JPH0233682B2 - SUICHUHOKAI * KAKUTENSEINORYOKONARYUJONOYAKU - Google Patents

Description

[Detailed description of the invention]

The present invention provides an alkyl sulfonic acid having 8 to 18 carbon atoms, α-
This article relates to a method for producing granular pesticides containing anionic surfactants such as alkali metal salts or ammonium salts of olefinsulfonic acid or fatty acid-N-methyltauride, and its characteristics include disintegration and spreadability in water. Our goal is to create excellent granular pesticides. In recent years, granular pesticides have played an important role in saving labor in controlling pests, diseases, and weeds. In addition, granular pesticides are safe and convenient to use, and have been used in soil treatment and water surface application, and have a relatively long-lasting dosage form, so much research has been conducted on them. Generally, these granules include a liquid or finely pulverized solid raw material, a mineral powder carrier such as kaolin, clay, talc, bentonite, clay, calcium carbonate, etc.
PVA, CMC, gelatin, sodium alginate, lignin sulfonate, polyacrylate as binders, and various surfactants and adjuvants as disintegration/diffusion promoters in water.
After adding and mixing approximately 10% to 20% water, granulate it using an extrusion type or rolling type granulator, or pre-granulate it from each base material other than the above raw material, It is manufactured by adsorbing, impregnating, or coating the raw material. It is particularly important that the granular pesticides produced in this way disintegrate quickly after application, release the drug substance contained therein, and spread as widely and uniformly as possible. The quality of the drug is an important factor that determines the efficacy of the drug. In order to promote the disintegration and spreading of granules in water, conventional disintegration and spreading aids include polymers of inorganic phosphates, acrylates and their derivatives, and oxidants such as malates and citrates. carboxylate,
Polyanions such as glycolate, alkylbenzene sulfonate, polystyrene sulfonate, anionic properties such as alkyl sulfate, dialkyl sulfosuccinate, polyoxyethylene alkyl phenyl ether sulfate, polyoxyethylene alkyl phenyl ether phosphate, etc. Surfactants, polyethylene glycol sulfates and phosphates, etc., have been used, but the disintegration and spreadability of the granules is often insufficient with the combination of these substances, making it particularly difficult to apply them in highly hard water. In such cases, the effect of promoting collapse and expansion tends to be extremely low, and a solution has been sought. In Japan, it has been said that normal tap water and river water generally have a water quality of about 3 to 5 degrees Celsius.
If a large amount of fertilizer is applied or if the water is flooded, the field water may have a hardness of 10 degrees or higher, so the granules may not disintegrate sufficiently in practical fields, or may not spread sufficiently even if they disintegrate. , the medicinal efficacy is often not fully expressed. In order to solve the above-mentioned drawbacks of conventionally used disintegration/spread accelerators, the present inventors have developed a material that quickly disintegrates and spreads widely and uniformly in both soft and highly hard water conditions. As a result of various studies on auxiliary agents for creating granules that spread, the present invention was completed by discovering that a sulfonic acid-based anionic surfactant that does not contain a benzene structure is suitable. The anionic surfactant is a water-soluble salt of alkanesulfonic acid, α-olefin sulfonic acid, fatty acid-N-methyltauride, etc., having 8 to 18 carbon atoms, ie, sodium, potassium, or ammonium salt. These anionic surfactants have traditionally been used in fields such as the textile industry, paper industry, and detergents.
In addition, in terms of agricultural chemical formulations, it has been used in part as an auxiliary agent for wettable powders, but it is difficult to disintegrate and disintegrate granular agricultural chemicals in water.
The excellent expansion promoting effect was discovered for the first time through extensive research by the present inventors. These sulfonates are derived from kerosene or paraffin and are sulfonated with 8 to 18 carbon atoms.
It is synthesized from alkanesulfonic acid consisting of α-olefin, α-olefin sulfonic acid consisting of 8 to 18 carbon atoms obtained by sulfonation of α-olefin, higher fatty chloride consisting of 8 to 18 carbon atoms, and N-methyltaurine. It belongs to the substances known in the world. If I were to describe these synthesis examples in more detail,
An example of the synthesis of C ₁₀ -C ₁₆ alkyl sulfonate sodium is as follows. 300 g of C ₁₀ to C ₁₆ paraffin is reacted with a mixed gas of chlorine and sulfur dioxide under ultraviolet irradiation at 40 to 45° C. for 3.5 hours. Next, add 497g of 30% caustic soda solution and heat to 100℃.
Stir for 15 minutes to hydrolyze, then add another 500 g of water. Then, after adding 200 g of carbon tetrachloride and extracting the unreacted oil with a solvent, the aqueous phase was concentrated to 60% C ₁₀ ~
C ₁₆ sodium sulfonate was obtained and powdered using a spray dryer. An example of the synthesis of sodium α-olefin sulfonate consisting of C ₁₄ to C ₁₈ is as follows. SO ₃ gas 5 to 300 g of C ₁₄ to C ₁₈ α-olefin
Contact reaction for 30 seconds and then add 10% caustic soda solution.
Neutralize with 25g, hydrolyze at 160℃ for 20 minutes, and
Obtain powdered α-olefin sodium sulfonate using a spray dryer. An example of the synthesis of soda salt of fatty acid N-methyltauride consisting of _C18 is as follows. 645g of aqueous solution containing 50g of N-methyltaurine
Add 9 g of 30% caustic soda aqueous solution to make it alkaline, and add 118 g of stearic acid chloride on top of this.
Add 16 g of 30% caustic soda solution over a period of 5 hours. The mixture was heated to 50°C, neutralized with hydrochloric acid, 280 g of common salt was added, and the total amount was made up to 1397 g with water. It is then dried in a spray dryer to obtain a material containing 30% of the soda salt of _C18 fatty acid-N-methyltauride. The preferred range of carbon number is 8 to 18, but it is not necessarily limited to this range. When the number of carbon atoms exceeds 18, the water solubility tends to decrease rapidly, and the disintegration and spreadability of the granules generally deteriorate. On the other hand, when the number of carbon atoms is less than 8, surface activity such as surface tension decreases, and the effect of promoting collapse and expansion tends to deteriorate. However, in the case of carbon atoms of 8 to 18, they exhibit a strong disintegration/spread promoting effect and have strong surface activity, such as excellent surface tension lowering ability and permeation ability, making them difficult to use as conventional disintegration/spread accelerators. In comparison, it tends to be effective in accelerating or preventing a decline in the medicinal efficacy of granules, and not only can it generally be recognized to have an excellent effect on soil penetration and adhesion promotion, but also during granulation, plasticization occurs when the granulation agent passes through the slits. This is because it has the effect of showing action and facilitating granulation. Further, the salts of these sulfonic acids generally include sodium, potassium, ammonium, etc. salts, but are not necessarily limited to these ranges. In other words, lithium salts and water-soluble amines such as mono-, di-, and tri-ethanolamines and isopropanolamines are also effective, but they are not necessarily common salts. These anionic surfactants according to the present invention are
When used, it is sufficient to mix it in an amount of about 0.5 to 3% (based on granules), and there is no problem in using it in combination with other types of surfactants, inorganic salts, binders, etc. The active substances to which these anionic surfactants according to the present invention are applied are mainly related to kneading type granulation and surface coating type granulation, so herbicides are the main target in many cases. Since the essence of the technology of the invention is to promote the disintegration and spread of granules in water, it can of course be applied to insecticides, fungicides, plant growth regulators, and the like. Next, in order to specifically explain the present invention, typical examples and comparative examples will be given, but the present invention should not be limited to these examples. In addition, the granulation method and drying method in the present invention are almost the same as the conventional method, but in the following examples and comparative examples, the grain size was sized to 0.8 mm in diameter x 3 mm in length and tested. It was used as a material. Example 1 4 parts of 2-isopropylphenyl-N-methyl carbamate (mipsin), 25 parts of bennite, 69 parts of talc, 1 part of polyvinyl alcohol, carbon number 10-
Sodium paraffin sulfonate with a distribution of 16
The mixture was mixed with 20 parts of water, and then granulated using an extruder to obtain granules. Comparative Example 1 4 parts of 2-isopropylphenyl-N-methyl carbamate (mipsin), 25 parts of bentonite, 69 parts of talc, 1 part of polyvinyl alcohol, and 1 part of sodium dodecylbenzenesulfonate were mixed, and 20 parts of water was added. The mixture was mixed and granulated using an extruder to obtain granules. Example 2 7 parts of P-nitrophenyl-2,4,6-trichlorophenyl ether (CNP), bentonite
30 parts, 61 parts of clay, 1 part of sodium lignin sulfonate
1 part of potassium paraffin sulfonate having a carbon number distribution of 10 to 16, and water was added.
Granules were obtained using an extruder. Comparative Example 2 7 parts of P-nitrophenyl-2,4,6-trichlorophenyl ether (CNP), 30 parts of bennite,
61 parts of clay, 1 part of sodium lignin sulfonate, and 1 part of polyexyethylene (10 mol) nonylphenyl ether were mixed, water was added, and the mixture was sludged using an extruder to obtain granules. Example 3 5 parts of 2-chloro-2.6-diethyl-N-(butoxymethyl)acetanilide (butachlor),
Mix 30 parts of bentonite, 62.5 parts of talc, 2 parts of sodium ligninsulfonate, and 0.5 part of sodium α-olefin sulfonate consisting of 14 to 18 carbon atoms, and add 20 parts of water.
1 part was added thereto, and granules were obtained using an extruder. Comparative Example 3 5 parts of 2-chloro-2.6-diethyl-N-(butoxymethyl)acetanilide (butachlor),
30 parts of bentonite, 62.5 parts of talc, 2 parts of sodium lignin sulfonate, and 0.5 parts of sodium polyacrylate were mixed, 20 parts of water was added, and the mixture was summed using an extruder to obtain granules. Example 4 α consisting of 30 parts of bentonite, 59.5 parts of kaolin, 2 parts of sodium lignin sulfonate, and 14 to 18 carbon atoms
- Mix 1 part of potassium olefin sulfonate,
After adding 20 parts of water, a granular base material was obtained using an extruder. Next, 1.5 parts of 2-methylthio-4.6-bis-ethylamino-S-triazine (simetrine) and S-
A mixture of 6 parts of ethyl hexahydro-1H-azepine-1-carbothioate (molinate) was sprayed onto the above granule substrate to obtain coated granules. Comparative Example 4 30 parts of bentonite, 59.5 parts of kaolin, 2 parts of sodium ligninsulfonate, polyoxyethylene (10 parts)
1 part of nonyl phenyl ether phosphate (Na salt) was mixed, 20 parts of water was added, and a granular base material was obtained using an extruder. Next, 1.5 parts of 2-methylthio-4.6-bis-ethylamino-S-triazine (simetrine) and S-
A mixture of 6 parts of ethyl hexahydro-1H-azepine-1-carbothioate (molinate) was sprayed onto the above granule substrate to obtain coated granules. Example 5 7 parts of 2.4-dichlorophenyl-P-nitrophenyl ether (NIP), 30 parts of bentonite, 58.5 parts of clay, 2.5 parts of sodium ligninsulfonate, 1.0 ammonium α-olefin sulfonate having 14 to 18 carbon atoms 1 part and 1.0 part of sodium hexametaphosphate were mixed, 20 parts of water was added, and the mixture was simmered using an extruder to obtain granules. Comparative Example 5 7 parts of 2.4-dichlorophenyl-P-nitrophenyl ether (NIP), 30 parts of bentonite, 58.5 parts of clay, 2.5 parts of sodium lignin sulfonate, 1.0 part of polyacrylic acid/sodium methacrylate, 1.0 part of sodium hexametaphosphate 20 parts of water were added to the mixture, and granules were obtained using an extruder. Example 6 5 parts of N-methyl-1-naphthyl carbamate (NAC), 1 part of CMC, 30 parts of bentonite,
After mixing 63 parts of talc and 1.0 part of stearoyl-N-methyltaurine soda, 20 parts of water was added.
Granules were obtained by granulation using an extruder. Comparative Example 6 5 parts of N-methyl-1-naphthyl carbamate (NAC), 1 part of CMC, 30 parts of bentonite,
63 parts of talc, dioctyl sodium sulfosuccinate
After mixing 1.0 part, 20 parts of water was added and the mixture was mixed and granulated using an extruder to obtain granules. Example 7 2-chloro-4.6-bis(ethylamino)-S
- Mix 2 parts of triazine (simazine), 2 parts of polyvinyl alcohol, 30 parts of bentonite, 64 parts of talc, and 2.0 parts of myristoyl-N-methyltaurine soda, mix with water, and granulate with an extruder to make granules. I got it. Comparative example 7 2-chloro-4.6-bis(ethylamino)-S
- 2 parts of triazine (simazine), 2 parts of polyvinyl alcohol, 30 parts of bentonite, 64 parts of talc, and 2 parts of sodium citrate were mixed, water was added, and the mixture was granulated using an extruder to obtain granules. The results of the disintegration and expansion test in water of the granules obtained in the above Examples and Comparative Examples are shown in the following table and. Collapse and expansion test (1) Method Water temperature: 20℃, water hardness:
3. Pour 50ml of water in 10 and 20 each, drop one granule into the center, measure the diameter of the disintegrated and expanded area after 5, 10, 20, and 30 minutes, average value of 3 times. is calculated and shown in Table ~. Measurement unit mm
It is.

【table】

【table】

[Table] The above examples all showed good disintegration spreadability over a wide range of water from soft water to hard water compared to the corresponding comparative examples. By the way, inorganic electrolyte substances, water-soluble polymer substances, etc. can be expected to disintegrate and spread in soft water, but cannot be expected to have the effect of leaching pesticide active ingredients into water, so surfactants are used in combination to increase permeability. Although it is inevitable, all the surfactants according to the present invention have excellent surface activity, and can be expected to promote and elute agricultural active ingredients into water, and to adhere to and penetrate soil, weeds, and pests. . Surface tension test (1) Method Disintegrate 1g of granules in ion-exchanged water to 1%
The suspension was made into a suspension, left standing for 10 minutes, and the surface tension was measured using the Duneuil method. The results are shown in the table. (2) Results

[Table] From the above results, it is clear that all of the examples are granules that have a high disintegration and expansion effect in water ranging from soft water to hard water, and have sufficiently low surface tension values.

Claims (1)

[Claims] 1 Alkyl sulfonate consisting of 8 to 18 carbon atoms, α-olefin sulfonate or fatty acid-N
- A granular pesticide with good disintegration and dispersibility in water, characterized by containing one or more methyltauride salts.