KR890000061B1 - Process for preparation of germicidal composition for agricultural and horticultural use - Google Patents

Abstract

Long-release germicidal compsns. contg. 5-methyl-S-triazolo (3,4-b) benzothiazole (A), isocyanate cpds. (I) (n=0-8) and acrylpolyol cpds. (II) (R1=H, Me; R2=H, OH, (un)substd. alkyl) were prepd.. Thus, a mixt. of (A) 45, alkylbenzenesulfonate-Na 10, polyvinylalcohol 20, bentonite 100, clay 825 parts and appropricate amt. of H2O was granulated to give granules with < 0.8mm and dried at 80≰C using a fluid-dryer. The dried granules were sieved with a screen of 16-32 mesh. 900 part sieved granule was coated with 100 part tolylenediisocyanate using a mixer to give a granular compsn. contg. 4 wt.% A.

Description

Production method of agricultural horticultural sterilization composition

The present invention relates to a method for producing agrohorticultural bactericidal composition comprising 5-methyl-S-triazolo (3,4-b) benzothiazole (hereinafter referred to as tricyclazole) as an active ingredient.

Tricyclazole is particularly effective at low concentrations in conventional blast control agents, and tricyclazole is characterized by strong anti-invasive action against pathogens and excellent penetration performance of upper leaves in roots. Tricyclazole has a low vapor pressure but water solubility of about 700 ppm at room temperature.

Tricyclazole is formulated into granules, hydrating powders, powders, etc. using air preparation technology, sprayed on seedling boxes of rice seedlings, and seedlings are transplanted into paddy fields. When sprayed on rice fields, the leaf tip of seedlings may be yellowed depending on environmental conditions such as shallow water, deep water, and climate, and in severe cases, it may cause death. In addition, if tricyclazole sprayed by deep water or leaking floats and exhibits an effect of only 30 to 40 days against rice fever, and therefore, when tricyclazole is sprayed on seedlings, Without spraying, leaf crust and ear cough cannot be completely prevented. As a rice fever control agent, of course, its sterilizing effect is excellent, and its longevity is long, and it is preferable that rice is not harmful to rice.

Background Art Conventionally, various methods for controlling the elution of a drug in water have been known as a method for improving the long-term disease control effect due to weakening of rice or floating by deep water or water leakage.

For example, it is possible to microencapsulate a drug (Japanese Patent Laid-Open No. 55-130903), or to dissolve it in solids at room temperature, such as paraffins of low melting point, higher fatty acids, higher alcohols, fats and oils, hardened oils, and heat-modified resins. There is a method (Japanese Patent Application No. 55-4356). However, in order to microcapsulate tricyclazole, a solvent that dissolves tricyclazole in high concentrations is required, and a solvent that dissolves tricyclazole in high concentrations can only be found in chloroform. The complicated manufacturing process makes the cost expensive. In addition, as a method of encapsulating a drug in a solid material, a method of spray melting and assembling a low melting solid material and a clay mineral by mixing and melting is gathered in a part of the rice paddy by floating the water as the manufactured pesticide composition is water repellent. It is not used effectively because it floats together or part of the drug is completely enclosed in solid matter and does not elute in water for a very long time. In addition, temperature control is essential at the time of manufacture, and it is extremely difficult to always produce a drug that provides a control effect over a long period of time at a specific dissolution rate.

The present inventors have diligently studied the problems of weakness and residual activity of tricyclazole, thereby reducing the weakening of rice seedlings by controlling the water dissolution of tricyclazole in paddy fields, and foliar fever in rice fever. In addition, they found long-term control of Isaac fever with one drug spray.

The present invention is made by adding an isocyanate compound or an isocyanate compound and an acryl polyol compound in the preparation of agrohorticultural disinfectant composition by using tricyclazole as an active ingredient and adding a diluent, and, if necessary, a surfactant, a binder and an auxiliary agent. .

Next, the cycyanate compound and acryl polyol compound used by this invention are demonstrated. An isocyanate compound means the compound which has an isocyanate group and superposes | polymerizes by water or an acryl polyol compound. For example, tolylene 2, 4-diisocyanate, tolylene 2, 6-diisocyanate, naphthalene 1,5-diisocyanate, paraxylylene diisocyanate, methaxylene diisocyanate, butyl isocyanate, hexamethylene diisocyanate, octa Decyl isocyanate, m-nitrophenyl isocyanate, trimethylene isocyanate, dimasane diisocyanate, polymethylene polyphenylpolyisocyanate, tolidine diisocyanate, cyanidin diisocyanate, 4, 4'-methylenebis (cyclohexyl isocyanate), methylcyclohexane -2,4-diisocyanate methylcyclohexane-2, 6-diisocyanate, 1, 3-bis (isocyanomethyl) cyclohexane, isophorone diisocyanate, lidin isocyanate (2, 6-diisocyanate methyl caproate) Etc. can be mentioned. Particularly suitable examples include tolylene-2, 4-diisocyanate, tolylene-2, 6-diisocyanate, 1, 3-bis (isocyanomethyl) cyclohexanone, hexamethylene diisocyanate, isophorone Diisocyanate, 4, 4'-methylenebis (cyclohexylisocyanate) and general formula

And polymethylene polyphenylpolyisocyanate represented by (wherein n represents an integer of 1 to 8). You may use these isocyanate compounds combining 1 type or 2 or more types. The acryl polyol compound is a general formula

(Wherein R ¹ represents a hydrogen atom or a methyl group, and R ² represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms substituted with a hydroxyl group or a carboxyl group.)

Polymer of the compound represented by the formula (average molecular weight: 500 to 10000) or this and general formula,

(However, R ³ represents hydrogen or a methyl group, R ⁴ represents an alkyl group having 1 to 12 carbon atoms.)

The polymer (average molecular weight: 500-1000) of the compound represented by these is mentioned.

These isocyanate compounds and acryl polyol compounds can also be used with a solvent or surfactant.

As the diluent, surfactant, binder, and auxiliary agent used in the present invention, bentonite, clay, silica sand, sodium alkylbenzenesulfonate, polyvinyl alcohol, white carbon and the like can be used.

The amount of tricyclazole used in the agricultural and horticultural sterilizing composition of the present invention is 0.5 to 80% by weight, more preferably 1 to 60% by weight based on the total amount of the composition. In addition to tricyclazole, other red pesticide active ingredients can be added. As these pesticide active ingredients, p-methylthiophenyl 0,0-dipropyl phosphate [propaphos], S, S <^1> -[2- (dimethylamino)-trimethylene] bis (thiocarbamate) [car Tarp], 0,0-dienyl 0- (2-isopropyl-4-methyl-6-pyrimidinyl) phosphothioate [diazinone], S-benzyl 0,0-diisopropyl phosphorothiolate (IBP) and the like.

Next, the use ratio of the isocyanate compound and the acryl polyol compound is 0.5 to 20% by weight, more preferably 1 to 10% by weight based on the total amount of the agricultural and horticultural sterilizing composition of the present invention. Moreover, the compounding ratio of an isocyanate compound and an acryl polyol compound is 1: 0.1-10.

In preparing agricultural horticultural germicidal compositions of the present invention, the addition of the isocyanate compound and the acryl polyol compound is as follows.

(1) Tricyclazole and white carbon mixed with one or two or more of isocyanate compounds or isocyanate compounds with acryl polyol compounds and ground as raw materials. Diluents, surfactants, auxiliary agents, etc. are added to this material to hydrate and powder them. , Prepared by granulation.

(2) Tricyclazole is mixed with other pesticides, diluents, surfactants, binders, and auxiliaries to adsorb one or two or more kinds of isocyanate compounds or isocyanate compounds and acryl polyol compounds to granular acid granules.

(3) An isocyanate compound is added to the non-oil-absorbing granular material, and further coated with tricyclazole and white carbon, or after addition of an isocyanate compound or acryl polyol compound, followed by tricyclazole, isocyanate compound and white carbon.

(4) A mixture of one or two or more of isocyanate compounds or isocyanate compounds with acryl polyol compounds in tricyclazole is adsorbed to natural granules or granulated bases.

(5) One or two or more kinds of tricyclazole, isocyanate compound or isocyanate compound and acryl polyol compound are adsorbed to the isocyanate compound or granular material containing one or two or more kinds of acryl polyol compound.

The agricultural and horticultural disinfecting composition of the present invention prepared in this way can be used conventionally known techniques without the need for heat treatment or special processes such as spray assembly, the elution is constantly controlled, and all of the slowly administered drugs Elution results in stable control for a long time. As a result, as described above, the rice seedlings are sprayed only once with a seedling box or one time, and do not harm the rice for a long time from the seedlings of the rice to the rice milling machine, and exhibit excellent resistance to rice fever. This saves energy and reduces the effort and time required for pesticide control against rice.

The present invention will be described in more detail with reference to the following Examples. "Part" or "%" in a following example shows all the "weight part" or the "weight%."

Example 1

To 45 parts of fine powder of tricyclazole, 10 parts of alkylbenzenesulfonate, 20 parts of polyvinyl alcohol, 100 parts of bentonite and 825 parts of clay were added and mixed with kneader (Fuji Powder Industries, Ltd., KDH-10 type). An appropriate amount of water was added to knead. This was assembled by attaching a screen of 0.8 mm in diameter to a granulator (EXD-60, manufactured by Fuji Powder Co., Ltd.). This granulated material was dried by warm air at 80 ° C. with a fluidized bed dryer (manufactured by Fuji Denki Co., Ltd., MD-B-400 type). After drying, the mixture was formed into standard bodies of 16 meshes and 32 meshes to obtain a tricyclazole incorporation base (containing 4.5% of tricyclazole) having a particle size of 32 meshes from 16 meshes.

Next, 900 parts of tricyclazole injection bases were added to a Nauter mixer (HOSKAWADEK Co., Ltd. model NX-S), and 100 parts of the tolylene diisocyanate described below were added with stirring to uniformly adsorb the bases. A granule containing 4% of tricyclazole was obtained.

The tolylene diisocyanate used here is formed of two types of isomers of 65% of 2,4-tolylene diisocyanate and 35% of 2,6-tolylene diisocyanate. The characteristics are as follows.

TABLE 1

Example 2

In a Nauter mixer, 900 parts of tricyclazole injecting agents prepared in Example 1 were mixed and 60 parts of propaphos, 20 parts of the tolylene diisocyanate, and 20 parts of hexamethylene diisocyanate to be added were stirred. It was added to the mixer, and it was made to adsorb | suck uniformly to the blowing base, and the granule containing 4% of triclasol was obtained.

The hexamethylene diisocyanate used here had the following characteristics.

TABLE 2

Example 3

In the outer mixer, 900 parts of silica sand (sieved from 12 mesh to 24 mesh) are put and mixed. 40 parts of polymethylene polyphenyl polyisocyanate mentioned later are added, and after confirming that a silica sand is uniformly wet, 40 parts of fine powders of tricyclazole and 20 parts of white carbon are added. The mixture was sufficiently mixed until the tricyclazole and the white carbon were uniformly attached to the silica sand to obtain a granule containing 4% of the tricyclazole.

The polymethylene polyphenylpolyisocyanate used here has the following characteristics.

TABLE 3

Example 4

Nitrader (KDH-10 type) was added to 45 parts of fine powder of tricyclazole by adding 100 parts of late acryl polyol, 10 parts of sodium alkylbenzenesulfonate, 20 parts of polyvinyl alcohol, 45 parts of white carbon, 100 parts of bentonite and 680 parts of clay. After mixing with an appropriate amount of water was kneaded. This is assembled by attaching a screenin with a hole diameter of 0.8 mm to a granulator (EXD-60 type). This granulated material is dried by warm air of 80 degreeC by the fluidized bed dryer (MD-B-400 type). After drying, it was established as a standard of 16 mesh and 32 mesh, and a 32 mesh tricyclazole sol injection base (containing 4.5% of tricyclazole) was obtained from 16 mesh.

Subsequently, 900 parts of this bridging base were added into a Nauter mixer (type NX-S), and 60 parts of propaps and 40 parts of tetramethylene pentaphenylpenta isocyanate were added thereto while stirring, and the mixture was adsorbed to the bridging base uniformly to give Tricyclila. A granule containing 4% of a sol was obtained. In addition, the acryl polyol and tetramethylene pentaphenyl penta isocyanate were used for the following.

Polymer of acrylic ester represented by (polymerization degree: 4 to 20, molecular weight: 500 to 2400)

Tetramethylenepentaphenylpenta isocyanate:

Example 5

45 parts of fine powder of tricyclazole, 45 parts of fine powder of cartaf hydrochloride, 10 parts of sodium alkylbenzenesulfonate, 20 parts of polyvinyl alcohol, 100 parts of bentonite and 780 parts of clay were mixed and mixed with a kneader (KDH-10 type). Add water and knead. This is assembled by attaching a screenin with a hole diameter of 0.8 mm to a granulator (EXD-60 type). This granulated material is dried by warm air of 80 degreeC by the fluidized bed dryer (MD-B-400 type). After drying, the mixture was formed into standard bodies of 16 meshes and 32 meshes to obtain 32 meshes of tricyclazole incorporation base (containing 4.5% of tricyclazole).

Subsequently, 900 parts of this bridging base are placed in a outer mixer (NX-S type), 20 parts of acryl polyol and 80 parts of hexamethylene octaphenyloctaisocyanate are mixed with stirring, and added into the outer to adsorb uniformly to the bridging base. The granules which contain 4% of tricyclazole were obtained. In addition, the following were used for the acryl polyol and the isocyanate compound.

(n=5 내지 8)Acryl polyol: general formula

(n = 5 to 8)

(m=3 내지 6)Compound represented by general formula

(m = 3 to 6)

Polymer of the compound represented by (average molecular weight 2000 to 4600)

Heptamethyleneoctaphenyloctaisocyanate:

Example 6

In the outer mixer, 880 parts of silica sand (sieved from 12 mesh to 24 mesh) are put and mixed. 30 parts of acrylic polyol were added thereto, and 40 parts of fine powder of triclasol was added after confirming that the silica sand was uniformly wetted. Next, 30 parts of an adduct of trimethylolpropane (1 mol) and tolylene diisocyanate (3 mol) is added. Mix briefly and add 20 parts of white carbon. The mixture was sufficiently mixed until the tricyclazole and the white carbon adhered uniformly to obtain a granule containing 4% of the tricyclazole. In addition, the following were used for the acryl polyol and the isocyanate compound.

Copolymer of (average molecular weight 3700-7800)

Adduct of 1 mol of trimethylolpropane and 3 mol of tolylene2,4 diisocyanate:

Example 7

To 45 parts of fine powder of tricyclazole, 10 parts of alkylbenzenesulfonate, 20 parts of polyvinyl alcohol, 100 parts of bentonite, and 825 parts of clay are added, mixed with a kneader (KDH-10 type), and then kneaded by adding an appropriate amount of water. This is assembled by attaching a screenin with a hole diameter of 0.8 mm to a granulator (EXD-60 type). This granulated material is dried by 80 degreeC warm air with a fluidized bed drier (MD-B-400). After drying, it was established as a standard body of 16 mesh and 32 mesh, and a 32 mesh triclazol penetration base (containing 4.5% of triclazol) was obtained from 16 mesh.

Subsequently, 900 parts of this bridging base was put into a Nauter mixer (NX-S type), and 50 parts of diazide and 10 parts of phenylmethane-4,4'-diisocyanate and tolylene diisocyanate used in Example 1 were stirred therein. 10 parts and 20 parts of acryl polyol were added and uniformly adsorbed on a bridging base to obtain a granule containing 4% of tricyclazole. In addition, the acrylic polyol

OH(n=8내지 12)General formula

OH (n = 8-12)

The polymer (mean molecular weight: 5300-10000) of methacrylic acid ester represented by was used.

Example 8

To 25 parts of fine powder of tricyclazole, 10 parts of alkylbenzenesulfonate, 20 parts of polyvinyl alcohol, 100 parts of bentonite and 845 parts of clay are mixed and mixed with a kneader (KDH-10 type), followed by kneading with an appropriate amount of water. This is assembled by attaching a screenin with a hole diameter of 0.8 mm to a granulator (EXD-60 type). This granulated material is dried by warm air of 80 degreeC with a fluidized bed drier (MD-B-400 type). After drying, it was established as a standard body of 16 mesh and 32 mesh, and a 32 mesh triclazol penetration base (containing 4.5% of triclazol) was obtained from 16 mesh.

Next, 800 parts of this bridging base were put into a Nauter mixer (type NX-S), and 150 parts of IBP, 15 parts of nona methylene decaphenyl decaisocyanate and 35 parts of acryl polyol were added thereto while stirring, and uniformly added to the base of bridging. It adsorbed and obtained the granule containing 4% of tricyclazole. In addition, the following was used for the isocyanate compound and the acryl polyol.

Nonnamethylenedecaphenyldecaisocyanate:

OH (n : 4 내지 7)Acryl polyol: general formula

OH (n: 4 to 7)

Compound represented by

(m : 1 내지 4)General formula

(m: 1 to 4)

Polymerized compound (average molecular weight 2500 to 5000) represented by

Next, the effect of the present invention will be described using a test example. In the test, the following drugs were prepared and used for comparison.

Reference Example 1

To 40 parts of fine powder of tricyclazole, 10 parts of sodium alkylbenzenesulfonate, 20 parts of polyvinyl alcohol, 100 parts of bentonite and 830 parts of clay are mixed and mixed with a kneader (KDH-10 type), followed by kneading with an appropriate amount of water. This is assembled by attaching a screen of 0.8 mm in pore size to a granulator (EXD-60 type), and the granulated product is dried by warm air at 80 ° C. with a fluid bed dryer (MD-B-400). After drying, it was established as a standard of 16 mesh and 32 mesh, and granules containing 4% of triclazole of 32 mesh in 16 mesh were obtained.

Reference Example 2

40 parts of fine powder of tricyclazole and 560 parts of clay are sufficiently mixed and then added to 400 parts of paraffin (melting point 48 to 50 ° C., manufactured by Wako Pure Chemical Industries, Ltd.) at about 90 ° C. and sufficiently stirred with a homogenizer. The mixture is warmed to about 90 ° C. and a viscous suspension is obtained. This suspension is spray-assembled by a spray assembly device (manufactured by Kawasaki Heavy Industries Co., Ltd.). The granulated material was established as a standard body of 16 mesh to 32 mesh, and granules containing 4% of spherical to hemispherical tricyclazole having a particle diameter of 16 mesh to 16 mesh were obtained.

Reference Example 3

After mixing 45 parts of fine powder of tricyclazole and 600 parts of fine powder of calcium carbonate, it is added to 360 parts of Uji fatty acid (melting point 42 ° C Nihon Oil Co., Ltd., brand Uji Fatty Acid No. 100) melted at about 80 ° C. Stir well. This mixture is spray-assembled by an injection granulator (Kawasaki Heavy Industries, Ltd.). The granulated material is established as a standard body of 16 meshes and 32 meshes, and granules containing 4% of spherical to hemispherical tricyclazole having a particle size of 32 meshes are obtained at 16 meshes.

Reference Example 4

1000 parts of water is added to 100 parts of β-cyclodextrin and dissolved by heating. Separately, 20 parts of tricyclazole are dissolved in 400 parts of methanol, and both are stirred and mixed (the molar ratio of β-cyclodextrin and tricyclazole is 1: 1.1 at this time). The precipitate formed by cooling this is filtered off and dried under reduced pressure at 60 ° C. This product contained 12.5% of tricyclazole.

10 parts of alkylbenzenesulfonate sodium, 20 parts of polyvinyl alcohol, 100 parts of bentonite and 550 parts of clay are mixed with 320 parts of the product, mixed with a kneader (KDH-10 type), and then kneaded by adding an appropriate amount of water. This was granulated by attaching a screen with a hole diameter of 0.8 mm to a granulator (EXD-60 type), and the granulated product was dried in a warm bed at 80 ° C. using a fluidized bed dryer (MD-B-400 type). After drying, it was established as a standard of 16 mesh and 32 mesh, and granules containing 4% of tricyclazole 3% of 32 mesh were obtained from 16 mesh.

Test Example 1 Blast Control Test

(1) Test method

① Nursery

Seedling boxes (30 × 60 × 3 cm) were provided with 2.5 leafy rice seedlings (variety: Aichi Asahi).

② Pharmaceutical treatment

The granules prepared according to the above examples were tested.

Pharmaceutical treatment was applied to the soil surface of the seedling box on the day before transplantation. After sprinkling, the tube was treated with 500 ml of water.

③cultivation of rice

One day after the chemical treatment, rice was cut with a rice transplanter, and four trees of one stem were planted in containers (TS-36, 54 × 36 × 15 cm), respectively. In addition, 4 trees per container of planting density correspond to about 20,000 trees / 10a of field planting.

④Test of rice blast control effect

The container is transferred to a greenhouse bed where the blast is severely infected, and then naturally infected, and irradiated on the 10th day after transplantation (weakening), the 55th day after transplantation (leaf blasting) and the 100th day after transplantation (espinal febrile disease) to control and control the disease. Assay. Investigation of sweet leaf blast was carried out at the diseased area ratio per tree according to the criteria of Japanese garden patrol survey. In addition, the ear disease degree (%) was calculated according to the following formula.

Lee Byung-do

In addition, evaluation of weakening was performed based on the following references | standards.

-: Healthy leaves (no harm).

+: About 20 to 30% of the leaves are considered weak.

++: At least 30% of the leaves are recognized as weak.

(2) Test result

The results are shown in Table 4.

TABLE 4

As is clear from the results shown in Table 4, the horticultural sterilizing composition according to the present invention is treated only once in the seedling box, and the control effect lasts for 100 days or more after transplantation.

Test 2 Plague Control Test

(1) Test method

① Nursery

2.5 leaves of rice grown in seedling boxes (30 x 60 x 3 cm) (variety: Kanto 5, 90) were used for the test.

② Pharmaceutical treatment

The granules prepared according to the above examples were provided for the test.

Drug treatment was sprayed on seedling boxes the day before transplantation. In the case of granulation, water of 500 ml per box after granulation was performed.

③ Assess the effect of rice cultivation and control

Seedling boxes treated as described above were implanted into rice fields in 18 boxes per 10a. Weakness was assessed on June 5, 7 days after transplantation, leaf blast area ratio on July 28, 62 days after transplantation, and the pathology of Isaac blast on September 25, 121 days after transplantation. In addition, the calculation method of Lee Byeong-do was based on the test example 1.

(2) Test result

The results are shown in Table 5.

TABLE 5

As is clear from the results shown in Table 5, it was recognized that the agricultural and horticultural sterilizing composition according to the present invention can control leaf blast and ear fever in the main field after transplantation by treating the seedling nursery one day before transplantation.

Test Example 3 Dissolution Test

Tricyclazole 4% containing particles prepared according to Examples and Reference Examples were tested for the solubility of tricyclazole in water. The test method is as follows.

A 3 l beaker is prepared, and 900 ml of 3rd degree hard water is placed in a yellow greenhouse at 20 ° C. per day. 90 mg of granules having known ingredient values are uniformly sprayed into the beaker. (Corresponds to 3 kg spray per 10 ar) 50 ml of water is collected with a 50 ml hollow pipette at the center of the beaker (1 cm depth) after 1, 10, 25, 50 and 100 days of spraying, extracted with chloroform and concentrated. It was added to the chloroform liquid containing the internal standard, and quantitatively analyzed by gas chromatography to measure the concentration of each tricyclazole in water.

The dissolution rate was determined by the following equation from the amount of tricyclazole eluted in water (μg) and the amount of trisclesol contained in the sprayed granules (μg). The results are shown in Table 6.

TABLE 6

As evident from the above test examples, the horticultural sterilization composition according to the present invention controls rice febrile disease for a long period of time up to the water extraction period without damaging the rice by treating the medicine once after seedling box of rice seedling period or main field transplant. .

Claims (4)

A method for producing agrohorticultural germicidal composition, wherein an isocyanate compound is added to prepare agrohorticultural germicidal composition containing 5-methyl-S-triazolo (3,4-b) benzothiazole as an active ingredient. Isocyanate compound and general formula in preparing agricultural horticultural germicidal composition containing 5-methyl-S-triazolo (3,4-b) benzothiazole as an active ingredient

Wherein R ¹ represents a hydrogen atom or a methyl group and R ² represents an alkyl group having 1 to 12 carbon atoms substituted with a hydrogen atom or a hydroxyl group or a carboxyl group (average molecular weight: 500 to 10000) or this And general formula

(1, wherein R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents an alkyl group having 1 to 12 carbon atoms.) One kind of acryl polyol compound selected from the polymers (average molecular weight: 500 to 10,000) of the compound represented by A method for producing a horticultural germicidal composition, characterized by adding two or more kinds. The compound of claim 1 wherein the isocyanate compound is of the general formula:

(However, n represents 0 or an integer of 1 to 8) polymethylene polyphenyl polyisocyanate production method characterized in that the agricultural and horticultural sterilization composition. The compound of claim 2 wherein the isocyanate compound is of the general formula:

(Wherein n represents an integer of 0 or 1 to 8). A method for producing a agricultural horticultural germicidal composition, characterized in that the polymethylene polyphenylpolyisocyanate.