporated such as surfactants, powdery inorganic substances, 
water-absorbing polymer fine particles, water-soluble polymer fine 
particles, thermosetting resins and/or hardly water-soluble or 
water-insoluble biodegradable polymers. The critical strength of the film 
is substantially dependent upon the film-forming components and the 
thickness of the film, for example, the kinds of thermoplastic resins 
used, the thickness and the uniformity of the film. The swelling 
properties of the granular pesticide vary depending on the kinds of the 
water-swelling substances as an ingredient of the granular pesticide. 
According to the present invention, the film-disintegration time as defined 
above can be elongated by combining a thick and uniform film having high 
critical strength and poor moisture permeability with a water-swelling 
substance having poor swelling properties. On the other hand, the 
film-disintegration time can be reduced by combining a thin and uneven 
film having low critical strength and excellent moisture permeability with 
a water-swelling substance having good swelling properties. 
In particular, the film-disintegration time is susceptible to the moisture 
permeability of the film and therefore, special attention should be paid 
to the control of the moisture permeability of the film. 
If the moisture permeability of the film is extremely high, the 
water-swelling substance may rapidly swell and the film may be 
disintegrated almost at the same time when the coated granular pesticide 
is applied to a water-rich area such as a paddy field. 
According to the present invention, various coated granular pesticides 
adapted for crops to which they are pplied and cultivating conditions of 
the crops can be obtained by appropriately controlling the moisture 
erasability and critical strength of such a film and the water-swelling 
properties of the granular pesticide. 
The coated granular pesticide according to the present invention comprises, 
as an active ingredient, a hardly water-soluble active ingredient having 
an insecticidal, fungicidal or herbicidal effect or a plant growth 
regulating effect. In addition, the hardly water-soluble active ingredient 
may be a single ingredient or a combination of a plurality of ingredients 
and the kinds of the ingredients and combinations thereof are not 
particularly restricted to specific ones. 
The term "hardly water-soluble active ingredient" herein used means those 
having a solubility in water of not more than 1000 ppm (at 20.degree. C.). 
In the present invention, preferably used are hardly water-soluble active 
ingredients having a solubility in water of not more than 1000 ppm (at 
25.degree. C.), in particular, not more than 600 ppm and more preferably 
not more than 50 ppm. 
In this respect, if using an active ingredient having a higher solubility 
in water, a large amount of the active ingredient is released at the 
initial stage when the coated granular pesticide initiates the release of 
the active ingredient, and thus the chemical injury of crops can be caused 
and the sustained release effect of the pesticide cannot be attained. 
Specific examples of the hardly water-soluble active ingredients usable 
herein are 
1-(6-chloro-3-pyridylmethyl)-N-nitroimidazolidine-2-ylideneamine, 
5-methyl-1,2,4-triazolo(3,4-b)benzothiazole, 
3-allyloxy-1,2-benzoisothiazole-1,1-dioxide, 
2-chloro-4-ethylamino-6-isopropylamino-s-triazine, 
1-(2-chloroimidazo[1,2-a]pyridin-3-ylsulfonyl)-3-(4,6-dimethoxypyrimidin-2 
-ylurea, 2-chloro-4,6-bis(ethylamino)-s-triazine, 
2-benzothiazol-2-yloxy-N-methylacetoanilide, 
methyl=-.alpha.-(4,6-dimethoxypyrimidin-2-ylcarbamoylsulfamoyl)-o-toluate, 
S-(4-chlorobenzyl)-N,N-diethylthiocarbamate, 
S-benzyl=1,2-dimethylpropyl(ethyl)thiocarbamate, 
2,4-dichlorophenyl-3'-methoxy-4'-nitrophenyl ether, 
2-methylthio-4-ethylamino-6-(1,2-dimethylpropylamino)-s-triazine, 
4-(2,4-dichlorobenzoyl)-1,3-dimethyl-5-pyrazolyl-p-toluenesulfonate, 
2-methylthio-4,6-bis(ethylamino)-s-triazine, 
S-1-methyl-1-phenylethyl=piperidine-1-carbothioate, 1-(.alpha., 
.alpha.-dimethylbenzyl)-3-(p-tolyl) urea, 
2-chloro-N-(3-methoxy-2-tenyl)-2',6'-dimethylacetoanilide, 
2-chloro-2',6'-diethyl-N-(butoxymethyl)acetoanilide, ethyl 
2,4-dichlorophenoxy acetate, ethyl 2-methyl-4-chlorophenoxy acetate, 
(E)-(S)-1-(4-chlorophenyl)-4,4-dimethyl-2-(1H-1,2,4-triazol-1-yl)pent-1-en 
-3-ol, (2RS, 
3RS)-1-(4-chlorophenyl)-4,4-dimethyl-2-(1H-1,2,4-triazol-1-yl)pentan-3-ol 
and 4'-chloro-2'-(.alpha.-hydroxybenzyl)isonicotinanilide. 
The water-swelling substance used in the coated granular pesticide 
according to the present invention is a substance capable of undergoing a 
volume-expansion through absorption of water and examples thereof include 
bentonites, starches and highly water-absorbing polymers. 
As has been well-known in the art, the water-swelling properties of 
bentonite vary depending on the composition and particle size thereof. Any 
particular problem does not arise even when using, for example, calcium 
type bentonite which is rich in calcium ions and magnesium ions and has a 
low swelling ability and activated type bentonite which is treated with 
soda to artificially impart the swelling activity, but preferred are 
sodium type bentonite which has a high swelling ability, i.e., which is 
capable of absorbing a large amount of water. 
Examples of starches are naturally occurring starches such as corn starch 
and potato starch; and a variety of processed starch products such as 
oxidized starches, methylated starches and carboxymethylated starches. 
Examples of highly water-absorbable polymers include highly 
water-absorbable cellulosic polymers, highly water-absorbable polyvinyl 
alcoholic polymers and highly water-absorbable acrylic polymers. 
These water swelling substances may be used alone or in any combination and 
the kinds and combinations thereof are not restricted to specific ones. 
In the present invention, the foregoing hardly water-soluble active 
ingredient and the foregoing substance having a water-swelling ability are 
mixed together to give a granular pesticide. The granular pesticide 
preferably has a particle size ranging from 0.5 to 10 mm and more 
preferably 1 to 5 mm. Such a granular pesticide is obtained through 
granulation according to the currently used method, but may easily be 
produced using granulation through extrusion. Moreover, in this respect, 
the foregoing granular pesticide can easily be produced if an auxiliary 
agent for granulation and/or a binder are used during the granulation. 
Examples of auxiliary agents for granulation include powdery inorganic 
substances such as clay, kaolin and vermiculite powder; powdery organic 
substances such as powdered rice husk; and fertilizers such as urea, 
ammonium sulfate and ammonium chloride. 
Examples of binders are gum arabic, carboxymethyl cellulose, hydroxyethyl 
cellulose and polyvinyl alcohol. 
In the present invention, the foregoing granular pesticide is covered with 
a film mainly comprising a thermoplastic resin. 
The thermoplastic resin used as a principal component for the film is 
preferably resins having low water permeability and specific examples 
thereof include olefinic polymers such as polypropylene, polyethylene, 
polybutene and polystyrene; olefinic copolymers mainly comprising olefins 
such as ethylene/propylene copolymer, ethylene/carbon monoxide copolymer, 
butene/ethylene copolymer, butene/propylene copolymer, ethylene/vinyl 
acetate copolymer, ethylene/vinyl acetate/carbon monoxide copolymer, 
ethylene/acrylic acid copolymer and ethylene/methacrylate copolymer; 
vinylidene chloride type copolymers such as vinylidene chloride/vinyl 
chloride copolymer; diene type polymers such as butadiene polymer, 
isoprene polymer, chloroprene polymer, butadiene/styrene copolymer, EPDM 
polymer and styrene/isoprene copolymer; and waxes such as bees wax, haze 
wax and paraffins. Among these thermoplastic resins, preferred are 
olefinic polymers and olefinic copolymers mainly comprising olefins. 
These thermoplastic resins may be used alone or in any combination of at 
least two of them. In addition, they may optionally be used in combination 
with natural resins such as naturally occurring gums and rosins; fats and 
oils; and/or modified fats and oils. The kinds and combinations thereof 
are not restricted to any specific one. 
Thermoplastic resins each having a high elastic modulus such as 
ethylene/vinyl acetate copolymer, ethylene/vinyl acetate/carbon monoxide 
copolymer and diene type polymers may serve to control the 
film-disintegration time since the resins can impart flexibility to the 
film and has an effect of relieving the internal stress due to the 
swelling of the granular pesticide, but if these polymers are present in 
the film in a large amount, the film-disintegration time may extremely be 
prolonged and the resulting film may not form cracks. Therefore, the 
amount of the polymer to be incorporated into the film is preferably less 
than 20% by weight and more preferably not more than 15% by weight. 
In the present invention, a surfactant may be added to the film to control 
the moisture permeability of the film and to thus control the 
disintegration time of the resulting film of the coated granular 
pesticide. The surfactant permits the improvement of the moisture 
permeability of the film and accordingly, shows an effect of reducing the 
film-disintegration time. The moisture permeability of the resulting film 
is sometimes reduced to a level practically acceptable depending on the 
kinds of the thermoplastic resins used for forming the film and cracks may 
be formed with difficulty. The use of a surfactant is quite effective in 
such cases. 
The surfactants usable herein suitably have an HLB value ranging from 6 to 
20, preferably 9 to 16 and more preferably 11 to 13. In this regard, the 
hydrophilicity of the surfactant is increasingly strong as the HLB value 
thereof exceeds 20. For this reason, such a surfactant cannot uniformly be 
dispersed in the resulting film and this may become a cause of defects of 
the film. On the other hand, if the surfactant used is highly lipophilic 
and has an HLB value of less than 6, it may sometimes be impossible to 
achieve an intended effect of increasing the moisture permeability of the 
film to thus reduce the film-disintegration time. 
The surfactant usable herein may be anionic, cationic, nonionic and 
amphoteric surfactants, which may be used alone or as a mixture of a 
plurality of these surfactants while adjusting the HLB value to the level 
falling within the range defined above. In the present invention, 
particularly preferred are nonionic surfactants. 
Examples of anionic surfactants are higher fatty acid salts, higher alkyl 
dicarboxylic acid salts, sulfuric acid ester salts of higher alcohols, 
higher alkyl-sulfonic acid salts, higher alkyl-disulfonic acid salts, 
sulfonated higher fatty acid salts and higher alkyl phosphoric acid ester 
salts; examples of cationic surfactants are higher alkyl-amine salts and 
quaternary ammonium salts; and examples of nonionic surfactants are fatty 
acid esters of polyols and polyethylene oxide condensates. In addition, 
examples of amphoteric surfactants are betaine type, glycine type, alanine 
type and sulfobetaine type ones. 
Among these surfactants, preferred are, for instance, polyoxyethylene alkyl 
allyl ethers, polyoxyethylene alkyl ethers and polyoxyethylene alkyl 
phenyl ethers. 
The amount of the surfactants to be added to the film preferably ranges 
from 0.01 to 20% by weight and more preferably 0.05 to 10% by weight, on 
the basis of the total weight of the film. This is because if the amount 
thereof is less than 0.01% by weight, it is difficult to achieve the 
intended effect of the surfactant used, while the use thereof in an amount 
of more than 20% by weight is unfavorable from the economical standpoint. 
The molecular weight of the surfactant preferably ranges from 100 to 1000. 
Moreover, the film used in the present invention may further comprise a 
powdery inorganic substance for the purpose of adjusting the 
film-disintegration time of the resulting coated granular pesticide. 
Powdery inorganic substances show an effect of reducing the 
film-disintegration time. The powdery inorganic substances usable herein 
are preferably those insoluble or hardly soluble in water. Specific 
examples thereof are talc, clay, metal oxides, silicate mineral powder, 
glass, carbonates or sulfates of alkaline earth metals and sulfur. 
These powdery inorganic substances must completely be embedded in the 
resulting film and accordingly, those having a particle size smaller than 
the thickness of the film. For instance, the particle size thereof is 
preferably not more than 50 .mu.m and more preferably 1 to 20 .mu.n. The 
amount of the inorganic powder to be added to the film is preferably not 
less than 50% by weight on the basis of the total weight of the film, but 
it is not particularly restricted to this specific range. 
The coated granular pesticide may comprise, in the film, fine particles of 
a water-absorbing polymer and/or a water-soluble polymer in order to 
adjust the film-disintegration time of the pesticide. These fine particles 
of water-absorbing and/or water-soluble polymers show an effect of 
reducing the film-disintegration time of the film. 
Examples of fine particles of water-absorbing and/or water-soluble polymers 
are fine particles of polyvinyl alcohol, polyvinylpyrrolidone, methyl 
cellulose, hydroxypropyl cellulose, hydroxyethyl cellulose, sodium 
carboxymethyl cellulose, hydroxypropylmethyl cellulose, calcium 
carboxymethyl cellulose, carboxymethylethyl cellulose, dextrin, alginates, 
gelatin, pectin, pullulan, polyacrylic acid, sodium polyphosphate, 
isobutylene copolymers and polyethylene oxide. 
The particle size of these fine particles ranges from 0.1 to 100 .mu.m and 
preferably 0.5 to 50 .mu.m. If the particle size is greater than 100 
.mu.m, they cannot easily be dispersed in the film. On the other hand, it 
is difficult to prepare a synthetic polymer having a particle size of less 
than 0.1 .mu.m, and such a polymer cannot show its characteristic 
properties. 
The amount of these fine particles to be added to the film preferably 
ranges from 0.1 to 30% by weight on the basis of the total weight of the 
film. 
The coated granular pesticide of the present invention may further 
comprise, in the coating film, a thermosetting resin for the purpose of 
controlling the film-disintegration time of the coated granule. Such a 
thermosetting resin shows an effect of reducing the film-disintegration 
time of the resulting film. 
Examples of such thermosetting resins are those obtained through reactions 
of acid anhydrides with amines and/or diamines such as polyamide, 
polyimide, bismaleimide, polyamideimide, polyetherimide, maleimide and 
polyetheramide. 
These thermosetting resins used herein may be in any form such as a 
solution, powder or an intermediate thereof. For instance, the 
thermosetting resin in a powdery state which can be used in the invention 
may be prepared by heat conditions of the soil in addition to the 
hydrolysis by the foregoing hydrolases. 
In case of the coated granular pesticide whose coating film comprises such 
a biodegradable polymer hardly soluble or insoluble in water, the cleavage 
of the backbone chain of the biodegradable polymer is gradually proceeds 
immediately after the application thereof to fields to decompose and 
deteriorate the film, the strength of the film is reduced during the 
process, and the water in the fields rapidly penetrates into the coated 
granule through the film after the lapse of a predetermined period of 
time, resulting in the release of the active ingredient of the coated 
granule. Moreover, the biodegradable polymer likewise serves to easily 
break the coating film made of the thermoplastic resin remaining after the 
complete release of the active ingredient into pieces to thus improve the 
decomposition speed of the film, i.e., the rate of film-decomposition or 
disappearance. 
In the present invention, the biodegradable polymer hardly soluble or 
insoluble in water is not restricted to specific ones inasmuch as they can 
gradually be decomposed under natural environmental conditions, but is 
preferably an ester of a hydroxycarboxylic acid such as an aliphatic 
polyester represented by the following general formula (I): 
EQU H--(O--R.sub.1 --O--CO--R.sub.2 --CO).sub.n --O--R.sub.1 --OH(I) 
treating a polyamino acid solution obtained by reacting an acid anhydride 
with an amine and/or a diamine at a temperature ranging from 100 to 
200.degree. C., preferably 110 to 160.degree. C. to remove the solvent and 
then pulverizing the solid product in a ball mill or a mixer. The heat 
treatment may be carried out at a lower temperature so far as the solvent 
can be removed, but most of solvents in which thermosetting resins are 
soluble are in general polar ones and frequently have a high boiling point 
of not less than 100.degree. C. 
The thermosetting resins in a powdery state preferably have a particle size 
ranging from 0.1 to 100 .mu.m and the amount thereof to be added to the 
film preferably ranges from 0.1 to 30% by weight on the basis of the total 
weight of the film. 
The particulate coated pesticide according to the present invention may 
comprise, in the coating film, a biodegradable polymer hardly soluble or 
insoluble in water in order to control the film-disintegration time of the 
film. The biodegradable polymer hardly soluble or insoluble in water shows 
an effect of reducing the film-disintegration time of the resulting film. 
The backbone chain of the biodegradable polymer hardly soluble or insoluble 
in water used in the present invention is cleaved by the action of 
metabolites of microorganisms in soil, in particular, hydrolases or other 
hydrolases, for example, introduced into soil from air or water or 
artificially mixed with soil. The biodegradable polymer may further be 
hydrolyzed under the usual environmental (wherein R.sub.1 and R.sub.2 each 
independently represents an alkylene group having 2 to 10 carbon atoms and 
n is a numerical value ranging from 10 to 2000). 
Specific examples of the polymeric hydroxycarboxylic acids represented by 
formula (I) are polylactones such as poly-.epsilon.-caprolactone, 
poly-.delta.-valerolactone, poly-.beta.-propiolactone, 
poly-.gamma.-butyrolactone, polylactic acid and polyglycolic acid; 
polyhydroxy alkanoates such as poly-3-hydroxybutyric acid and 
poly-3-hydroxyvaleric acid; polyacid anhydrides, polyorthoesters, urethane 
bond-containing aliphatic polyesters and copolymers thereof. These 
biodegradable polymer hardly soluble or insoluble in water may be combined 
with any thermoplastic substance. The molecular weight of such a 
thermoplastic substance preferably ranges from about 2000 to about 
300,000. The polylactic acid monomer may be present in any kinds of three 
optical isomers, i.e., L-, D- and D, L-isomers, and all of these isomers 
may ensure the intended purpose of the present invention. 
The amount of the biodegradable polymer hardly soluble or insoluble in 
water to be added to the coating film preferably in the range of from 0.1 
to 30% by weight on the basis of the total weight of the film. 
The coated granular pesticide according to the present invention may be 
produced by spraying a granular pesticide which is in the fluidized state 
by the action of a hot gas flow with a mixed solution obtained by 
dissolving film-forming materials in a solvent while drying and removing 
the solvent sprayed on the pesticide to thus form a film on the surface of 
the granular pesticide. 
An example of a preferred coating device usable in the method for producing 
the coated granular pesticide according to the present invention is shown 
in FIG. 2. 
In FIG. 2, a granular pesticide (5) is fed to a spouting column (1) through 
an opening (2) for introducing granular pesticides disposed on the side of 
the column. A fluid gas, preferably air which is introduced into the 
device by a blower (10), passes through an orifice flowmeter (9) and is 
heated in a heat exchanger (8), upwardly passes through the spouting 
column (1) and is discharged through an outlet for exhaust gas (3) 
disposed on the upper portion of the spouting column (1). The heating of 
the fluid gas can be carried out using, for instance, steam (SL). The hot 
fluid gas having a temperature of T.sub.1 heats the granular pesticide (5) 
up to a temperature of T.sub.2, while maintaining the fluidized state of 
the granular pesticide. On the other hand, a thermoplastic resin as a 
film-forming material is dissolved in an organic solvent in a dissolution 
tank (11) while applying heat thereto using, for instance, steam (SL) and 
optionally other additives are dissolved or mixed with the solution. The 
resulting mixed solution (12) of the film-forming materials is sprayed on 
the granular pesticide (5) flowing through the spouting column (1), 
through a pump (6) and a spray nozzle (4), thus the mixed solution (12) of 
the film-forming materials is adhered to the surface of the granular 
pesticide simultaneous with or in parallel with the evaporation of the 
solvent present in the mixed solution (12) through heating to thus form a 
film on the granular pesticide (5). The solvent thus evaporated is 
discharged through the outlet for exhaust gas (3) together with the fluid 
gas. They can be separated from one another and can be recovered by the 
usual method. The operation of this device can be optimized by 
appropriately adjusting, for instance, the flow rate and the temperature 
T.sub.1 of the fluid gas, the temperature T.sub.2 of the granular 
pesticide (5) and the temperature T.sub.3 of the exhaust gas depending on 
the characteristic properties (for instance, particle size) of the 
granular pesticide (5), the composition of the mixed solution (12) of the 
film-forming materials or the like. The completed granular pesticide is 
removed from the device through an opening (7) for withdrawal fitted to 
the lower end of the spouting column (1). 
In the present invention, it is possible to use a mixture of at least two 
coated granular pesticides which have a different release-suppression term 
of the active ingredient from one another. Such a mixture is particularly 
useful since the release-suppression term and the released amount of the 
active ingredient having insecticidal, fungicidal or herbicidal effect 
required for the cultivation and management of field crops and garden 
crops can be controlled or adjusted by a single application thereof. 
When using an active ingredient having insecticidal and/or fungicidal 
effects as the hardly water-soluble active ingredient, the combination of 
a plurality of coated granular pesticides having different 
release-suppression terms is not limited to specific ones inasmuch as any 
specific combination permits the long-lasting release of the active 
ingredient having insecticidal and/or fungicidal effects required for the 
cultivation and management of field crops over the entire growing period, 
but it is preferred to appropriately combine an early release-intiation 
type coated granular pesticide which can initiate the release of the 
active ingredient after 2 to 5 weeks from the application thereof to 
fields and a late release-intiation type one which can initiate the 
release of the active ingredient after 6 to 9 weeks from the application 
thereof to fields. 
Such a combination of the early release-intiation type coated granular 
pesticide with the late release-intiation type one is suitably used for 
controlling blast of paddy rice (for controlling leaf blast which would be 
developed after one month from the rice transplanting and head blast which 
would be developed after 2.5 months from the rice transplanting). 
When using an active ingredient having a herbicidal effect as the hardly 
water-soluble active ingredient, the combination of a plurality of coated 
granular pesticides having different release-suppression terms is not 
limited to specific ones inasmuch as any specific combination permits the 
long-lasting release of the active ingredient having a herbicidal effect 
required for the cultivation and management of field crops over the entire 
growing period, but it is preferred to appropriately combine an early 
release-intiation type coated granular pesticide which can initiate the 
release of the active ingredient after 1 to 14 days from the application 
thereof to fields and a late release-intiation type one which can initiate 
the release of the active ingredient after 15 to 40 days from the 
application thereof to fields. 
The coated granular pesticide of the present invention permits the 
initiation of the release of the hardly water-soluble active ingredient at 
the time when crops require the active ingredient. Therefore, the 
pesticide of the present invention does not cause any chemical injury of 
crops and also permits the sustained release of the active ingredient at a 
low concentration which does not adversely affect the growing environment 
of the crops. 
For this reason, even if the coated granular pesticide is applied to fields 
simultaneously with the transplantation of seedlings, the granular 
pesticide initiates the release of its hardly water-soluble active 
ingredient after the rooting of the transplanted seedlings and the 
released hardly water-soluble active ingredient is completely consumed for 
weed-killing, pasteurization and for controlling insects. Accordingly, the 
transplanted seedlings are not adversely affected by the pesticide and the 
production of field crops with safety is permitted. 
It is optionally possible to use a coated granular pesticide comprising a 
coated water-soluble active ingredient in combination with the pesticide 
of the present invention, in such an extent that the initial release 
thereof does not have any adverse influence. In this case, the 
release-initiation time corresponds to the time when cracks are formed on 
the film. 
In the present invention, the coated granular pesticide and a mixture 
thereof may be applied to fields at any desired period, but they are 
preferably applied simultaneously with or immediately before the 
transplantation of seedlings since the time required for farm working can 
substantially be reduced. Particularly preferably, they are applied to 
holes or furrow formed on the side of seedlings simultaneously with 
transplantation of seedlings, or alternatively they are applied to a 
substrate for raising seedlings immediately before the transplantation 
thereof and immediately thereafter, the seedlings are transplanted to 
fields. It is also possible to combine the coated granular pesticide 
according to the present invention or a mixture thereof with a 
commercially available pesticide and to apply the resulting mixture so 
that the latter would be released during the controlled release term of 
the pesticide of the present invention. 
The coated granular pesticide of the present invention can likewise be 
incorporated into a seedling-support substance having water holding 
properties (hereinafter referred to as "water-holding material") and used 
as a substrate for raising seedlings. Such a substrate for raising 
seedlings consisting of the coated granular pesticide and the 
water-holding material is suitably used in the cultivating method which 
comprises seeding rice seeds in a nursery box, raising the seedlings and 
then transplanting the resulting seedlings to fields. The use of the 
substrate for raising seedlings according to the present invention can 
eliminate the application of any granular pesticide having an 
insecticidal, fungicidal or herbicidal effect prior to transplantation of 
seedlings and this accordingly permits the substantial reduction in the 
quantity of work during transplantation, in particular, that of a 
large-scale farm household who raises seedlings using a large number of 
nursery boxes. In addition, if raising seedlings by the use of the 
substrate for raising seedlings according to the present invention, the 
seedlings are transplanted while the coated granular pesticide is held 
around the rooting of the seedlings and therefore, this leads to 
improvement in the absorption and utilization efficiency of the active 
ingredient released from the coated granular pesticide, substantial 
reduction of the active ingredient washed away into the soil and reduction 
of environmental loads. 
The water-holding materials usable herein are not restricted to any 
specific one inasmuch as they have good water holding properties and 
examples thereof are natural soil, naturally occurring organic substances 
such as wood chips, scum of pulp, peat-moss, sphagnum and coir; foamed 
resins; and inorganic porous materials such as perlite and vermiculite, 
but preferred are vermiculite, peat-moss and coconut meal because they are 
inexpensive and stable supply thereof can be ensured. These water-holding 
materials may be used alone or in a blend of at least two of them. In 
addition, these water-holding substances may further comprise various 
kinds of additives for controlling physicochemical properties such as pH 
and electrical conductivity (EC). 
To the substrate for raising seedlings according to the present invention, 
there may, if needed, be added fertilizers. In this respect, however, if 
using fast-acting fertilizers, they are preferably used in amounts of 
about 1 to 4 g, respectively, as expressed in terms of N (nitrogen), 
P.sub.2 O.sub.3 (phosphoric acid) and K.sub.2 O (potash) per unit nursery 
box (internal size: 28 cm (length).times.58 cm (width).times.3 cm (depth). 
If these fertilizer components each exceeds 4 g, young seedlings may 
suffer from concentration injury. 
To the substrate for raising seedlings according to the present invention, 
there may be applied, in addition to fast-acting fertilizers, coated 
granular fertilizer whose release rate is physically controlled by coating 
each granular fertilizer with a film and micro elements. 
Examples of such micro elements are compounds of, for instance, magnesium, 
calcium, iron, manganese, boron, zinc, copper and molybdenum. 
Water-soluble micro elements are fast-acting fertilizers and therefore, 
they are effective for soil deficient in these component, but have such a 
tendency that they are washed away if the amount of water used for 
irrigation increases. Moreover, if the added amount of the micro elements 
is large, seedlings are damaged due to their excess and for this reason, 
the use of micro elements soluble in citric acid is recommended. Such 
citric acid-soluble micro elements are hardly soluble in water and the 
elements thereof are slowly released even if they are added to the 
substrate in a large amount during raising seedlings, and therefore, the 
use of such micro elements are particularly preferred in order to prevent 
any deficiency of these trace elements during raising seedlings. 
Examples of the foregoing coated granular fertilizers are those disclosed 
in JP-A 56567/1994 or JP-A 4887/1993 in which an oil modified alkyd resins 
is used as a coating film; and those disclosed in JP-A 147888/1988 wherein 
a polyolefinic resin is used as such a coating film and specific examples 
thereof usable herein include coated granular fertilizers commercially 
available under the trade names of Long (Asahi Chemical Industry Co., 
Ltd.), LP Coat (Chisso Corporation), Celacoat (Central Glass Co., Ltd.) 
and M Coat (Mitsubishi Chemical Co.). If these fertilizers are used for 
raising seedlings, roots of seedlings are formed around the granular 
fertilizer and thus the fertilizer-absorption and -utilization 
efficiencies are markedly improved. 
The coated granular fertilizer preferably has a release rate during the 
seedling-raising term ranging from 0.5 to 10% and more preferably 1 to 7%. 
Fertilizers having a release rate beyond the range defined above may also 
be used, but if the release rate exceeds 10%, seedlings may suffer from 
concentration injury due to the fertilizer component, while if it is less 
than 0.5%, the seedlings may insufficiently grow. Moreover, it is 
necessary to adjust the amount of the fertilizer to be applied depending 
on the term for raising seedlings to be transplanted. 
These coated granular fertilizers may be mixed with the water-holding 
materials in such an amount that does not impair the functions of the 
water-holding materials (water-holding and seedling-supporting functions). 
More specifically, if the amount of the coated granular fertilizer is 
excessively large, the water-holding properties of the resulting substrate 
are impaired, while if it is extremely small, sufficient fertilization 
during raising seedling cannot be ensured. Accordingly, it is preferable 
to admix 5 to 50 parts by weight of the coated granular fertilizer with 50 
to 95 parts by weight of the water-holding material. These numerical 
values defined above correspond to cases where the water-holding material 
is assumed to be a mineral substance such as natural soil. In case of, for 
instance, water-holding materials having a smaller specific gravity such 
as vermiculite and peat-moss, however, the amount thereof to be used may 
be less than 50 parts by weight so far as the resulting mixture exhibits 
functions of water-holding materials. Therefore, the foregoing range is 
simply a standard for judgment. 
The amount of the coated granular pesticide to be used varies depending on 
the content of the active ingredient thereof, but it is in general 
sufficient to use the same in a small amount and thus the pesticide does 
not impair the functions of the water-holding material. The amount of the 
coated pesticide as a standard is preferably not more than 100 g per 
nursery box having the size specified above. 
Moreover, the substrate for raising seedling according to the present 
invention may likewise comprise a further component such as a growth 
regulator, a growth promoter or the like. 
The substrate for raising seedling according to the present invention may 
be prepared by any conventionally known method. For instance, it can be 
prepared by admixing a water-holding material and the coated granular 
pesticide as well as optional components such as a fertilizer and micro 
elements in a mixing machine. The resulting mixture (the substrate for 
raising seedling according to the present invention) may be used in a 
variety of methods. For instance, it may be used as bed soil and/or soil 
cover in fields or nursery boxes; or it may be mixed with seeds upon 
seeding. In particular, when it is used in a nursery box, it can be 
recommended that a layer of a mixture of seeds with the substrate for 
raising seedling according to the present invention, which comprises a 
water-holding material, the coated granular pesticide and coated granular 
fertilizers, should be arranged between a bed soil layer and a soil cover 
layer. This is because the active ingredient, fertilizer components and 
micro elements are present in the vicinity of seeds and therefore, these 
components are absorbed through roots and used with a high efficiency, 
after rooting the seeds. 
The present invention will hereinafter be described in more detail with 
reference to the following Production Experiments of Granular Pesticides 
and Production Experiments and Examples, but the present invention is not 
limited to these specific Examples. In the following Examples, the term 
"%" means "% by weight" unless otherwise specified. 
Production of Granular Pesicide 
Granular Pesticides (G.P.) A to M 
Each mixture of ingredients for granules having each corresponding 
composition shown in Table 1 was kneaded in a kneader while adding water, 
followed by granulation through extrusion and forming into spherical 
granules using a shaping machine. Then the granulated product was dried to 
thus give each granular pesticide containing a hardly water-soluble active 
ingredient and having a particle size ranging from 0.8 to 1.4 mm. In the 
foregoing preparation, the polymer used for preparing the granular 
pesticide D was used after dissolving in water. 
TABLE 1 
______________________________________ 
Composition of G.P. (% by weight) 
G. Active 
P. Ingredient Material I Material II Material III 
______________________________________ 
A A.M..sup.1) A 
10 bentonite 
50 clay 40 
B A.M. A 5 bentonite 95 
C A.M. B 20 bentonite 40 starch 20 clay 20 
D A.M. C 5 bentonite 5 kao- 85 polymer 5 
lin 
E A.M. D 2 starch 95 gel- 1 ammonium 2 
atin phosphate 
F A.M. A 15 bentonite 60 clay 25 
G A.M. A 15 bentonite 30 clay 55 
H A.M. E 7 bentonite 30 clay 63 
I A.M. F 10 bentonite 30 clay 60 
J A.M. E 7 bentonite 30 clay 53 
A.M. F 10 
K A.M. A 14.5 bentonite 30 clay 55.5 
L A.M. C 3.5 bentonite 30 clay 66.5 
M A.M. C 1 bentonite 30 clay 69 
______________________________________ 
FNT 1) A.I.=Active Ingredient. 
*: Active Incrredient: 
A.I. A: 2-benzothiazol-2-yloxy-N-methylacetoanilide (content=87%) 
A.I. B: 2-chloro-4-ethylamino-6-isopropylamino-s-triazine (content=75%) 
A.I. C: 1-(6-chloro-3-pyridylmethyl)-N-nitroimidazolidin-2-ylideneamine 
(content=71%) 
A.I. D: 2-chloro-4,6-bis(ethylamino)-s-triazine (content=50%) 
A.I. E: 5-methyl-1,2,4-triazolo(3,4-b)benzothiazole (content=75%) 
A.I. F: 1,3-bis(carbamoylthio)-2-(N,N-dimethylamino)propane hydrochloride 
(content=50% by weight) 
*: Water-Swelling Material 
Bentonite: a product available from Wako Pure Chemical Industry Co., Ltd. 
Starch: corn starch available from Wako Pure Chemnical Industry Co., Ltd. 
Gelatin 
*: Binder, Auxiliary Agent for Granulation or the Like 
Polymer: sodium polyacrylate (degree of polymerization: 15 22,000 to 
70,000) 
Ammonium Phosphate: diammonium phosphate 
Clay 
Kaolin 
Synthesis of Thermosetting Resin 
To a 300 ml four-necked flask, there was added 100 ml of diethylene glycol 
dimethyl ether, followed by dissolution of 18.9 g of .alpha., 
.omega.-bis(3-aminopropyl)polydimethyl siloxane, cooling the content of 
the flask down to a temperature of 10.degree. C. while stirring with a 
stirring machine, subsequent addition of 4.6 g of maleic anhydride and 
reaction of these ingredients to give a thermosetting resin A. 
In the same manner, to a 300 ml four-necked flask, there was added 100 ml 
of N,N-dimethylacetamide, followed by dissolution of 4.7 g of 
p-aminobenzoic acid, cooling the content of the flask down to a 
temperature of 7.degree. C. while stirring with a stirring machine, 
subsequent addition of 18.9 g of benzophenone tetracarboxylic acid 
dianhydride and reaction of these ingredients to give a thermosetting 
resin B. 
Production of Coated Granular Pesticide (C.G.P.) 
As has been shown in FIG. 2, hot air having a high temperature was passed 
through the interior of a spouting column (1) which was in a shape having 
a column diameter of 250 mm, a height of 2000 mm, an air jet-outlet 
diameter of 50 mm and an angle at the conical part of 50 degrees, from its 
bottom to the top, i.e., upwardly passed through the column. A blower (10) 
was used to introduce air, through an orifice flowmeter (9), into a heat 
exchanger (8) in which the air was heated to a desired high temperature 
and was then guided to the spouting column (1) and finally discharged 
through an outlet (3) for exhaust gas which was positioned at the upper 
portion of the spouting column (1). Then there was introduced 10 kg of 
each granular pesticide (5) listed in Tables 2 to 7 (provided that 3 kg of 
each pesticide was introduced when producing coated granular pesticides 33 
to 46) into the interior of the spouting column (1) through which the hot 
air was circulated, through an opening (2) for introducing granules 
positioned on the side of the spouting column (1) to thus fluidize the 
granular pesticide (5) in the powdery state. In this regard, the flow rate 
and temperature of the hot air were appropriately controlled depending on 
the kinds of samples. The flow rate of the granule (5) was controlled 
while monitoring the same by the orifice flowmeter and the temperature 
thereof was adjusted while monitoring the hot air temperature (T.sub.1), 
the granule temperature (T.sub.2) and the exhaust gas temperature 
(T.sub.3). The production of each coated granular pesticide was carried 
out at a flow rate as determined by flowmeter (9) of 4 m.sup.3 /min and 
the hot air temperature (T.sub.1) of 100.degree. C..+-.2.degree. C. 
(provided that T.sub.1 was set at 80.degree. C..+-.2.degree. C. when 
producing coated granular pesticides 33 to 40). 
On the other hand, there were introduced, into a dissolution bath (11), 
ingredients for films listed in Tables 2 to 7 and tetrachloroethylene as a 
solvent (provided that toluene was used when producing coated granular 
pesticides 33 to 40), followed by admixing and stirring these components 
to give a 2.5% solution (12) of film-forming materials (provided that a 
5.0% solution of film-forming materials was used when producing coated 
granular pesticides 41 to 46, 49 and 50). In the foregoing preparation, 
the thermosetting resins in liquid states were used as such, while those 
in powdery states were pulverized in a ball mill, then classified using a 
sieve having a pore size of 75 .mu.m and particles which could pass 
through the sieve were used. 
The solution (12) was fed to a spray nozzle (4), which was a full cone type 
hydraulic nozzle having a diameter of 0.6 mm and positioned at a lower 
portion of the spouting column (1), by the action of a pump (6), at a flow 
rate of 0.3 kg/min (provided that it was set at 0.2 kg/min when producing 
coated granular pesticides 33 to 40), then injected toward and sprayed on 
the granular pesticide (5) in a fluidized condition. 
Such a spraying operation was initiated when the temperature (T.sub.2) of 
the granular pesticide (G.P.) which was in the fluidized state reached a 
given level, and the operation was continued for a given period of time, 
followed by drying the product for a predetermined time. After the drying 
was completed, the blower (10) was stopped and the coated granular 
pesticide (5) was discharged through an opening (7) for withdrawal 
positioned at the lowest portion of the spouting column (1) to thus obtain 
each coated granular pesticide (C.G.P.) 1 to 55 having a covering ratio 
listed in the following Table 2 to Table 7. 
TABLE 2 
__________________________________________________________________________ 
Coating 
Composition of Coating Material Ratio 
C.G.P. 
Resin 1 
Resin 2 
Resin 3 
Filler 
S.A.A. G.P. 
(%) 
__________________________________________________________________________ 
1 PE-1 
40 talc 
60 
Nonion 
10 A 15 
2 PE-1 20 talc 80 Nonion 5 A 15 
3 PE-1 20 talc 80 Nonion 3 A 15 
4 PE-1 20 talc 80 Nonion 2 A 15 
5 PE-1 20 talc 80 Nonion 1 A 15 
6 PE-1 20 talc 80 Nonion 0.5 A 15 
7 PE-2 28 EVA 2 clay 70 B 20 
8 PE-2 69 WAX 30 PCL 1 C 20 
9 PE-2 5 talc 95 C 15 
10 PP-1 30 PCL 5 CaCO.sub.3 65 D 20 
11 PP-1 20 clay 80 Nonion 0.1 E 15 
12 WAX 70 talc 30 E 25 
__________________________________________________________________________ 
*: The amount of the surfactant (S.A.A.) is expressed in terms of % by 
weight on the basis of the total weight of the Resin 1, Resin 2, Resin 3 
and Filler (which is 100% by weight). 
TABLE 3 
__________________________________________________________________________ 
Composition of Coating Material Coating Ratio 
C.G.P. 
Resin 1 
Resin 2 
Filler 1 
Filler 2 
S.A.A. 
G.P. 
(%) 
__________________________________________________________________________ 
13 PE-3 
10 IB 1 talc 
89 F 20 
14 PE-3 20 IB 1 talc 79 F 20 
15 PE-3 30 IB 1 talc 69 F 20 
16 PE-3 20 MC 3 talc 77 F 20 
17 PE-3 10 PE-4 10 MC 5 talc 75 F 20 
18 PE-3 10 PE-4 10 HPC 3 talc 67 F 20 
19 PE-2 20 IB 1 talc 79 Nonion 0.5 F 20 
20 PE-2 20 MC 10 talc 70 F 20 
21 PE-2 20 HPC 1 talc 79 F 15 
22 PE-2 20 HPC 5 talc 75 F 15 
__________________________________________________________________________ 
*: The amount of the surfactant (S.A.A.) is expressed in terms of % by 
weight on the basis of the total weight of the Resin 1, Resin 2, Filler 1 
and Filler 2 (which is 100% weight). 
TABLE 4 
__________________________________________________________________________ 
Composition of Coating Material Coating 
Thermosetting Ratio 
C.G.P. Resin 1 Resin 2 Resin Filler S.A.A. G.P. (%) 
__________________________________________________________________________ 
23 PE-3 
10 Solution 1 
1 talc 
89 F 20 
24 PE-3 20 Solution 1 1 talc 79 F 20 
25 PE-3 30 Solution 1 1 talc 69 F 20 
26 PE-3 10 PE-2 10 Solution 2 2 talc 78 F 20 
27 PE-2 10 Powder 1 5 talc 85 F 20 
28 PE-2 20 PP-2 10 Powder 1 3 talc 77 F 20 
29 PE-2 20 Powder 1 1 talc 69 Nonion 0.5 F 20 
30 PP-2 35 Solution 2 10 talc 55 F 20 
31 PP-2 20 Powder 2 1 talc 79 F 15 
32 PP-2 20 Powder 2 5 talc 75 F 15 
__________________________________________________________________________ 
*: The amount of the surfactant (S.A.A.) is expressed in terms of % by 
weight on the basis of the total weight of the Resin 1, Resin 2, 
Thermosetting Resin and Filler (which is 100% by weight). 
TABLE 5 
______________________________________ 
Coating 
Composition of Coating Material Ratio 
C.G.P. 
Resin 1 Resin 2 Filler G.P. (%) 
______________________________________ 
33 PE-3 20 EVA 20 talc 60 G 20 
34 PE-2 18 Water-sol. 2 talc 80 G 20 
35 Biodegrad. 1 1 PE-2 19 talc 80 G 20 
36 Biodegrad. 1 3 PE-2 17 talc 80 G 20 
37 Biodegrad. 1 10 PE-2 30 talc 60 G 20 
38 Biodegrad. 2 5 PE-2 15 talc 80 G 20 
39 Biodegrad. 3 2 PE-2 18 talc 80 G 20 
40 Biodegrad. 4 10 PE-2 20 talc 70 G 20 
______________________________________ 
TABLE 6 
______________________________________ 
Composition of Coating Material 
Coating Ratio 
C.G.P. Resin 1 Resin 2 Filler G.P. (%) 
______________________________________ 
41 PE-2 20 paraffin 
2 talc 80 H 20 
42 PE-2 18 paraffin 2 talc 80 H 20 
43 PE-2 18 paraffin 2 talc 80 I 20 
44 PE-2 15 paraffin 5 talc 80 I 20 
45 PE-2 18 paraffin 2 talc 80 J 20 
46 PE-2 15 paraffin 5 talc 80 J 20 
47 PE-2 18 talc 82 K 20 
48 PE-2 18 talc 82 L 20 
49 PE-2 15 talc 85 L 20 
50 PE-2 15 WAX 2 5 talc 80 M 20 
______________________________________ 
TABLE 7 
__________________________________________________________________________ 
Coating 
Composition of Coating Material Ratio 
C.G.P. 
Resin 1 
Resin 2 
Filler 1 
Filler 2 
S.A.A. 
G.P. 
(%) 
__________________________________________________________________________ 
51 PE-2 
15 talc 
85 Nonion 
1 F 20 
52 PE-2 25 talc 75 Nonion 2 F 20 
53 PE-2 30 talc 70 Nonion 1 F 20 
54 PE-2 10 PE-3 20 talc 67 HPC 3 F 20 
55 PE-3 10 talc 89 Powder 1 1 F 20 
__________________________________________________________________________ 
*: The amount of the surfactant (S.A.A.) is expressed in terms of % by 
weight on the basis of the total weight of the Resin 1, Resin 2, Filler 1 
and Filler 2 (which is 100% by weight). 
PE-1: low density polyethylene: MI=20; d=0.922 g/cmn.sup.3 
PE-2: ethylene-carbon monoxide copolymer: MI=0.75; CO=0.95% by weight 
PE-3: low density polyethylene: MI=23; d=0.916 g/cm.sup.3 
PE-4: low density polyethylene: MI=70; d=0.915 g/cm.sup.3 
PP-1: copolymer type atactic polypropylene having an ethylene content of 
3%: Mw=60,000 
PP-2: polypropylene: Mw=10,000; d=0.9 g/cm.sup.3 
EVA: ethylene-vinyl acetate copolymer: MI=20; vinyl acetate content=30% by 
weight 
WAX: polyethylene wax: Mn=8,000; d=0.97 g/cm.sup.3 
WAX 2: polyethylene wax: Mn=2,000; d=0.92 g/cm.sup.3 
paraffin: mp=68 to 70.degree. C. 
PCL: poly-.epsilon.-caprolactone: Mw=50,000 
IB: isobutylene type copolymer 
MC: methyl cellulose 
Biodegrad. 1: 1,4-butanediol-succinic acid co-polycondensate: Mn=59,000 
Biodegrad. 2: poly-L-lactic acid: Mw=60,000 
Biodegrad. 3: polycaprolactone: Mw=50,000 
Biodegrad. 4: 3-hydroxybutyric acid/3-hydroxyvaleric acid copolymer: 
Mw=150,000, 3-hydroxyvaleric acid content=20 mole % 
Water-Sol.: polyethylene oxide: Mw=150,000 to 400,000 
HPC: hydroxypropyl cellulose: 150 to 400 cp 
Nonion: hexaoxyethylene nonyl phenyl ether: HLB=13 
talc: average particle size=5 .mu.m 
CaCO.sub.3 : calcium carbonate having an average particle size of 5 .mu.m 
clay: average particle size=5 .mu.m 
Solution 1: thermosetting resin A 
Solution 2: thermosetting resin B 
Powder 1: thermosetting resin A 
Powder 2: thermosetting resin B 
Production of Coated Granular Pesticide Mixture 
The coated granular pesticides (C.G.P.) 41 to 46 (Table 6) produced in the 
foregoing Production Experiments were blended in the rates specified below 
and each blend was uniformly stirred in a kneader to give various coated 
granular pesticide mixtures (coated granular pesticide mixtures 1 to 16). 
C.G.P. Mixture 1: 
(C.G.P. 41: C.G.P. 42=1:1) 
C.G.P. Mixture 2: 
(C.G.P. 41: C.G.P. 42=2:1) 
C.G.P. Mixture 3: 
(C.G.P. 41: C.G.P. 42 1:2) 
C.G.P. Mixture 4: 
(C.G.P. 43: C.G.P. 44=1:1) 
C.G.P. Mixture 5: 
(C.G.P. 43: C.G.P. 44=2:1) 
C.G.P. Mixture 6: 
(C.G.P. 43: C.G.P. 44=1:2) 
C.G.P. Mixture 7: 
(C.G.P. 41: C.G.P. 43=1:1) 
C.G.P. Mixture 8: 
(C.G.P. 42: C.G.P. 44=1:1) 
C.G.P. Mixture 9: 
(C.G.P. 42: C.G.P. 45=1:1) 
C.G.P. Mixture 10: 
(C.G.P. 41: C.G.P. 46=1:1) 
C.G.P. Mixture 11: 
(C.G.P. 51: C.G.P. 53=1:1) 
C.G.P. Mixture 12: 
(C.G.P. 51: C.G.P. 53=7:3) 
C.G.P. Mixture 13: 
(C.G.P. 51: C.G.P. 53=6:4) 
C.G.P. Mixture 14: 
(C.G.P. 51: C.G.P. 52: C.G.P. 53=60:25:15) 
C.G.P. Mixture 15: 
(C.G.P. 53: C.G.P. 55=1:9) 
C.G.P. Mixture 16: 
(C.G.P. 53: C.G.P. 54: C.G.P. 55=15:15:70) 
Release-Confirmation Test 
Release-confirmation tests were carried out using coated granular 
pesticides 1 to 12 (Table 2) produced in the foregoing experiments for the 
production of these granules. In these tests, there was determined the 
period required for the formation of cracks on the pesticides, the 
breakage of the films thereof and the outward release of the granular 
pesticides present therein (release-suppression term), according to the 
following manner. 
To a beaker, there were added 500 ml of distilled water and 0.1 g of each 
coated granular pesticide 1 to 12, followed by the inspection of the 
coated granular pesticide for film-disintegration behavior with period. In 
addition, the distilled water in the beaker was sampled at regular 
intervals, the hardly water-soluble active ingredient present in the 
sampled distilled water was analyzed by high performance liquid 
chromatography to thus determine the priod required till the release of 
the active ingredient was detected and the period thus determined was 
defined to be the release-suppression term of the granular pesticide. The 
temperature of the distilled water was maintained at 20.degree. C. and the 
determination was carried out for 30 days after the addition of the 
granule to distilled water. The results thus obtained are summarized in 
Table 8. 
TABLE 8 
______________________________________ 
Release-Suppression 
Sample Term (day) 
______________________________________ 
Example 1 C.G.P. 1 10 
Example 2 C.G.P. 2 6 hrs. 
Example 3 C.G.P. 3 0.5 
Example 4 C.G.P. 4 1.0 
Example 5 C.G.P. 5 1.5 
Example 6 C.G.P. 6 5 
Example 7 C.G.P. 7 15 
Example 8 C.G.P. 8 24 
Example 9 C.G.P. 9 0.5 
Example 10 C.G.P. 10 17 
Example 11 C.G.P. 11 10 
Example 12 C.G.P. 12 20 
______________________________________ 
The disintegration process of the coated granular pesticide 2 is shown in 
FIG. 3. FIGS. 3A, 3B and 3C are photographs taken at 6 hours, 6 hours and 
5 minutes, and 6 hours and 10 minutes after the coated granular pesticide 
2 was introduced into a beaker, respectively. 
As will be seen from the photographs shown in FIGS. 3A to 3C, it takes a 
constant time period till cracks are formed on the film of this coated 
granular pesticide and any hardly water-soluble active ingredient is not 
released at all before the formation of the cracks, but if once such 
cracks are formed, the disintegration of the film proceeds acceleratedly 
and the granular pesticide present therein is rapidly released. 
Moreover, the results observed for the coated granular pesticides 2 to 6 
which differ from one another in the added amount of the surfactant 
indicate that the larger the amount of the surfactant added, the shorter 
the release-suppression term and that the addition of a surfactant is 
effective for the control of the release-suppression term. 
Test 1 for Release in Water 
Tests for release in water were carried out using the coated granular 
pesticides 13 to 32 (Tables 3 and 4) produced in the foregoing Production 
Experiments. To a beaker, there were added 1000 ml of distilled water and 
0.1 g of each coated granular pesticide (C.G.P.), followed by the 
inspection of the coated granular pesticide for film-disintegration 
behavior with term. In addition, the distilled water in the beaker was 
sampled at regular intervals, the hardly water-soluble active ingredient 
present in the sampled distilled water was analyzed by high performance 
liquid chromatography. The temperature of the distilled water was 
maintained at 25.degree. C. during the test and the determination was 
carried out for 28 days after the addition of the granule to distilled 
water. The results thus obtained are summarized in Tables 9 and 10. In 
Comparative Example 1, the foregoing granular pesticide F free of coating 
film was used. 
TABLE 9 
______________________________________ 
Concn. of Active Ingredient 
in Water (ppm) 
day day day day day 
Sample 1 3 7 14 28 
______________________________________ 
Ex. 13 C.G.P. 13 0.0 0.3 0.8 1.2 1.6 
Ex. 14 C.G.P. 14 0.0 0.0 0.3 0.8 1.5 
Ex. 15 C.G.P. 15 0.0 0.0 0.0 0.1 1.0 
Ex. 16 C.G.P. 16 0.0 0.0 0.0 0.6 1.3 
Ex. 17 C.G.P. 17 0.0 0.0 0.0 0.8 1.8 
Ex. 18 C.G.P. 18 0.0 0.0 0.0 0.0 0.7 
Ex. 19 C.G.P. 19 0.0 1.0 1.6 2.0 2.5 
Ex. 20 C.G.P. 20 0.0 0.0 0.4 1.0 2.0 
Ex. 21 C.G.P. 21 0.0 0.0 0.0 0.7 1.4 
Ex. 22 C.G.P. 22 0.0 0.0 0.1 0.9 1.8 
Comp. G.P. F 0.8 1.2 2.5 2.9 3.0 
Ex. 1 
______________________________________ 
The results listed in Table 9 indicate that the granules of Comparative 
Example 1 initiates the release of the active ingredient immediately after 
the introduction thereof into water, whereas for C.G.P. Nos. 13 to 22 
according to the present invention, which comprise water-absorbing polymer 
fine particles and/or water-soluble polymer fine particles, any active 
ingredient is not detected, on day 1 after the introduction, clearly 
showing that the release of the active ingredient is initially inhibited 
and the active ingredient certainly undergoes sustained release in the 
samples of the present invention. 
Moreover, the results observed for C.G.P. Nos. 13 to which differ from one 
another in the amount of Resin 1 included in the water-absorbing polymer 
fine particles and/or the water-soluble polymer fine particles with 
respect to the isobutylene type copolymer (Table 3) also indicate that the 
larger the amount of Resin 1, the later the release-suppression term of 
the active ingredient and that the control of the amount of Resin 1 would 
be effective for the adjustment of the release-suppression term. 
TABLE 10 
______________________________________ 
Concn. of Active Ingredient 
in Water (ppm) 
day day day day day 
Sample 1 3 7 14 28 
______________________________________ 
Ex. 23 C.G.P. 23 0.0 0.1 0.6 1.3 1.7 
Ex. 24 C.G.P. 24 0.0 0.0 0.4 0.9 1.4 
Ex. 25 C.G.P. 25 0.0 0.0 0.0 0.0 1.1 
Ex. 26 C.G.P. 26 0.0 0.0 0.0 0.5 1.2 
Ex. 27 C.G.P. 27 0.0 0.2 0.4 0.8 1.9 
Ex. 28 C.G.P. 28 0.0 0.0 0.2 0.5 1.4 
Ex. 29 C.G.P. 29 0.0 0.0 0.8 1.5 2.3 
Ex. 30 C.G.P. 30 0.0 0.4 0.7 1.0 2.0 
Ex. 31 C.G.P. 31 0.0 0.0 0.3 0.8 1.5 
Ex. 32 C.G.P. 32 0.0 0.5 1.0 1.5 1.8 
Comp. G.P. F 0.8 1.2 2.5 2.9 3.0 
Ex. 1 
______________________________________ 
The results listed in Table 10 indicate that the granules of Comparative 
Example 1 initiates the release of the active ingredient immediately after 
the introduction thereof into water, whereas for C.G.P. Nos. 23 to 32 
according to the present invention, which comprise thermosetting resins, 
any active ingredient is not detected, on day 1 after the introduction, 
clearly showing that the release of the active ingredient is initially 
inhibited and the active ingredient certainly undergoes controlled release 
in the samples of the present invention. 
Moreover, the results observed for C.G.P. Nos. 23 to 25 which differ from 
one another in the amount of Resin 1 with respect to the thermosetting 
resin (Table 4) also indicate that the larger the amount of Resin 1, the 
later the release-initiation time of the active ingredient and that the 
control of the amount of Resin 1 would be effective for the adjustment of 
the release-suppression term. 
Test for Examining Decomposition and Deterioration of Film 
There was introduced, into a polypropylene nonwoven fabric having a size of 
3 cm.times.10 cm, 10 g of each coated granular pesticide (C.G.P.) 33 to 40 
(Table 5) produced in the foregoing Production Experiments. The soil in 
the field within a glasshouse (Tobata-Ku, Kitakyushu-Shi, Fukuoka-Ken, 
Japan) was digged out to a depth of 3 cm and the polypropylene nonwoven 
fabric was placed in the digged portion, followed by returning the soil 
digged out above to heap up the earth. The temperature in the glasshouse 
was appropriately controlled and the maximum temperature and the minimum 
temperature were found to be 30 and 20.degree. C., respectively. An 
appropriate amount of water was supplied to the ground by sprinkling water 
over the ground at 8:30 and 12:30 every day using an automatic water 
sprinkler. These samples of the granules were taken out from the soil 
every two months to examine the granules for their conditions. After one 
year, the granules were taken out, washed with water and examined for the 
conditions of the films thereof. The results thus obtained are listed in 
the following Table 11. 
TABLE 11 
______________________________________ 
Results Observed in 
Sample Film-Decomposition Test 
______________________________________ 
Ex. 33 C.G.P. 33 Any change in shape was not 
observed even after one year. 
Ex. 34 C.G.P. 34 The film was disintegrated after 
two months, but there was observed 
film residues. 
Ex. 35 C.G.P. 35 The film was disintegrated after 
two months, and crumbled into decay 
upon water-washing after one year. 
Ex. 36 C.G.P. 36 The film was disintegrated after 
two months, and crumbled into decay 
after 8 months. 
Ex. 37 C.G.P. 37 The film was disintegrated after 
two months, and crumbled into decay 
upon water-washing after one year. 
Ex. 38 C.G.P. 38 The film was disintegrated after 
two months, and crumbled into decay 
after 6 months. 
Ex. 39 C.G.P. 39 The film was disintegrated after 
two months, and crumbled into decay 
upon water-washing after one year. 
Ex. 40 C.G.P. 40 The film was disintegrated after 
two months, and crumbled into decay 
atter 4 months. 
______________________________________ 
As seen from the results listed in Table 11, it was confirmed that for the 
coated granular pesticide (C.G.P.) Nos. 35 to 40 which comprised 
biodegradable polymers hardly soluble or insoluble in water, the films 
crumbled into decay after one year and disappeared. In respect of C.G.P. 
Nos. 33 to 34, it was confirmed that C.G.P. No. 34 showed disintegration 
of the film, but the decomposition of film residues was not affected so 
much. The effect of decomposing the film would be ascribed to the addition 
of biodegradable polymers thereto and thus the reduction in the film 
strength would contribute to the disappearance of the film. 
Test 2 for Release in Water 
The coated granular pesticides (C.G.P.) Nos. 34 to 40 (Table 5) produced in 
the foregoing production experiments were subjected to tests for examining 
the release of the active ingredients in water. To a test tube (12 
mm.times.72 mm) equipped with a cap, there was added 1.5 ml of water and 
each granular pesticide was introduced into the test tube in a rate of one 
granule per tube and thereafter the test tubes were capped. Using 100 test 
tubes (or granules) per each test division, they were allowed to stand 
under a predetermined condition, i.e., at a water temperature of 
25.degree. C. and the number of the granules for pesticide thus 
disintegrated was counted. The test tubes were observed every day for one 
week after the initiation of the test and thereafter the observation was 
carried out once a week. The results thus obtained are shown in FIG. 4. 
The cumulative release rate means the number of granules tested which are 
disintegrated. 
The data shown in FIG. 4 indicate that all of the coated granular 
pesticides 34 to 40 exhibit almost identical release characteristics. 
Test 3 for Release in Water 
The coated granular pesticides (C.G.P.) Nos. 41 to 46 (Table 6) produced in 
the foregoing Production Experiments were subjected to tests for examining 
the release of the active ingredients in water. After immersing C.G.P. 
Nos. 41 to 46 in water maintained at 25.degree. C., the number of days 
required for the 10% release of the granular pesticide (G.P.) was 
determined and it was defined to be release-supression term. Using 100 
granules per test, the amount of the released G.P. was observed once a 
week to thus determine the number of G.P. granules disintegrated. The 
results obtained are summarized in the following Table 12. 
TABLE 12 
______________________________________ 
Release-Supression 
Sample Term (Day) 
______________________________________ 
Example 41 C.G.P. 41 
56 
Example 42 C.G.P. 42 28 
Example 43 C.G.P. 43 56 
Example 44 C.G.P. 44 28 
Example 45 C.G.P. 45 56 
Example 46 C.G.P. 46 28 
______________________________________ 
The coated granular pesticide (C.G.P.) mixture Nos. 1 to 3 produced in the 
foregoing Production Experiments were immersed in water maintained at 
25.degree. C., then the release rate of the active ingredient released 
from each C.G.P. was determined every 7 days to thus give an differential 
release rate. The differential release rate as days after application is 
shown in FIG. 5 as a bar graph. In addition, C.G.P. Nos. 41 and 42, each 
of which is a single substance, were also examined for the accumulated 
release rates. The resulting differential release rate as days after 
application is shown in FIG. 6 in the form of a bar graph. 
As has been shown in FIG. 6, each of C.G.P. Nos. 41 and 42, as single 
substances, has a peak of the release rate at a relatively early stage and 
accordingly they undergo rapid release of the active ingredients, but the 
duration of the release is short. On the other hand, as shown in FIG. 5, 
C.G.P. mixture Nos. 2 and 3 have peaks of the release rates lower than 
those observed for the C.G.P. Nos. 41 and 42 as single substances, but the 
mixtures each maintains a relatively high release rate over a long period 
of time, before and behind the peak. Moreover, it is found that C.G.P. 
mixture No. 1 does not have any particular peak, but maintains a 
relatively high release rate over a very long period of time. 
The coated granular pesticide (C.G.P.) mixture Nos. 4 to 6 are mixtures of 
the coated granular pesticide (C.G.P.) Nos. 43 and 44 (they both comprise 
the pesticide F having an insecticidal effect). When determining the 
differential release rates of these mixtures, it was found that they had 
release terms after the film-disintegration slightly shorter than those 
observed for the C.G.P. mixture Nos. 1 to 3, high peaks of release rates 
and they exhibits initial release of trace amounts of active ingredients 
because of the presence of the water-soluble active ingredient F, but it 
was also found that they had tendencies approximately identical to those 
observed for the C.G.P. mixture Nos. 1 to 3. 
C.G.P. mixture 7 is a mixture of the C.G.P. 41 comprising the pesticide E 
exhibiting a fungicidal effect and C.G.P. 43 comprising the pesticide F 
having an insecticidal effect. When examining the accumulated release rate 
of the mixture, it was found that the release rate of the mixture had a 
tendency almost identical to that observed for C.G.P. 45 (Table 12). It 
was also found that C.G.P. mixture 8 and C.G.P. 46 had approximately the 
same tendency. More specifically, it was found that almost the same effect 
could be obtained using either a coated granular pesticide produced by 
coating a granular pesticide which comprised active ingredients (active 
ingredients E and F) different in the effect such as the granular 
pesticide J, or a mixture comprising coated granular pesticides different 
from one another in the effect such as the coated granular pesticide 
mixture Nos. 7 and 8. In order to cope with various kinds of field crops, 
it is rather preferred to arbitrarily combine coated granular pesticides 
having different effects in such a manner that any desired effects can be 
obtained because of easy handling. 
C.G.P. mixture 9 is a mixture whose ingredients are blended in such a 
manner that they can continuously release active ingredients having 
fungicidal effects and can release active ingredients having insecticidal 
effects at the later half of the growing period of field crops, and C.G.P. 
mixture 10 is a mixture whose ingredients are blended in such a manner 
that they can release active ingredients having insecticidal effects at 
the early half of the growing period of field crops. 
Test 1 for Confirming Effect of Coated Granular Pesticide Mixture 
A miniature paddy field of 1/2000a was provided in a Wagner pot and three 
young seedlings were transplanted to the pot to thus cultivate paddy rice 
(cv. Hinohikari). This cultivation of the paddy rice was carried out 
according to the currently used cultivation method except that the depth 
of water upon the transplantation was set at 3 cm. In this cultivation 
method, the active ingredients were used according to various methods of 
application and the effects the reof were evaluated. The active 
ingredients were used in the cultivation according to the following three 
methods: 
Application Method A (AM: A): 
A method comprises the steps of applying 0.1 g of a coated granular 
pesticide mixture and 0.1 g of a commercially available granular pesticide 
(containing 4% of the active ingredient E used in the granular pesticide 
H) to the side furrows of the rice seedlings simultaneously with the 
transplantation of the seedlings and then covering them with soil 
immediately after the application. 
Application method B (AM: B): 
A method comprises the steps of sowing seeds in a nursery box, growing to 
young seedlings, applying a coated granular pesticide mixture and the 
foregoing commercially available granular pesticide to the nursery box at 
this stage, wherein the amounts of these granules were adjusted so that 
they are equal to those used in the application method A, and then 
transplanting the young seedlings to a Wagner pot. 
Application Method C (AM: C): 
A method wherein young seedlings were transplanted without application of 
the coated granular pesticide mixture and the foregoing commercially 
available granular pesticide at all. 
The coated granular pesticides (C.G.P.) 1 to 3 each was used according to 
the application methods A and B and the seedlings were examined for their 
growing conditions. As a control test division, the application method B 
was carried out without using any coated granular pesticide and the 
application method C was separately carried out as a treatment-free 
division, to thus examine the seedlings for their growing conditions. The 
results thus obtained are listed in Table 13. 
TABLE 13 
______________________________________ 
Results of Examination 
______________________________________ 
C.G.P. AM: A There was not observed any lesion 
Mixture 1 and chemical injury throughout the 
growing period. 
AM: B There was not observed any lesion 
and chemical injury throughout the 
growing period. 
C.G.P. AM: A There was not observed any lesion 
Mixture 2 and chemical injury throughout the 
growing period. 
AM: B There was not observed any lesion 
and chemical injury throughout the 
growing period. 
C.G.P. AM: A There was not observed any lesion 
Mixture 3 and chemical injury throughout the 
growing period. 
AM: B There was not observed any lesion 
and chemical injury throughout the 
growing period. 
Control Division 
There was not observed any lesion 
(applied to immediately after the 
nursery box) transplantation, but there were 
observed a large number of lesions 
after 7 weeks from the 
transplantation. 
Untreated In each pot, there were observed a 
Division large number of lesions immediately 
after the transplantation.* 
______________________________________ 
*: Any chemical injury was not observed at all. 
The data listed in Table 13 clearly indicate that the use of C.G.P. 
mixtures 1 to 3 by the side furrow-application (AM: A) or nursery 
box-application (AM: B) permits the effective control of the leaf blast 
and the head blast through the application thereof only one time. 
Paddy Field-Application Test 1 
This paddy field-application test was carried out using samples of C.G.P. 
51 to 55 (Table 7) produced by the foregoing Poduction Experiments and 
C.G.P. mixture 11 to 16 produced by the foregoing Production Experiments. 
To a Wagner pot of 1/5000a, there were added 2.5 kg of the paddy soil 
(collected from Minamata-Shi, Kumamoto-Ken, Japan) on which a large 
quantity of wild barnyard millet had grown and then water. After the pot 
was allowed to stand for one day, water was further added so as to be a 
depth of water (distance from the level of the soil to the surface of 
water) was 5 cm to thus establish conditions for a paddy field. In this 
respect, the thickness of the soil layer as measured from the bottom of 
the pot was found to be 10 cm. Three rice seedlings (cv. Hinohikari) which 
had been raised in a nursery box in advance were transplanted to each pot 
and 0.1 g of each sample granule was applied thereto. Separately, the 
granular pesticide (G.P.) F free of any coating was applied to the pot so 
that the application amount of the active ingredient was equal to that of 
each sample (Comparative Example 2). After the transplantation, the 
cultivation was carried out while appropriately supplementing water so as 
to compensate the reduced amount thereof. The cultivation was continued 
over 10 days and the seedlings were inspected for the presence of any 
chemical injury. The results thus obtained are summarized in Table 14. 
Paddy Field-A--lication Test 2 
Subsequent to the paddy field-application test 1, the rice plants were 
reaped at 10 days after the transplantation, followed by allowing the pots 
to stand without altering the other conditions over 40 days after the 
transplantation to observe growth of weeds and to thus evaluate the 
sustained effects of the granular pesticides. The results thus obtained 
are also listed in Table 14. 
TABLE 14 
______________________________________ 
Sample Chemical Injury 
Growth of Weeds.sup.1) 
______________________________________ 
Comp. G.P. F Observed. Weeds severely 
Ex. 2 The rice seedlings grew. 
were withered within 
10 days. 
Ex. C.G.P. Only slight chemical Weeds slightly 
47 51 injury was observed. grew. 
The plant was 
slightly undergrown. 
Ex. C.G.P. No chemical injury Weeds moderately 
48 52 was observed. grew. 
Ex. C.G.P. No chemical injury Weeds severely 
49 53 was observed. grew. 
Ex. C.G.P. No chemical injury Weeds severely 
50 54 was observed. grew. 
Ex. C.G.P. No chemical injury Weeds slightly 
51 55 was observed. grew. 
Ex. C.G.P. No chemical injury Weeds did not 
52 Mx. 11 was observed. grow at all. 
Ex. C.Q.P. No chemical injury Weeds did not 
53 Mx. 12 was observed. grow at all. 
Ex. C.G.P. No chemical injury Weeds did not 
54 Mx. 13 was observed. grow at all. 
Ex. C.G.P. No chemical injury Weeds did not 
55 Mx. 14 was observed. grow at all. 
Ex. C.G.P. No chemical injury Weeds did not 
56 Mx. 15 was observed. grow at all. 
Ex. C.G.P. No chemical injury Weeds did not 
57 Mx. 16 was observed. grow at all. 
______________________________________ 
.sup.1) Weeds: Wild Barnyard Millet. 
As seen from the results listed in Table 14, the granular pesticide (G.P.) 
F (free of any coating) caused chemical injury, while C.G.P. 51 caused 
only slight chemical injury, C.G.P. Nos. 52 to 55 and C.G.P. mixture Nos. 
11 to 16 did not cause any chemical injury and the seedlings 
satisfactorily grew. This clearly indicates that if the transplantation of 
seedlings and the application of a herbicide are carried out at the same 
time, the release of the active ingredients should be inhibited over a 
certain period. It has been proved that the use of the coated granular 
pesticides according to the present invention such as C.G.P. Nos. 51 to 55 
and C.G.P. mixture. Nos. 11 to 16 is quite effective for this purpose. 
G.P. F and C.G.P. Nos. 51 to 55 showed herbicidal effect or 
weed-growth-inhibitory effect till the 30th day after the transplantation, 
but wild barnyard millet grew on the 40the day thereafter. This clearly 
indicates that the foregoing granules have an only slight residual 
activity. The quantity of wild barnyard millet developed was remarkable, 
in particular, when C.G.P. Nos. 53 to 54 were used. When using C.G.P. 
mixture Nos. 11 to 16, wild barnyard millet did not grow at all or 
scarcely grew. Therefore, it would be clearly proved that these granules 
showed a residual activity. These mixtures exhibited 
weed-growth-inhibitory effect even on and after the 40th day. 
Paddy Field-Aoplication Test 3 
The test was performed under the same conditions used in the foregoing 
paddy field-application tests 1 and 2 except that any rice seedling was 
not transplanted at the same period and further the opening of the pot was 
covered with a polyvinylidene chloride wrap to prevent the evaporation of 
water. The aqueous solution was periodically sampled from the center of 
the aqueous phase and the sample was inspected for the amount of the 
active ingredient. The average water temperature during the test period 
was 20.degree. C. and the analysis was carried out over 40 days after the 
application of the pesticides. At the same time, C.G.P. Nos. 51 to 55 were 
also tested. As typical examples, the change in the concentration of the 
active ingredient of C.G.P. 55 present in the water is shown in FIG. 7 and 
those observed for C.G.P. mixture Nos. 11 to 16 are shown in FIG. 8. 
The data plotted on FIG. 7 indicate that C.G.P. 55 is an early 
release-initiation type coated granular herbicide, it is confirmed that 
the release of the active ingredient is inhibited for 3 days and 
thereafter the active ingredient is rapidly released and discharged in 
water. In addition, the concentration of the active ingredient is reduced 
on the 20th day after the application of the granule and thus it would be 
assumed that the granule would lose the efficacy. The results shown in 
FIG. 8 clearly indicate that C.G.P. mixture Nos. 11 to 16 permit the 
maintenance of each active ingredient's concentration to a desired level 
and the efficacy thereof lasts over a long period of time, although the 
amount of each C.G.P. mixture 11 to 16 is identical to those of the G.P. F 
and C.G.P. Nos. 51 to 55. 
Test 3 for Release in Water 
C.G.P. 47 and 48 (Table 6) produced in the foregoing Production Experiments 
were subjected to tests for examining the release of the active 
ingredients in water. There were added, to a beaker, 1000 ml of distilled 
water and 0.1 g of each C.G.P. and each C.G.P. was inspected for the film 
disintegration conditions with the lapse of time. In addition, the 
distilled water in the beaker was periodically sampled, followed by 
analyzing the hardly water-soluble active ingredients present in the 
sampled distilled water using high performance liquid chromatography and 
detection of the peak to thus determine the release initiation time. The 
water temperature during the determination was set at 25.degree. C. and 
the determination was carried out over 28 days after the application of 
the granule. The results obtained are summarized in the following Table 
15. 
Test 4 for Release in Water 
C.G.P. 49 and 50 produced in the foregoing production experiments were 
subjected to tests for examining the release of the active ingredients in 
water. There were added, to a beaker, 500 ml of distilled water and 1 g of 
each C.G.P. and each C.G.P. was inspected for the film disintegration 
conditions with the lapse of time. In addition, the distilled water in the 
beaker was periodically sampled, followed by analyzing the hardly 
water-soluble active ingredients present in the distilled water thus 
sampled using high performance liquid chromatography and detection of the 
peak to thus determine the release-initiation time. The water temperature 
during the determination was set at 25.degree. C. and the determination 
was carried out over 35 days after the application of the granule. The 
results obtained are also summarized in the following Table 15. 
TABLE 15 
______________________________________ 
Release-Initiation 
Sample Time (Day) 
______________________________________ 
Example 58 C.G.P. 47 20th 
Example 59 C.G.P. 48 20th 
Example 60 C.G.P. 49 30th 
Example 61 C.G.P. 50 18th day after the 
application 
______________________________________ 
Production of Substrate for Raising Seedlings 
Substrate 1 for Raising Seedlings 
To a concrete mixer, there were added a mixture of 2900 g of diluvial 
volcanic ash soil (maximum water-holding capacity: 120%; particle size: 
not more than 2 mm) and 100 g of vermiculite (particle size: not more than 
10 mm) as a water-holding material (3000 g in total); compound fertilizer 
(N-P.sub.2 O.sub.5 -K.sub.2 O=13-13-13, Chisso Corporation, trade name: 
Kumiai Ryuukarinan No. 11) in such an amount that the amounts of N, 
P.sub.2 O.sub.5 and K.sub.2 O each was equal to 1 g, as a fertilizer for 
raising seedlings; and 50 g of C.G.P. 47 produced in the foregoing 
production experiment, followed by admixing these ingredients till a 
uniform mixture was obtained to give a substrate for raising seedlings of 
a paddy rice. 
Substrate 2 for Raising Seedlings 
The same procedures used for preparing the substrate 1 for raising 
seedlings except for using a blend containing 50 g of coated compound 
fertilizer (N-P.sub.2 O.sub.5 -K.sub.2 O=14-12-14, Asahi Chemical Industry 
Co., Ltd., trade name: Long 424) and Ryuukarinan as a quick-acting 
fertilizer for raising seedlings in such an amount that the amounts of N, 
P.sub.2 O.sub.5 and K.sub.2 O each was equal to 1 g, in place of the 
fertilizer used in the substrate 1 to thus give a substrate for raising 
seedlings of a paddy rice. 
Substrate 3 for Raising Seedlings 
To a concrete mixer, there were added 3000 g of diluvial volcanic ash soil 
(maximum water-holding capacity: 120%; particle size: not more than 2 mm) 
as a water-holding material and Ryuukarinan as a quick-acting fertilizer 
for raising seedlings in such an amount that the amounts of N, P.sub.2 
O.sub.5 and K.sub.2 O each was equal to 1 g, followed by admixing these 
ingredients till a uniform mixture was obtained to thus give a substrate 
for raising seedlings of a paddy rice. 
Substrate 4 for Raising Seedlings 
To a concrete mixer, there were added 3000 g of diluvial volcanic ash soil 
(maximum water-holding capacity: 120%; particle size: not more than 2 mm) 
as a water-holding material and compound fertilizer (N-P.sub.2 O.sub.5 
-K.sub.2 O=13-13-13, Chisso Corporation, trade name: Kumiai Ryuukarinan 
No. 11) as a fertilizer for raising seedlings in such an amount that the 
amounts of N, P.sub.2 O.sub.5 and K.sub.2 O each was equal to 1 g, 
followed by admixing these ingredients till a uniform mixture was obtained 
to thus give a substrate for raising seedlings of a paddy rice. 
Substrate 5 for Raising Seedlings 
To a concrete mixer, there were added 3000 g of diluvial volcanic ash soil 
(maximum water-holding capacity: 120%; particle size: not more than 2 mm) 
as a water-holding material, compound fertilizer (N-P.sub.2 O.sub.5 
-K.sub.2 O=13-13-13, Chisso Corporation, trade name: Kumiai Ryuukarinan 
No. 11) as a fertilizer for raising seedlings in such an amount that the 
amounts of N, P.sub.2 O.sub.5 and K.sub.2 O each was equal to 1 g and 50 g 
of the coated granular pesticide 48 produced in the foregoing Production 
Experiment, followed by admixing these ingredients till a uniform mixture 
was obtained to thus give a substrate for raising seedlings of a paddy 
rice. 
Substrate 6 for Raising Seedlings 
A substrate for single cell transplanting, "Yosaku N-150" (Kyushu Chemical 
Industry Co., Ltd.), comprising vermiculite and peat-moss as principal 
components was used as the water-holding material. This water-holding 
material has such physico-chemical properties as an apparent specific 
gravity of 0.38 kg/L, a pH value (1:5 water) of 6.7, an electric 
conductivity (EC) (1:5 water) of 0.7 mS/cm and a water content of 30% and 
the contents of fertilizer components are 150 mg/L of N, 1000 mg/L of 
P.sub.2 O.sub.5 and 150 mg/L of K.sub.2 O. Among these, all of the 
ammonium nitrogen is originated from acetaldehyde-condensed urea (CDU). 
Furthermore, it also comprised citric acid-soluble MnO and B.sub.2 O.sub.3 
in amounts of 0.2 mg/kg and 0.05 mg/kg, respectively. 
A 9 cm plastic pot (having inner volume of about 300 ml) was filled with 
the mixture containing the water-holding material, followed by applying 1 
g of C.G.P. 49 produced in the foregoing production experiment on the 
mixture and then stirring it to give a substrate for vegetable. 
Substrate 7 for Raising Seedlings 
A water-holding material was produced by a vermiculite-substrate for 
horticulture, "Yosaku No. V1" (Kyushu Chemical Industry Co., Ltd.), 
comprising vermiculite and peat-moss as principal components, and 
disinfected diluvial volcanic ash soil (maximum water-holding capacity: 
120%; particle size: not more than 2 mm) in a volume ratio of 1:3 and then 
uniformly mixing these ingredients. This vermiculite-substrate for 
horticulture has such physico-chemical properties as an apparent specific 
gravity of 0.35 kg/L, a pH value (1:5 water) of 6.8, an EC value (1:5 
water) of 1.3 mS/cm and a water content of 30% and the contents of 
fertilizer components are 500 mg/L of N, 4400 mg/L of P.sub.2 O.sub.5 and 
400 mg/L of K.sub.2 O. In this respect, 300 mg/L of the nitrogen is 
originated from acetaldehyde-condensed urea (CDU) and 200 mg/L of the 
ammonium nitrogen. Furthermore, it also comprised citric acid-soluble MnO 
and B.sub.2 O.sub.3 in amounts of 0.2 mg/kg and 0.05 mg/kg, respectively. 
A 9 cm plastic pot (having inner volume of about 300 ml) was filled with 
the mixed soil, followed by applying 1 g of C.G.P. 49 produced in the 
foregoing Production Experiment on the mixed substrate and then stirring 
it to give a substrate for vegetable. 
Substrate 8 for Raising Seedlings 
A substrate for vegetable growing was produced by the same procedures used 
in the production of the substrate 7 for raising seedlings except that 
there was applied, to the substrate 7 for raising seedlings, 1 g of a 
coated compound fertilizer, "Micro Long Total 201-100" (Asahi Chemical 
Industry Co., Ltd.) and that the resulting mixture was then uniformly 
stirred. 
Substrate 9 for Raising Seedlings (Comparative) 
Disinfected diluvial volcanic ash soil (maximum water-holding capacity: 
120%; particle size: not more than 2 mm) was used and fertilizer 
components were added so that each pot comprised 150 mg/L of N, 1000 mg/L 
of P.sub.2 O.sub.5 and 150 mg/L of K.sub.2 O. Micro elements included 
therein were water-soluble MnO and B.sub.2 O.sub.3 whose contents were 0.2 
mg/kg and 0.05 mg/kg, respectively. 
A 9 cm plastic pot (having inner volume of about 300 ml) was filled with 
the foregoing mixture containing the water-holding material to give a 
substrate for vegetable. 
Substrate 10 for Raising Seedlings 
A substrate for vegetable was produced according to the same procedures 
used for producing the substrate 6 for raising seedlings except that 
C.G.P. 49 was not incorporated into the substrate. 
Substrate 11 for Raising Seedlings 
A substrate for single cell transplanting, "Yosaku N-100" (Kyushu Chemical 
Industry Co., Ltd.), comprising vermiculite, peat-moss and perlite as 
principal components was used as the water-holding material. This 
water-holding material has such physico-chemical properties as an apparent 
specific gravity of 0.38 kg/L, a pH value (1:5 water) of 6.3, an EC value 
(1:5 water) of 0.5 mS/cm and a water content of 40% and the contents of 
fertilizer components are 100 mg/L of N, 500 mg/L of P.sub.2 O.sub.5 and 
100 mg/L of K.sub.2 O. Among these, all of the nitrogen is originated from 
acetaldehyde-condensed urea (CDU). Furthermore, it also comprised citric 
acid-soluble MnO and B.sub.2 O.sub.3 in amounts of 0.2 mg/kg and 0.05 
mg/kg, respectively. In addition, 2 g of C.G.P. 50 produced in the 
foregoing production experiment was applyed on the mixture and then the 
mixture was stirred to give a substrate for flowers and ornamental plants. 
Substrate 12 for Raising Seedlings 
A substrate for flower growing was produced according to the same 
procedures used for producing the substrate 11 for raising seedlings 
except that C.G.P. 50 was not incorporated into the substrate. 
Raising Seedling Test 
Example 62 
The substrate 1 for raising seedlings (2000 g) was introduced into a 
nursery box, followed by smoothing the surface of the substrate and 
uniformly sowing 150 g of rice seeds of a paddy rice (cv. Hinohikari) in 
the substrate. Moreover, the seeds were covered with 1000 g of the same 
substrate. Thereafter the nursery boxes were placed in a glasshouse 
(Tobata-Ku, Kitakyushu-Shi, Fukuoka-Ken, Japan) to thus grow young 
seedlings. The cultivation management was performed by appropriately 
watering to prevent drying of the superficial layer of the substrate and 
carrying out additional manure two times, i.e., applying 0.5 g each (as 
expressed in terms of the amount of N) of the foregoing Ryuukarinan 
(twice) per nursery box. Other management for raising seedlings was 
carried out according to the methods currently used. 
Example 63 
A raising seedling test was carried out according to the same procedures 
used in Example 62 except that the substrate 2 for raising seedlings was 
substituted for the substrate 1 for raising seedlings and that the 
additional manure was omitted. 
Example 64 
The substrate 3 for raising seedlings (2000 g) was introduced into a 
nursery box, followed by smoothing the surface of the substrate and 
uniformly sowing the substrate with a mixture comprising 150 g of rice 
seeds of a paddy rice (cv. Hinohikari) and 600 g of coated urea (N-P.sub.2 
O.sub.5 -K.sub.2 O=40-0-0, Chisso Corporation, trade name: LP Coat S100) 
showing sigmoid type fertilizer-release characteristics. The soil cover 
used was a composition produced by uniformly mixing 1000 g of the same 
substrate with 50 g of C.G.P. 47 produced in the foregoing Production 
Experiment. Thereafter the nursery boxes were placed in the same 
glasshouse used in Example 62 to thus grow young seedlings. The 
cultivation management was performed by appropriately watering to prevent 
drying of the superficial layer of the substrate and additional manure was 
omitted. Other management for raising seedlings was carried out by the 
same procedures used in Example 62. 
Comparative Example 3 
A substrate (2000 g) produced by uniformly mixing 3000 g of the substrate 4 
for raising seedlings with 34.5 g of the granular pesticide K produced in 
the foregoing poduction experiment was introduced into a nursery box, 
followed by smoothing the surface of the substrate and uniformly sowing 
150 g of rice seeds of a paddy rice (cv. Hinohikari) in the substrate. The 
same substrate (1000 g) was used as the soil cover. Thereafter the nursery 
boxes were placed in the same glasshouse used in Example 62 to thus grow 
young seedlings. The cultivation management was performed by appropriately 
watering to prevent drying of the superficial layer of the substrate and 
carrying out additional manure two times, i.e., applying 0.5 g each (as 
expressed in terms of the amount of N) of the foregoing Ryuukarinan 
(twice) per nursery box. Other management for raising seedlings was 
carried out by the same procedures used in Example 62. 
Example 65 
The substrate 5 for raising seedlings (2000 g) was introduced into a 
nursery box, followed by smoothing the surface of the substrate and 
uniformly sowing 150 g of rice seeds of a paddy rice (cv. Hinohikari) in 
the substrate. Moreover, the seeds were covered with 1000 g of the same 
substrate 5. Thereafter the nursery boxes were placed in the same 
glasshouse used in Example 62 to thus grow young seedlings. The 
cultivation management was performed by appropriately watering to prevent 
drying of the superficial layer of the substrate and carrying out 
additional manure two times, i.e., applying 0.5 g each (as expressed in 
terms of the amount of N) of the foregoing Ryuukarinan (twice) per nursery 
box. Other management for raising seedlings was carried out according to 
the currently used method. 
Comparative Example 4 
The substrate 4 for raising seedlings was introduced into a nursery box and 
the granular pesticide L produced in the foregoing production experiments 
was applied to the substrate in the nursery box immediately before 
transplantation of seedlings according to the currently used method. 
Thereafter the nursery boxes were placed in the same glasshouse used in 
Example 62 to thus grow young seedlings. The cultivation management was 
performed according to the currently used method. 
Triplicate divisions treated according to each method disclosed in Example 
62 to 65 or Comparative Example 3 or 4 were examined for chemical injury 
during the seedling-raising term. The results thus obtained are listed in 
Table 16. 
TABLE 16 
______________________________________ 
Sample 
(Substrate 
for Day after sowing (Day) 
Raising) 1 3 7 14 21 
______________________________________ 
Ex. 62 1 --- --- --- --- --- 
Ex. 63 2 --- --- --- --- --- 
Ex. 64 3 --- --- --- --- --- 
Ex. 65 5 --- --- --- --- --- 
Comp. 4 --- .+-..+-..+-. .+-..+-..+-. +++ +++ 
Ex. 3 
Comp. 4 --- --- --- --- --- 
Ex. 4 
______________________________________ 
-: Any chemical injury was not observed. 
.+-.: There was observed slight chemical injury, but any practical problem 
did not arise. 
+: There was observed chemical injury. 
As seen from the results shown in Table 16, seedlings could satisfactorily 
be raised in Examples 62 to 65 and Comparative Example 4 without causing 
any chemical injury. In Comparative Example 3, a growth-inhibitory effect 
was observed shortly after the application of the pesticide and it has 
thus been proved that the seedlings were damaged from the pesticide and 
that the formulation prepared by such a conventional method is not 
favorably used as a substrate for raising seedlings of a paddy rice. 
Moreover, it was also confirmed that good seedlings could satisfactorily 
be raised without being damaged from the pesticide during the raising term 
in Example 65 wherein a different active ingredient was used. 
Paddy Rice Cultivation Test I 
Young seedlings of a paddy rice were raised over 3 weeks according to the 
procedures disclosed in either of Examples 62 to 64 and Comparative 
Example 3 and then the young seedlings were transplanted to and cultivated 
in each Wagner pot of 1/2000a at a rate of three seedlings per pot. The 
cultivation was carried out according to the currently used method except 
that the depth of water upon the transplantation was set at a level of 3 
cm. Regarding the test divisions of Comparative Example 3, the granular 
pesticide K was applied thereto on the 7the day after the transplantation. 
As a result, the observation of the seedlings throughout the cultivation 
term proved that the efficacies of the active ingredients observed in 
Examples 62 to 64 were identical to or superior to that observed in 
Comparative Example 3 and that barnyard millet at its bifoliate period was 
controlled in both Examples 62 to 64 and Comparative Example 3. In 
particular, the seedlings in Example 64 did not require any additional 
manure during the cultivation period. Accordingly, this would considerably 
contribute to the reduction of labor required for application of 
pesticides and/or fertilizers. 
Paddy Rice Cultivation Test II 
Young seedlings of a paddy rice were raised over 3 weeks according to the 
procedures disclosed in either of Example 65 and Comparative Example 4 and 
then cultivation tests were carried out using 30 bundles (3 stocks/bundle) 
selected from 5 among the foregoing nursery boxes. In the tests, the 
transplantation and cultivation were carried out using Wagner pots of 
1/5000a under paddy conditions (depth of water: 3 cm). 
As a result, there was observed irregularity in the efficacy of the 
granular pesticide L in Comparative Example 4 and part of the leaves were 
damaged from the active ingredient of the pesticide L adhered thereto. 
This fact proves that it is difficult to uniformly apply the granular 
pesticide L as a conventional pesticide on the nursery boxes comprising 
seedlings of paddy rice which has grown to some extent and whose leaves 
have grown thick. Both Example 65 and Comparative Example 4 exhibited 
sufficient efficacies and, in particular, Example 65 showed a duration of 
efficacy longer than that observed in Comparative Example 4. 
Test for Confirming Effects Using Cucumber 
A test for raising seedling and cultivation of cucumber (cv. Kinseishiyo 
No. 2; "KURUME GENSHU IKUSEI KAI (Society of Kurume-Foundation Stock 
Growth)") was carried out using the substrates 6 to 10 for raising 
seedlings as substrate for vegetable. The raising seedlings and the 
cultivation thereof were carried out in a glasshouse (Tobata-Ku, 
Kitakyushu-Shi, Fukuoka-Ken, Japan) and the management for raising of 
seedlings and cultivation thereof was carried out according to the methods 
currently used. 
In every test divisions other than the substrate 8 for raising seedlings, 
additional manure was carried out several times during the raising of 
seedlings. The raising seedlings was terminated after 30 days and then the 
seedlings were transplanted to Wagner pots of 1/2000a filled with 
disinfected diluvial volcanic ash soil. The substrate 10 for raising 
seedlings was subjected to the hole treatment according to the currently 
used method using 1 g of kneaded granules containing 2% of an active 
ingredient (pesticide C). The test was carried out four times using 3 
stocks per each test division and each test division was observed and 
examined. The results thus obtained are summarized in the following Table 
17. 
TABLE 17 
______________________________________ 
Examination of 
Plant 
Sample (after 2 weeks) Status After 3 Weeks 
(No. of Length No. of from the Transplantation 
Substrate) (cm) Leaves of Seedlings 
______________________________________ 
Ex. 66 7 19.2 2.5 There was not observed 
any chemical injury; 
there was not observed 
any breeding of aphids. 
Ex. 67 8 21.5 2.5 There was not observed 
any chemical injury; 
there was not observed 
any breeding of aphids. 
Ex. 68 9 22.0 2.5 There was not observed 
any chemical injury; 
there was not observed 
any breeding of aphids. 
Comp. 10 19.5 3.0 There was observed the 
Ex. 5 breeding of aphids. 
Comp. 11 20.8 3.0 There was not observed 
Ex. 6 any chemical injury; 
there was not observed 
any breeding of aphids. 
______________________________________ 
As seen from the results listed in Table 17, the substrates 6 to 8 for 
raising seedlings permitted satisfactory raising and cultivation of 
seedlings without causing any damage from the pesticide throughout the 
cultivation period including that required for raising the seedlings. On 
the other hand, in case of the substrate 9 for raising seedlings, aphids 
came flying immediately after the transplantation and the seedlings 
suffered from disease injury. There were observed dead aphids in the 
vicinity of the stocks transplanted to the substrates 6 to 8 and 10 and 
accordingly, the efficacies of the pesticides would be sufficient in these 
substrates. 
In addition, there was observed a tendency of suffering from micro element 
(iodine)-excess symptom on the seedlings transplanted to the substrate 9. 
This would be caused due to the water-solubility of the micro element, but 
the excess symptom could be ignored from the viewpoint of cultivation. 
The substrates 6 to 8 can eliminate the use of the hole treatment and 
therefore, the transplantation operation of the seedlings required only a 
short period of time. The substrate 10 required a great deal of labor 
since the substrate 10 required the use of the hole treatment and the use 
of this substrate further required additional operations for weighing and 
applying the granular pesticide in addition to the operations required for 
digging holes. 
Effect-Confirmation Test Using Chrysanthemum 
Tests for raising seedlings of chrysanthemum and for cultivating thereof 
were carried out using the substrates 11 and 12 for raising seedlings. The 
chrysanthemum to be tested (cv. Oki No Shiranami) was subjected to 
herbaceous cutting in a cell tray (circular connected tray having an upper 
diameter of 23 mm, a bottom diameter of 18 mm, a depth of 35 mm and a 
volume of 12 ml) and the seedlings were raised under the lighting 
conditions. The raising seedlings and the cultivation thereof were carried 
out in a glasshouse (Tobata-Ku, Kitakyushu-Shi, Fukuoka-Ken, Japan) and 
the management of the raising seedlings and the cultivation thereof were 
performed according to the currently used methods. In every test 
divisions, additional manure was carried out several times during the 
raising seedlings. The raising seedlings was terminated after 2 weeks at 
which the roots of the seedlings had grown to densely fill the substrate 
in the cell and then the seedlings were transplanted to Wagner pots of 
1/2000a filled with disinfected diluvial volcanic ash soil (the pH value 
thereof was adjusted to 6.3). The substrate 13 for raising seedlings was 
subjected to the hole treatment according to the currently used method 
using 2 g of kneaded granules (containing 0.5% by weight of an active 
ingredient of the pesticide C). The cultivation test was carried out four 
times using 3 stocks per each test division and each test division was 
observed and examined. The results thus obtained are summarized in the 
following Table 18. 
TABLE 18 
______________________________________ 
Substrate 
for 
Raising 
Seedling Results Observed after One Week 
No. from the Transplantation 
______________________________________ 
Example 12 There was not observed any damage 
69 from pesticide. Aphids were 
exterminated. 
Comp. 13 
Example There was not observed any damage 
7 frorn pesticide. Aphids were 
exterminated. 
______________________________________ 
As will be clear from the results listed in Table 18, the substrate 11 for 
raising seedlings permitted satisfactory raising and cultivation of 
seedlings without causing any damage from the pesticide through out the 
cultivation period including that required for raising the seedlings. 
There were observed dead aphids in the vicinity of the stocks transplanted 
to the substrates 11 to 12 and accordingly, the efficacies of the 
pesticides would be sufficient in these substrates. The substrate 11 did 
not require the use of the hole treatment and the seedlings were raised in 
a cell tray filled with the substrate 11. Therefore, the transplantation 
operation of a large number of the seedlings required only a short period 
of time and this results in a substantial reduction of labor. The 
substrate 12 required a great deal of labor since the substrate 12 
required the use of the hole treatment and the use of this substrate 
further required additional operations for weighing and applying the 
granular pesticide in addition to the operations required for digging 
holes. 
Effects of the Invention 
As has been explained above in detail, the coated granular pesticide 
according to the present invention can initiate the release of the active 
ingredient of the pesticide after the lapse of a predetermined time, since 
a film of a thermoplastic resin is formed on the surface of a granular 
pesticide which comprises a hardly water-soluble active ingredient and a 
water-swelling substance. More specifically, the following effects can be 
accomplished by the present invention. 
(1) The conventional pesticide comes in contact with the environmental 
water simultaneous with the application thereof and therefore, it 
initiates the release of the active ingredient thereof immediately after 
the application. On the other hand, the coated granular pesticide of the 
present invention permits the inhibition of the release of the hardly 
water-soluble active ingredient of the pesticide over a predetermined 
period of time. 
(2) The conventional coated granular pesticide releases the active 
ingredient of the pesticide through migration of water while making use of 
the permeability of the film instead of making use of the disintegration 
of the film. Accordingly, such conventional technique is not effectively 
applied to pesticides comprising hardly water-soluble active ingredients. 
Contrary to this, the coated granular pesticide of the present invention 
permits the external release of the active ingredient through the 
disintegration of the film due to the co-operated interaction of the water 
permeability of the film and the water-swelling properties of the 
water-swelling substance present in the granular pesticide. For this 
reason, the present invention permits the use of hardly water-soluble 
active ingredients and thus the present invention can make the range of 
choice of usable active ingredients more wider. 
(3) The coated granular pesticide of the present invention permits the 
release of the granular pesticide containing the hardly water-soluble 
active ingredient through the disintegration of the film thereof. 
Therefore, the pesticide does not result in the reduction of the release 
rate as the concentration on the active ingredient in the aqueous solution 
within the film is reduced and the active ingredient does not remain 
within the film over a long time period, unlike the conventional 
controlled release type coated granular pesticides, and the coated 
pesticide of the present invention can completely release the hardly 
water-soluble active ingredient, ensure a high utilization factor and is 
not accompanied by any danger due to residues. Moreover, the present 
invention also permits the reduction of the amount of the hardly 
water-soluble active ingredient to be used. 
(4) The use of a mixture of at least two coated granular pesticides which 
differ in the release-inhibitory period permits the sustained release of 
required active ingredients over a long period of time depending on the 
kinds of field crops. 
(5) The present invention can inhibit the appearance of any peak of the 
released active ingredient and accordingly, can prevent any damage of 
field crops from the pesticide due to temporary excess release of the 
active ingredient. 
(6) The conventional insecticides and/or fungicides must be applied to 
field crops several times during the whole growth period thereof, while if 
the coated granular pesticide mixture of the present invention is used, 
any desired effect can be obtained by a single application thereof to the 
crops and the present invention can thus further reduce labor required for 
farm working. With respect to the paddy rice, in particular, both leaf 
blast and head blast can be controlled by a single application of the 
foregoing mixture. 
(7) In the present invention, it is very easy to control the release rate 
of the active ingredient by appropriately selecting components to be added 
to the film. 
(8) The substrate for raising seedlings according to the present invention 
which can be prepared by admixing the coated granular pesticide, a 
water-holding material and optionally a fertilizer or the like can easily 
be handled, is effective for the reduction of labor required for farm 
working and is quite useful as substrates for raising seedlings of paddy 
rice and substrates for raising seedlings used for other agricultural 
and/or horticultural purposes.