JPH1171202A - Powdery bactericide composition and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition quickly soluble in water, giving a dissolved liquid free from precipitate and having high concentration by including a bactericidal agent selected from an ampholytic surfactant-type bactericide, a biguanide compound, etc., a soluble starch and/or a specific organic solvent and/or water. SOLUTION: This composition contains (A) a bactericide selected from (i) a compound expressed by the formula (R1 to R4 are each a 1-22C alkyl or the like; X<-> is an anion), (ii) an ampholytic surfactant-type bactericide (e.g. an alkylaminoethylglycine) and (iii) a biguanide compound (e.g. chlorhexidine hydrochloride), (B) a soluble starch (e.g. amylodextrin) and (C) optionally an organic solvent which is a non-solvent of the soluble starch and/or (D) water. The weight ratio of A/B is 10/90 to 90/10, the sum of the components A and B is 80-100 wt.% based on the total composition and the content of the component D is <=5%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a powdered fungicide composition, and more particularly, to a powdered fungicide composition used in livestock pens, poultry houses, and the like.

[0002]

2. Description of the Related Art Conventionally, floors, walls,
For disinfecting equipment, disinfectants such as didecyldimethylammonium chloride and methyldodecylbenzyltrimethylammonium chloride are effective ingredients and are usually supplied as a 5-20% aqueous solution or a solution containing alcohol, and used. It is used 50 to 2000 times dissolved in tap water. However, the high-concentration liquid disinfectant has a problem in safety because it adheres to the skin when it dissolves, for example, when it dissolves. In addition, there are also problems with container processing of cans, drums, and the like, because there are few container processing companies and the cost is high. In order to solve these problems, powdering has been studied, and zeolite (JP-A-4-214025) and magnesium carbonate (JP-A-1-129854) are used as powdering bases. However, in the case of a zeolite, when a zeolite is used as a solution, the powdered base does not dissolve and becomes a sediment, and there is a possibility that pipes or the like for spraying the solution are clogged. Further, magnesium carbonate has a problem that it takes a long time to dissolve.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a high-concentration powdered fungicide composition which has a high rate of dissolution in water and has no precipitate in the solution.

That is, the present invention provides a compound (a1) represented by the following general formula (1), an amphoteric surfactant type fungicide (a
2) one or more fungicides (A) and a soluble starch (B) selected from the group consisting of biguanide compounds (a3);
And optionally an organic solvent (C) and / or water (D) which are non-solvents for soluble starch,
(A) / (B) weight ratio of 10/90 to 90/10,
The total amount of (A) and (B) is 80 in the powdered fungicide composition.
1 to 100% by weight and the content of (D) in the composition is 5% by weight or less; and a method for producing the same. General formula [Wherein, R ₁ , R ₂ , R ₃ and R ₄ are the same or different and each have a linear or branched alkyl group having 1 to 22 carbon atoms, a hydroxyalkyl group, a (substituted) aryl group, a (substituted) aralkyl or cycloalkyl group; X ^- represents an anion. ]

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The powdery bactericide composition of the present invention comprises:
Compound (a1) represented by the following general formula (1), amphoteric surfactant type fungicide (a2), biguanide compound (a3)
And at least one fungicide (A) selected from the group consisting of: a soluble starch (B); and, if necessary, an organic solvent (C) and / or water (D) which is a non-solvent for the soluble starch. And the weight ratio of (A) / (B) is 1
0/90 to 90/10, the total amount of (A) and (B) is 80 to 100% by weight in the powdered fungicide composition, and the content of water (D) in the composition is 5% It is a powdered bactericide composition that is less than or equal to% by weight. General formula [Wherein, R ₁ , R ₂ , R ₃ and R ₄ are the same or different and each have a linear or branched alkyl group having 1 to 22 carbon atoms, a hydroxyalkyl group, a (substituted) aryl group, a (substituted) aralkyl or cycloalkyl group; X ^- represents an anion. ]

The compound (a1) of the fungicide (A) used in the present invention is a quaternary ammonium salt compound represented by the above general formula (1), wherein R ₁ , R ₂ , R ₃ and R ₄ are the same or different and each have a linear or branched alkyl group having 1 to 22 carbon atoms, a hydroxyalkyl group, a (substituted) aryl group, a (substituted) aralkyl group or a cycloalkyl group. Of these, R ₁ , R ₂ , R
_{When 3} and R ₄ are a linear or branched alkyl group having 1 to 22 carbon atoms, specifically, the following [1] and [2]
Is raised. [1] R ₁ and R ₂ are linear or branched alkyl groups having 6 to 12 carbon atoms, and R ₃ and R ₄ are alkyl groups having 1 to 3 carbon atoms. [2] R ₁ is a C 6 to 22 carbon atom. Wherein R ₂ , R ₃ and R ₄ are alkyl groups having 1 to 3 carbon atoms, preferably [1], and more preferably [1] R ₁ and R ₂ are both decyl groups and R ₃
And R ₄ are both methyl groups. Specific examples include the following compounds. [1] Dimethyl octyl decyl ammonium, dimethyl dioctyl ammonium, dimethyl didecyl ammonium, dimethyl didodecyl ammonium, methyl ethyl octyl decyl ammonium, methyl ethyl dioctyl ammonium, methyl ethyl didecyl ammonium, methyl ethyl didodecyl ammonium, methyl propyl didecyl ammonium [2] trimethyl dodecyl ammonium, trimethyl tetradecyl ammonium, trimethyl hexadecyl ammonium, trimethyl octadecyl ammonium, trimethyl coco oil alkyl ammonium, dimethyl ethyl dodecyl ammonium, dimethyl ethyl tetradecyl ammonium, dimethyl ethyl hexadecyl ammonium ,
Dimethyl ethyl octadecyl ammonium, dimethyl ethyl coconut oil alkyl ammonium, methyl diethyl dodecyl ammonium, methyl diethyl tetradecyl ammonium, methyl diethyl hexadecyl ammonium, methyl diethyl octadecyl ammonium, methyl diethyl coconut oil alkyl ammonium, etc.

Examples of the group other than a linear or branched alkyl group having 1 to 22 carbon atoms include a hydroxyalkyl group (hydroxymethyl group, hydroxyethyl group, hydroxypropyl group, etc.); and an aryl group (phenyl group, naphthalene A substituted aralkyl group (such as a benzyl group); a substituted aralkyl group (such as a nonylbenzyl group or a methyldodecylbenzyl group); a cycloalkyl group (such as a cyclohexyl group); And so on. Specifically, cetyl hydroxyethyl dimethyl ammonium,
Lauryl dihydroxyethyl benzyl ammonium, lauryl dimethyl benzyl ammonium, dodecyl dimethyl phenyl ammonium, methyl dodecyl benzyl trimethyl ammonium, dimethyl dodecyl cyclohexylammonium and the like.

[0008] X in the general formula (1) representing the compound of the present invention (a1) ^- as the anion represented by the chlorine, bromine, halogen atom such as iodine, alkyl carbonate, alkyl sulfuric acid, phosphoric acid, phosphoric acid Examples include esters, carboxylate anions (sebacic acid, gluconic acid, adipic acid, lactic acid, acetic acid, etc.), sulfonic acid anions and the like. Preferred are chlorine and carboxylate anions, and particularly preferred are carboxylate anions.

The amphoteric surfactant type fungicide of the present invention (a2)
Are usually amino acid-type amphoteric surfactants and betaine-type amphoteric surfactants. Specific examples of the amino acid type amphoteric surfactant include alkylaminoethyl glycine or a salt thereof, myristyl diaminoethyl glycine or a salt thereof, lauryl diaminoethyl glycine or a salt thereof, and the like. Examples of betaine-type amphoteric surfactants include alkyl betaine-type surfactants, amidopropyl betaine-type surfactants, imidazolinium betaine-type surfactants, sulfobetaine-type surfactants, and phosphobetaine-type surfactants. Of these, preferred are amino acid-type amphoteric surfactants.

The biguanide compound (a3) of the present invention includes polyhexamethylene biguanide hydrochloride, chlorhexidine gluconate, chlorhexidine hydrochloride and the like.

The fungicide (A) of the present invention comprises a compound (a)
1) The amphoteric surfactant bactericide (a2) and the biguanide compound (a3) may be used alone or in combination. Of these, preferred are (a1) and (a)
3), and more preferably (a1).

The soluble starch (B) of the present invention is a modified starch soluble in water.
Acids such as oxalic acid, and degradation products that are initially generated when an enzyme such as α-amylase is used alone or in combination, specifically, amylodextrin, erythrodextrin,
Dextrins such as acrodextrin and maltodextrin are exemplified.

The organic solvent (C) which is a non-solvent for soluble starch in the present invention has a solubility in soluble starch of 0.1 g / 100 g or less.
Specifically, lower alcohols (methanol, ethanol, isopropanol, etc.), ketones (acetone, methyl ethyl ketone, etc.), carbitols (ethyl carbitol, butyl carbitol, etc.), glycols (ethylene glycol, propylene glycol, etc.) Is raised. Further, as described above, the soluble starch is liable to be degraded by heating when the solvent is removed under normal pressure or reduced pressure, and therefore, the organic solvent (C) of the present invention is preferably an organic solvent having a boiling point of 100 ° C. or lower.

The weight ratio of the fungicide (A) and the soluble starch (B) contained in the powdered fungicide composition of the present invention (A) /
(B) is usually 10/90 to 90/10, preferably 30/70 to 70/30. When the weight ratio of (A) / (B) is less than 10/90, the cost per bactericide component is increased, and when it exceeds 90/10, it takes a long time to dissolve in water, which is not preferable. In the case of producing a powdered bactericide using a conventional zeolite, magnesium carbonate, or the like, the bactericide does not become powder unless the concentration of the bactericide is low. However, when a powdered bactericide is produced using the soluble starch (B) of the present invention, the bactericide becomes powdery even at a high concentration. The total amount of (A) and (B) is usually 80 to 100% by weight of the composition, preferably 90 to 100% by weight.
And particularly preferably 95 to 100% by weight.
If the total amount of (A) and (B) is less than 80% of the composition, a large amount of the organic solvent (C) insoluble in soluble starch is contained, so that the appearance does not become powdery, which is not preferable.
The content of water (D) in the composition is usually 5% by weight or less,
It is preferably at most 3% by weight, particularly preferably at most 1% by weight. If the content of water (D) in the composition exceeds 5% by weight, the appearance of the composition does not become powdery, and the dissolution time in water is undesirably long.

As the fungicide (A) used for producing the powdered fungicide composition of the present invention, a commercially available fungicide can be used as it is. However, since the commercial fungicide of the compound (a1) type usually contains 80 to 10% of water, it is added so that the water content in the final powdered fungicide becomes 5% by weight or less according to the water content. Adjust the volume. In order to obtain a powdered bactericide having a high concentration of the active ingredient, it is necessary to dissolve the soluble starch in a higher concentration of the bactericide (a1) obtained by dehydrating a commercially available bactericide so that it can be uniformly mixed with the soluble starch. Organic solvent (C), which is a non-solvent, can be added. When the fungicide (a1) is synthesized and produced from the beginning, the fungicide (a1) obtained by reacting soluble starch instead of water with an organic solvent (C), which is a non-solvent, is used. ) Can also be used. Fungicide (A)
Solvent (C) which is a non-solvent for starch and soluble starch
Is mixed in advance if necessary, and then soluble starch (B)
When the total content of the organic solvent (C) and water insoluble in the soluble starch in the powdered fungicide composition obtained by mixing Do. At this time, dehydration may be performed simultaneously. It is preferable to further remove the solvent and dehydrate even if it is 10% by weight or less.
In addition, since a disinfectant (A) uses a commercial disinfectant, for example,
When water is contained in advance, dehydration and desolvation are performed simultaneously. Dehydration and desolvation may be performed at normal pressure or reduced pressure. Since the soluble starch (B) is liable to be deteriorated (colored, solidified, etc.) by heating, the temperature during mixing or desolvation is as low as possible, usually 60 ° C. or lower, preferably 40 ° C. or lower.

If necessary, anionic surfactants and nonionic surfactants for the purpose of imparting detergency can be added to the powdery bactericide composition of the present invention so as not to impair the effects of the present invention. A stimulant for alleviating the skin irritation of the solution, an antifoaming agent (such as a silicone emulsion) for defoaming the solution, and a chelate for the hard water resistance of the solution. An agent may also be included. Furthermore, a water-soluble polymer for the purpose of adjusting the viscosity of the solution or a low-molecular compound for the purpose of coloring and smelling can be contained.

Examples of the anionic surfactant include an alkali salt of an alkyl sulfate, an alkali salt of an alkyl phosphate, an alkali salt of a polyoxyalkylene alkyl sulfate, an alkali salt of a polyoxyalkylene alkyl phosphate, and a monoalkyl sulfosuccinate alkali. Examples thereof include salts, alkali salts of polyoxyethylene alkyl ether acetate, and sulfates of animal and vegetable oils, and the salts may be metal salts or amine salts.

The nonionic surfactants include those having 4 carbon atoms.
Alkylene oxide adducts of monohydric alcohols, ethylene oxide adducts of alkylphenols,
Sorbitan ester of higher fatty acid, alkylene oxide adduct of sorbitan ester of higher fatty acid, higher fatty acid ester of polyethylene glycol, block copolymer of polyoxyethylene polyoxypropylene glycol and random of polyoxyethylene polyoxypropylene glycol And copolymers.

Gluconic acid, pyrrolidone carboxylic acid, sodium hyaluronate, glycerin,
Sorbitol, lactic acid, alkali metal salts of lactic acid, and the like.

Examples of the chelating agent include ethylenediaminetetraacetic acid and hydroxyethylethylenediaminetriacetic acid.

Examples of the water-soluble polymer include polyoxyethylene glycol, polyvinyl alcohol, and polyvinylpyrrolidone. Examples of the low molecular weight compound include lactose, sucrose, methylene blue, food blue No. 1, food yellow No. 4, food red No. 2, Various flavors and the like can be mentioned.

As a machine used for mixing, for example, a screw-type mixer, a ribbon-type mixer, a rotary mixer, or the like can be used in addition to a rotary container-type mixer.

The powdered bactericidal composition of the present invention is used by dissolving it in tap water or the like as a bactericidal disinfectant for livestock pens, poultry pens and the like. For germicidal disinfection of floors, walls, devices, instruments, etc., about 10 to 5000 ppm, preferably 50 to 20 ppm as an active ingredient.
Dissolve and spray to about 00 ppm. Also,
The obtained powdered bactericide composition can be filled into a water-soluble film and water-soluble paper in a fixed amount, and can be put into water together with the water-soluble film by packaging the used amount as an internal content, It is safe because it does not directly touch the finger skin during use, and weighing errors are eliminated.

[0024]

The present invention will be further described with reference to the following examples, but the present invention is not limited to these examples. Parts in Examples are parts by weight, and% means% by weight.

Example 1 Didecylmethylamine and dimethyl carbonate were reacted in methanol, and further reacted with adipic acid. 500 parts of an 80% methanol solution of didecyldimethylammonium adipate having a water content of 0.3% was obtained. After mixing 500 parts of Pineflow-S (Dextrin, manufactured by Matsutani Chemical Industry Co., Ltd.) with a water content of 0.5%, the solvent was removed at 30 to 50 ° C. under reduced pressure to remove the fungicide composition of the present invention. A 46% powder as decyldimethylammonium adipate was obtained. [1] was powdery, the evaporation residue was 96%, and the water content was 0.3%.

Example 2 Didecylmethylamine and dimethyl carbonate are reacted in methanol, and further reacted with gluconic acid. 500 parts of an 80% methanol solution of 1.0% water-containing didecyldimethylammonium gluconate obtained. And pine flow S
After mixing 500 parts, the solvent was removed at 40 to 50 ° C. under reduced pressure to obtain a 42% powder as the fungicidal composition [2] didecyldimethylammonium gluconate of the present invention.
[2] was powdery, the evaporation residue was 95%, and the water content was 0.4%.

EXAMPLE 3 Trimethylhexadecyl ammonium chloride obtained by reacting trimethylhexadecylamine with methyl chloride in 6 parts by weight of water / 14 parts by weight of methanol was used.
% Water / methanol solution and Pineflow-S50
0 parts were mixed to obtain a 40% powder as the fungicidal composition [3] trimethylhexadecyl ammonium chloride of the present invention. [3] was powdery, the evaporation residue was 93%, and the water content was 3%.

Example 4 400 parts of benzalkonium chloride aqueous solution (400 parts) was mixed with 50 parts of ethyl alcohol, and then mixed with 550 parts of Pine Flow S. The solvent and water were removed at 30 to 50 ° C. under reduced pressure to remove the fungicide of the present invention. Composition [4] A 35% powder of benzalkonium chloride was obtained. [4] was in the form of a powder, the evaporation residue was 96%, and the water content was 3%.

Example 5 After mixing 50 parts of ethyl alcohol with 400 parts of an 80% aqueous solution of methyl dodecylbenzyltrimethylammonium chloride, 550 parts of Pine Flow S were mixed.
The solvent and water were removed at 0 to 50 ° C. to obtain 35% powder of the fungicidal composition [5] methyldodecylbenzyltrimethylammonium chloride of the present invention. [5] was powdery, the evaporation residue was 96%, and the water content was 3%.

Example 6 A mixture of 800 parts of polyhexamethylene biguanidine 80% isopropyl alcohol solution and 200 parts of Pineflow S was mixed, and the solvent was removed under reduced pressure at 30 to 50 ° C. to remove the fungicide composition [6] polyhexa of the present invention. 70% of methylene biguanidine
A powder was obtained. [6] was powdery, the evaporation residue was 91%, and the water content was 0.3%.

COMPARATIVE EXAMPLE 1 100 parts of an 80% aqueous solution of didecyldimethylammonium chloride and 100 parts of Pineflow-S were mixed and mixed under reduced pressure.
The solvent and water were removed at 0 to 50 ° C. to obtain 42% powder of a disinfectant composition [ratio 1] didecyldimethylammonium chloride. [Ratio 1] is that the evaporation residue is 93% and the water content is 7
%Met.

Comparative Example 2 Didecylmethylamine and dimethyl carbonate were reacted in methanol, and further reacted with adipic acid. 200 parts of a 0.3% water-containing 80% methanol solution of didecyldimethylammonium adipate was obtained. After mixing 800 parts of zeolite, the solvent was removed at 30 to 50 ° C. under reduced pressure to obtain a [ratio 2] 16% powder as didecyldimethylammonium adipate. [Ratio 2] is that the evaporation residue is 96%,
The water content was 0.6%.

Comparative Example 3 Water 1 of 80% Didecyldimethylammonium Chloride
0 parts by weight / 200 parts by weight of 10 parts by weight of ethanol and 800 parts of magnesium carbonate are mixed, and water and a solvent are removed at 40 to 50 ° C. under reduced pressure. I got
[Ratio 3] is that the evaporation residue is 97% and the water content is 1.5%
Met.

The appearance of the fungicidal compositions themselves obtained in Examples 1 to 6 and Comparative Examples 1 to 3, the appearance of a 1000 ppm aqueous solution,
The solubility in water (dissolution rate) was evaluated. Table 1 shows the results.

[Evaluation of appearance of fungicide composition itself] ：: powder ×: paste [evaluation of appearance of 1000 ppm aqueous solution and solubility in water (dissolution rate)] ：: clear solution with no sediment ×: There is sediment [Evaluation of solubility in water (dissolution rate)] Tap water is placed in a 1 L beaker, and the temperature is adjusted to 5 ° C. After dissolving in it,
The powdered bactericide compositions of Examples 1 to 5 and Comparative Examples 1 to 3 were added so that the bactericide content was 1000 ppm, and the time (minute) required for complete dissolution was measured.

[0036]

[Table 1]

From Table 1, it can be seen that although the fungicide composition of the present invention is a high-concentration powdered fungicide, it dissolves when a 1000 ppm solution is prepared using low-temperature (5 ° C.) water. The required time is all within 1 to 3 minutes, which indicates that the dissolution rate in water is high. In addition, it can be seen that the appearance of the 1000 ppm dissolved liquid is free of sediment, is a transparent liquid, and has no risk of clogging pipes and the like.

[0038]

The antimicrobial composition of the present invention has the following effects. (1) It is in the form of powder with high concentration. (2) There is no sediment in the solution, and there is no risk of clogging the piping and the like. (3) The dissolution rate in water is high.

Continued on the front page (51) Int.Cl. ⁶ Identification code FI A01N 25/12 AJA A01N 25/12 AJA 101 101 37/44 37/44 47/44 47/44 A61L 9/01 A61L 9/01 K 9 / 14 9/14 (72) Inventor Yoshimi Kataoka 1 at 11-11 Hitotsubashi-Honcho, Higashiyama-ku, Kyoto Inside Sanyo Chemical Industry Co., Ltd.

Claims (5)

[Claims] A compound (a) represented by the following general formula (1)
1) at least one fungicide (A) selected from the group consisting of an amphoteric surfactant-type fungicide (a2) and a biguanide compound (a3) and a soluble starch (B); It comprises an organic solvent (C) and / or water (D) as a solvent, the weight ratio of (A) / (B) is 10/90 to 90/10, and the total amount of (A) and (B) is powder. A powdered fungicide composition comprising 80 to 100% by weight of the fungicidal composition and having a content of (D) of 5% by weight or less in the composition. General formula [Wherein, R ₁ , R ₂ , R ₃ and R ₄ are the same or different and each have a linear or branched alkyl group having 1 to 22 carbon atoms, a hydroxyalkyl group, a (substituted) aryl group, a (substituted) aralkyl or cycloalkyl group; X ^- represents an anion. ] 2. The powdery fungicide composition according to claim 1, wherein the total content of the organic solvent (C) and water is 10% by weight or less in the composition. 3. The powdery fungicide composition according to claim 1, wherein the boiling point of the organic solvent (C) is 100 ° C. or less. 4. A mixture of the disinfectant (A) or an aqueous solution thereof and the organic solvent (C) mixed with a soluble starch (B) and, if necessary, desolvation and / or dehydration.
The method for producing a powdery fungicide composition according to any one of claims 1 to 3, comprising producing a powdery fungicide composition having a content of 5% by weight or less. General formula [Wherein, R ₁ , R ₂ , R ₃ and R ₄ are the same or different and each have a straight-chain or branched-chain alkyl group having 1 to 22 carbon atoms, a hydroxyalkyl group, a (substituted) aryl group,
(Substituted) aralkyl group or a cycloalkyl group; X ^- represents an anion. ] 5. The method for producing a powdery bactericide composition according to claim 4, wherein part or all of the organic solvent (C) is removed under normal pressure or reduced pressure.