KR930008436B1 - Thermally stabilized bis alkyl-thio-alkylamino-n-alkyl carbamates - Google Patents

Abstract

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Description

[Name of invention]

Thermally stable bis alkylthio-alkylimino-N-alkyl carbamate

Detailed description of the invention

[Field of Invention]

The present invention relates to a method of stabilizing alkylthio-alkylimino carbamate insecticides against heat. More particularly, the present invention relates to a method for delaying or preventing pyrolysis of sulfur-bonded bis alkylthio-alkylimino carbamates by incorporating a multioxygen inorganic compound in a formulation containing the pesticide.

[Background of invention]

Sulfur-bonded bis alkylthioalkylimino-N-alkyl carbamate pesticides of the general formula are used in various ways to control insects and other agronomic pests:

The active compounds have a very high pesticidal activity and substantially reduced toxicity to mammals and plants when compared to other pesticidal compounds having an activity spectrum comparable to those described above.

These compounds are labile to heat in the presence of various contaminants. Heavy metals and their salts, in particular the chloride salts, are not particularly preferred. Decomposition takes place extremely severely in the presence of copper metal, copper chloride, ferrous metal, iron chloride and iron oxide in rust form. Other problematic metals include cobalt, nickel and aluminum. Given sufficient time at temperatures above 60 ° C, decomposition occurs in concentrations as low as 10 ppm. Although typically slower than the rate of decomposition of the chloride-containing system, sulfur and sulfide salts can also cause degradation. In addition, several organic degradation initiators have been identified, including pyridine, pyridine hydrochloride, di- and trisulfides, amines, peroxides and acids (eg, acetic acid and citric acid). It can also be degraded by the presence of at least 5% metomil or its oxime.

The main object of the present invention is to avoid the pyrolysis process that can occur in large amounts of this pesticide when the sulfur-bonded bis alkylthio-alkylimino-N-alkyl carbamate insecticide is dried at elevated temperatures or stored for a long time, especially in a warm environment. It is to provide a method of suppressing or delaying. Another object is to provide stable wetting powdery and dispersible granular formulations of such pesticides.

Detailed description of the invention

The present invention is prepared by mixing the insecticide of general formula (I) with about 0.01% to about 95% by weight of a substantially non-alkali inorganic compound containing at least two oxygen atoms bonded to a cationic polyvalent atom. Provided are methods for delaying or inhibiting pyrolysis of pesticides:

Wherein R ₁ is alkyl having 1 to 5 carbon atoms; R ₂ is alkyl, alkylthio, alkoxy, alkanoyl or alkoxycarbonyl, all of which may contain from 1 to 5 carbon atoms and are unsubstituted or one or more cyano, nitro, alkylthio, alkylsulfinyl, _May be aliphatic substituted by a specific combination of alkylsulfonyl, alkoxy or R ₄ R ₅ -NCO- groups, or R ₂ is phenyl, R ₄ R ₅ -NCO- or R ₆ CON (R ₄ ) [where R ₄ And R ₅ are each hydrogen or alkyl and R ₆ is hydrogen, alkyl or alkoxy; R ₃ is hydrogen, cyano, or alkyl or alkylthio having 1 to 5 carbon atoms; Provided that the total number of carbon atoms in R ₂ and R ₃ cannot exceed 8, and when R ₂ is alkyl substituted with alkylthio, R ₃ is alkyl.

In addition, the present invention provides (a) an insecticide compound of the general formula (I) in an amount effective as an insecticide and (b) two oxygen atoms bonded to the cationic polyvalent atom in an amount effective to inhibit or delay the thermal decomposition of the compound. It provides the pesticide composition containing the substantially non-alkali inorganic compound containing the above.

A. Definition

The term "powdery composition or granular composition" refers to actual particles (e.g., No. 2) up to 5 mm in size from finer dusts (e.g., dust passing through the US body from No. 400 to No. 100). Solid particles of up to 4 US particles).

“Substantially non-alkaline inorganic compounds” are compounds that, when dissolved or dispersed in water in an amount useful in the present invention, may not have a pH greater than 9 or may be buffered to a pH of less than 9.

"Thiodicarb" is the generic name of an insecticide of the general formula:

The term “compatability agent” refers to an additive that allows different pesticides to be mixed into a single liquid formulation. Such admixtures may be incorporated into solid or liquid compositions containing one or all of the pesticides to be mixed.

B. Pesticides

The organic compound of the present invention is an alkylthio-alkylimino-N-alkyl carbamate. They are widely used to control various pests. These can be prepared by well known methods (see US Pat. Nos. 4,004,031 and 4,382,957).

Preferred compounds of the invention are compounds wherein R ₁ and R ₃ are alkyl and R ₂ is alkyl or alkylthio. Thiodicarb compounds are particularly preferred in practicing the present invention.

C. Thermodynamic Stability

Table I lists typical degradation times for thiodicarb in the presence of various contaminants. This data was collected using the following method. 1 g of thiodicarb sample is homogeneously mixed with the specified weight percent contaminants. The solid is placed in a test tube, covered with a rubber septum stopper and immersed in a constant temperature bath maintained at 100 ° C. Conduct under similar conditions using uncontaminated standards. Degradation is demonstrated in various forms. Some samples show a rapid change from solid to black liquid. ; Dark yellow smoke is usually observed. Other samples gradually fade and moist. In these experiments the degradation time is the point at which the sample becomes dark brown semisolid. The values reported are the average values repeated several times for each sample.

The destabilizing effect of metomil and other sulfur compounds is apparent in B of Table I. Thiodicarb is stable at low concentrations (up to 1% by weight) of metomil, one of its major degradation products. However, as the concentration of metomil increases, the rate increases significantly. Likewise, the effect of metomil oxime is also significant. As the amount of other degradation products such as dimethyltrisulfide and dimethyldisulfide increases, the rate of decomposition accelerates significantly.

TABLE I

Stability of Contaminated Thiodicarb Stored at 100 ° C

The results of testing using contaminants that may be introduced during the manufacture or storage of the pesticide material are shown in Table IC. As already mentioned, heavy metal ions, in particular copper and iron, are particularly harmful. Manufacturing apparatus or storage vessels made of these metals in a form that can corrode and produce harmful salts should be avoided if possible. For example, because other organic materials are found in the solvents used in the manufacturing process, these compounds have been included to account for the impact that these materials may have on the product.

It is evident from Table II that certain silicon-based carriers can reverse the degradation of contaminated thiodicarb. In this experiment, one gram of thiodicarb sample was first contaminated with the designated weight percent cupric chloride and ferric chloride, followed by homogeneous mixing with various silicas and silicates. This sample is then placed in a test tube and immersed in a water bath at 50 ° C., 70 ° C. and 100 ° C. until degradation is observed. The decomposition time is measured when the solid is converted to a dark brown liquid. All values represent the average value repeated several times. In some cases several times of stabilization is observed compared to the standard containing no silica.

TABLE II

Thiodicarb Stabilization with Silica-Base Carrier

Thermodynamic instability is measured more accurately and reproducibly by the detection of heat in a dual thermocouple test performed as follows. The test mixture is prepared by homogeneously mixing the standard pesticide with the desired amount of stabilizer (the standard pesticide is thiodicarb containing sulfur as a synthetic impurity; no additional contaminants are added). The thermocouple is placed into 2 g of dried sample in the measuring vessel. The second thermocouple is placed in the vessel 1 inch above the mixture surface. The vessel is then placed in a thermal breaker and heated to 160 ° C. as soon as possible; The heating rate is reproducible and does not matter as long as the mixture reaches 160 ° C. before exotherm occurs in the untreated pesticide. The time to exotherm for the mixture is compared to that containing only untreated standard, i.e. pesticide. Measurements for a single mixture of additives and pesticides are usually made 5 to 10 times to ensure reproducibility. In all cases, pesticides are taken in the same batch to avoid differences in the degree of contamination often observed in one batch and the next. The time to exotherm is directly proportional to the thermal stability of the mixture.

Groups of substantially nonalkali inorganic compounds containing two or more oxygen atoms bonded to cationic polyvalent atoms are surprisingly effective in delaying or inhibiting exotherm in sulfur-bonded carbamate insecticides such as thiodicarb. Phosphorous acid in these groups; Alkali metal monobasic phosphates, metaphosphates, sulfites or hydrogen sulfites; Alkali metal or alkaline earth metal aluminosilicates (zeolites or molecular sieves); Alkali metal hydrogencarbonate; And silicon dioxide in the form of silicates and silica. Particularly effective compounds for delaying fever include sodium or potassium monobasic phosphates, sulfites or hydrosulfite; Hexametaphosphate; And phosphoric acid. Mixtures of these compounds are also effective. The ability of several preferred stabilizers to retard exotherm in thiodicarb as measured in the double thermocouple test described above is evident from the results shown in Table III. These results indicate that potassium monobasic phosphate is a particularly preferred stabilizer for thiodicarb.

TABLE III

Time to fever for stabilized thiodicarb

Decomposition of thiodicarb and increasing concentrations of metomil are investigated at 100 ° C. in the presence of sodium monobasic phosphate (Table IV). Untreated thiodicarb samples and thiodicarb samples treated with various amounts of sodium monobasic phosphate are maintained at 100 ° C. for several days. These are analyzed periodically for thiodicarb and metomil by standard HPLC methods. As the thiodicarb concentration decreases, the metomil concentration increases. However, the results indicate that as the decomposition process continues, other products are also formed; As decomposition proceeds, the sum of the weight percent of metomil and thiodicarb gradually decreases. As the decomposition reaction proceeds over several days, thiodicarb appears to stabilize as the amount of monobasic phosphate increases; Decomposition products, in particular metomil, accelerate the decomposition process. These results also support the hypothesis that bis alkylthio-alkylimino-N-alkyl carbamates undergo a procatalytic cracking process involving a number of sulfide compounds and also catalyze the cracking process.

Stabilizers of the invention may be incorporated in amounts of 0.01 to 95% by weight of the total mixture to stabilize sulfur-bonded bis alkylthio-alkylimino-N-alkyl carbamates. Although the concentration of certain inorganic stabilizers must be determined experimentally, generally a concentration of about 0.01 to about 10 weight percent in solid formulations and 0.0001 to about 6 weight percent in liquid formulations is preferred. If the stabilizer is one of the phosphate compounds described above, stabilization will be observed even with 0.01 intrinsic 2% by weight. Sulfite stabilizers are effective in the range of 0.1 to 5% by weight.

Table IV

Thiodicarb Degradation and Metomil Formation in the Presence of NaH ₂ PO ₄

D. Formulation

The compositions of the present invention can be used as solids or as liquid dispersions or solutions in both fields and grasses to control pests. It is used in a manner well known to those skilled in the art. The effective amount of active pesticide is about 0.05 to about 20 lbs per acre.

Formulations useful in the practice of the present invention are solids (eg wettable powders or dispersible granules) and liquids (eg solutions or dispersions). Preferred wettable powder and dispersible granular formulations include (a) about 1 to about 98 weight percent bis alkylthio-alkylimino-N-alkyl carbamate insecticide; (b) from about 0.01% to about 10% by weight of a substantially nonalkali inorganic compound containing at least two oxygen atoms bonded to a cationic polyvalent atom; (c) about 0.01 to about 20 weight percent wetting agent; And (d) about 1 to about 12 weight percent of a dispersant.

Preferred formulations include (a) about 0.01 to about 75 weight percent bis alkylthio-alkylimino-N-alkyl carbamate insecticide; (b) about 0.0001 to about 6 weight percent of a substantially non-alkali inorganic compound containing at least two oxygen atoms bonded to a cationic polyvalent atom; (c) about 0.01 to about 20 weight percent wetting agent; (d) 0 to about 10 weight percent dispersant; And (e) about 5 to about 80 weight percent of an inert liquid carrier. Suitable carriers include contamination of water, unsubstituted aliphatic hydrocarbons and aromatic hydrocarbons or their homologues containing, for example, alkyl, halo or hydroxy substituents, fatty acids, and linseed oil and cottonseed oil derived from natural extracts.

Among the pesticides useful in the present invention, a preferred compound is thiodicarb. Preferred oxygen-containing inorganic compounds are phosphoric acid and sodium or potassium monobasic phosphate, meta phosphate, sulfite or hydrogen sulfite.

Many such anionic, cationic or nonionic wetting agents can be used in such formulations. Examples of the humectant include alkali metal salts of fatty alkyl or alkenyl sulfates or sulfonates containing 8 to 20 carbon atoms; Ethoxylated alkylphenols in which the alkyl group contains 8 to 12 carbon atoms; Dialkyl esters of sodium sulfonsuccinic acid in which the dialkyl group contains 5 to 10 carbon atoms; Or polyalkylene oxide modified dimethylpolysiloxanes in which the alkylene group is ethylene or propylene, or mixtures thereof. In addition, other suitable wetting agents can be used.

Dispersants are substances that interact with the solid components in the formulation and the liquid medium used to suspend such solids for use. They must be soluble in the liquid phase and usually act as binders for the solid powder or granules. Examples of representative dispersants useful in practicing the present invention include starch, alkali metal or alkaline earth metal salts of lignin sulfonic acid salts; And condensates of alkali metal alkylnaphthalene sulfonates with organic compounds containing 1 to 3 carbon atoms and one or more oxygen atoms (eg, condensates of formaldehyde with sodium naphthalene sulfonic acid).

A further component particularly useful in the formulation of the invention is an antifoam. They prevent or reduce foaming during the preparation and dispersion of powders or granules and when using the composition. It also stabilizes the resulting dispersion and redisperses more quickly if solids solidify in the dispersion. Particularly useful antifoaming agents are dialkylpolysiloxanes. Particularly useful are dimethylpolysiloxanes formulated as emulsions or pastes. Such additives do not act as stabilizers for pesticides.

Pesticide types containing multiple insecticides are common for the obvious reason of convenience. Only one application is necessary to provide all the active ingredients. Many complex formulations can be readily prepared by mixing all the active ingredients, whereas the formulations of the present invention may require admixtures that prevent aggregation in the final solution or dispersion to be applied to the subject plant. The presence of additional chemically irrelevant pesticides, such as parathion, may destabilize dispersions prepared for spray application. Preferred admixtures for such compositions are condensates of hydrophobic bases with alkylene oxides prepared by condensing alkylene oxides with alkylene glycols, where all alkyl substituents contain 2 to 4 carbon atoms. Particularly effective admixtures are paste condensates of hydrophobic bases and ethylene oxide prepared by condensing propylene oxide and propylene glycol.

If a number of other well known ingredients do not fall short of the ability of inorganic compounds to stabilize insecticides or the stability and dispersibility or wettability of powders or granules, they may be incorporated into the wettable powders and dispersible granules of the present invention. Such additives may include buffers, carriers or diluents, dyes, fragrances, humectants, thickeners, biocides and evaporation inhibitors.

The solid compositions of the present invention may be prepared by a variety of methods well known in the art, such as pan graulation, fluidized bed mixing and drying, spray drying, thorough mixing flocculation, extrusion, densification or pelletization. Can be. In fan granulation and fluidized bed processes, a mixture of anhydrous components is prepared and transferred to a mixing / drying chamber containing water and liquid components; The slurry is mixed well and then dried. The particles are then ground to the desired size. When using the spray drying method, it is preferable to grind a mixture or slurry of anhydrous components.

There are several ways to obtain a solid with a spectrum representing moisture content and particle size. Useful products are those having the particle size required for a particular use, containing less than 5% by weight, preferably less than 2% by weight, and are well dispersed in water or oil. In the particulate composition, the good dispersibility is U.S. Screen no. Particles retained above 100 (149μ) are obtained, and optimum particle stability is obtained with less than 2% moisture. Particles that are too small, too large or too wet can be recycled back to the manufacturing or drying apparatus.

Liquid compositions of the present invention can be prepared by methods known in the art. Useful dispersion formulations do not separate into liquid and solid phases during prolonged storage at ambient temperature. To increase stability, the size of the dispersed particles can be reduced by techniques known in the art, such as air and wet milling.

The following examples serve to illustrate the useful formulations of the invention and to demonstrate the effectiveness of various stabilizers.

Example 1

To demonstrate the effect of the phosphate stabilizer on dispersible granules, the following two formulations are prepared by mixing the components in an aqueous slurry, spray drying until the water is less than 2%, and comparing their thermal stability. ; All values are in weight percent of anhydrous components.

Time to fever

46 minutes〉 120 minutes

It is evident that the thermal stability of these formulations significantly increased with as little NaH ₂ PO ₄ as 0.5%. Formulation B can be stored at elevated temperatures (approximately 45-55 ° C.) for much longer than Formulation A and will be much less degraded while Formulation B is drying than Formulation A.

Example 2

Dispersible granules stabilized with silica were prepared by dispersing 86.5% thiodicarb containing approximately 3% silica and 3% sulfur (1.5 wt% starch, 6.8 wt% sulfonated naphthalene formaldehyde condensate). Salts and 3.0% by weight polyalkylene glycol ethers); Wetting agent (1.0% by weight of dioctyl ester of sodium sulfosuccinic acid); Antifoaming agent (1.0% by weight of magnesium stearate); And a buffer (0.2 wt% citric acid). The content of stabilizer (ie silica) in this formulation is approximately 2.6% by weight. The mixture is triturated into powders with an average particle size of less than 101 micron, then transferred to a fluid bed chamber for mixing with water and then dried.

After passing the product through a sieve in the range of -12 to +40 mesh (U.S grid size), the product has the following properties:

CIPAC suspension rate 76%

Time to fever 104 minutes

Example 3

A very stable sample containing two stabilizers was found in water: 86.1% thiodicarb containing 5% sulfur and 1.0% silica; 10.1% of a dispersant (sodium salt of sulfonated naphthalene formaldehyde condensate); 2.5% wetting agent (sodium salt of sulfonated lauryl acid); 0.6% of an antifoaming emulsifier (dimethylpolysiloxane emulsion); And 0.7% of heat stabilizer (KH ₂ PO ₄ ) components (all weight percents are based on the added weight of the components except water). The slurry was wet milled to yield No. Pass through a 325 screen (US eye size) and spray dry until moisture content is less than 2%. Approximately 95% of the resulting granules have a particle size distribution over a limited range of -14 to +100 mesh (US eye size).

Granules within this particle size range exhibit the following properties:

90% CIPAC suspension rate

Time to fever〉 120 minutes

Claims (19)

Phosphoric acid as an insecticide of the following general formula (I); Phosphoric acid; Alkali metal monobasic phosphates, metaphosphates, sulfites or hydrogen sulfites; Alkali metal or alkaline earth metal aluminum silicates; Alkali metal hydrogencarbonate; 0/01 to 95% by weight of at least one thermal stabilizer selected from silicon dioxide, provided that the thermal stabilizer is a compound of the phosphate type selected from phosphoric acid and salt derivatives thereof in an amount of up to 2% by weight; A method for delaying or inhibiting pyrolysis of the insecticide of general formula (I), characterized in that it is homogeneously mixed so that a solid mixture having a water content of 2% by weight or less is obtained.

Wherein R ₁ is alkyl having 1 to 5 carbon atoms; R ₂ is alkyl, alkylthio, alkoxy, alkanoyl or alkoxycarbonyl, all of which may contain from 1 to 5 carbon atoms and are unsubstituted or one or more cyano, nitro, alkylthio, alkylsulfinyl, _May be aliphatic substituted by alkylsulfonyl, alkoxy or R ₄ R ₅ -NCO-groups, or R ₂ is phenyl, R ₄ R ₅ -NCO- or R ₆ CON (R ₄ ) [where R ₄ and R ₅ Are each hydrogen or alkyl, and R ₆ is hydrogen, alkyl or alkoxy; R ₃ is hydrogen, cyano, or alkyl or alkylthio having 1 to 5 carbon atoms; Provided that the total number of carbon atoms in R ₂ and R ₃ cannot exceed 8, and when R ₃ is alkyl substituted with alkylthio, R ₃ is alkyl. a. Organic compounds of the general formula (I) in amounts effective as insecticides; And b. Phosphorous acid for delaying or inhibiting thermal decomposition of a compound of general formula (I); Phosphoric acid; Alkali metal monobasic phosphates, metaphosphates, sulfites or hydrogen sulfites; Alkali metal or alkaline earth metal aluminum silicates; Alkali metal hydrogencarbonate; And 0.01 to 95% by weight of at least one thermal stabilizer selected from silicon dioxide, provided that the thermal stabilizer is used in an amount of up to 2% by weight if the thermal stabilizer is a phosphate type compound selected from phosphoric acid and its salt derivatives. A solid insecticide composition having a content of less than 2% by weight.

Wherein R ₁ is alkyl having 1 to 5 carbon atoms; R ₂ is alkyl, alkylthio, alkoxy, alkanoyl or alkoxycarbonyl, all of which may contain from 1 to 5 carbon atoms and are unsubstituted or one or more cyano, nitro, alkylthio, alkylsulfinyl, _May be aliphatic substituted by alkylsulfonyl, alkoxy or R ₄ R ₅ -NCO-groups, or R ₂ is phenyl, R ₄ R ₅ -NCO- or R ₆ CON (R ₄ ) [where R ₄ and R ₅ Are each hydrogen or alkyl, and R ₆ is hydrogen, alkyl or alkoxy; R ₃ is soso, cyano, or alkyl or alkylthio having 1 to 5 carbon atoms; Provided that the total number of carbon atoms in R ₂ and R ₃ cannot exceed 8, and when R ₂ is alkyl substituted with alkylthio, R ₃ is alkyl. The insecticide composition according to claim 2, wherein in the organic compound R ₁ and R ₃ are alkyl and R ₂ is alkyl or alkylthio. 4. The pesticide composition according to claim 3, wherein R ₁ , R ₂ and R ₃ are methyl. The method of claim 2, wherein the heat stabilizer is sodium or potassium monobasic phosphate, sulfite or hydrogen sulfite salts; Hexametaphosphate; Phosphoric acid; Or a mixture thereof. The insecticide composition according to claim 2, wherein the amount of thermal stabilizer is 0.01 to 10% by weight, and the thermal stabilizer is 2% by weight or less when the compound is a phosphate type compound selected from phosphoric acid and derivatives thereof. The method of claim 2 wherein a. 2 to 98% by weight of the organic compound of claim 2; b. 0.01 to 10% by weight of the thermal stabilizer according to claim 2, provided that the thermal stabilizer is 2% by weight or less when the compound is a phosphate type compound selected from phosphoric acid and derivatives thereof; c. 0.01 to 20 wt% wetting agent; And d. A pesticide composition comprising 1 to 12% by weight of a dispersant, wherein the insecticidal composition is wettable powder or dispersible granular. 8. The insecticide composition according to claim 7, wherein the organic compound is thiodicarb. 8. The method according to claim 7, wherein the heat stabilizer is sodium or potassium monobasic phosphate, metaphosphate, sulfite or hydrogen sulfite salt; Alkali metal hydrogencarbonate; Phosphoric acid; Silicon dioxide; Or a mixture thereof. 8. The alkali metal salt of claim 7, wherein the humectant is an alkali metal salt of fatty alkyl or alkenyl sulfate or sulfonate containing 8 to 12 carbon atoms; Alkali metal salts of alkylbenzyl or alkylnaphthyl sulfonates whose alkyl chains contain 8 to 12 carbon atoms; Ethoxylated alkylphenols in which the alkyl group contains 8 to 12 carbon atoms; Dialkyl esters of sodium sulfosuccinic acid in which dialkyl contains 5 to 10 carbon atoms; Or a polyalkylene oxide modified dimethylpolysiloxane wherein the alkylene group is ethylene or propylene, or mixtures thereof. 8. The insecticide composition according to claim 7, wherein the dispersant is a condensate of starch, an alkali metal or alkaline earth metal salt of lignin sulfonate, or an organic compound containing 1 or 3 carbon atoms containing at least one oxygen atom and an alkali metal alkylnaphthalene sulfonate. . 8. The insecticide composition according to claim 7, which contains an antifoam emulsifier. 13. The insecticide of claim 12, wherein the antifoam emulsifier is a polymerized dimethylsiloxane or a mixture of alkaline earth metal stearate and polyalkylene glycol ether or a mixture of sugar-free kraft lignin with sodium sulfonate. Composition. 8. The insecticide composition according to claim 7, which also contains a admixture. The pesticide composition according to claim 14, wherein the admixture is a condensation product of ethylene oxide with a hydrophobic base prepared by condensing alkylene oxide with alkylene glycol, wherein all alkyl substituents contain 2 to 4 carbon atoms. 16. The pesticide composition according to claim 15, wherein the condensate contains a hydrophobic base and ethylene oxide prepared by condensing propylene oxide with propylene glycol. 70 to 95% by weight thiodicarb; 2-3% by weight of sodium salt of sulfonated lauryl acid; 8-15% by weight of sulfonated naphthalene formaldehyde condensate; 1 to 3% by weight of dimethylpolysiloxane; And 0.5 to 1.5 percent by weight of sodium or potassium monobasic phosphate, or phosphoric acid. 18. The pesticide composition according to claim 17, which also contains a nonionic condensate of hydrophobic base and ethylene oxide prepared by condensing propylene oxide with propylene glycol. (a) 0.01 to 75% by weight bis alkylthio-alkyl imino-N-alkyl carbamate insecticide; (b) phosphorous acid; Phosphoric acid; Alkali metal monobasic phosphates; Methiphosphate; Sulfite or hydrogen sulfite; Alkali metal or alkaline earth metal aluminum silicates; Alkali metal hydrogencarbonate; And at least one heat stabilizer selected from silicon dioxide, provided that the heat stabilizer is used in an amount of 2% by weight or less when the compound is a phosphate type compound selected from phosphoric acid and salt derivatives thereof; 0.0001 to 6% by weight; (c) 0.01 to 20 wt% wetting agent; (d) 0 to 10% by weight of dispersant; And (e) 5 to 80% by weight of an inert liquid carrier, wherein the amount of water, if present, is 2% by weight or less.