U.S. patent application number 10/508162 was filed with the patent office on 2005-11-10 for granular agricultura-chemical composition.
Invention is credited to Kurita, Kazunori, Ohkawa, Tetsuo, Ozaki, Eisuke.
Application Number | 20050250648 10/508162 |
Document ID | / |
Family ID | 28671857 |
Filed Date | 2005-11-10 |
United States Patent
Application |
20050250648 |
Kind Code |
A1 |
Ozaki, Eisuke ; et
al. |
November 10, 2005 |
Granular agricultura-chemical composition
Abstract
Provided is a granular agrochemical composition by which the
problems accompanying the prior art granular agrochemical
compositions can be overcome, which can be prepared in a simple
formulation and by which sustained releasability of the
agrochemically active ingredient is obtained so that the load on
the environments can be decreased and the chemical damages caused
by the agrochemically active ingredient can be alleviated or
prevented. The granular agrochemical composition contains an acidic
agrochemically active ingredient, a cationic surfactant and a basic
substance. Inter alia, a pH of 5 or higher is obtained in a 1% by
mass aqueous suspension thereof. Preferably, the acidic
agrochemically active ingredient should have a pKa of 2 to 7 and
the cationic surfactant should be one which is gelled or exhibits
swellability in water.
Inventors: |
Ozaki, Eisuke; (Tokyo,
JP) ; Kurita, Kazunori; (Tokyo, JP) ; Ohkawa,
Tetsuo; (Tokyo, JP) |
Correspondence
Address: |
WENDEROTH, LIND & PONACK, L.L.P.
2033 K STREET N. W.
SUITE 800
WASHINGTON
DC
20006-1021
US
|
Family ID: |
28671857 |
Appl. No.: |
10/508162 |
Filed: |
September 17, 2004 |
PCT Filed: |
March 24, 2003 |
PCT NO: |
PCT/JP03/03542 |
Current U.S.
Class: |
504/239 ;
504/367 |
Current CPC
Class: |
A01N 47/36 20130101;
A01N 2300/00 20130101; A01N 25/30 20130101; A01N 25/14 20130101;
A01N 2300/00 20130101; A01N 25/12 20130101; A01N 25/30 20130101;
A01N 2300/00 20130101; A01N 25/14 20130101; A01N 43/54 20130101;
A01N 43/54 20130101; A01N 25/30 20130101; A01N 25/32 20130101; A01N
25/12 20130101; A01N 43/54 20130101 |
Class at
Publication: |
504/239 ;
504/367 |
International
Class: |
A01N 043/54; A01N
025/12 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 29, 2002 |
JP |
2002-97125 |
Claims
1. A granular agrochemical composition containing an acidic
agrochemically active ingredient, a cationic surface-active agent
and a basic substance.
2. The granular agrochemical composition described in claim 1,
wherein the acidic agrochemically active ingredient has a pKa of 2
to 7.
3. The granular agrochemical composition described in claim l,
wherein the cationic surface-active agent causes gelation or shows
swelling in water.
4. The granular agrochemical composition described in claim 1,
wherein the acidic agrochemically active ingredient is a
herbicide.
5. The granular agrochemical composition described in claim 4,
wherein the herbicide is a sulfonylurea-based compound.
6. The granular agrochemical composition described in claim 4,
wherein the herbicide is a difluoromethane-sulfonylanilide
derivative or a salt thereof expressed by the general formula
3(R.sup.1 in the formula is a hydrogen atom, alkyl group or
alkoxyalkyl group).
7. The granular agrochemical composition described in claim 1,
wherein a 1% by mass aqueous suspension thereof has a pH of 5 or
higher.
8. The granular agrochemical composition described in claim 1,
wherein a 1% by mass aqueous suspension thereof has a pH which is
equal to or higher than the pKa value of the agrochemically active
ingredient.
9. A mixed granular agrochemical composition which is a blend of
the granular agrochemical composition described in claim 1 and
agrochemical granules without containing either one or both of the
cationic surface active agent and the basic substance in a mass
proportion of from 1:9 to 9:1.
Description
TECHNICAL FIELD
[0001] The invention relates to a granular agrochemical composition
capable of alleviating or preventing chemical damages and
decreasing environmental load along with capability of exhibiting
efficacy over a long duration.
BACKGROUND ART
[0002] Conventionally, to alleviate chemical damages of granular
agrochemical compositions containing agrochemically active
ingredients and to retain the effectiveness, various methods for
formulation capable of controlling dissolution of the
agrochemically active ingredients have been studied. There have
been proposed many methods including, for example, methods
imparting sustained releasability by the addition of a paraffin
wax, activated carbon, foamed granules and clay type minerals in
combination (Japanese Patent Application Laid-Open Nos. 63-35504,
63-45201 and 2-288803), methods of blending dymron to alleviate
chemical damages of sulfonylurea-based compounds (Japanese Patent
Application Laid-Open Nos. 62-161702 and 3-72407).
[0003] However, such prior art methods for imparting sustained
releasability are not necessarily effective and there are problems
that the preparation methods of the granular agrochemical
compositions are complicated: and that a large portion of the
agrochemically active ingredient remained unutilized effectively in
the granular agrochemical composition due to insufficient release
of the agrochemical composition. In the case of the methods of
adding other agrochemically active ingredients such as dymron for
alleviate chemical damages of a certain agrochemically active
ingredient, there is a problem that agrochemically active
ingredients are released more than needed to the environments,
resulting in an increase in the load on the environments.
DISCLOSURE OF THE INVENTION
[0004] Under these circumstances, the invention has an object to
overcome the problems of conventional granular agrochemical
compositions and to provide a granular agrochemical composition
which can be prepared in a simple formulation, capable of showing
the efficacy of the agrochemically active ingredients over a long
time, decreasing the environmental load, and alleviating or
preventing chemical damages caused by the agrochemically active
ingredients.
[0005] The inventors have conducted extensive investigations on a
granular agrochemical composition, as a result, to find that the
above-mentioned problems can be solved by obtaining a composition
by compounding an acidic agrochemically active ingredient with a
cationic surfactant and a basic substance and have accomplished the
invention based on this finding.
[0006] That is, the invention provides the following compositions
including:
[0007] (1) a granular agrochemical composition characterized by
containing an acidic agrochemically active ingredient, a cationic
surfactant and a basic substance;
[0008] (2) a granular agrochemical composition described in (1)
above, wherein the acidic agrochemically active ingredient has a
pKa in the range of 2 to 7;
[0009] (3) a granular agrochemical composition described in (1) or
(2) above, wherein the cationic surfactant causes gelation or shows
swelling in water;
[0010] (4) a granular agrochemical composition described in either
one of (1), (2) or (3) above, wherein the acidic agrochemically
active ingredient is a herbicide;
[0011] (5) a granular agrochemical composition described in (4)
above, wherein the herbicide is a sulfonylurea-based compound;
[0012] (6) a granular agrochemical composition described in (4)
above, wherein the herbicide is a difluoromethanesulfonylanilide
derivative or a salt thereof expressed by the general formula (I):
1
[0013] (wherein R.sup.1 is a hydrogen atom, alkyl group or
alkoxyalkyl group);
[0014] (7) a granular agrochemical composition described in either
one of (1) to (6) above, wherein a 1% by mass aqueous suspension
thereof has a pH 5 or higher;
[0015] (8) a granular agrochemical composition described in either
one of (1) to (7) above, wherein a 1% by mass aqueous suspension
thereof has a pH which is equal to or higher than the pKa value of
the agrochemically active ingredient; and
[0016] (9) a mixed granular agrochemical composition which is a
blend of the granular agrochemical composition described in either
one of the descriptions (1) to (8) above and agrochemical granules
without containing either one or both of the cationic surfactant
and the basic substance in a ratio of from 1:9 to 9:1 by mass.
BEST MODE FOR CARRYING OUT THE INVENTION
[0017] The type of an acidic agrochemically active ingredient to be
used for the granular agrochemical composition of the invention is
not particularly limited, however, it is generally a herbicide, a
plant growth regulator, a fungicide, or an insecticide and
specially, those having a pKa in the range of 2 to 7 are preferable
and geometrical isomers and optical isomers are also included.
[0018] The herbicide is not particularly limited and those having a
pKa in the range of 2 to 7 are preferable and especially, those
comprising mainly sulfonylurea-based compounds, or
difluoromethanesulfonylanilide derivatives expressed by the general
formula (I): 2
[0019] (wherein R.sup.1 is a hydrogen atom, alkyl group or
alkoxyalkyl group);
[0020] or salts thereof are further preferable.
[0021] Examples of the sulfonylurea-based compound include
1-(4,6-dimethoxypyrimidin-2-yl)-3-[1-methyl-4-(2-methyl-2H-tetrazol-5-yl)-
pyrazol-5-ylsulfonyl]urea (Azimsulfuron),
1-(2-chloroimidazo[1,2-a]pyridin-
-3-ylsulfonyl)-3-(4,6-dimethoxypyrimidin-2-yl)urea (imazosulfuron),
ethyl
5-(4,6-dimethoxypyrimidin-2-ylcarbamoylsulfamoyl)-1-methylpyrazole-4-carb-
oxylate (pyrazosulfuron-ethyl), methyl
.alpha.-(4,6-dimethoxypyrimidin-2-y- lcarbamoylsulfamoyl)-o-toluate
(bensulfuron-methyl),
1-(4,6-dimethoxypyrimidin-2-yl)-3-(2-ethoxyphenoxysulfonyl)urea
(ethoxysulfuron),
1-[2-(cyclopropylcarbonyl)anilinesulfonyl]-3-(4,6-dimet-
hoxypyrimidin-2-yl)urea (cyclosulfamuron),
1-(4,6-dimethoxy-1,3,5-triazin--
2-yl)-3-[2-(2-methoxyethoxy)phenylsulfonyl]urea (cinosulfuron),
methyl
3-(4-methoxy-6-methyl-1,3,5-triazin-2-ylcarbamoylsulfamoyl)-2-thenoate
(thifensulfuron-methyl),
2-(4,6-dimethoxypyrimidin-2-ylcarbamoylsulfamoyl-
)-N,N-dimethylnicotinamide (nicosulfron), methyl
3-chloro-5-(4,6-dimethoxy-
pyrimidin-2-ylcarbamoylsulfamoyl)-1-methylpyrazole-4-carboxylate
(halosulfuron-methyl),
1-(4,6-dimethoxypyrimidin-2-yl)-3-(3-trifluorometh-
yl-2-pyridylsulfonyl)urea (flazasulfuron) and
1-(4,6-dimethoxypyrimidin-2--
yl)-3-(3-ethylsulfony1-2-pyridylsulfonyl)urea (rimsulfuron).
[0022] Examples of the difluoromethanesulfonylanilide derivatives
and salts thereof include compounds described in Japanese Patent
Application Laid-Open No. 2000-44546, such as
2-[(4,6-dimethoxypyrimidin-2-yl)hydroxy-
methyl]-N-difluoromethanesulfonylanilide,
2-[(4,6-dimethoxypyrimidin-2-yl)-
hydroxymethyl]-6-methoxymethyl-N-difuloromethanesulfonylanilide and
2-[(4,6-dimethoxypyrimidin-2-yl)hydroxymethyl]-6-ethyl
-N-difuloromethanesulfonylanilide.
[0023] Examples of other herbicides include S-ethyl
2-methyl-4-chlrophenoxythioacetate (phenothiol),
.alpha.-2-naphthoxypropi- onanilide (naproanilide), methyl
5-(2,4-dichlorophenoxy)-2-nitrobenzoate (bifenox),
S-(4-chlorobenzyl)-N,N-diethylthiocarbamate (benthiocarb), S-benzyl
1,2-dimethylpropyl(ethyl)thiocarbamate (esprocarb), S-ethyl
hexahydro-1H-azepine-1-carbothioate (molinate),
S-1-methyl-1-phenylethyl piperidine-1-carbothioate (dimepiperate),
0-3-tert-butylphenyl 6-methoxy-2-pyridyl(methyl)thiocarbamate
(pyributicarb),
2-chloro-2',6'-diethyl-N-(2-butoxymethyl)acetanilide (butachlor),
2-chloro-2',6'-diethyl-N-(2-propoxyethyl)acetanilide
(pretilachlor),
(RS)-2-bromo-N-(.alpha.,.alpha.-dimethylbenzyl)-3,3-dimethylbutylamide
(bromobutide), 2-benzothiazol-2-yloxy-N-methylacetanilide
(mefenacet), 1-(.alpha.,.alpha.-dimethylbenzyl)-3-(p-tolyl)urea
(dymron), 2-methylthio-4,6-bis(ethylamino)-s-triazine (simetryn),
2-methylthio-4,6-bis(isopropylamino)-s-triazine (prometryn),
2-methylthio-4-ethylamino-6-(1,2-dimethylpropylamino)-s-triazine
(dimethametryn), 2,4-dichlorophenyl-3'-methoxy-4'-nitrophenyl ether
(chlometoxyfen),
5-tert-butyl-3-(2,4-dichloro-5-isopropoxyphenyl)-1,3,4-o-
xadiazol-2(3H)-one (oxadiazon),
4-(2,4-dichlorobenzoyl)-1,3-dimethyl-5-pyr-
azolyl-p-toluenesulfonate (pyrazolynate),
2-[4-(2,4-dichlorobenzoyl)-1,3-d-
imethylpyrazol-5-yloxy]acetophenone (pyrazoxyfen),
(RS)-2-(2,4-dichloro-m-- tolyloxy)propionanilide (clomeprop),
2-[4-(2,4-dichloro-m-toluoyl)-1,3-dim-
ethylpyrazol-5-yloxy]-4'-methylacetophenone (benzofenap),
S,S'-dimethyl
2-difluoromethyl-4-isobutyl-6-trifluoromethylpyridine-3,5-dicarbothioate
(dithiopyr),
2-chloro-N-(3-methoxy-2-thenyl)-2',6'-dimethylacetanilide
(thenylchlor), butyl
(R)-2-[4-(4-cyano-2-fluorophenoxy)-phenoxy]propionat- e
(cyhalofop-butyl),
3-[1-(3,5-dichlorophenyl)-1-methylethyl]-2,3-dihydro--
6-methyl-5-phenyl-4H-1,3-oxazin-4-one (oxadichlomefon),
3-(4-chloro-5-cyclopentyloxy-2-fluorophenyl)-5-isopropylidene-1,3-oxazoli-
dine-2,4-dione (pentoxazone),
1-(diethylcarbamoyl)-3-(2,4,6-trimethylpheny-
lsulfonyl)-1,2,4-triazole (cafenstrole) and methyl
2-[(4,6-dimethoxypyrimi-
din-2-yl)oxy]-6-[(E)-1-(methoxyimino)ethyl]benzoate
(pyriminobac-methyl).
[0024] The plant growth regulator is not particularly limited and
examples thereof include
4'-chloro-2'-(.alpha.-hydroxybenzyl)isonicotinanilide (inabenfide),
(2RS,3RS)-1-(4-chlorophenyl)-4,4-dimethyl-2-(1H-1,2,4-triaz-
ol-1-yl)-pentan-3-ol (paclobutrazol),
(E)-(S)-1-(4-chlorophenyl)-4,4-dimet-
hyl-2-(1H-1,2,4-triazol-1-yl)pent-1-en-3-ol (uniconazole), calcium
3-oxido-5-oxo-4-propionylcyclohexa-3-enecarboxylate
(prohexadione-calcium) and choline salt of maleic hydrazide. Among
these, those having a pKa in the range of 2 to 7 are preferably
used.
[0025] The fungicide is not particularly limited and examples
thereof include O,O-diisopropyl s-benzyl thiophosphate
(iprobenfos), 3'-isopropoxy-2-methylbenzanilide (mepronil),
.alpha.,.alpha.,.alpha.-tri- fluoro-3'-isopropoxy-O-toluanilide
(fultolanil), 3,4,5,6-tetrachloro-N-(2,-
3-dichlorophenyl)-phthalamic acid (tecloftalam),
1-(4-chlorobenzyl)-1-cycl- opentyl-3-phenylurea (pencycuron),
6-(3,5-dichloro-4-methylphenyl)-3(2H)-p- yridazinone (diclomezine),
methyl N-(2-methoxyacetyl)-N-(2,6-xylyl)-DL-ala- ninate
(metalaxyl),
(E)-4-chloro-.alpha.,.alpha.,.alpha.-trifluoro-N-(1-im-
idazol-1-yl-2-propoxyethylidene)-o-toluidine (trifulmizole),
kasugamycin, validamycin, 3-allyloxy-1,2-benzoisothiazole
1,1-dioxide (probenazole), diisopropyl
1,3-dithiolan-2-ylidenemalonate (isoprothiolane),
5-methyl-1,2,4-triazolo[3,4-b]benzothiazole (tricyclazole),
1,2,5,6-tetrahydropyroro[3,2,1-ij]quinolin-4-one (pyroquilon),
5-ethyl-5,8-dihydro-8-oxo[1,3]dioxolo[4,5-g]quinoline-7-carboxylic
acid (oxolinic acid), (Z)-2'-methylacetophenone
4,6-dimethylpyrimidin-2-ylhydr- azone-4,5,6,7-tetrachlorophtalide
(ferimzone) and 3-(3,5-dichlorophenyl)-N-
-isopropyl-2,4-dioxoimidazolidine-1-carboxamide (iprodione). Among
these, those having a pKa in the range of 2 to 7 are preferably
used.
[0026] The insecticide is not particularly limited and examples
thereof include O,O-dimethyl
O-(3-methyl-4-nitrophenyl)thiophosphate (MEP),
(2-isopropyl-4-methylpyrimidin-6-yl)-diethylthiophosphate
(diazinon), 1-naphthyl N-methylcarbamate (carbaryl), O,O-diethyl
O-(3-oxo-2-phenyl-2H-pyridazin-6-yl) phosphorothioate
(pyridaphenthion), O,O-dimethyl 0-3,5,6-trichloro-2-pyridyl
phosphorothioate (chlorpyrifos-methyl), dimethyl dicarbethoxyethyl
dithiophosphate (malathion), O,O-dimethyl
S-(N-methylcarbamoylmethyl) dithiophosphate (dimethoate),
O,O-dipropyl O-4-methylthiophenyl phosphate (propaphos),
O,S-dimethyl N-acetylphosphoroamidothioate (acephate), ethyl
p-nitrophenyl thionobenzenephosphonate (EPN), 2-sec-butylphenyl
N-methylcarbamate (BPMC),
2,3-dihydro-2,2-dimethyl-7-benzo[b]furanyl
N-dibutylaminothio-N-methylcarbamate (carbosulfan), ethyl
N-[2,3-dihydro-2,2-dimethylbenzofuran-7-yloxycarbonyl(methyl)aminothio]-N-
-isopropyl-.beta.-alaninate (benfuracarb),
(RS)-.alpha.-cyano-3-phenoxyben- zyl
(RS)-2,2-dichloro-1-(4-ethoxyphenyl) cyclopropanecarboxylate
(cycloprothrin), 2-(4-ethoxyphenyl)-2-methylpropyl 3-phenoxybenzyl
ether (etofenprox),
1,3-bis(carbamoylthio)-2-(N,N-dimethylamino)propane hydrochloride
(cartap), 5-dimethylamino-1,2,3-trithiane hydrogen oxalate
(thiocyclam), S,S'-2-dimethylaminotrimethylene
di(benzenthiosulfonate) (bensultap) and
2-tert-butylimino-3-isopropyl-5-phenyl-1,3,5,6-tetrahydro-
-2H-1,3,5-thiadiazin-4-one (buprofezin). Among these, those having
a pKa in the range of 2 to 7 are preferably used.
[0027] In the case of using the above-described acidic
agrochemically active ingredient having the prescribed pKa, the pKa
of the ingredient can be measured by, for example, a method
described in "Jikken Kagaku Koza 5, (Thermal measurement and
Equilibrium)", Maruzene, p. 469-474, Jan. 20 (1958) and the
like.
[0028] The cationic surfactant to be used in the invention is not
particularly limited and can be exemplified preferably by those of
amine salt type, pyridinium salt type and quaternary ammonium salt
type.
[0029] Examples of the amine salt type cationic surfactants include
laurylamine hydrochloride, stearylamine hydrochloride, oleylamine
acetate, stearylamine acetate and stearylaminopropylamine
acetate.
[0030] Examples of the pyridinium salt type cationic surfactants
include laurylpyridinium chloride, myristylpyridinium chloride and
cetylpyridinium chloride.
[0031] Examples of the quaternary ammonium salt type cationic
surfactants include alkyldimethylbenzylammonium chloride,
lauryltrimethylammonium chloride, cetyltrimethylammonium chloride,
stearyltrimethylammonium chloride, dilauryldimethylammonium
chloride, dioleyldimethylammonium chloride,
dicocoyldimethylammonium chloride, distearyldimethylammonium
chloride, lauryldi(hydroxyethyl)methylammonium chloride,
oleylbis(polyoxyethylene)methylammonium chloride,
stearylhydroxyethyldime- thylammonium chloride,
lauryldimethylbenzylammonium chloride,
lauroylaminopropyldimethylethylammonium ethosulfate, and
lauroylaminopropyldimethylhydroxyethylammonium perchlorate.
[0032] Those particularly preferable as the cationic surfactant are
compounds which are gelled or exhibit swellability in water such as
dialkyldimethylammonium chloride, the alkyl part of which is
C.sub.8 to C.sub.22, particularly, dilauryldimethylammonium
chloride, dioleyldimethylammonium chloride,
dicocoyldimethylammonium chloride and distearyldimethylammonium
chloride. These surfactants may be used either singly or in
combination of two kinds or more.
[0033] The basic substance to be used in the invention is not
particularly limited, however preferable are those having a pH 7.5
or higher or, more preferably 9 to 12, in the case that they are in
the form of 1% by mass aqueous solution or 1% by mass aqueous
suspension. Examples of the basic substances include hydroxides of
alkali metals and alkaline earth metals, alkali metal salts,
alkaline earth metal salts, and chemical substances and minerals
containing them and more particular examples include sodium
hydroxide, potassium hydroxide, sodium hydrogen carbonate, sodium
carbonate, calcium hydroxide, calcium carbonate, calcium oxide,
basic fumed silica and basic acid clay. These basic substances may
be used either singly or in combination of two kinds or more.
[0034] The granular agrochemical composition of the invention may
contain additive components used usually in agrochemical
preparations, based on the necessity. As the additive components,
an extender or an auxiliary component may be used.
[0035] As the extender, a solid carrier such as a mineral carrier
and a water-soluble salt may be used and particular examples
thereof include clays, calcium carbonate, bentonite, talc,
diatomaceous earth, acid clay, silica sand, granulated calcium
carbonate, calcium stearate, fumed silica, potassium chloride,
sodium sulfate anhydride, potassium sulfate, urea, ammonium sulfate
and the like. These may be used either singly or in combination of
two kinds or more.
[0036] As the auxiliary component, for example, a binder for
preparing the granular composition may be included and particular
examples include carboxymethyl cellulose sodium salt, dextrin,
water-soluble starch, xanthan gum, guar gum, sucrose,
poly(vinylpyrrolidone), poly(vinyl alcohol), poly(sodium acrylate),
polyethylene glycol having an average molecular weight of 6,000 to
20,000 and polyethylene oxide having an average molecular weight of
100,000 to 5,000,000. Particular examples of the organic solvent to
be used at the time of dissolving the acidic agrochemically active
ingredient and the cationic surfactant and adsorption thereof on a
carrier include alkylnaphthalenes, dimethylformamide, dimethyl
sulfoxide, N-methyl-2-pyrrolidone, N-octylpyrrolidone and various
polyhydric alcohols. Besides, according to need, stabilizers,
inorganic hollow granules, plastic hollow granules and plant
segments may be used. These may be used either singly or as a
combination of two kinds or more.
[0037] The composition ratios of the respective components of the
agrochemical granular composition of the invention are selected in
the ranges, usually, as an acidic agrochemically active ingredient
0.01 to 50% by mass, a cationic surfactant 0.1 to 20% by mass and a
basic substance 0.1 to 95% by mass and when the total amount of the
foregoing three components does not reach 100%, the balance is an
optional additive component. The composition ratios of the
respective components are selected so that a pH of a 1% by mass
aqueous suspension of the granular agrochemical composition is
adjusted to 5 or higher, preferably, 7 or higher or, further
preferably, 7.5 to 11.5 and especially that a pH of a 1% by mass
aqueous suspension of the granular agrochemical composition
indicates a value higher than the pKa of the agrochemically active
ingredient or, particularly, in the range larger than the pKa value
by 2 to 6.
[0038] In the case that the extender and auxiliary agents are
contained, the contents in the total amount of the composition are
generally selected in the ranges of 5 to 95% by mass for the
extender and 0.1 to 30% by mass for the auxiliary agents.
[0039] The granular agrochemical composition of the invention is
preferably to be a granular material having a particle diameter of
0.01 to 5 mm or, more preferably, 0.1 to 3 mm or having a diameter
of 0.1 to 10 mm or, more preferably, 0.5 to 7 mm and a length of
0.3 to 30 mm or, more preferably, 1.5 to 20 mm.
[0040] While the granular agrochemical composition of the invention
may be a type (a disintegration type) that granules are
disintegrated and lose the master blend of granules by division or
dispersion or may be a type (a non-disintegration type) that the
granules are not disintegrated and keep granular master blend of
granules, after treatment in a field, the non-disintegration type
is preferable and especially the non-disintegration type which keep
the master blend of granules, in which disintegration of the
granules are not found or scarcely found even after 15 to 30
minutes from addition in water, is preferable.
[0041] Further, the non-disintegration type granular agrochemical
composition of the invention can be added to disintegration type
floating-in-water granules dispersing on water surface to obtain a
saved agrochemical preparation having sustained releasability of
dissolution of the agrochemically active ingredients.
[0042] The invention also includes a mixed granular agrochemical
composition which is a blend of the above-mentioned granular
agrochemical composition and agrochemical granules without
containing either one or both of the cationic surfactant and the
basic substance in a mass proportion of from 1:9 to 9:1.
[0043] A method for the preparation of the granular agrochemical
composition of the invention is not particularly limited although,
usually, the following methods may be employed:
[0044] a method including steps of adding a suitable amount of
water to a mixture of all of base materials, kneading the mixture,
successively carrying out granulation by extruding the mixture
through a screen having an opening of a specified size, and drying
the granules;
[0045] a method including steps of either dissolving an acidic
agrochemically active ingredient and a cationic surfactant in an
organic solvent and subjecting the mixture to be adsorbed on a
basic carrier, or dissolving an acidic agrochemically active
ingredient and a cationic surfactant in an organic solvent,
subjecting the mixture adsorbed on a carrier and then subjecting
same to be coated or adsorbed with a basic substance and, according
to need, an agrochemically active ingredient having no sustained
releasability; and
[0046] a method including steps of mixing the granular agrochemical
composition having sustained releasability obtained by the
above-mentioned methods, an agrochemically active ingredient having
no sustained releasability and auxiliary agents, kneading the
mixture after addition of a suitable amount of water, carrying out
granulation by extruding the mixture through a screen having mesh
opening diameter larger than the particle diameter of the granules
of the agrochemical composition having sustained releasability and
drying the granules.
[0047] Hereinafter, the invention will be described in details with
reference to Examples and Test Examples but the invention should
not be limited to these Examples. Additionally, the term of parts
in the respective Examples refers to parts by mass.
[0048] Each of the basic substances in Examples was used as a 1% by
mass aqueous solution or 1% by mass aqueous suspension having a pH
of 7.5 or higher.
[0049] Each of the cationic surfactants used in Examples 1, 3, 5 to
8, 10 and 12 to 25 caused gelation in water.
EXAMPLE 1
[0050] A 0.5 part portion of bensulfuron-methyl (pKa 5.03) and 5
parts of calcium carbonate were uniformly blended and crushed with
a hammer mill. Together with the powder thus obtained, 2 parts of
distearyldimethylammonium chloride, 3 parts of .alpha. starch and
89.5 parts of clay were uniformly blended in a high speed agitator
and kneaded with addition of a suitable amount of water followed by
extrusion by using a basket-type granulator through a screen of 1.2
mm mesh opening and the granulated material was dried by standing
at 60.degree. C. to obtain a granular agrochemical composition
having a diameter of 1.1 to 1.3 mm and a length of 3 to 7 mm and
containing 0.5% by mass of bensulfuron-methyl (pH of a 1% by mass
aqueous suspension 8.28). The granular agrochemical composition
thus obtained was put into water and observed after 30 minutes for
the disintegrability of the granules to obtain a result that it was
of a non-disintegration type.
EXAMPLE 2
[0051] A 0.5 part portion of pyrazosulfuron-ethyl (pKa 3.91), 10
parts of clay and 0.2 part of sodium hydroxide were uniformly
blended and crushed with a hammer mill. Together with the powder
thus obtained, 2 parts of laurylamine hydrochloride, 5 parts of
polyvinyl alcohol, 10.0 parts of sodium bentonite and 72.3 parts of
clay were uniformly blended in a high speed agitator and kneaded
with addition of a suitable amount of water followed by extrusion
by using a basket-type granulator through a screen of 1.2 mm mesh
opening and the granulated material was dried by standing at
60.degree. C. to obtain a granular agrochemical composition having
a diameter of 1.1 to 1.3 mm and a length of 3 to 7 mm and
containing 0.5% by mass of pyrazosulfuron-ethyl (pH of a 1% by mass
aqueous suspension 10.51). The granular agrochemical composition
thus obtained was put into water and observed after 30 minutes for
the disintegrability of the granules to obtain a result that it was
of a non-disintegration type.
EXAMPLE 3
[0052] A 0.5 part portion of the compound of the general formula
(I) in which R.sup.1 was a methoxymethyl group (hereinafter,
referred to as Compound A, pKa 5.75), 2 parts of
distearyldimethylammonium chloride, 3 parts of .alpha. starch and
94.5 parts of calcium carbonate were uniformly blended in a high
speed agitator and kneaded with addition of a suitable amount of
water followed by extrusion by using a basket-type granulator
through a screen of 1.2 mm mesh opening and the granulated material
was dried by standing at 60.degree. C. to obtain a granular
agrochemical composition having a diameter of 1.1 to 1.3 mm and a
length of 3 to 7 mm and containing 0.5% by mass of Compound A (pH
of a 1% by mass aqueous suspension 9.08). The granular agrochemical
composition thus obtained was put into water and observed after 30
minutes for the disintegrability of the granules to obtain a result
that it was of a non-disintegration type.
EXAMPLE 4
[0053] A 0.3 part portion of bensulfuron-methyl (pKa 5.03), 0.06
part of azimsulfuron (pKa 3.60), 5 parts of
stearyltrimethylammonium chloride, 5 parts of basic fumed silica, 2
parts of sodium polyacrylate and 87.64 parts of clay were uniformly
blended in a high speed agitator and kneaded with addition of a
suitable amount of water followed by extrusion by using a
basket-type granulator through a screen of 1.2 mm mesh opening and
the granulated material was dried by standing at 60.degree. C. to
obtain a granular agrochemical composition having a diameter of 1.1
to 1.3 mm and a length of 3 to 7 mm and containing 0.3% by mass of
bensulfuron-methyl and 0.06% by mass of azimsulfuron (pH of a 1% by
mass aqueous suspension 10.28). The granular agrochemical
composition thus obtained was put into water and observed after 30
minutes for the disintegrability of the granules to obtain a result
that it was of a non-disintegration type.
EXAMPLE 5
[0054] A 0.5 part portion of Compound A (pKa 5.75), 3 parts of
.alpha. starch and 96.5 parts of calcium carbonate were uniformly
blended in a high speed agitator and kneaded with addition of a
suitable amount of water followed by extrusion by using a
basket-type granulator through a screen of 1.2 mm mesh opening and
the granulated material was dried by standing at 60.degree. C. to
obtain a granular agrochemical composition containing 0.5% by mass
of Compound A. A 20 parts portion of the granular agrochemical
composition and 80 parts of the granular agrochemical composition
containing 0.5% by mass of Compound A in Example 3 were blended by
a blender to obtain a mixed granular agrochemical composition
having a diameter of 1.1 to 1.3 mm and a length of 3 to 7 mm and
containing 0.5% by mass of Compound A (pH of a 1% by mass aqueous
suspension 8.44). The granular agrochemical composition thus
obtained was put into water and observed after 30 minutes for the
disintegrability of the granules to obtain a result that it was of
a non-disintegration type.
EXAMPLE 6
[0055] A 0.5 part portion of Compound A (pKa 5.75), 3 parts of
.alpha. starch and 96.5 parts of calcium carbonate were uniformly
blended in a high speed agitator and kneaded with addition of a
suitable amount of water followed by extrusion by using a
basket-type granulator through a screen of 1.2 mm mesh opening and
the granulated material was dried by standing at 60.degree. C. to
obtain a granular agrochemical composition containing 0.5% by mass
of Compound A. A 50 parts portion of the granular agrochemical
composition and 50 parts of the granular agrochemical composition
containing 0.5% by mass of Compound A in Example 3 were blended by
a blender to obtain a mixed granular agrochemical composition
having a diameter of 1.1 to 1.3 mm and a length of 3 to 7 mm and
containing 0.5% by mass of Compound A (pH of a 1% by mass aqueous
suspension 8.90). The granular agrochemical composition thus
obtained was put into water and observed after 30 minutes for the
disintegrability of the granules to obtain a result that it was of
a non-disintegration type.
EXAMPLE 7
[0056] A 0.5 part portion of Compound A (pKa 5.75), 3 parts of
.alpha. starch and 96.5 parts of calcium carbonate were uniformly
blended in a high speed agitator and kneaded with addition of a
suitable amount of water followed by extrusion by using a
basket-type granulator through a screen of 1.2 mm mesh opening and
the granulated material was dried by standing at 60.degree. C. to
obtain a granular agrochemical composition containing 0.5% by mass
of Compound A. A 80 parts portion of the granular agrochemical
composition and 20 parts of the granular agrochemical composition
containing 0.5% by mass of Compound A in Example 3 were blended by
a blender to obtain a mixed granular agrochemical composition
having a diameter of 1.1 to 1.3 mm and a length of 3 to 7 mm and
containing 0.5% by mass of Compound A (pH of a 1% by mass aqueous
suspension 9.06). The granular agrochemical composition thus
obtained was put into water and observed after 30 minutes for the
disintegrability of the granules to obtain a result that it was of
a non-disintegration type.
EXAMPLE 8
[0057] A 0.5 part portion of the compound of the general formula
(I) in which R.sup.1 was a ethyl group (hereinafter, referred to as
Compound B, pKa 6.17), 5 parts of dilauryldimethylammonium
chloride, 5 parts of basic fumed silica, 2 parts of sodium
polyacrylate and 87.5 parts of clay were uniformly blended in a
high speed agitator and kneaded with addition of a suitable amount
of water followed by extrusion by using a basket-type granulator
through a screen of 1.2 mm mesh opening and the granulated material
was dried by standing at 60.degree. C. to obtain a granular
agrochemical composition having a diameter of 1.1 to 1.3 mm and a
length of 3 to 7 mm and containing 0.5% by mass of Compound B (pH
of a 1% by mass aqueous suspension 10.41). The granular
agrochemical composition thus obtained was put into water and
observed after 30 minutes for the disintegrability of the granules
to obtain a result that it was of a non-disintegration type.
EXAMPLE 9
[0058] A 0.5 part portion of bensulfuron-methyl (pKa 5.03), 10
parts of cetylpyridinium chloride and 8 parts of
N-methyl-2-pyrrolidone were blended to obtain a bensulfuron-methyl
solution. The bensulfuron-methyl solution prepared as above was
added on 81.5 parts of basic acid clay, which had a particle size
of 16 to 35 mesh (1000 to 425 .mu.m) and gave a 1% by mass aqueous
suspension having a pH of 7 to 10, to be adsorbed thereon for
granulation to give granules of the agrochemical composition having
a particle diameter of 0.4 to 1.1 mm and containing 0.5% by mass of
bensulfuron-methyl (pH of a 1% by mass aqueous suspension 7.69).
The granulated agrochemical composition thus obtained was put into
water and observed after 30 minutes for the disintegrability of the
granules to obtain a result that it was of a non-disintegration
type.
EXAMPLE 10
[0059] A 3 parts portion of polyvinyl alcohol and 85.5 parts of
calcium carbonate were uniformly blended in a high speed agitator
and kneaded with addition of a suitable amount of water followed by
extrusion by using a basket-type granulator through a screen of 1.2
mm mesh opening and the granulated material was dried by standing
at 60.degree. C. to obtain a base. Separately, 2 parts of
fentrazamide and 2 parts of basic fumed silica were uniformly
blended and crushed with a hammer mill to obtain
fentrazamide-containing powder. A 0.5 part portion of Compound A
(pKa 5.75), 2.0 parts of dilauryldimethylammonium chloride and 5
parts of tributyl phosphate were blended to obtain a Compound A
solution. The base prepared as above was added to the Compound A
solution to be adsorbed thereon for granulation and coated with the
fentrazamide-containing powder to give granules of the agrochemical
composition having a particle diameter of 1.1 to 1.3 mm and a
length of 3 to 7 mm and containing 2% by mass of fentrazamide (pH
of a 1% by mass aqueous suspension 9.45). The granular agrochemical
composition thus obtained was put into water and observed after 30
minutes for the disintegrability of the granules to obtain a result
that it was of a non-disintegration type.
EXAMPLE 11
[0060] A 2.5 parts portion of pentoxazone and 2 parts of calcium
carbonate were uniformly blended and crushed with a hammer mill to
obtain pentoxazone-containing powder. A 0.5 part portion of
imazosulfuron (pKa 4.00), 5 parts of cetyltrimethylammonium
chloride, 5 parts of dimethyl sulfoxide and 10 parts of dimethyl
naphthalene were blended to obtain an imazosulfuron solution.
Further, the imazosulfuron solution prepared as above was added to
75 parts of granulated bentonite, which had a particle size of 12
to 42 mesh (1400 to 355 .mu.m) and gave a 1% by mass aqueous
suspension having a pH of 9 to 10, to be adsorbed thereon for
granulation and, then, coated with pentoxazone-containing powder to
give granules of the agrochemical composition having a particle
diameter of 0.3 to 1.5 mm and containing 0.5% by mass of
imazosulfuron and 2.5% by mass of pentoxazone (pH of a 1% by mass
aqueous suspension 7.96). The granular agrochemical composition
thus obtained was put into water and observed after 30 minutes for
the disintegrability of the granules to obtain a result that it was
of a non-disintegration type.
EXAMPLE 12
[0061] A 2 parts portion of bensulfuron-methyl (pKa 5.03), 4 parts
of distearyldimethylammonium chloride, 3 parts of polyvinyl
alcohol, 2 parts of basic fumed silica and 15 parts of calcium
carbonate were uniformly blended in a high speed agitator and
kneaded with addition of a suitable amount of water followed by
extrusion by using a basket-type granulator through a screen of 0.6
mm mesh opening and the granulated material was dried by standing
at 60.degree. C. to obtain a bensulfuron-methyl containing base
having a diameter of 0.5 to 0.7 mm and a length of 1 to 6 mm.
Together with the bensulfuron-methyl containing base, 2 parts of
enzyme modified dextrin, 5 parts of sodium
alkylnaphthalenesulfonate, 2 parts of sodium lauryl sulfate, 14
parts of hollow plastic bodies containing 85% by mass of moisture
and 62.9 parts of sodium sulfate anhydride were uniformly blended
in a high speed agitator and kneaded with addition of a suitable
amount of water followed by extrusion by using a basket-type
granulator through a screen of 5 mm mesh opening and the granulated
material was dried by standing at 60.degree. C. to obtain a
granular agrochemical composition having a diameter of 3 to 7 mm
and a length of 3 to 20 mm and containing 0.5% by mass of
bensulfuron-methyl (pH of a 1% by mass aqueous suspension 8.85).
The granular agrochemical composition thus obtained was put into
water and observed after 30 minutes for the disintegrability of the
granules to obtain results that the granular agrochemical
composition having a diameter of 3 to 7 mm and a length of 3 to 20
mm disintegrated immediately after being put into water while the
bensulfuron-methyl containing base having a diameter of 0.5 to 0.7
mm and a length of 1 to 6 mm and containing
distearyldimethylammonium chloride, which is a cationic surface
active agent, was of a non-disintegration type.
EXAMPLE 13
[0062] A 1 part portion of Compound B (pKa 6.17), 3 parts of
dioleyldimethylammonium chloride and 5 parts of
N-methyl-2-pyrrolidone were blended to obtain a Compound B
solution. The Compound B solution prepared as above was added to 20
parts of basic acid clay, which had a particle size of 16 to 35
mesh (1000 to 425 .mu.m) and gave a 1% aqueous suspension having a
pH of 7 to 10, to be adsorbed thereon for granulation to give a
Compound B containing base having a particle diameter of 0.4 to 1.1
mm. Together with the Compound B containing base, 1 part of
Compound B, 0.5 part of sodium polyacrylate, 5 parts of sodium
alkylnaphthalenesulfonate, 2 parts of dioctyl sulfosuccinate, 20
parts of hollow inorganic bodies and 42.5 parts of sodium benzoate
were uniformly blended in a high speed agitator and kneaded with
addition of a suitable amount of water followed by extrusion by
using a basket-type granulator through a screen of 5 mm mesh
opening and the granulated material was dried by standing at
60.degree. C. to obtain a granular agrochemical composition having
a diameter of 3 to 7 mm and a length of 3 to 20 mm and containing
2% by mass of Compound B (pH of a 1% by mass aqueous suspension
8.34). The granular agrochemical composition thus obtained was put
into water and observed after 30 minutes for the disintegrability
of the granules to obtain results that the granular agrochemical
composition having a diameter of 3 to 7 mm and a length of 3 to 20
mm disintegrated immediately after being put into water while the
Compound B containing base having a particle diameter of 0.4 to 1.1
mm and containing dioleyldimethylammonium chloride, which is a
cationic surface active agent, was of a non-disintegration
type.
EXAMPLE 14
[0063] A 0.5 part portion of Compound A (pKa 5.75), 1 part of
distearyldimethylammonium chloride, 3 parts of .alpha. starch and
95.5 parts of calcium carbonate were uniformly blended in a high
speed agitator and kneaded with addition of a suitable amount of
water followed by extrusion by using a basket-type granulator
through a screen of 1.2 mm mesh opening and the granulated material
was dried by standing at 60.degree. C. to obtain a granular
agrochemical composition having a diameter of 1.1 to 1.3 mm and a
length of 3 to 7 mm and containing 0.5% by mass of Compound A (pH
of a 1% by mass aqueous suspension 8.44). The granular agrochemical
composition thus obtained was put into water and observed after 30
minutes for the disintegrability of the granules to obtain a result
that it was of a non-disintegration type.
EXAMPLE 15
[0064] A 0.5 part portion of Compound A (pKa 5.75), 3 parts of
distearyldimethylammonium chloride, 3 parts of .alpha. starch and
93.5 parts of calcium carbonate were uniformly blended in a high
speed agitator and kneaded with addition of a suitable amount of
water followed by extrusion by using a basket-type granulator
through a screen of 1.2 mm mesh opening and the granulated material
was dried by standing at 60.degree. C. to obtain a granular
agrochemical composition having a diameter of 1.1 to 1.3 mm and a
length of 3 to 7 mm and containing 0.5% by mass of Compound A (pH
of a 1% by mass aqueous suspension 8.68). The granular agrochemical
composition thus obtained was put into water and observed after 30
minutes for the disintegrability of the granules to obtain a result
that it was of a non-disintegration type.
EXAMPLE 16
[0065] A 0.5 part portion of Compound A (pKa 5.75) and 5 parts of
calcium carbonate were uniformly blended and crushed with a hammer
mill. Together with the powder thus obtained, 2 parts of
distearyldimethylammonium chloride, 3 parts of .alpha. starch and
89.5 parts of clay were uniformly blended in a high speed agitator
and kneaded with addition of a suitable amount of water followed by
extrusion by using a basket-type granulator through a screen of 1.2
mm mesh opening and the granulated material was dried by standing
at 60.degree. C. to obtain a granular agrochemical composition
having a diameter of 1.1 to 1.3 mm and a length of 3 to 7 mm and
containing 0.5% by mass of Compound A (pH of a 1% by mass aqueous
suspension 8.51). The granular agrochemical composition thus
obtained was put into water and observed after 30 minutes for the
disintegrability of the granules to obtain a result that it was of
a non-disintegration type.
EXAMPLE 17
[0066] A 0.5 part portion of Compound B (pKa 6.17) and 5 parts of
calcium carbonate were uniformly blended and crushed with a hammer
mill. Together with the powder thus obtained, 2 parts of
distearyldimethylammonium chloride, 3 parts of .alpha. starch and
89.5 parts of clay were uniformly blended in a high speed agitator
and kneaded with addition of a suitable amount of water followed by
extrusion by using a basket-type granulator through a screen of 1.2
mm mesh opening and the granulated material was dried by standing
at 60.degree. C. to obtain a granular agrochemical composition
having a diameter of 1.1 to 1.3 mm and a length of 3 to 7 mm and
containing 0.5% by mass of Compound B (pH of a 1% by mass aqueous
suspension 8.93). The granular agrochemical composition thus
obtained was put into water and observed after 30 minutes for the
disintegrability of the granules to obtain a result that it was of
a non-disintegration type.
EXAMPLE 18
[0067] A 0.5 part portion of Compound B (pKa 6.17) and 1 part of
calcium carbonate were uniformly blended and crushed with a hammer
mill. Together with the powder thus obtained, 2 parts of
dilauryldimethylammonium chloride, 3 parts of .alpha. starch and
93.5 parts of clay, which gave a 1% by weight aqueous suspension
having a pH of 4.2, were uniformly blended in a high speed agitator
and kneaded with addition of a suitable amount of water followed by
extrusion by using a basket-type granulator through a screen of 1.2
mm mesh opening and the granulated material was dried by standing
at 60.degree. C. to obtain a granular agrochemical composition
having a diameter of 1.1 to 1.3 mm and a length of 3 to 7 mm and
containing 0.5% by mass of Compound B (pH of a 1% by mass aqueous
suspension 4.28). The granular agrochemical composition thus
obtained was put into water and observed after 30 minutes for the
disintegrability of the granules to obtain a result that it was of
a non-disintegration type.
EXAMPLE 19
[0068] A 0.5 part portion of Compound B (pKa 6.17) and 5 parts of
calcium carbonate were uniformly blended and crushed with a hammer
mill. Together with the powder thus obtained, 2 parts of
dilauryldimethylammonium chloride, 3 parts of .alpha. starch and
89.5 parts of clay, which gave a 1% by weight aqueous suspension
having a pH of 4.2, were uniformly blended in a high speed agitator
and kneaded with addition of a suitable amount of water followed by
extrusion by using a basket-type granulator through a screen of 1.2
mm mesh opening and the granulated material was dried by standing
at 60.degree. C. to obtain a granular agrochemical composition
having a diameter of 1.1 to 1.3 mm and a length of 3 to 7 mm and
containing 0.5% by mass of Compound B (pH of a 1% by mass aqueous
suspension 5.81). The granular agrochemical composition thus
obtained was put into water and observed after 30 minutes for the
disintegrability of the granules to obtain a result that it was of
a non-disintegration type.
EXAMPLE 20
[0069] A 0.5 part portion of Compound B (pKa 6.17) and 10 parts of
calcium carbonate were uniformly blended and crushed with a hammer
mill. Together with the powder thus obtained, 2 parts of
dilauryldimethylammonium chloride, 3 parts of .alpha. starch and
84.5 parts of clay were uniformly blended in a high speed agitator
and kneaded with addition of a suitable amount of water followed by
extrusion by using a basket-type granulator through a screen of 1.2
mm mesh opening and the granulated material was dried by standing
at 60.degree. C. to obtain a granular agrochemical composition
having a diameter of 1.1 to 1.3 mm and a length of 3 to 7 mm and
containing 0.5% by mass of Compound B (pH of a 1% by mass aqueous
suspension 8.62). The granular agrochemical composition thus
obtained was put into water and observed after 30 minutes for the
disintegrability of the granules to obtain a result that it was of
a non-disintegration type.
EXAMPLE 21
[0070] A 0.5 part portion of Compound A (pKa 5.75) and 1 part of
calcium carbonate were uniformly blended and crushed with a hammer
mill. Together with the powder thus obtained, 2 parts of
dilauryldimethylammonium chloride, 3 parts of .alpha. starch and
93.5 parts of clay, which gave a 1% by weight aqueous suspension
having a pH of 4.2, were uniformly blended in a high speed agitator
and kneaded with addition of a suitable amount of water followed by
extrusion by using a basket-type granulator through a screen of 1.2
mm mesh opening and the granulated material was dried by standing
at 60.degree. C. to obtain a granular agrochemical composition
having a diameter of 1.1 to 1.3 mm and a length of 3 to 7 mm and
containing 0.5% by mass of Compound A (pH of a 1% by mass aqueous
suspension 4.07). The granular agrochemical composition thus
obtained was put into water and observed after 30 minutes for the
disintegrability of the granules to obtain a result that it was of
a non-disintegration type.
EXAMPLE 22
[0071] A 0.5 part portion of Compound A (pKa 5.75) and 5 parts of
calcium carbonate were uniformly blended and crushed with a hammer
mill. Together with the powder thus obtained, 2 parts of
dilauryldimethylammonium chloride, 3 parts of .alpha. starch and
89.5 parts of clay were uniformly blended in a high speed agitator
and kneaded with addition of a suitable amount of water followed by
extrusion by using a basket-type granulator through a screen of 1.2
mm mesh opening and the granulated material was dried by standing
at 60.degree. C. to obtain a granular agrochemical composition
having a diameter of 1.1 to 1.3 mm and a length of 3 to 7 mm and
containing 0.5% by mass of Compound A (pH of a 1% by mass aqueous
suspension 8.51). The granular agrochemical composition thus
obtained was put into water and observed after 30 minutes for the
disintegrability of the granules to obtain a result that it was of
a non-disintegration type.
EXAMPLE 23
[0072] A 2 parts portion of tricyclazole (pKa 1.6) and 5 parts of
calcium carbonate were uniformly blended and crushed with a hammer
mill. Together with the powder thus obtained, 2 parts of
distearyldimethylammonium chloride, 3 parts of .alpha. starch and
88 parts of clay were uniformly blended in a high speed agitator
and kneaded with addition of a suitable amount of water followed by
extrusion by using a basket-type granulator through a screen of 1.2
mm mesh opening and the granulated material was dried by standing
at 60.degree. C. to obtain a granular agrochemical composition
having a diameter of 1.1 to 1.3 mm and a length of 3 to 7 mm and
containing 2% by mass of tricyclazole (pH of a 1% by mass aqueous
suspension 8.17). The granular agrochemical composition thus
obtained was put into water and observed after 30 minutes for the
disintegrability of the granules to obtain a result that it was of
a non-disintegration type.
EXAMPLE 24
[0073] A 2 parts portion of EDDP (pKa 10.5), 5 parts of calcium
carbonate and 1 part of fumed silica were uniformly blended and
crushed with a hammer mill. Together with the powder thus obtained,
2 parts of distearyldimethylammonium chloride, 3 parts of .alpha.
starch and 87 parts of clay were uniformly blended in a high speed
agitator and kneaded with addition of a suitable amount of water
followed by extrusion by using a basket-type granulator through a
screen of 1.2 mm mesh opening and the granulated material was dried
by standing at 60.degree. C. to obtain a granular agrochemical
composition having a diameter of 1.1 to 1.3 mm and a length of 3 to
7 mm and containing 2% by mass of EDDP (pH of a 1% by mass aqueous
suspension 7.53). The granular agrochemical composition thus
obtained was put into water and observed after 30 minutes for the
disintegrability of the granules to obtain a result that it was of
a non-disintegration type.
EXAMPLE 25
[0074] A 2 parts portion of PHC (pKa 11.5) and 5 parts of calcium
carbonate were uniformly blended and crushed with a hammer mill.
Together with the powder thus obtained, 2 parts of
distearyldimethylammonium chloride, 3 parts of .alpha. starch and
88 parts of clay were uniformly blended in a high speed agitator
and kneaded with addition of a suitable amount of water followed by
extrusion by using a basket-type granulator through a screen of 1.2
mm mesh opening and the granulated material was dried by standing
at 60.degree. C. to obtain a granular agrochemical composition
having a diameter of 1.1 to 1.3 mm and a length of 3 to 7 mm and
containing 2% by mass of PHC (pH of a 1% by mass aqueous suspension
8.86). The granular agrochemical composition thus obtained was put
into water and observed after 30 minutes for the disintegrability
of the granules to obtain a result that it was of a
non-disintegration type.
COMPARATIVE EXAMPLE 1
[0075] A 0.5 part portion of bensulfuron-methyl and 10.0 parts of
calcium carbonate were uniformly blended and crushed with a hammer
mill. Together with the powder thus obtained, 2 parts of sodium
alkylbenzenesulfonate, 3 parts of .alpha. starch and 84.5 parts of
clay were uniformly blended in a high speed agitator and kneaded
with addition of a suitable amount of water followed by extrusion
by using a basket-type granulator through a screen of 1.2 mm mesh
opening and the granulated material was dried by standing at
60.degree. C. to obtain a granular agrochemical composition
containing 0.5% by mass of bensulfuron-methyl and 2% by mass of
sodium alkylbenzenesulfonate (pH of a 1% by mass aqueous suspension
8.35).
COMPARATIVE EXAMPLE 2
[0076] A 0.5 part portion of pyrazosulfuron-ethyl, 2 parts of
paraffin (melting point 68 to 70.degree. C.) and 1 part of basic
fumed silica were blended under melting at 80.degree. C. and, after
being cooled to room temperature, crushed with a hammer mill.
Together with the powder thus obtained, 3 parts of .alpha. starch,
25 parts of sodium bentonite and 68.5 parts of talc were uniformly
blended in a high speed agitator and kneaded with addition of a
suitable amount of water followed by extrusion by using a
basket-type granulator through a screen of 1.2 mm mesh opening and
the granulated material was dried by standing at 60.degree. C. to
obtain a granular agrochemical composition containing 0.5% by mass
of pyrazosulfuron-ethyl (pH of a 1% by mass aqueous suspension
9.35).
COMPARATIVE EXAMPLE 3
[0077] A 0.5 part portion of bensulfuron-methyl, 15 parts of sodium
bentonite and 5 parts of activated carbon were uniformly blended
and crushed with a hammer mill. Together with the powder thus
obtained, 3 parts of .alpha. starch and 76.5 parts of talc were
uniformly blended in a high speed agitator and kneaded with
addition of a suitable amount of water followed by extrusion by
using a basket-type granulator through a screen of 1.2 mm mesh
opening and the granulated material was dried by standing at
60.degree. C. to obtain a granular agrochemical composition
containing 0.5% by mass of bensulfuron-methyl (pH of a 1% by mass
aqueous suspension 7.89).
COMPARATIVE EXAMPLE 4
[0078] A 0.5 part portion of bensulfuron-methyl and 8 parts of
N-methyl-2-pyrrolidone were blended to obtain a bensulfuron-methyl
solution. The bensulfuron-methyl solution prepared as above was
added on 91.5 parts of a natural base of basic acid clays, which
had a particle size of 16 to 35 mesh (1000 to 425 .mu.m) and gave a
1% aqueous suspension having a pH of 7 to 10, to be adsorbed
thereon for granulation to give granules of the agrochemical
composition containing 0.5% by mass of bensulfuronmethyl (pH of a
1% by mass aqueous suspension 8.39).
COMPARATIVE EXAMPLE 5
[0079] A 0.5 part portion of bensulfuron-methyl, 4.5 parts of
dymron, 25 parts of sodium bentonite, 3 parts of .alpha. starch and
67 parts of talc were uniformly blended in a high speed agitator
and kneaded with addition of a suitable amount of water followed by
extrusion by using a basket-type granulator through a screen of 1.2
mm mesh opening and the granulated material was dried by standing
at 60.degree. C. to obtain a granular agrochemical composition
containing 0.5% by mass of bensulfuron-methyl and 4.5% by mass of
dymron (pH of a 1% by mass aqueous suspension 9.12).
COMPARATIVE EXAMPLE 6
[0080] A 0.5 part portion of Compound A, 2 parts of sodium
alkylbenzenesulfonate, 3 parts of .alpha. starch and 94.5 parts of
calcium carbonate were uniformly blended in a high speed agitator
and kneaded with addition of a suitable amount of water followed by
extrusion by using a basket-type granulator through a screen of 1.2
mm mesh opening and the granulated material was dried by standing
at 60.degree. C. to obtain a granular agrochemical composition
containing 0.5% by mass of Compound A (pH of a 1% by mass aqueous
suspension 8.85).
COMPARATIVE EXAMPLE 7
[0081] A 2 parts portion of bensulfuron-methyl, 3 parts of
polyvinyl alcohol, 2 parts of basic fumed silica and 15 parts of
calcium carbonate were uniformly blended in a high speed agitator
and kneaded with addition of a suitable amount of water followed by
extrusion by using a basket-type granulator through a screen of 0.6
mm mesh opening and the granulated material was dried by standing
at 60.degree. C. to obtain a bensulfuron-methyl containing base.
Together with the bensulfuron-methyl containing base thus obtained,
2 parts of enzyme modified dextrin, 5 parts of sodium
alkylnaphthalenesulfonate, 2 parts of sodium lauryl sulfate, 14
parts of hollow plastic bodies containing 85 parts of moisture and
66.9 parts of sodium sulfate anhydride were uniformly blended in a
high speed agitator and kneaded with addition of a suitable amount
of water followed by extrusion by using a basket-type granulator
through a screen of 5 mm mesh opening and the granulated material
was dried by standing at 60.degree. C. to obtain a granular
agrochemical composition containing 0.5% by mass of
bensulfuron-methyl (pH of a 1% by mass aqueous suspension
8.89).
COMPARATIVE EXAMPLE 8
[0082] A 2 parts portion of Compound B, 3 parts of polyvinyl
alcohol, 2 parts of basic fumed silica and 15 parts of calcium
carbonate were uniformly blended in a high speed agitator and
kneaded with addition of a suitable amount of water followed by
extrusion by using a basket-type granulator through a screen of 0.6
mm mesh opening and the granulated material was dried by standing
at 60.degree. C. to obtain a bensulfuron-methyl containing base.
Together with the bensulfuron-methyl containing base thus obtained,
2 parts of enzyme modified dextrin, 5 parts of sodium
alkylnaphthalenesulfonate, 2 parts of sodium lauryl sulfate, 14
parts of hollow plastic bodies containing 85 parts of moisture and
66.9 parts of sodium sulfate anhydride were uniformly blended in a
high speed agitator and kneaded with addition of a suitable amount
of water followed by extrusion by using a basket-type granulator
through a screen of 5 mm mesh opening and the granulated material
was dried by standing at 60.degree. C. to obtain a granular
agrochemical composition containing 2% by mass of Compound B (pH of
a 1% by mass aqueous suspension 9.80).
COMPARATIVE EXAMPLE 9
[0083] A 0.5 part portion of bensulfuron-methyl (pKa 5.03) and 5
parts of calcium carbonate were uniformly blended and crushed with
a hammer mill. Together with the powder thus obtained, 3 parts of
.alpha. starch and 91.5 parts of clay were uniformly blended in a
high speed agitator and kneaded with addition of a suitable amount
of water followed by extrusion by using a basket-type granulator
through a screen of 1.2 mm mesh opening and the granulated material
was dried by standing at 60.degree. C. to obtain a granular
agrochemical composition containing 0.5% by mass of
bensulfuron-methyl (pH of a 1% by mass aqueous suspension 9.01).
The granular agrochemical composition thus obtained was put into
water and observed after 30 minutes for the disintegrability of the
granules to obtain a result that it was of a non-disintegration
type.
COMPARATIVE EXAMPLE 10
[0084] A 0.5 part portion of Compound A (pKa 5.75) and 5 parts of
calcium carbonate were uniformly blended and crushed with a hammer
mill. Together with the powder thus obtained, 3 parts of .alpha.
starch and 91.5 parts of clay were uniformly blended in a high
speed agitator and kneaded with addition of a suitable amount of
water followed by extrusion by using a basket-type granulator
through a screen of 1.2 mm mesh opening and the granulated material
was dried by standing at 60.degree. C. to obtain a granular
agrochemical composition having a diameter of 1.1 to 1.3 mm and a
length of 3 to 7 mm and containing 0.5% by mass of Compound A (pH
of a 1% by mass aqueous suspension 8.68). The granular agrochemical
composition thus obtained was put into water and observed after 30
minutes for the disintegrability of the granules to obtain a result
that it was of a non-disintegration type.
COMPARATIVE EXAMPLE 11
[0085] A 0.5 part portion of Compound A (pKa 5.75), 2 parts of
dilauryldimethylammonium chloride, 3 parts of .alpha. starch and
94.5 parts of clay, which gave a 1% by weight aqueous suspension
having a pH of 4.2, were uniformly blended and crushed with a
hammer mill. The powder thus obtained was uniformly blended in a
high speed agitator and kneaded with addition of a suitable amount
of water followed by extrusion by using a basket-type granulator
through a screen of 1.2 mm mesh opening and the granulated material
was dried by standing at 60.degree. C. to obtain a granular
agrochemical composition having a diameter of 1.1 to 1.3 mm and a
length of 3 to 7 mm and containing 0.5% by mass of Compound A (pH
of a 1% by mass aqueous suspension 4.54). The granular agrochemical
composition thus obtained was put into water and observed after 30
minutes for the disintegrability of the granules to obtain a result
that it was of a non-disintegration type.
COMPARATIVE EXAMPLE 12
[0086] A 0.5 part portion of Compound B (pKa 6.17) and 5 parts of
calcium carbonate were uniformly blended and crushed with a hammer
mill. Together with the powder thus obtained, 3 parts of .alpha.
starch and 91.5 parts of clay were uniformly blended in a high
speed agitator and kneaded with addition of a suitable amount of
water followed by extrusion by using a basket-type granulator
through a screen of 1.2 mm mesh opening and the granulated material
was dried by standing at 60.degree. C. to obtain a granular
agrochemical composition having a diameter of 1.1 to 1.3 mm and a
length of 3 to 7 mm and containing 0.5% by mass of Compound B (pH
of a 1% by mass aqueous suspension 8.72). The granular agrochemical
composition thus obtained was put into water and observed after 30
minutes for the disintegrability of the granules to obtain a result
that it was of a non-disintegration type.
COMPARATIVE EXAMPLE 13
[0087] A 0.5 part portion of Compound B (pKa 6.17), 2 parts of
dilauryldimethylammonium chloride, 3 parts of .alpha. starch and
94.5 parts of clay, which gave a 1% by weight aqueous suspension
having a pH of 4.2, were uniformly blended and crushed with a
hammer mill. The powder thus obtained was uniformly blended in a
high speed agitator and kneaded with addition of a suitable amount
of water followed by extrusion by using a basket-type granulator
through a screen of 1.2 mm mesh opening and the granulated material
was dried by standing at 60.degree. C. to obtain a granular
agrochemical composition having a diameter of 1.1 to 1.3 mm and a
length of 3 to 7 mm and containing 0.5% by mass of Compound B (pH
of a 1% by mass aqueous suspension 4.77). The granular agrochemical
composition thus obtained was put into water and observed after 30
minutes for the disintegrability of the granules to obtain a result
that it was of a non-disintegration type.
COMPARATIVE EXAMPLE 14
[0088] A 2 parts portion of tricyclazole (pKa 1.6) and 5 parts of
calcium carbonate were uniformly blended and crushed with a hammer
mill. Together with the powder thus obtained, 3 parts of .alpha.
starch and 90 parts of clay were uniformly blended in a high speed
agitator and kneaded with addition of a suitable amount of water
followed by extrusion by using a basket-type granulator through a
screen of 1.2 mm mesh opening and the granulated material was dried
by standing at 60.degree. C. to obtain a granular agrochemical
composition having a diameter of 1.1 to 1.3 mm and a length of 3 to
7 mm and containing 2% by mass of tricyclazole (pH of a 1% by mass
aqueous suspension 8.79). The granular agrochemical composition
thus obtained was put into water and observed after 30 minutes for
the disintegrability of the granules to obtain a result that it was
of a non-disintegration type.
COMPARATIVE EXAMPLE 15
[0089] A 2 parts portion of EDDP (pKa 10.5), 5 parts of calcium
carbonate and 1 part of fumed silica were uniformly blended and
crushed with a hammer mill. Together with the powder thus obtained,
3 parts of .alpha. starch and 89 parts of clay were uniformly
blended in a high speed agitator and kneaded with addition of a
suitable amount of water followed by extrusion by using a
basket-type granulator through a screen of 1.2 mm mesh opening and
the granulated material was dried by standing at 60.degree. C. to
obtain a granular agrochemical composition having a diameter of 1.1
to 1.3 mm and a length of 3 to 7 mm and containing 2% by mass of
EDDP (pH of a 1% by mass aqueous suspension 8.32). The granular
agrochemical composition thus obtained was put into water and
observed after 30 minutes for the disintegrability of the granules
to obtain a result that it was of a non-disintegration type.
COMPARATIVE EXAMPLE 16
[0090] A 2 parts portion of PHC (pKa 11.5) and 5 parts of calcium
carbonate were uniformly blended and crushed with a hammer mill.
Together with the powder thus obtained, 3 parts of .alpha. starch
and 90 parts of clay were uniformly blended in a high speed
agitator and kneaded with addition of a suitable amount of water
followed by extrusion by using a basket-type granulator through a
screen of 1.2 mm mesh opening and the granulated material was dried
by standing at 60.degree. C. to obtain a granular agrochemical
composition having a diameter of 1.1 to 1.3 mm and a length of 3 to
7 mm and containing 2% by mass of PHC (pH of a 1% by mass aqueous
suspension 9.27). The granular agrochemical composition thus
obtained was put into water and observed after 30 minutes for the
disintegrability of the granules to obtain a result that it was of
a non-disintegration type.
TEST EXAMPLE 1
In-Water Dissolution Test
[0091] Into a glass vessel having an inner diameter of 15 cm, 900
ml of hard water of degree 3 were taken to make up a depth of 5 cm.
Each of the granular agrochemical compositions of Examples 1, 2, 4
and 8-11 and Comparative Examples 1-7 was added thereto in such an
amount as to correspond to 1 kg per 10 ares. After 1, 3, 7, 21 and
35 days from the treatment, water was taken to determine the
concentration of the active ingredient in water by analyzing with
the high-performance liquid chromatography (HPLC) thereby to obtain
the proportion relative to the overall content in the granular
material as the dissolved ratio in water. The results are shown in
Table 1.
[0092] As is understood from Table 1, the granular agrochemical
composition in each Example, with respect to the sulfonylurea-based
compound or difluoromethanesulfonylanilide derivative or salt
thereof as the herbicide, which was the active ingredient of the
agrochemical, had the dissolution ratio in water moving low in all
of the tests one day through 35 days after the treatment as
compared with the comparative examples excepting Comparative
Examples 2 and 3.
[0093] In Comparative Examples 2 and 3, the in-water concentration
moved low throughout indicating that dissolution of the
agrochemically active ingredient was limited to the very beginning
stage not to be continued. Accordingly they were apparently
inferior because a large portion of the agrochemically active
ingredient in the granular agrochemical composition remained
unutilized.
1 TABLE 1 Agrochemically Dissolved ratio in water (%) active 1 3 7
21 35 ingredient day days days days days Example 1 bensulfuron- 42
56 64 76 82 methyl Example 2 pyrazosulfuron- 58 72 80 83 86 ethyl
Example 4 bensulfuron- 49 61 69 79 86 methyl azimsulfuron 62 68 76
83 89 Example 8 Compound B 25 32 40 45 50 Example 9 bensulfuron- 57
67 78 84 92 methyl Compound A 19 23 31 35 41 Example 10
fentrazamide 32 78 97 100 100 imazosulfuron 56 72 77 86 89 Example
11 Pentoxazone 4 9 12 12 18 Comparative bensulfuron- 98 100 100 100
100 Example 1 methyl Comparative pyrazosulfuron- 12 9 11 15 9
Example 2 ethyl Comparative bensulfuron- 4 0 3 0 0 Example 3 methyl
Comparative bensulfuron- 100 100 100 100 100 Example 4 methyl
Comparative bensulfuron- 97 100 100 100 100 Example 5 methyl dymron
27 51 68 82 94 Comparative Compound A 100 100 100 100 100 Example 6
Comparative Compound B 99 100 100 100 100 Example 8
TEST EXAMPLE 2
In-Water Dissolution: Influence of Amount of Cationic Surfactant
Added
[0094] Into a glass vessel having an inner diameter of 15 cm, 900
ml of hard water of degree 3 were taken to make up a depth of 5 cm.
Each of the granular agrochemical compositions of Examples 3, 14
and 15 and Comparative Example 6 was added thereto in such an
amount as to correspond to 1 kg per 10 ares. After 1, 3, 7, 21 and
35 days from the treatment, water was taken to determine the
concentration of the active ingredient in water by the HPLC
analysis as the dissolved ratio in water. The results are shown in
Table 2.
[0095] It is understood from Table 2 that, as the content of the
cationic surfactant in the granular agrochemical composition was
increased, the dissolved ratio in water of the compound A was
reduced moving low as compared with Comparative Example 6 where no
cationic surfactant was added.
2 TABLE 2 Content of Dissolved ratio in water (%) cationic 1 3 7 21
35 surfactant day days days days days Example 14 1% 33 48 56 67 71
Example 3 2% 24 31 42 46 50 Example 15 3% 12 18 22 29 33
Comparative -- 99 97 100 100 100 Example 6
TEST EXAMPLE 3
In-Water Dissolution: Control of Sustained Releasability
[0096] Into a glass vessel having an inner diameter of 15 cm, 900
ml of hard water of degree 3 were taken to make up a depth of 5 cm.
Each of the granular agrochemical compositions of Examples 3, 5, 6
and 7 and Comparative Example 6 was added thereto in such an amount
as to correspond to 1 kg per 10 ares. After 1, 3, 7, 21 and 35 days
from the treatment, water was taken to determine the concentration
of the active ingredient in water by the HPLC analysis as the
dissolved ratio in water. The results are shown in Table 3.
[0097] It is understood from Table 3 that, as compared with the
granular agrochemical composition of the Comparative Example
without sustained releasability, the sustained releasability of the
compound A could be controlled in the granular agrochemical
compositions in the Examples.
3 TABLE 3 Dissolved ratio in water (%) 1 3 7 21 35 day days days
days days Example 3 20 28 38 42 47 Example 5 33 41 49 55 60 Example
6 58 62 67 71 72 Example 7 82 86 90 91 95 Comparative 100 100 99
100 100 Example 6
TEST EXAMPLE 4
In-Water Dissolution
[0098] Into a 75 cm by 35 cm wide container, 9 liters of hard water
of degree 3 were introduced to make up a depth of 5 cm. Each of the
granular agrochemical compositions of Examples 12 and 13 and
Comparative Examples 7 and 8 was applied for treatment in such an
amount as to correspond to 0.25 kg per 10 ares. After 1, 3, 7, 21
and 35 days from the treatment, the water was taken to determine
the concentration of the active ingredient in water by the HPLC
analysis as the dissolved ratio in water. The results are shown in
Table 4.
[0099] As is understood from Table 4, the in-water concentration in
Examples moved low as compared with the Comparative Example
indicating that the agrochemical active ingredient was imparted
with sustained releasability.
4 TABLE 4 Agrochemically Dissolved ratio in water (%) active 1 3 7
21 35 ingredient day days days days days Example 12 bensulfuron- 48
58 65 71 74 methyl Example 13 Compound B 58 62 70 78 85 Comparative
bensulfuron- 100 100 100 100 100 Example 7 methyl Comparative
Compound B 100 100 100 100 100 Example 8
TEST EXAMPLE 5
Biological Effectiveness Test: Paddy Rice
[0100] A 100 cm.sup.2 wide plastic pot was filled with a paddy
field soil and, after watering and shuffling, seeds of each of
early watergrass (Echinochloa oryzoides), heartshape false
pickerelweed (Monochoria vaginalis) and HOTARU-I (Scirpus
juncoides) were sowed in a depth of 0.5 cm. Further, two paddy rice
plants at the two-leaves stage were transplanted in a transplanting
depth of 2 cm followed by pooling of water in a depth of 5 cm. On
the next day of transplantation, each of the granular agrochemical
compositions obtained in Examples 3, 5, 6 and 7 and Comparative
Example 6 was evenly applied for treatment in an amount relative to
the amount of the effective ingredient corresponding to 5 g/10 ares
by weighing. The plants on these plastic pots were grown in a
greenhouse and, after 28 days, evaluation was made by the following
criteria for the herbicidal effects and the extent of chemical
damages. The results are shown in Table 5.
[0101] It is noted from Table 5 that the granular agrochemical
compositions of the Examples exhibited excellent herbicidal effects
almost without chemical damages to the paddy rice while
considerable chemical damages were found in Comparative Example 6
against paddy rice.
[0102] Evaluation criteria for herbicidal effects (growth
suppression and chemical damages
[0103] 5: 90% or higher
[0104] 4 or higher but lower than 5: 70% or higher but lower than
90%
[0105] 3 or higher but lower than 4: 50% or higher but lower than
70%
[0106] 2 or higher but lower than 3: 30% or higher but lower than
50%
[0107] 1 or higher but lower than 2: 10% or higher but lower than
30%
[0108] 0 or higher but lower than 1: 0% or higher but lower than
10%
5 TABLE 5 Herbicidal effects heartshape false Chemical early
pickerel- damages watergrass weed HOTARU-I paddy rice Example 3 4.5
5.0 5.0 0 Example 5 5.0 5.0 5.0 0 Example 6 5.0 5.0 5.0 0.5 Example
7 5.0 5.0 5.0 0.5 Comparative 5.0 5.0 5.0 1.5 Example 6
TEST EXAMPLE 6
Biological Effectiveness Test: Effect Retention Test
[0109] A 200 cm.sup.2 wide plastic pot filled with a paddy field
soil was watered and the soil was shuffled followed by introduction
of water to give a water depth of 5 cm and one of the granular
agrochemical compositions obtained in Examples 5, 6 and 7 and
Comparative Example 6 was applied thereto by weighing in such an
amount as to correspond to 2.5 g/10 ares relative to the amount of
the effective ingredient. From just after this treatment, water
leak was caused from the bottom of the plastic pot for 3 days at a
rate of 2 cm per day and the water leak was followed by
introduction of water from above the plastic pot to make up a water
depth of 5 cm. On the 0th, 20th and 40th days from the treatment,
respective seeds of early watergrass, heartshape false pickerelweed
and HOTARU-I were sowed and growth of the weeds was observed on the
30th day from sowing. The evaluation criteria of the herbicidal
effects were in accordance with those in Test Example 5. The
results are shown in Table 6. It is understood from Table 6 that
the granular agrochemical compositions in the Examples exhibited
superior effect retention as compared with the Comparative
Example.
6 TABLE 6 Herbicidal effects early watergrass heartshape false
pickerelweed HOTARU-I 0 20 40 0 20 40 0 20 40 day days days day
days days day days days Example 5 4.3 4.5 4.0 4.7 4.9 4.5 4.7 4.9
4.8 Example 6 4.5 4.5 3.5 4.9 4.8 4.5 4.8 4.9 4.5 Example 7 4.8 4.5
3.7 4.9 4.3 3.5 4.9 4.8 4.5 Comparative 4.3 3.5 3.0 4.8 4.3 3.0 4.8
4.8 3.7 Example 6
TEST EXAMPLE 7
In-Water Dissolution
[0110] Into a glass vessel having an inner diameter of 15 cm, 900
ml of hard water of degree 3 were taken to make up a depth of 5 cm.
Each of the granular agrochemical compositions of Examples 1, 16
and 17 and Comparative Examples 9, 10 and 12 was added thereto in
such an amount as to correspond to 1 kg per 10 ares and each of the
granular agrochemical compositions of Examples 23, 24 and 25 and
Comparative Examples 14, 15 and 16 was added thereto in such an
amount as to correspond to 3 kg per 10 ares. After 1, 3, 7, 21 and
35 days from the treatment, water was taken to determine the
concentration of the active ingredient in water by the HPLC
analysis as the dissolved ratio in water. The results are shown in
Table 7.
[0111] Table 7 indicates that, when the pKa of the acidic
agrochemically active ingredient was 2 to 7, the dissolved ratio in
water of the compound A and compound B as a difluoromethane
sulfonylanilide derivative in particular was strongly suppressed.
An effect of suppressing dissolved ratio in water was also noted in
Example 25 for an insecticidal agent and in Examples 23 and 24 for
a bactericidal agent.
7 TABLE 7 Dissolved ratio in water (%) 1 3 7 21 35 Active
ingredient day days days days days Example 23 tricyclazole 72 77 89
100 97 Example 1 bensulfuron-methyl 55 60 69 82 87 Example 16
Compound A 15 30 32 48 53 Example 17 Compound B 11 28 25 35 44
Example 24 EDDP 6 11 21 25 23 Example 25 PHC 64 70 69 75 74
Comparative tricyclazole 100 100 100 94 98 Example 14 Comparative
bensulfuron-methyl 92 99 100 100 100 Example 9 Comparative Compound
A 97 100 100 100 100 Example 10 Comparative Compound B 100 99 100
98 100 Example 12 Comparative EDDP 18 31 48 41 37 Example 15
Comparative PHC 81 100 95 91 89 Example 16
TEST EXAMPLE 8
In-Water Dissolution)
[0112] Into a glass vessel having an inner diameter of 15 cm, 900
ml of hard water of degree 3 were taken to make up a depth of 5 cm.
Each of the granular agrochemical compositions of Examples 18, 19,
20, 21 and 22 and Comparative Examples 11 and 13 was added thereto
in such an amount as to correspond to 1 kg per 10 ares. After 1, 3,
7, 21 and 35 days from the treatment, water was taken to determine
the concentration of the active ingredient in water by the HPLC
analysis as the dissolved ratio in water. The results are shown in
Table 8.
[0113] Table 8 indicates that the dissolved ratio in water was
suppressed by increasing the content of the basic substance while
the dissolved ratio in water was suppressed when the pH of the
granular agrochemical composition as a 1% by weight aqueous
suspension was higher than the pKa of the acidic agrochemically
active ingredient.
8 TABLE 8 Dissolved ratio in water (%) Activate 1 3 7 21 35
ingredient day days days days days Example 18 Compound B 54 68 68
71 75 Example 19 Compound B 42 59 55 61 65 Example 20 Compound B 12
10 24 40 45 Example 21 Compound A 39 54 47 52 75 Example 22
Compound A 9 18 21 40 42 Comparative Compound B 82 87 95 100 96
Example 13 Comparative Compound A 79 84 96 96 100 Example 11
[0114] Industrial Applicability
[0115] The granular agrochemical composition of the invention can
be prepared in a simple formulation and can moderately impart
sustained releasability to the dissolution of the agrochemically
active ingredient, thereby, to exhibit the efficacy of the
agrochemically ingredient over a long time and a remarkable effect
can be obtained that, by decreasing the rate of release of the
agrochemically ingredient into the environments, the load on the
environments can be decreased and the chemical damages, such as the
chemical damages against target crops, caused by the agrochemically
active ingredient can be alleviated or prevented.
* * * * *