WO2002011538A2

WO2002011538A2 - Floating type formulation of agricultural agents

Info

Publication number: WO2002011538A2
Application number: PCT/EP2001/007947
Authority: WO
Inventors: Yasuhiro Kamata; Haruki Innami
Original assignee: Bayer Cropscience Gmbh
Priority date: 2000-08-08
Filing date: 2001-07-10
Publication date: 2002-02-14
Also published as: AU2001270626A1; CN1292654C; TWI230582B; WO2002011538A3; JP2002053405A; CN1446047A; KR20030018070A

Abstract

The present invention aims to supply formulas of agricultural agents with no undesirable effect on crops and low risk of running off of agricultural agents from a paddy field, due to the excellent dispersion of the active ingredients of agricultural agents as well as quick sank of the carriers into the water after dispersion, and being prepared at reasonably low costs. Formulation of agricultural agents characterized by containing active ingredients of agricultural agent, a porous carrier of which average particle diameter is in the range of 10 to 100 microns, a surfactant, a binder and a polymer of high water absorption.

Description

Specification

Floating type formulation of agricultural agents

The present invention relates to floating type formulation of agricultural agent, in more detail, so called " jumbo formulation " characterized by applying active ingredient into a paddy field without any machine, by dropping agricultural agent itself, or agricultural agent being, prepared by packing beforehand in a water soluble bag.

In these days, due to the progress of decreasing in the population of agricultural workers, the higher average age of agricultural workers, and the change of farming as side business, there is a high demand of less manpower spray methods for agricultural agents without using any machine, as well as without walking into a paddy field. On the other hand, due to the high social interest in the environmental effects of agricultural agents, there is a high demand of formulation of agricultural agents and spraying techniques which become practical to apply easily an appropriate amount of agricultural agents in order to reduce running off of agricultural agents from a field being sprayed, and also to reduce the bad effects on a spraying person.

In this kind of situation, the development of so called " jumbo formulation " characterized by applying active ingredient into a paddy field without using any machine, by dropping a certain amount of several 10 g of agricultural agent itself, or agricultural agent being prepared by packing beforehand in a water soluble bag, became quite popular in these days, for their advantageous characters such as easy spray of an appropriate amount, less effect of weather at application time, low risk of running off of agricultural agent from a site being sprayed.

Since a product of jumbo formulation can be sprayed locally in a paddy field, good extension of the product in a paddy field is very important at the point of stability of the efficacy and reduction of phytotoxicity on rice plants. In addition, there is a need to reduce any undesirable effect of active ingredient and auxiliary agent on the crop to be targeted as well as on the environment. Furthermore, it is practically important to supply stable products at relatively low price.

Regarding product forms of jumbo formulation, there have been published, in the Japanese patent laid opening No. H6-192004, H6-211604 and H11-240803, about bubble-forming formulation by suspending active ingredient of agricultural agent into the water with carbon dioxide gas being generated at the time of dropping into the water by combination of solid acid and carbonate or bicarbonate salt. This kind of bubble-forming jumbo formulation has some effect on extension of active ingredient into the water by generating carbon dioxide gas. However, there is a high risk of causing phytotoxicity on the crop being applied or the crop being cultivated afterwards, due to the local remaining of active ingredient(s) on the site where a bubble-forming jumbo formula has sunk into the top soil of the paddy field.

There are more practical defects. Namely, the outside packing material will be sworn and no more foaming is available at the actual application time, due to the fact that a neutralizing reaction can initiate easily during storage time with a small amount of water being contained in a formulated product, and also the fact that such neutralizing reaction can be stimulated by the water being generated by the neutralization.

In the Japanese patent laid opening publication No. H11-1402, there has been disclosed a formula characterized by floating up to the water surface and dispersing into a paddy field with the air being stored in the granules containing active ingredient of agricultural agent, in accordance with the dissolution of the water soluble carriers into the water after being sunk once into the top soil. This formulation has a merit of less scattering even without packing into a water-soluble bag due to the heavy weight of the product itself. However, in case of agricultural agent with high soil absorption, some portion of the active ingredient remains at the site being sunk, and consequently it is hard to obtain a sufficient uniform dispersion. Furthermore, there are several technical problems. For example, requirement of special techniques for the preparation, corrosion of a machine being used for formulation by water soluble carriers, requirement of sensitive control of temperature and moisture of the room where a preparation facility is installed to protect water soluble carriers from deliquescence.

Among jumbo formulas, " a floating type formula" can be characterized by reaching the active ingredients to the crop, after dispersing and dissolving the active ingredients into the surface water, and has the following excellent characters. Namely, a floating type formula can keep the active ingredients floating on the water surface far from the topsoil which has a bad character of strong absorption of the agricultural agents being applied. The active ingredients can disperse rapidly into the water, dissolve uniformly into the water by the convection of water as well as the gravity, and consequently remain uniformly on the surface of topsoil.

In the Japanese patent laid. opening publications No. H8-99803, H 10-265302 and H10-287505, there have been disclosed preparation examples of floating formula by using granulation method by kneading. The granulation method by kneading is commonly used for preparation of agricultural agent, however, it costs relatively high because of complicity of the process and requirement of drying process. In case of preparation of floating formulas by using large granules having large holes inside with the kneading method, there are practical problems such as risk of destroying the screen during passing the granules through a screen, or requirement of a large amount of water for kneading. Generally speaking, powder material shall be pressed in the presence of binder to form granules with kneading method, therefore, there is a risk of destroying the granule structure in case of use of large granules having large holes inside, and consequently loose the floating capacity. In addition, by heat caused during the drying process, there are some practical risks, for example, decomposition of some active ingredients of agricultural agents, generating bad odor, and loosing function of a surfactant. In the Japanese patent laid opening No. H11-315004 and H6-336403, and the Japanese patent publication No. H3-76281 , there have been disclosed some techniques for preparation of a floating formula from a porous substance by coating or by absorption. These methods can dissolve the defects described in the kneading methods. However, the floating capacity of carriers being described in the application examples is very high, and consequently the carriers remain on the water surface of a paddy field for long time, even when the active ingredients have been released into the water after spraying the formulated product. As a result, there is a defect as growth inhibition of the crop growing around the site where the carriers are gathered by wind blowing, and a high risk of running off from a paddy field being applied.

In the Japanese patent laid opening No. H 10-109905, there has been disclosed a floating formula being applicable on the water surface, consisting of anionic surfactant and inorganic or organic carriers), and average particle diameter less than 50 microns. In the Japanese patent laid opening No. H8-99804, there has been disclosed a floating-expanding formula being applicable on the water surface. This formula can be characterized by holding active ingredient(s) of agricultural agent(s) in a water floating granule skeleton, and by combining a water surface extender and an emulsifying dispersion agent containing at least one glucose residue in the molecule structure. In the Japanese patent laid opening publication No. H5-155709, there has been disclosed a floating formula being applicable on the water surface, combining anionic surfactant and inorganic or organic carriers, and average particle diameter less than 50 microns. In these publications, there were cited some application examples of techniques by which the said technical defects above can be overcome. Namely, there is a possibility of less storage problem, less damage of manufacturing machine, and with relatively low cost. In addition, it seems to contain some techniques for preparing a floating type formula of less phytotoxicity on the plants caused by carriers remaining on the water surface, and of low risk of running off from a paddy field.

On the other hand, granules of which average particle diameter is less than 100 microns have an advantage to reduce the carriers to remain on the water surface after releasing the active ingredients. However, the surface squire per unit weight is very large by comparing with coarse granules, and consequently there is a tendency of forming cohesion of granules. As a result, a formulated product being sprayed over the water surface of a paddy field stays on the same place for long time without expanding, and the release and uniform distribution of active ingredients are prevented. Consequently, the efficacy of agricultural agents becomes to be insufficient, while phytotoxicity and local residue are caused.

The present invention aims to supply the following formula. After spaying, the active ingredients can be released finely, and the carriers can sink in relatively short time, agricultural agents can be expanding over the water surface of a paddy field against the cohesive force among granules, therefore, the active ingredients can be released quickly into the water. Particularly, the present invention aims to supply the following water floating type formula. It can be manufactured in simple process and at less expensive cost by using a usual facility for agricultural agents, with outstanding effect after spraying, and with less effect on crop as well as on the environment, and the carriers can sink in relatively short time. In addition, the present invention aims to supply agricultural agent formula which can be sprayed easily without any machine, by packing the said floating formula above with water soluble material such as polyvinyl alcohol film.

The present inventors observed the following characters of the agricultural agent formula containing an active ingredient, porous carriers of which average particle diameter is in the range of 10 to 100 microns, a surfactant, a binder, and a polymer of high water absorption. After spraying the agricultural agent formula on the water surface of a paddy field, the active ingredient can disperse rapidly and dissolved into the water by the stimulated extension of the enlarged distance among granules caused by swelling of a polymer of high water absorption with absorbing water.

Namely, the present invention relates to formulation of agricultural chemicals characterized by containing active ingredient(s), a porous carrier of which average particle diameter is in the range of 10 to 100 microns, a surfactant, a binder and a polymer of high water absorption. The average particle diameter of a porous carrier to be used for the present invention is in the range of 10 to 100 microns. In case that the average particle diameter is over 100 microns, the carriers are floating and remain on the water surface for long time period, and inhibit the growth of rice plants around which the carriers are driven together by wind blow, and there is a risk of running off from a paddy field being sprayed. On the other hand, in case that the average particle diameter is in the range of 10 to 100 microns, the porous carriers being floating and remaining on the water surface after spraying can sink into the water within a few hours by absorbing water gradually and loosing the floating capacity. Consequently, there is no undesirable effects on rice plants, and no risk of running off from a paddy field being applied. Thus, by using a porous carrier of which average particle diameter is in the range of 10 to 100 microns, it is available to prepare a formula with no undesirable effects on useful plants after being sprayed.

In addition, the present invention can enhance the dispersion capacity of a formula by combining at the same time a surfactant and a polymer of high water absorption to the formula, and prevent efficiently the stability reduction of formula by water being contained in the formula.

The combination ratio of the said substances above in the formula can be determined optionally in accordance with the kinds of porous carriers to be used, and deconstructing time period to be planned. However, by considering the effect of remained agricultural agent on crop, there can be cited, for example, 5-70 w/w % of porous carriers, 0.5-20 w/w % of a surfactant, 0.1-15 w/w % of a polymer of high water absorption. More preferably, there can be cited, for example, 10-60 w/w % of porous carriers, 3~15 w/w % of a surfactant, and 0.5-10 w/w % of a polymer of high water absorption.

By packing a portion of 10-100 g of the agricultural agent prepared in the way described above with water soluble material such as polyvinyl alcohol film, etc., the following formula of agricultural agent can be supplied. This formula has excellent characters such as enhanced storage stability, a model suitable for direct application into a paddy field without any machine, high efficacy, saving manpower, and less bad effect on a sprayer as well as on the environment.

In the present invention, there is no special limitation of active ingredient of agricultural agent to be used, therefore, there can be cited, for example, herbicides, insecticides or fungicides, such as Anilofos, Ethoxysulfuron, Benfuresate, Daimuron, Oxadiazon, Oxadiargyl, Benzofenap, Clomeprop, Biphenox, Prochloraz(e), Iprodion, Fossetyl, Fipronil, Ethiprole, Thiocarb, Endosulfan, NAC, Vamidothion and Silafluofen. The agricultural agents to be used in the present invention are not limited to these products, and these products can be used as a single component or as a mixture of more than two products.

As a porous carrier to be used in the present invention, there can be cited the following substances of which average particle diameter is in the range of 10 to 100 microns, for example, pumice stone, pumice stone- powder pulverized by burning, volcanic ash pulverized by burning, perlite powder pulverized by burning, diatomaceous earth, vermiculite, foamed glass, organic or inorganic particle being treated as water proof, vegetable origin powder, and particle being made of used paper, etc. The porous carriers to be used in the present invention are not limited to these products, and these products can be used as single component or as a mixture of more than two products. However, there can be cited preferably volcanic ash pulverized by burning, by the reason of the low density and consequently it is available to give floating capacity with small amount of addition.

As a surfactant, there can be cited, for example, fatty acid soap, sulfate of oil, sulfate ester of a high alcohol and an olefin, alkyl sulfate ester,¹ alkyl sulfonate, alkylaryl sulfonate, sulfosuccinate ester, fatty amide sulfonate, lignosulfonate, alkylphosphate ester, alkyletherphosphate ester, alkylether, alkylphenyl ether, alkylphenyl ether- condensed ether, alkyl ester, alkylamine, alkylamide, polyoxypropyrene ether, vegetable oil ether, allyl phenyl ether, glycerin-fatty acid ester, sorbitane-fatty acid ester, polyoxyethylene sorbitane-fatty acid ester, and polyether. The surfactants to be used in the present invention are not limited to these substances, and these substances can be used as a single component or as a mixture of more than two substances. The amount of addition can be in the range of 0.5-20 w/w %, and preferably 3-15 w/w %.

As a binder, there can be cited, for example, carbohydrate, chlorinated paraffin, polybutene, alcohol, ester, animal or vegetable oil, silicone oil, and ether. The binders to be used in the present invention are not limited to these substances, and these substances can be used as a single component or as a mixture of more than two substances. The amount of addition can be in the range of 0.5-30 w/w %, and preferably 1-20 w/w %.

As a polymer of high water absorption, there can be cited, for example, polyacrylate with bridging structure, isobutylene/maleate, starch/polyacrylate, polyvinyl alcohol(PVA)/polyacrylate, hydrated product of acryl fiber, PVA with bridging structure, and carboxy methyl cellulose (CMC) with bridging structure. However, there is no special limitation. Especially, there can be cited preferably starch/ polyacrylate, because of easy bio-decomposition. The amount of combination of polymers of high water absorption can be in the range of 0.1-15 w/w %, and preferably 5-10 w/w %.

In the formulation of the present invention, there can be used certain amount of a general inert carrier besides a porous carrier. As such a carrier, there can be cited, for example, a water soluble substance such as mineral fine powder, synthetic silica, natural or synthetic polymer powder, wooden powder, vegetable powder of weeds or trees, used paper, saccharide, salt, etc. However, there is no special limitation to these substances, and these substances can be used as a single component or as a mixture of more than two substances. The amount of use of these substances can be in the range of 1-80 w/w %, and preferably 2-50 w/w %. Furthermore, there can be added optionally a stabilizer, a conditioner for physical characters, a die, a deodorant, a flavor, etc. Furthermore, in the present invention, it is preferable to coat the formula with water soluble material, and as such material to be applicable for use, there can be cited, for example, polyvinyl alcohol film, chemically modified polyvinyl alcohol film, water soluble paper, starch film, and complex thereof. However, there is no special limitation.

Application examples of the present invention will be explained in the following. The amount of combination is shown as weight per weight percentage (w/w %).

Application Example 1

Anilofos 13.0

Benfuresate 12.0

Ethoxysulfuron 0.67

Surfactant ( olephine sulfonate ) 1.5

Surfactant ( alkylnaphthalene sulfonate ) 2.0

Surfactant ( dialkylsulfosuccinate ) 3.5

Surfactant ( copolymer resinate ) 3.0

Partial sodium salt of starch-acrylic acid graft polymer 4.0

Synthetic silica 10.0

Fine clay powder 10.0

Spindle oil 6.0 Volcanic ash pulverized by burning (average particle diameter is 80 microns ) was added to the above mixture to make 100 w/w % as total.

All substances except spindle oil and volcanic ash pulverized by burning were mixed well by a mixer, and pulverized by a hammer mil to obtain the original powder. In a mixing granulator, Spartan-Ryuder ( manufactured by Dalton Co., Ltd. ), volcanic ash pulverized by burning was added and permeated well by spindle oil with mixing. The original powder was added thereto, and Spartan-Ryuder was allowed to run for 5 minutes to obtain a formulated product. A portion of 33 g of the formula can be packed in a PVA pack, and 100 packs can be sprayed per one hectare of paddy field.

Application Example 2

Oxadichlomefone 2.4

Benzofenap 18.01 Ethoxysulfuron 0.67

Surfactant ( acethylene type ) 1.0

Surfactant ( alkylnaphthalene formaline condensed salt ) 4.0

Partial sodium salt of starch-acrylic acid graft polymer 4.0

Urea 15.0

Spindle oil 5.0 Volcanic ash pulverized by burning (average particle diameter is 80 microns ) was added to the above mixture to make 100 w/w % as total.

A floating formula was obtained by the same method as described in the application example 1. A portion of 33 g of the formulated product can be packed in a PVA pack, and 100 packs can be sprayed per one hectare of paddy field.

Application Example 3

Oxadichlomefone 2.4

Benzofenap 18.01 Ethoxysulfuron 0.67

Surfactant ( lauryl sulfate ) 2.0

Surfactant ( lignin sulfonate ) 4.0

Surfactant ( dialkylsulfosuccinate salt ) 3.5

Partial sodium salt of starch-acrylic acid graft polymer 4.0

Glucose 15.0 Spindle oil 5.0

Volcanic ash pulverized by burning (average particle diameter is 80 microns ) was added to the above mixture to make 100 w/w % as total.

A floating formula was obtained by the same method as described in the application example 1. A portion of 33 g of the formulated product can be packed in a PVA pack, and 100 packs can be sprayed per one hectare of paddy field. Application Example 4

Anilofos 8.0

Benfuresate 7.0

Ethoxysulfuron 0.4

Daimulone 6.0

Surfactant ( fatty acid-alkyloxide phosphate ester ) 2.0

Surfactant ( lignin sulfonate ) 4.0

Surfactant ( dialkylsulfosuccinate ) 3.5

Partial sodium salt of starch-acrylic acid graft polymer 4.0

Synthetic silica 10.0

Pottasium chloride 10.0

Kenafu powder 10.0

Rape oil 6.0 Pumice stone powder pulverized by burning (average particle diameter is 80 microns) was added to the above mixture to make 100 w/w % as total.

A floating formula was obtained by the same method as described in the application example 1 , but using a planetary movement type mixer as a mixing apparatus. A portion of 33 g of the formulated product can be packed in a PVA pack, and 100 packs can be sprayed per one hectare of paddy field.

Comparative example 1

A floating formula for comparative formula 1 was obtained by the same method as described in the application example 1, but without adding partial sodium salt of starch-acrylic acid graft polymer.

Comparative example 2

By changing the average particle diameter of volcanic ash pulverized by burning from 80 to 600 microns in the application example 1 , a floating formula for the comparative formula 2 was obtained by the same method as described in the application example 1. Test example 1

To a water pipe being made of hard vinyl chloride and closed at the both ends, of 16 cm in width, 12 cm in highness, and 400 cm in length, tap water was added to make 6 cm in depth ( water volume is 38.4 litters ). A portion of 0.21 g of the formula prepared by the experimental example 1 was packed in a bag made of polyvinyl alcohol film of 2 cm x 3 cm ( Solublon PT40 micron, manufactured by Aicello Chemical Co., Ltd. ), and dropped at the place being 10 cm far from the end of the water pipe. Water samples were taken periodically at the dropping site, as well as at the sites of 1.5 m, 3.0 m, and 3.8 m far from the dropping site, and used for the analysis of content of agricultural agent. At the same time, disappearance of formula being dropped in the water pipe was analyzed by observation with native eyes. Results of analysis and observation are shown in the Table 1.

Table 1 : Concentration of active ingredient of agricultural agent in the water analyzed periodically ( ppm )

Oxad. = Oxaziclomefone Benz. = Benzofenap Ethox. = Ethoxysulfuron

A pack of PVA was broken after dropping, fine granules were expanded on the water surface, and the active ingredients were well expanded all over the water surface within 3 minutes after dropping. No granules have been observed to remain at the bottom of the water pipe. All carriers sank into the water and nothing remained on the water surface after 5 hours from dropping.

Test example 2

The formulated product obtained in the application example 2 was tested in the same way as described in the test example 1. Results of analysis and observation are shown in the Table 2.

Table 2 : Concentration of active ingredient of agricultural agent in the water analyzed periodically ( ppm)

Almost the same results as the test example 1 were obtained in the test example 2. Namely, a pack of PVA was broken after dropping, fine granules were expanded on the water surface, and the active ingredients were well expanded all over the water surface within 3 minutes after dropping. Almost no granules have been observed to remain at the bottom of the water pipe. All carriers sank into the water and nothing remained on the water surface after 5 hours from dropping.

Test example 3

The formulated product obtained in the application example 3 was tested in the same way as described in the test example 1. Results of analysis and observation are shown in the Table 3.

Table 3 : Concentration of active ingredient of agricultural agent in the water analyzed periodically ( ppm )

Almost the same results as the test example 1 were obtained in the test example 3. Namely, a bag of PVA was broken after application, fine granules were expanded on the water surface, and the active ingredients were well expanded all over the water surface within 3 minutes after dropping. No granules have been observed to remain at the bottom of the water pipe. All carriers sank into the water and nothing remained on the water surface after 5 hours from dropping.

Test example 4

The formulated product obtained in the application example 4 was tested in the same way as described in the test example 1 with only one exception that dose of the agent was 0.32 g. Results of analysis and observation are shown in the Table 4.

Table 4 : Concentration of active ingredient of agricultural agent in the water analyzed periodically ( ppm)

Anil. = Anilofos Benf. = Benfuresate Ethox. = Ethoxysulfuron Daim. = Daimuron

Almost the same results as the test example 1 were obtained in the test example 4. Namely, a pack of PVA was broken after dropping, fine granules were expanded on the water surface, and the active ingredients were well expanded all over the water surface within 3 minutes after dropping. No granules have been observed, to remain at the bottom of the water pipe. All carriers sank into the water and nothing remained on the water surface after 5 hours from dropping.

Test example 5

The formulated product obtained in the comparative example 1 was tested in the same way as described in the test example 1. Results of analysis and observation are shown in the Table 5.

Table 5 : Concentration of active ingredient of agricultural agent in the water analyzed periodically ( ppm )

Compared to the application example 1 , the formulated product of the comparative example 1 , in which a polymer of high water absorption was omitted, showed worse results that solid substances remained on the water surface, and that the dispersion of active ingredients was poor. Namely, a pack of PVA was broken after dropping, and the granules were expanded somewhat on the water surface, but some solid substances remained during ail the time of experiment. In addition, almost no granules sank to the bottom of water pipe.

Test example 6

The formulated product obtained in the comparative example 2 was tested in the same way as described in the comparative example 1. Results of analysis and observation are shown in the Table 6. Table 6 : Concentration of active ingredient of agricultural agent in the water analyzed periodically ( ppm)

The pack of PVA was broken after dropping, and fine granules were well expanded all over the water surface within 3 minutes after dropping. Almost no granules have been observed to remain at the bottom of the water pipe, however, some carrier residue remained on the water surface during all the time of experiment. The formulated product of the preparative example 2, in which the average particle diameter of volcanic ash pulverized by burning was 600 microns instead of 80 microns in the application example 1 , showed fine extension of the formula on the water surface as well as fine dispersion of active ingredients in the water, however, the carrier residue remained even after 24 hours.

As described above, floating type formulas of agricultural agents prepared by the present invention can well release and disperse the active ingredients into a paddy field, give uniform effects, and cause no undesirable effects on crops.

Claims

Claims:

1. Formulation of agricultural agents characterized by containing agricultural chemical(s), porous carrier(s) of which average particle diameter is in the range of 10 to 100 microns, surfactant(s), binder(s) and polymer(s) of high water absorption.

2. Formulation of agricultural agents of the claim 1 characterized by containing 0.1-60 weight weight % of agricultural chemical(s), 3-60 weight/weight % of porous carriers) of which average particle diameter is in the range of 10 to 100 microns, 1-25 weight/weight % of surfactant(s), 1-30 weight weight % of binder(s) and 1-25 weight/weight % of polymer(s) of high water absorption.

3. Formulation of agricultural agents of either the claim 1 or the claim 2 characterized by containing one or more agricultural chemicals being selected from the chemical group consisting of Anilofos, Ethoxysulfuron, Benfuresate, Daimuron, Oxadiazon, Oxadiargyl, Benzofenap, Clomeprop, Bifenox, Prochloraz(e), Iprodion, Fosetyl, Fipronil, Ethiprole, Thiocarb, Endosulfan, NAC, Vamidothion and Silafluofen.

4. Formulation of agricultural agents of either the claim 1 or the claim 2 characterized by containing as porous carrier(s) one or more substance(s) being selected from the substance group comprehending pumice stone, pumice stone powder pulverized by burning, volcanic ash pulverized by burning, perlite powder pulverized by burning, diatomaceus earth, vermiculite, foamed glass, organic or inorganic particles being treated as water proof, vegetable origin powder, and particles being made of used paper.

5. Formulation of agricultural agents of either the claim 1 or the claim 2 characterized by containing as surfactant one or more substance(s) being selected from the substance group comprehending fatty acid soap, sulfate of oil, sulfate ester of a high alcohol and an olefin, alkyl sulfate ester, alkyl sulfonate, alkylaryl sulfonate, sulfosuccinate ester, fatty amide sulfonate, lignosulfonate, alkylphosphate ester, alkyletherphosphate ester, alkyl ether, alkylphenyl ether, alkylphenyl ether- condensed ether, alkyl ester, alkylamine, alkylamide, polyoxypropyrene ether, vegetable oil ether, allyl phenyl ether, glycerin-fatty acid ester, sorbitane-fatty acid ester, polyoxyethylene sorbitane-fatty acid ester, and polyether.

6. Formulation of agricultural agents of either the claim 1 or the claim 2 characterized by containing, as polymer of high water absorption, one or more substance(s) being selected from the substance group comprehending a polyacrylate salt with bridging structure, isobutylene/maleate, starch/polyacrylate, polyvinyl alcohol (PVA)/ polyacrylate, hydrated product of acryl fiber, PVA with bridging structure, and carboxy methyl cellulose (CMC) with bridging structure.

7. Formulation of agricultural agents of either the claim 1 or the claim 2 characterized by containing as binder one or more substance(s) selected from the substance group comprehending carbohydrate, chlorinated paraffin, polybutene, alcohol, ester, animal or vegetable oil, silicone oil, and ether.

8. Floating type formulation of agricultural agents characterized by preparing in the process of rapping a portion of 10 to 100 g of agricultural agent(s) described in the claim 1 to the claim 7 with water soluble material.

9. Floating type formulation of agricultural agents formulated as described in the claim 8 and characterized by containing, as water soluble material, one or more substance(s) being selected from the substance group comprehending polyvinyl alcohol film, chemically modified polyvinyl alcohol film, water soluble paper, starch film, and a complex thereof.

10. Use of any agricultural agents being formulated as described in the claim 1 to the claim 9.