CA1069328A - Agricultural chemical/resin compositions - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE:

An agricultural chemical which has improved efficiency, long range effectiveness, decreased phyto-toxicity in relation to useful plants, and resistance to water leaching and to vaporization. Agrochemicals have come into wide use in increasing yield of crops but they are quite often shortlived because of leaching by water, degradation by bacteria in the soil and/or vaporization. The agricultural chemical composition of the invention which overcomes these drawbacks comprises (A) an agricultural chemical and (B) a film-forming polymer having a soil fixity of at least 40% and a water vapor permeability of 400 - 1,500 g/m2/24 hrs.

Description

lO~9~Z8 BACKGROIJND OF TI~E INVENT ION

Field Of The Invention:
This invention relates to agricultural chemical ~agrochemical) compositions containi~g specific film-forming resins. More specifically, i~ relates to agrochemical compo-~itions which have improved efficiency, long range effectiveness and decrea~ed phytotoxicity in relati~n useful plants, and methods of Lmparting the above properties to agrochemicals.

DescriPtion Of Erior Art:

Recently, various agrochemicals have come into wi~e use for rationalization in farm work, e.g., labor saving, and the use of these chemicals has contributed much to ~ increased yield of crop~. Conventional ~ethod~ for their use,, however, have the disadvantage ~hat ayroche~icals have to be applied to plants or on soils in large amounts and at high frequency in order to obtain good results, bec~use, in a rather short tLme, they may be washed by rain into the ~ubsoil, be degraded by bacteria in the soil, or escape in vapor, result~lg in their meffectiveness, In addition, so~e herbicides te,nd to be so easily eluted with water from the upper soil into the subsoil that ~hey are rendered ineffective and, some~im,es, even adversely affect the germination or growth of useful plants, or possibly wither useful plants which usually hav~ their roots in the subsoil.
0~ the other hand, hazards resulting fro~ excessive use of agrochemicals has been o~e of the major problems of society which has Lncreaeed und~rstanding of enYironmental problems~ Therefore, solutions to the above-me~tioned drawbacks has been needed.

10~91:~28 ~o alleviate the~3e drawbacks, heretofore, spreaders (e.g., nonionic and anionic surfactants) have been incorporated in agrochemical compositions, but they are unsatis~actory in preventing agrochemicals ~rom being leached by water and escaping in vapor. Other methods have been proposed to overcome ~he above disadvantages in which methods agrochemicals are coated with a resin, or they are formulated with a resin, or, at the time of their application, ~hey are ~Lxed with a resin.
Some examples ofre~ins used are polyvinyl chloride, polyethylene, polystyrene, polyacrylates, polyvinyl acetate and epaxy resLns.
These method~ are insuf~icient to overcome theabove disadvantag~Q
and, furthermnre, some are eff~ctive only for ~ome l!~ited agrochemicals, and others are difficult to apply be~, e.g., too high in visc08ity, or too short in handling time to apply by a conventional sprayer.

; SUNMARY OF THE INV~NTION

Accordingly, it is an object of this invention to provide a~ agrochemical co~position which has Lmproved efficiency, continuous effectiveness and decreased phykotoxicity to use~ul plants.
It is ano~her object of this invention to provide an agrochemical ~ompositio~ which comprises a specific film-forming polymer (1) preventing an agrochemical from being lea~hed by water in~o the ~ubsoil, and from escaping in vapor, and (2) moderately controlling elution of an agrochemical.
It is a still another object of thi~ invention to provide a method of imparting the abova~mentioned properties to an agrochemical.

10~13~
These and other objects of thi~ invention, as will hereinafter become more resdily apparent, have been attained by a composition which comprises at least one agrochemical and a film-forming polymer having a 80il fixity of at least 40% and a water vapor permeability of 400 - 1,500 g/m2/24 hrs.

BRIEF D~SCRIPTION OF ~HE DRAWING

In describi~g this invention, reference shall b~
; made to the accompany~ng Drawing i~ which FIGURE 1 depicts by a graph the relation of ratio of dried weight of weeds to water vapor permeability.

DETAILED DESCRIPTIO~ OF THE INV~NTIO~

In this invention, the soil fixity of a resin is determined by the following method: 20 ml of 1 weight %
aqueous solution or water su~pengion of a resin to be tested is permeated Lnto a glass column (15 cm long, 2 cm in diameter~
filled dens~ly with 15g of fine sand (particle ~ize of 100 -300 me~h, moisture content of 6 weight %). The filtrated solution, (whish is obtained from the bottom of the column) is dried, and the residue is weighed. If the weight of residue is a gram, the soil fixity ~X %) is calculated from the following equation:

X(%) = 100 x (0.2 - ~) 0.2 In thi~ invention, the water vapor permeability (WVP) is determined by the method of JIS-Z-0208 (Japanese Industrial Standard). That is, a cup (15 mm deep, 60 mm Ln diameter) containing 10 g of dried CaC12 (particle size of 8 - 30 mesh) is campletely covered with the film 0.03 mm thick of a res~n ~0~ 3Z8 to be te~ted. The cup is allowed to stand for 24 hr8. in a box maintained at 40 + 1C and relative humidity of 90 + 2%, and weighed. The water vapor permeability (Y) i8 calculated from the following equation:
Y (g/m2/24 hrs.) =
~uP weiqht tg) after 24 hrs~ - tInitial cuP weiqht (q~
LPermeable area of the cup (m2~
The agrochemical used in the invention is, for example, herbicides, insecticides, fungicide~, nematocides, rodenticides, plant growth regulator~, repellents and attrac-tant8. Among these, the preferred are herbicides, insecticides and fungicides, and the most preferred are agrochemicals which are easily leached by water into the ~ub80il and/or volatile in the atmoæphere. Examples of the herbi~ide~ u~ed in the in~ention are:
A. Urea-type herbicide (A-l ) 3- ( 3, 4-dichloropher~yl ) -1, l-dimethylurea t ~A-2) 3-(4-chlorophenyl)-1,1-dLmethylurea [
(A-3 ) 3- ~4- (4-chlorophenoxy)phenyl~ -1, l-dimethylurea CTenora~
(A-4) 3-(3,4-dichloroph~nyl)-1-methoxy-1-methylurea [LLnuro~
t~-5) 1-(2-methylcyclohexyl)-3-phenylurea CSiduro~
~A-6) 3-~yclooctyl-1,1-dLmethyl urea rCycluro~
B. Triazine-tye~ herbicide (B-l) 2-chloro-4-ethylamino-6-isopropylamino-S-triazine ~Atrazin~
(B-2) 2-chloro-4,6-bis(ethylamino~-S-triazine ~Simazin~
(B-3) 2-m~thylthio-4,6-bis(isopropylamino)-S-triazine ometryn~
~ 4 -10~;'33Z8 C. Uracll-tyPe herbicide (C-l) 5-bromo-3-~ec-butyl-6-methyl uracil tBromaci~
(C-2) 3-cyclohexyl-5,6-trLmethylene uracil ~enaci~
D. Chloro-acetamide-tYpe herbicide ~D-l) 2-chloro-2',6'-diethyl-N-(methoxymethyl) acetanilide ~la~hlo~
(D-2) 2-~hloro-N-isopropyl acetanilide ~ opachlo~
(D-3) ~,N-diethyl-2-chloro acetamide [CD
(D-4) ~ diallyl-2-chloroacetamide ~CD~A]
E. kmide-tYpe herbicide (E-l) N~N-dImethyl-2,2-diphenyl acetamide ~Diphenami~
F. Aliphatic acid-ty~e herbicide (F-l) 2,2-dichloropropionic acid (Na salt~ ~DP~ -(F-23 trichloroacetic acid (Na salt) ~TCA
(F-3) 2,2,3,3-tetrafluror propionic a~id (Na salt) [TF~
G. Picolinic acid-tyPe herbicid~
(G-l) 4-amino-3,5,6-trichloropicolinic acid CPiclor _. Pheno ~-tYpe herbicide (~-1) 2,4-dichloropheAoxy acetic acid [2,4-D]
(~-2) 2-methyl-4-chlorophenoxy acetic a~id~MC~
(EI-3) 2-12'-methyl-4'-chlorophenoxy) propionic a~id [MCP~
(H-4) ~ -(2-methyl-4-chlorophenoxy)-butylic acid [~CP~
I. Carbamate-tYPe herbicide (I-l) isopropyl-N-(3-chlorophenyl~ carbamate ~C-I
(I-2) methyl-~-(3,4-dichlorophenyl) carba~ te ~SW~
(I-3) 2-chloroethyl-~-(3-~hlorop~enyl~carbamate rBIP~
J. Thiol carbamate-tyPe herbicide (J-l) S ethyl-N,N-di-n-propyl thiolcarbamate CEPT~
(J~2) S-~-propyl-N,N-di-~-propyl thiolcarbamate ~Vernolat~
_ ~ _ ;.

iO~9328 (J-3) S-n-propyl-N-ethyl-N-butyl-thiolcarbamate [Pebulate~
K. Nitrile-tYpe herbicide (K-l) 2,6-dichloro~enzonitrile [DB~
(K-2) 2,6-dichlorothiobenzamide ~ B~
L. Toluidine-tvpe herbicide (L~ -trifluoro-2,6-dinitro-N,~-dipropyl-P-toluidine CTriflurali~
(L-2) N-butyl-N-ethyl ~,~,d-trifluoro-2,6-dinitro-P-toluidine [Benefi~
(L-3) ~,N-dipropyl-2,6-dinitro-4-methylsulfonyl aniline ~itral ~
M. Phe~ol-type herbicide (~-1) 4,6-dinitro-0-sec-butyl phenol (alkanol amine salt) [DNB~
N. Okhers (N-l) 3-amino-1,2,4 triazole [AT~
(N-2~ 3,(2-methylphenoxy)-pyridazine ~Credazin~
(N-3) ~-l-naphtyl phthalamic acid (Na salt) ~P~
Among the above herbicides, the preferred are ur~a-, $riazine-, uracil-, chloroa~etamide- and amide- types when considerLng the prevention of being leached by water, and carbamate-, thiolcarbamate-, ni~rile-, toluidi~e- and phenol-kypes whe~ considerLng the prevention of escaping in vapor.
The film-forming re~in used in the invention is a hydrophilic resin having a soil fixity of at least 40%
(preferably at least 50%) ~nd a water vapor permeability of 400 - 1,509 g/m2/24 hrs. (preferably 600 - 1,000), and the objects of the invention are not attained by hydrophobic or water-soluble recin~ which do no~ have the above values. A

.

~o~
hydrophobic resin has fairly good effect in preventing leaching and eccaping in vapor, but it i8 very poor at controlling elution of an agroch~mical. On the other hand, a water-soluble resLn i8 insufficent for any of the above effects.
The film-forming, hydrophilic resin used in the invention generally belongs to the resins which have one or more hydrophilic groups such as polyoxyethylene chain, carboxyl (Lncluding anhydrides ~hereof~, carboxylic acid salt, amide, sulfonic acid, sulfonic acid salt, hydroxyl, quaternary ammonium salt groups. Typical examples of the resin used in the invention are as follows:
(1) Polyurethanes, which are produc~d by the reaction of organic polyisocyanates and polyol co~ponents having polyoxyethylene moiety (and optionally chain extenders).
Bxamples of the polyols are conven~ional polyetherpolyols ~obtained by adding ethylene oxide (optionally with other alkylene oxides such as propylene oxide, butylene oxides) to a compound having at lea t two active hydrogen atom~
Mnlecular weight of the polyols may be, for example, 500 - 20,000

(2) Polyester resins, which are produced by the condensation reaction of organic polycarboxylic acid~ or their alkyl esters and polyol components having polyoxyethylene moiety;

(3) Vinyl co-polymers, which are produced by the reaction of one or more water-soluble unsaturated nomers and other water-insoluble mo~omers. The water-soluble unsaturated monomers are, for example, carboxylic group-containing unæaturated monomers (e.g., acrylic acid, methacrylic acid, crotonic acid, maleic acid, fum~ric acid and maleic anhy-dxide, etc.3, sulfonic group-contaLning unsaturated 10~ 3'Z8 monomer (e.g., sulfopropyl ~meth)-acrylates, etc.), amide group-containing unsaturated monomer ~e.g., acrylamide, N-methylol acrylamide, etc.), hydroxyl group-containing unsaturated monomer (e.g., hydroxyethyl (meth)acrylates, etc.), and quaternary am~onium salt group-containing unsaturated nomer (e.g., N,~,N-trimethyl -N-acryloyloxyethyl ~monium halides, etc.). The salts of these monom~rs are also used (alkali metal ~alt~, ammonium salts, amine salts, etc.), if they are able to form salts. The water~ oluble unsaturated comonomers are, for example, alkyl(meth)-acrylateæ te.y., ~ethyl-methacrylate, butylacrylate), acrylonitrile, styreneD
vinyl acetate, vinylidene chloride, butadiene, alkens (e.g., ethylene, prolylene, butylene).
Among thes~ hydrophilic re~ins, the desirable ones æ e polyurethanes a~d polye~ter resins which con~aLn ~he polyoxyethylene moiety (mole~ulax weight of 300 - 10,000) a~
the hydrophilic group, because of the ease Ln ~ontrolli~g the soil fixity and WVP, excellent effects and low co-~ts. Particu-larly dssirable are the emNlsions of ~he above polyurethanesand polyester resins, becau~e of the ease in produ~ing agro-ch~mical-resin composi~ionO the ease i~ applying ~he co~position to the farm. The preparatio~ of these emulsion3 is carri~d ou~ by conventional methods. For example, they axe the method of e~ulsifying the a~ore#aid resin into the water with the aid of emulsifying or dispersing agents, and the method of emulsify mg a polyuretha~e pre-polymer (which is prepared by the reaction of 1 mole of a polyol and ~re than 1 mole of a polyi~ocyana~e~ into the water with the aid of emulsifying or 30 di~persing agents.

10~1~3'~8 The method of prepar-~ng agrochemical-resin compo-sitions of this invention i~ not particularly limited. When the resins are used with a spray-t~pe agrochemical (e.g., wettable powder, emulsion and solution formulation~, for example, the use of resin emul~io~ is preferable from the point of ease of application, because a conventional sprayer can be used. The mixing method may be selected from the following:
(1) fixed quantity of an agrochemical and a con-centrated resin emulsion are mixed with the diluting water, (2) a concentrated resin emul~ion is ~ixed with the dilutLng wat~r which conta~n~ an agrochemical, (3) an agrochemical is premixed with resin emulsion and then tho~e are diluted with water.
1~ ano~her ~ethod of preparing the agrochemical-resin composition o~ this Lnve~tion, a conce~trated emulsion-type compo~ition is prepared by mixing an agroohemical with the resin em~lsion of this invention during or af~er the producti~n of the resin emulsion, or by e~ulsifyin~ a mixture of agro-chemical a~d resin. The resulting concentrated composition is applied in a conven~ional manner.
The granular, pellet, dust type composition of this invention may be prepared by mixing and formNla~ing the agro-chemical and th0 resin of this Lnvention and, if nece~sary, a carrier (e.g., bentonite, clay, diatomaceous earth, talc, alu~Lnum oxide, ~i~e -~and and the like). Thus, it is prepared (1) by coating or mLxing an agrochemical with the emulsion or organic solvent ~olution of the resin, followed ~y changing into granule~ or dust, or (2) by preparing the resLn fi~m . 30 contaihing agroc~emicals, followed by cutting or pulverizing.

_ g _ 10~9~3Z8 In the present invention, the ratio of agrochemicals and resins may vary widely dep~nding upon final application methods and the type of agrochemicals. In general, they may be employed in the weight ratio of 1 part of agrochemicals (active ingredient) to 0.1 to 200 parts (preferably 0.2 - 100 parts) of resins (solid con~ent).
Other materials, such as surfactants, emulsion stabilizeræ, pigments, lubricants, fillers, plasticizers, antiseptic substances, ultraviolet stabilizers, dyes, and the like, may be included in the compositions of the invention.
The present invention has the following advantages:
(1) The phytotoxicity to useful plants is decreased in the case of prevention of agrochemicals from being lea~hQd by water into the subsoil, (2) Agrochemicals, which have been used only Ln autumn and winter ea~ons because of their volatility, can be used in all seasons in the case of prevention of escaping in vapor, (3) The dosage of agrochemicals is decreased resulti~g in improved efficiency, and therefore it is very economical and leads to pre~rvation of t~e environment,

(4) The frequen~y of application of agrochemical~ is decreased in the case of long range effectiveness, and therefore it leads to labor saving, (S) It is possible to control the duration period of the effectiveness of agrochemicals by controlling WVP or the amount of the resin used, and (6) A conventional agricultural applicator or sprayer may be used for the compositions of this invention.

-- 10 -- ~

10~ 328 The following examples will illustrate the nature and advantages of the pre~ent invention. It should be understood, however, that the examples are merely illustrative and are not to be regarded as limitations to the appended claims. Unless otherwise indicated, the parts are by weight.
Example 1 13 parts of poly(oxyethyleae oxyp~opylene)glycol ~average molecular weight (MW) is 4,000, molar ration of QXy-ethylene a~d oxypropylene is 80 : 20~, 65 partæ of polypropylene glycol ~MW 950) and 22 parts of tolylene-di-isocianate (TDI) were charged into a reaction ve~sel which is attached with agitator, nitrose~ bubbling pipe and thermo~eter. The above mixture was reacted at 75 - 85 C. for 8 hrs. Under nitrogen atmosphere to obtain the urethane prepolymer having 4.6% of free isocya~ate radicals. To 100 parts of this urethane pre-polymer was added S parts of polyoxyethylene nonylphenyl ether (nonionic emulsifier) and 10 parts of alkyl ethersulfa~e (anionic emulsifier) at 20C. and the whole was em~l~ified i~
170 parts of water with continuous agitatLng to obtain urethane emul~ion LA~. The film from the amulsion had WVP of 807 g/m2 /24 hr~. and a 50il fixity of 78%.

5 Kg of the emulsion [A] and each of the herbicides (the kind and amount of active ingredient are listed in Table 1) were mixed with 300 ~ of water to obtain the spraying samples.
In 1/100 m2 pots charged ~ith loam soil, radish and wheat were seeded respectively and covered with loam soil 3 cm deep which was mixed with weed seeds of Digitaria adscendens and Amaranthus retroflexus. Over the resultant pots, the above ~praying samples were sprayed uniformly in amounts of 300 ml/m~.

.: -10~9328 ~ fter 20 days, the herbicidal effects and th~ degree of phytotoxicity to radish and wheat were observed. The resulting data are presented in Table 1. In addition, result~
were obtained for use of the herbicides only in the spraying sample and for spraying sample~ containing no herbicide and also for complete non-treatment and are also presented in Table 1 for comparison.

10~91328 Tabl~ 1 Amount Herbicidal effect Phytotoxicity Herbicide of Emul~ion Herbicide Ç~J Digitaria Amaranthus (Kg) adscenden retro- Wheat Radi~h _ _ _ flexus D C M U 0.05 added 5 5 0 0 ~ 4 4 1 2 .. . .
Atrazine 0.05 added 5 5 0 0 " " _ 4 4 2 3 Bromacil 0.05 added 5 5 0 0 " " _ 5 5 2 5 .. . . .
Alachlor 0.05 added 5 5 0 0 " " 5 5 3 0 ~. ___. _ . . _ .
Diphen~id 0.1 added 4.5 4 0 0 " " 3 3 2 0 ..... _ . .. . . ... _ _ D P A 0.3 added 4 0 0 0 " " 2.5 0 2.5 0 Picloram 0.05 added 4.5 5 0 0 " " 2 5 0 2 D B N 0.1 added 4 5 0 0 " " 1.5 4 2 0 . . !
C`IPC 0.1 added 5 5 0 0 " " 3 2 0 0 E P T C 0.2 added 5 5 1 0 ~ " _ 4 2.5 5 0 Trifluralin 0.05 added 5 5 0 0 " " 3.5 ~ ~.S O
~ .
Non-~reatment O O O O
.

Urethane em~lsion ~ only O O O O
Note: Evaluation was indicated by number~ from O to 5.
O means non-effective as with untreatment, and 5 means a quit~ excellent result.

~0~i'93Z8 Table 1 shows that the composition of this invention gives excellent results for herbicidal effects and for the prevention of phytotoxicity to use~ul plants in comparison with the use of the commercial herbicides only.
These excellent results come ~rom preventing herbi-cides frQm being leached by wa~er into subsoil or ~rom escaping Ln vapor as indicated in Table 2 and 3. The data in Table 2 were m~asured by the following method:
The above prayLng samples were sprayed in amount of 300 ml/m2 in the po~s, which were made by piling up 10 pieces of ring (1 c~ high, 10 ~m in diameter~, and filled with loam 50il. After 24 hr~., 20 mm/hr. of artificial rainfall wa~ carried out for 1 hr., and then the soil was separated Lnto 10 pieces by the rings. In these soils, radish or sawa millet were seeded, and af~er 20 days the degree of phytotoxicity were observed.
The data in Table 3 wrre measured by the following method:
The above spraying sa~ples were sprayed uniformly in amou~ts of 300 ml/m2 on the soils whi~h contained the seeds of Digitaria adscendens and Am~ranthus retroflexus. For the first 4 days, the~e soils wsre kept under dry conditions without sprinkling water, and then were spriakled everyday. After 20 days, the herbi~idal effects were observed.

lo~s3zs Table 2 Phy*otoxicity to Phytotoxicity to Phytotoxicity to - Depthradish radish sawa miliet of the - ~~~ - ~~
soilAtrazine AtrazLnePicloram Picloran Bromaci~ Bro~acil only and ~A~ only ~nd lA] only and ~A3 0 - lcm 70 (%) 100 (%) - 50 (%) 1~0 (%) 100 (~) 100 (%) ,. _ -- --- :
2 - 3 ~0 40 80 50 lQ0 6~
~ . .. .

A_ . . . ~
4 - 5 3~ 0 40 0 10 0 S - 6 10 0 1~ 0 0 .. _.___._ - !

6 - 7 0 0 0 0 0 0 .. .. ~

7 - 8 0 0 0 ~ 0 0 _ . ~
9 - 10 Q . 0 0 0 0 0 . .

Note: lA~ means urethane emulsion rA].

- ~5 --~06C~328 Table 3 Amoun~ Herbicidal effect Herbicide of Urethane ~erbicide emul~ion Digitaria Amaranthus (K~) ~A~a~scenden~ retroflexus D B ~ 0.1 added 4.5 5 ~ 2 3 C-IPC 0.1 added 5 4 ~ 2 0 E P T C 0.2 added 4 3.5 " " O O

TrifluralinO.OS added 5 4.5 ~ _ 3 2 Non-treatment 0 0 . .

10~ '28 xample 2.
28 parts of polyethylene glycols (MW 2,000), 50 parts of polyester diol (M~ 1,000), prepared from bulanedîol and adipic acîd, and 22 par~s o~ TDI were reacted as in Example 1 with the exception that the reac~ion temperature was 80 -90 C. A urethane prepolymer having 5.2% of isocyanate radicals was obtained. To 100 parts of this prepolymer there were added 3 parts of polyoxyethylene nonylphenyl ether and 12 parts of alkylethersulfate at 20C~ and then the mLxture was emulsi-fied in 170 parts of water with continuous agitating to obtain urethane emulsion ~ ~ . The fil~ from the emulsion t~ had WVP of 1,052 g/m2/24 hrs. and a soil fixity of 84%. ~ing 5 Kg of urethane emulsio~ ~ , the herbicidal effect and the degree of phytotoxicity to radi~h and wheat were observed in the same method as described in ~xample 1. The resulting data are presented in Table 4.

Table 4 _ .
Amount Urethane Herbicidal effect Phvtotoxicity Herbicide of emulsion Dig~taria Amaranthus herbicide ~ adscendens retrofle- Wheat Radish (Kq ) XU9 ~ . _ Atrazine 0.05 added 5 5 0 0 ~ " 4 4 2 3 _ _ _ _ Broma~il 0.05 added 5 5 0 ., .. _ ~ ~ 2 5 . . . _ . . . . . . .
Diphenamid 0.1 added 5 4 0 0 ~ n 3 3 2 0 D P A 0.3 added 4 0 0 0 " " _ 2.5 ~ 2.5 0 .. .
Picloram 0.05 added 5 5 0 0 " ~ _ 2 5 0 2 ~ .
C-IPC 0.1 added 5 5 0 0 " " _ 3 2 0 0 ~ ~ ~ .
P T C0.2added 5 5 1 0 " " 4205 5 0 Trifluralin 0.05 added 5 5 0 O
" 3.5 4 2.5 0 .
Urethane emul~ion ~ only O O O O
-The results in Table 4 ~how that sLmilar excellent effects to those of kxample 1 are obtained in Example 2~
Th~se ex~ellent resul s are also ~upported by the data in Table 5 and 6.

l.O~i93'~8 Table S
Phytotoxicity to Phy~otoxicity to Phytotoxicity to Depth radish radish .sa~a millet of the soilAtrazine Atrazine Picloram Picloram Bromacil Bromacil - only and EBl only and [B] only and 1~]
.. . _ .. .. . . .
O - 1 cm 7~ 0 (~) 50 (~) 90 (%) 100 (%) 100 (%~
.. . . . ..

. .

. . . _ . .
4 - ~ 30 0 40 0 10 0 ~ .
5 - 6 10 0 10 ~ 0 Q

7 - ~ 0 0 0 0 0 0 .

8 - 9 0 . 0 0 a o

9 - 10 0 0 0 0 0 0 .

Note 1: [B] means uret11ane emulsion [B], Note 2: Test met~od is the sa~.e as in Table 2~Exa~ple 1).

~0693Z8 Table 6 A~ount Urc-thc~ne HerbiCiCIal effect Herbicide . . emulsion . .
herblclde rBl Dlgltarla /\marant}lus (Kg~ L ~ adscendens retroflex~ls . .
C-IPC 0.1 added 5 4 " " 2 0 .
E P T C 0.2 adcled 4 3.5 " " O O

Trifluralin 0.05 added 5 5 : - 3 2 Note: Test method is the same as in Table 30 _ 20 -.

~ 69~3Z8 Example 3.

10 parts of mixture ~I] (30 parts of methylmetha-crylate, 25 parts of butylacrylate, 25 parts of hydroxyethyl-methacrylate, 20 parts of acrylic acid), 30 parts of mLxture (3 parts of polyoxyethylene ponylphenyl ether, 5 parts o~ sodium laurylsulfosuccinate, 002 part of sodium bisulfite, 150 paxts of water~, and 4 parts of 2.5 weight % solution of potassium persulfate were charged to a reaction vessel attached wi~h agitator and were polymerized at 55C. for 1 hr., after substituting the air with nitrogen gas. Additionally, 90 parts of the mixture ~ , 120 parts of ~he mixture [I~
and 16 parts of 2.5 weight % solution of pota~sium persulfate were added dropwise separately over 4 hrs~, followed by aging for 3 hrs. to obtain an acrylic emulsio~ rc~. The film from this emulsion rC] had WVP of 495 g/m2/~4 hrs. and a soil fLXity of 52%.
Using 5.0 Kg of the emulsion ~ , the herbicidal effect and the degree of phytotoxicity to radish and wheat were observed by the same method as des~ribed in Bxample 1.
The resulting data are presented in Table 7.

_ 21 -l`able 7 Arnount Acrylic 11erbicidal ef:Eect Phytotoxicity 1-3erbicide herbicide emulsion 1)igitaria ~naranthus (~g) ~ ] Elexus Atrazine O.OS added 5 5 0 0 " " 4 ~ 2 3 Bromacil 0.05 added 5 5 0 " " 5 5 2 5 Diphenamid O.l added 4 4 0 0 " " 3 3 2 0 D P A 0.3 added 4 0 0 0 ~ 2.5 0 2.5 0 .
Piclorarn 0.05 added 4 5 0 0 " " 2 5 0 2 - -.. .. . .
C-IPC O.l added 4.5 4 0 0 " " 3 2 0 0 . _ _ . n __ __ ~ : ~ .
E P T C 0.2 added 5 4 1 0 " " 4 2.5 5 0 . . _ . .
Trifluralin 0.05 ac1ded 5 5 0 0 " " 3.5 4 2.5 0 Acrylic emulsion [C] only 0 0 0 0 ~ 0~;93Z8 le 4.
47 parts of dimethylterephtalate, 53 parts of polyethylene glycol (MW 200), 0.2 part of ferrous benzoate, and 0.1 part of sodium phosphite were charged into a reaction vessel attached with agitator, thermometer, nitrogen bubbling tube and high vacuum evaporator. The mixture was reacted at 180C. for 3 hrs. and then at 270C. below 1 mm ~g for 16 hrs.
Condensed ~ethanol escaped during the reaction. 100 parts of the polyester resin obtained was dissolved in 60 parts of 10 dimethyl formamide and then 10 parts of ethyleneoxide adducts of hydrogenated castor oil and 5 parts of sodium alkylbenzene-sulfonate were added. The above mixture was emulsified Lnto 205 parts of water to obtain polyester emNlsion tD~ . The ~ilm from this ~mulsion t~ had WVP of 674 g/m2/24 hrs. and soil fixity of 70%.
Using 6.7 K~. of the emulsion CD~, the herbicidal effect and the degree ofphytotoxicity to radish and wheat were observed by the same method as de~cribed Ln ~xa~ple 1.
The resulting da~a are prese~ted in Table 8.

'10693Z8 'I'able 8 ... .
~nount Polyester ~lerbiciclal ef~ect Phytotoxicity l~erhici~1e ~lerbicide emulsion Digitaria ~.!ar~nthus l~heat l~adish (Kg) [D] aclscenclens retro-_ fl xus Atrazine 0.05 added 5 5 0 0 " " 4 4 2 3 Bromacil 0.05 added 5 5 0 0 " " 5 5 2 3 .
Diphenarnid 0.1 added 4.5 4 0 0 " " 3 3 2 0 .
V P A 0.3 added 4 0 0 0 " " 2.5 0 2.5 0 ' Picloram 0.05 added 4.5 5 0 0 " '; 2 5 2 _, C-IPC 0.1 added 5 4.5 0 0 " " 3 2 0 0 .
P 'I` C 0.2 added 5 4.5 ) 0 " " 4 2.5 5 0 Tri1uralin O.OS added 5 5 0 0 " " 3.5 4 2.5 0 Polyester emulsion (I)) only 0 0 0 0 -- 2~ -10~;93Z8 Exa~ple 5.
100 parts of urethane emulsion [A~ obtained in Example 1, 30 parts of Bromacil and 230 parts of bentonite were kneaded for about 15 minutes. The massive mixtuxe obtained was formed by pelletizer and dried to obtain small pellets (1 - 2 mm long, 0.8 mm in di2meter) containing 10 wt % of Bromacil.
Example 6.
Five experimental plots were arranged in the testLng farm. To experLmental plots 1 - 4 (Ex. - 1~ 4) spraying samples, which were prepared according to the followi~g table, were sprayed in amounts of 200 ml/m2.

10~9328 Table 9 13xperimental SpraYing sam~le plotsHerbicide Resins Water Hybar -X Ur~th2me emulsion L~ 200 0. 8 Kg 10 Kg Ex-2 Hybar -X Urethane emulsion ~BJ 200Q
0. 8 Kg 10 Kg Ex-3 Hybar -X Acrylic~ emulRion ~C~ 200 Q
0. 8 Kg 10 Kg .
Ex-4 Hybar -X Polyester emulsit)n L~ 20G
0.8 Kg 13 Kg ~ote: Hybar -X is a trade mark identifying a herbicide con~aining Uracil as active ingredient (80%).

10~;93Z8 To experimental plot 5 (Ex. - S) the Bromacil pellets, which were prepared in Example 5, were applied at the rate of 6.4 g/m2. Then, the dried weight of weeds per 1 m2 ~n 5 plots was determined periodically. The resulting data are showed in Table 10 along with the data, for comparison, in check plot 1 - 6 (Ck - 1~ 6). Ck-l was the untreated plot, Ck-2 was treated with 0.8 g/m2 of ~ybar -X solution in 200 ml water. Ck-3 was trea~ed with the mixture, spray of Hybar -X
0.8 g, the conventional polyacrylic emulsion 8 g (concentration 50 wt %) and 200 ml water per m2. Ck-4 was treated with the mLxture spray of ~ybar -X 0.8 g, polyvinylacetate-ethylene copolymer emulsion ~concentration 50 wt %) 8 g and 200 ml water per m2. Ck-5 was treated with the mLxture spray of ~ybar -X 0.8 g, reaction product ~of 80 parts of poly (~xyethy-lene oxypropylene) glycol (MM 4,000, ~0/POt80/20 molar ratio) and 20 parts of tolylenediisocyanate3 8 g, and 160 ml water per m2, and Ck-6 waæ treated with the mixture -spray of Hybar -X
0.8 g, water-soluble polyacrylate (acrylamide/acrylic acid =
80/20 weight ratio: concentxation 25 wt %~ 16 g, and 200 ml water per m2.
Weeds used Ln this testing farm were in the weight ratio of ~ramLneous weed/Compositous weed~Broadleaved weed/
others = 25/40/20/15. This test started at ~he middle of February.

10~i9328 Table 10 - ~ ~ried Dried Dried Permeabili~y Soil Dried weigh~ wei~ht ~eight weight Plo~s of resin y ore spray after after a~ter ~g/m2/Z4hT~ ~%~ (g/m2) spra~d sprayed sprayed (g/m ) (g/m2) (g~m2) .. ._ _ . _ .. _ . . .. _ . .~
Ex-l 807 78 73 0 116 1~7 .. . .. .. _ _ , . ... _ _ .. . . . .. .
Ex-2 1,052 84 62 0 98 92 .._ . . . . _ _ . . _ _ . .
Ex-3 - 495 52 57 i8 212 245 ~, _ , . ~....... ~_ _ ._ .. . . . _.
Ex-4 674 70 66 14 -147 163 _ . . __ . . _ _ . ~ . . _ E~-5 807 78 45 . 47 155 171 . _ . . . __ .. _ . _ . _ _ . . . . , __ Ck-l - - 50 508 2,02~ 2,17 - Ck-2 - _ - 47 - 86 1,088 1,269 : _ . . _ __ . .__ . . . ,_ , .
Ck-3 125 21 59 205. 1~182 1,317 ,, : ....
Ck-4 369 46 64 107 856 878 ~ .. _ .__ . .. _ . _ . _ .. _ .. .. _ , . _ .. .. .
Ck-5 1,807 96 77 53 818 844-.. .. _ . ... _ .. _ , .
Ck-~ a3 oo~st 34 56 9S . 1,103 1,347 ~ . . . . . . .
Note: ~he dried weight (g~m2) me~ns the weight o weeds in 1 ~2 in the plots after drying at 80C. ~or 24 hrs.

.. -. .

10~;9~28 The results in Table 10 show that the composition of this invention gives excellent results in relation to long range effectiveness i~ comparison with Check plot~ 1 - 6.
Figure 1 illustrates the above result in graph form, in whi~h the X - axiq indicates the WV~ of resins used and t~e Y - axi5 indicates the ratio of dried weight of weeds after 10 months to dried weight of weeds before spray.
~xample 7.
The continuous effect of the emulsion E~ obtained in Exa~ple 1 was observed by using the mLxture of 10 ml of DDVP emulsion ~Dimethyl-2,2-dichlorovi~yl-phosphate~ insect-icide), 200 g of the emulsion [A] , and loQ of water. A
tomato seedling was treated with t~e resulting ~Lxture and the occurrence of plant-louse 30 days after sprayed was observed. The resulting data is ~hown in Table 11. Additio~-ally, comparative example 1 was the result from the untreated plot, comparative ex~mple 2 was the resul~ rom the check plot which wa~ treated with a single application of a mixture of DDVP emul~ion 10 ml and 10~ water, comparative exaQple 3 was the result from the check plot which w~s treated with three applications of a mixture of DDVP emulsion 10 ml and 10~ water at 7 day intervals, and co~parative ~xample 4 was the result from the check plot which was treated with the mixture spray of polyvinyl aceta~e-ethylene copolymer emulsion (mentioned in Example 6) 160 g, DDVP emulsion 10 ml and water 10 ~.

10~;93,'~

Table 11 . .
Spray Occurrence Example 7 8.2 Comparative example 1 100 " " 2 73.5 " " 3 7.
" " 4 84.0 . _ . .

Note: Occurrence was determined on the base ~ of occurrence (100~) in the ~mtreated plot.

--3~) -

Claims (11)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. An agrochemical composition which comprises an agricul-tural chemical, and a film-forming polymer having at least one polyoxyethylene moiety per molecule and having a soil fixivity of at least 40% and a water vapour permeability of 400 to 1,500 g/m2/24 hrs.

2. An agrochemical composition according to claim 1 wherein the polymer is in the form of a polymer emulsion.

3. An agrochemical composition according to claim 1 wherein the polymer is a polyurethane or polyester resin.

4. An agrochemical composition according to claim 3 wherein the polyoxyethylene moiety has a molecular weight of 300 to 10,000.

5. An agrochemical composition according to claim 3 or 4, wherein the polyurethane is a reaction product of a polyol having a polyoxyethylene moiety in the molecule and a polyisocyanate.

6. An agrochemical composition according to claim 3 or 4, wherein the polyester resin is a reaction product of a polyol having a polyoxyethylene moiety in the molecule and a polycarboxylic acid or ester.

7. An agrochemical composition according to claim 1 wherein the polymer is a copolymer of an unsaturated monomer having at least one hydrophilic group which is a polyoxyethylene moiety and of a water-insoluble unsaturated comonomer.

8. An agrochemical composition according to claim 7, wherein the water-insoluble unsaturated comonomer is an alkyl acrylate, an alkyl methacrylate, acrylonitrile, styrene, vinylidene chloride, vinyl acetate, an alkene or butadiene.

9. An agrochemical composition according to claim 1, 2 or 3, wherein the agricultural chemical is a herbicide, fungicide, insecticide, nematocide, rodenticide, plant growth regulator, repellent or attractant.

10. An agrochemical composition according to claim 1, 2 or 3, wherein the agricultural chemical is a herbicide, fungicide, insecticide, nematocide, rodenticide, plant growth regulator, repellent or attractant and is a urea-type, triazine-type, uracil-type, chloroacetamide-type, amide-type, aliphatic acid-type, picolinic acid-type, phenoxy-type, carbamate-type, thiol-carbamate-type, nitrile-type, toluidine-type or phenol-type herbicide.

11. An agrochemical composition according to claim 1, 2 or 3, wherein the weight ratio of agricultural chemical:polymer is 1:0.1 - 200.