JP2736998B2 - Organic iodine bactericidal smoker - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to an antibacterial and antifungal smoke agent having an organic iodine fungicide as an active ingredient and having excellent stability over time and smoke rate. .

[Conventional technology]

2. Description of the Related Art In recent years, the airtightness of buildings has been significantly improved due to advances in fittings and the like. However, on the one hand, there is a problem that molds are generated and easily spread in the building, which impairs the appearance and causes allergies.

The fumigation agent targeted by the present invention is an agent used for controlling fungi and preventing such harm of fungi.

Conventionally, spraying agents using an aqueous solution of hypochlorites, spraying agents using an aqueous solution of hydrogen peroxide adduct of sodium carbonate, and 2- (4) '-Thiazolyl) benzimidazole and the like as an active ingredient.
However, since these medicines are of a spray type, there is a possibility that the medicine scattered at the time of use may enter the eyes and nose or adhere to the skin, which has a problem in terms of safety to the human body. In order to solve these problems, it is better to use a smoke agent that does not require direct application by a person. The fumigation agent is a mixture of exothermic base and bactericidal substance or insecticidal substance as an active ingredient, if necessary, with an extender, binder, etc., which burns or decomposes the exothermic base at the time of use. This is because sterilization or insecticide can be performed by volatilizing the effective nodes by the generated combustion heat or decomposition heat.

In fact, based on this idea, 2-
A (4'-thiazolyl) benzimidazole-based smoking agent has been developed and is commercially available. However, this smoker has an insufficient effect on fungi, and a smoker having a better effect has been desired.

Therefore, the present inventors have paid attention to an organic iodine-based bactericide which has higher efficacy against fungi and is also excellent in safety, and has tried to use this as a smoking agent. However, organic iodine fungicides have poor heat stability, low stability over time in pharmaceutical preparations, and have a problem that the smoke rate is low even when smoked in accordance with the conventional method. It was difficult to do.

The smoke rate is a rate (%) defined by the following equation.

On the other hand, as a technique for improving the smoke rate of a smoking agent, the active ingredient is not an organic iodine bactericide, but 2,6-di-ter
A method using a phenolic antibody oxidizing agent such as t-butyl-4-methylphenol (see JP-A-59-25305)
It has been known. However, even if this method is used for an organic iodine-based fungicide, as expected in Comparative Examples 15 and 18 in Table 1 of Test Examples described below, both the smoke rate and the stability over time were improved as expected. Cannot be adopted.

Attempts have also been made to use an epoxy compound as a stabilizer for an organophosphorus insecticide instead of an organic iodine fungicide (see Japanese Patent Publication No. 48-43860). When used as a fumigation agent, it was completely unknown what effect it had on the rate of smoke formation, stability over time, and the like.

[Problems to be solved by the invention]

The present invention has been made in view of the above situation, and aims to develop and provide an antibacterial and antifungal smoke agent excellent in stability over time and an excellent smoke rate using an organic iodine fungicide as an active ingredient. Is what you do.

[Means for solving the problem]

Thus, the present inventors have conducted intensive studies on a technique for converting an organic iodine-based bactericide into a fumigation agent. As a result, the above-described problems have been solved by using a specific epoxy-based compound as a stabilizing agent and using a specific-form dosage form. Have been found, and the present invention has been completed.

That is, the present invention relates to 4-chlorophenyl-3-iodopropargyl formal, 1-[(diiodomethyl) sulfonyl] -4-methylbenzene, 2,4,5-trichloroiodopropargyl ether, 2,3,3-triiodide Allyl alcohol, 1-bromo-3-ethoxycarbonyloxy-1,2-diiodo-1-propene, 3-iodo-2
-One or more organic iodine compounds selected from propynyl butyl carbamate and phenyl-11-iodo-10-undecenoate, and an epoxy group having a weight of the compound containing 1 gram equivalent of epoxy group (gram) of 150 to 2500. A compound and at least one exothermic base selected from nitrocellulose, potassium chlorate and azodicarbonamide, and a granular organic iodine-based bactericidal smoker having a diameter of 0.5 to 5.0 mm. To provide.

The compound having an epoxy group (hereinafter referred to as epoxy compound) used in the present invention is a compound having a compound weight (g) containing 1 gram equivalent of epoxy group (hereinafter referred to as epoxy equivalent) of 150 to 2500. Specific examples thereof include an epoxy resin synthesized by a condensation reaction between bisphenol A and epichlorohydrin, for example, Epikote 828 (trade name, Yuka Shell Epoxy, epoxy equivalent 1
82-194), Araldite epoxy resin GY280 (trade name, Ciba-Geigy, epoxy equivalent 225-280), Araldite epoxy resin 7072 (trade name, Ciba-Geigy, epoxy equivalent 550-700), Epicron 3050 (trade name, Dai Nippon Ink) Chemical, epoxy equivalent 740-860), epicron 7050
(Product name, Dainippon Ink and Chemicals, epoxy equivalent 1750-210
0), Adeka Resin EP4200 (trade name, Asahi Denka, epoxy equivalent 180-200), Adeka Resin EP4520 (trade name, Asahi Denka, epoxy equivalent 195-215) and the like, and novolak type epoxy resin, for example, Epicoat 152 (trade name, oilification) Shell epoxy, epoxy equivalent 172 to 179), Epiclon N665 (trade name, Dainippon Ink Chemical, epoxy equivalent 200 to 230), araldite epoxy resin EPN1139 (trade name, Ciba Geigy, epoxy equivalent 172 to 179), and cycloaliphatic resin,
For example, Araldite epoxy resin CY117 (trade name, Ciba Geigy, epoxy equivalent of about 200) and the like, and bisphenol F type epoxy compound such as epicron 830 (trade name, Dainippon Ink and Chemicals, epoxy equivalent of 170 to 190), etc.
And epoxidized soybean oil (epoxy equivalent of about 270) and epoxidized linseed oil (epoxy equivalent of about 280).

In the present invention, the epoxy compound having an epoxy equivalent of 150 to 2500 is used alone or in a mixture of two or more kinds in an amount of 0.2 to 20% by weight, preferably 0.5 to 5% by weight based on the total weight of the preparation. You.

Next, the organic iodine compound used as an active ingredient in the present invention is 4-chlorophenyl-3-iodopropargyl formal, 1-[(diiodomethyl) sulfonyl] -4-methylbenzene, 2,4,5-trichloroiodo. Propargyl ether, 2,3,3-triiodoallyl alcohol, 1-bromo-3-ethoxycarbonyloxy-1,2-diiodo-1-propene, 3-iodo-2-propynylbutylcarbamate and phenyl-11-iodo- One or more organic iodine compounds selected from 10-undecenoate.

The use amount of these organic iodine compounds is preferably in the range of 1 to 40% by weight based on the total weight of the preparation.

The exothermic base used in the present invention is at least one selected from nitrocellulose, potassium chlorate, and azodicarbonamide.

The amount used is 25 to 40% by weight for nitrocellulose, 7 to 20% by weight for potassium chlorate, and 40 to 40% for azodicarbonamide based on the total formulation weight when used alone. It is preferred to use up to 95% by weight. When two or three of these are mixed and used, the combination is appropriately selected and used depending on the purpose. In practice, however, it is preferable to determine and use the mixing ratio and amount by preliminary experiments.

Specific examples thereof are shown in Examples 2, 3, 7, and 10 described later.

In addition, in formulating the smoking agent of the present invention, a bulking agent, a binder, a combustion regulator and the like can be added as necessary. Clay, talc, diatomaceous earth, benite,
Kaolin, calcium carbonate and the like are used, as binders, carboxymethylcellulose, methylcellulose, hydroxypropylmethylcellulose, starch, polyvinyl alcohol and the like are used, and as combustion control agents, melamine, magnesium oxide, zinc oxide and the like are used. It is preferable to use appropriate amounts of these additives determined appropriately by experiments.

The smoking agent of the present invention needs to take a specific dosage form. That is, it is necessary to form granules having a diameter of 0.5 to 5.0 mm. As shown in Table 1 below, as a result of the test and research by the present inventors, other than the above-mentioned dosage forms, for example, powder (Comparative Example 7), tablet (Comparative Example 8), rod-shaped (Comparative Example 10) In each case, it is a requirement derived from the fact that an undesirable result is obtained.

〔Example〕

Hereinafter, the present invention will be specifically described with reference to Examples, Comparative Examples, and Test Examples, but the present invention is not limited to these Examples. In the Examples and Comparative Examples, “parts” means “parts by weight”.

Example 1 4-Chlorophenyl-3-iodopropargyl formal: 10 parts, Epikote 828 (epoxy equivalent: 182-19)
4): 1 part, nitrocellulose: 30 parts, melamine: 5 parts, carboxymethylcellulose: 5 parts, starch: 3 parts, and clay: 46 parts are put into a grinder and mixed and stirred. About 20 pieces of water
After adding and mixing the parts, granulation is performed using a granulator (die diameter 2.5 mm). The obtained granules were dried at about 60 ° C. to obtain granules having a diameter of about 2.5 mm.

Example 2 4-chlorophenyl-3-iodopropargyl formal: 10 parts, epoxidized soybean oil (epoxy equivalent: about 27
0): 3 parts, nitrocellulose: 15 parts, azodicarbonamide: 40 parts, melamine: 1 part, hydroxypropylmethylcellulose: 4 parts, and clay: 27 parts, and the die diameter of the granulator was 1 mm. Others are the same as in Example 1,
mm granules were obtained.

Example 3 4-Chlorophenyl-3-iodopropargyl formal: 10 parts, Epicron 7050 (epoxy equivalent: 1750-21)
00): 5 parts, azodicarbonamide: 40 parts, potassium chlorate: 7 parts, starch: 10 parts, magnesium oxide: 5 parts, carboxymethyl cellulose: 5 parts, kaolin: 18 parts,
Granules having a diameter of about 4 mm were obtained in the same manner as in Example 1 except that the die diameter of the granulator was changed to 4 mm.

Example 4 3-Iodo-2-propynylbutyl carbamate: 5
Part, Araldite epoxy resin CY177 (Epoxy equivalent:
About 200): 2 parts, azodicarbonamide: 90 parts, hydroxypropyl methylcellulose: 3 parts, and the diameter of the granulator was about 0.7 mm in the same manner as in Example 1 except that the die diameter was 0.7 mm.
Granules were obtained.

Example 5 3-Iodo-2-propynylbutyl carbamate: 8
Parts, Epicron 830 (epoxy equivalent: 170-190): 1 part, nitrocellulose: 30 parts, melamine: 5 parts, starch: 4 parts,
Granules having a diameter of about 2.5 mm were produced in the same manner as in Example 1 using 4 parts of polyvinyl alcohol and 48 parts of calcium carbonate.

Example 6 1-[(diiodomethyl) sulfonyl] -4-methylbenzene: 7 parts, Epicron 3050 (epoxy equivalent: 740 to 86)
0): 2 parts, nitrocellulose: 30 parts, melamine: 3 parts, starch: 4 parts and diatomaceous earth: 54 parts, and granules having a diameter of about 2.5 mm were produced in the same manner as in Example 1.

Example 7 2,4,5-Trichloroiodopropargyl ether: 7
Parts, Epicoat 828 (epoxy equivalent: 182 to 194) 3 parts, nitrocellulose: 7 parts, potassium chlorate: 4 parts, azodicarbonamide: 40 parts, starch: 3 parts, and talc: 36 parts Granules having a diameter of about 2.5 mm were produced in the same manner as in Example 1.

Example 8 2,3,3-triiodoallyl alcohol: 5 parts, Epikote 152 (epoxy equivalent: 172 to 179): 4 parts, potassium chlorate: 14 parts, lactose: 20 parts, magnesium oxide: 5 parts, starch : 4 parts and kaolin: 48 parts to produce granules having a diameter of about 2.5 mm in the same manner as in Example 1.

Example 9 1-bromo-3-ethoxycarbonyloxy-1,2-
Diiod-1-propene: 10 parts, Epiclone 7050 (epoxy equivalent: 1750-2100): 5 parts, nitrocellulose: 30 parts,
Granules having a diameter of about 2.5 mm were produced in the same manner as in Example 1 using 5 parts of starch, 3 parts of melamine and 47 parts of clay.

Example 10 Phenyl-11-iodo-10-undecenoate: 10
Parts, Epicron N665 (epoxy equivalent: 200-230): 4 parts,
Granules having a diameter of about 2.5 mm were produced in the same manner as in Example 1 using 8 parts of nitrocellulose, 4 parts of potassium chlorate, 40 parts of azodicarbonamide, 5 parts of methylcellulose and 29 parts of clay. .

Comparative Example 1 Granules having a diameter of about 2.5 mm were produced in the same manner as in Example 1 except that Epicoat 828: 1 part was removed from the components used in Example 1, and 47 parts of clay was used.

Comparative Example 2 Granules having a diameter of about 1 mm were produced in the same manner as in Example 2, except that 3 parts of epoxidized soybean oil was removed from the components used in Example 2 and that the amount of clay was 30 parts.

Comparative Example 3 Granules having a diameter of about 4 mm were produced in the same manner as in Example 3 except that 5 parts of Epicron 7050 was removed from the components used in Example 3, and 23 parts of kaolin was used.

Comparative Example 4 The same procedure as in Example 1 was carried out except that epichlorohydrin (epoxy equivalent: about 90): 3 parts was added instead of the component used in Example 1 except for Epicoat 828: 1 part and the clay was 44 parts. 2.5 mm granules were produced.

Comparative Example 5 Three parts of butyl glycidyl ether (Nissan Epiol B, manufactured by NOF CORPORATION, epoxy equivalent: about 130) were added to the components used in Example 1 except that 1 part of Epicoat 828 was removed, and 44 parts of clay were added. A granule having a diameter of about 2.5 mm was produced in the same manner as in Example 1 except that the above parts were used.

Comparative Example 6 Epicoat 828: 1 part was removed from the components used in Example 1, and instead, 3 parts of Epicron 9055-40AX (trade name, Dainippon Ink, epoxy equivalent 2850-3150) was added, and 44 parts of clay were added. Approximately 2.5 m in diameter in the same manner as in Example 1 except that
m granules were produced.

Comparative Example 7 The same components as in Example 1 were placed in a grinder, mixed and stirred to obtain a powder.

Comparative Example 8 The powder obtained in Comparative Example 7 was formed into a tablet having a diameter of 30 mm using a tableting machine.

Comparative Example 9 The same components as in Example 3 were placed in a grinder, mixed and stirred to obtain a powder.

Comparative Example 10 The same components as in Example 3 were put in a crusher, mixed and stirred, then about 20 parts of water was added and kneaded, and the obtained kneaded product was extruded with a diameter of 20 mm and a length of 100 mm using an extruder. It was rod-shaped. Next, this was dried at about 60 ° C. to obtain a rod-shaped smoke agent.

Comparative Example 11 Granules having a diameter of about 0.7 mm were produced in the same manner as in Example 4 except that 92 parts of azodicarbonamide were used, except that 2 parts of the araldite epoxy resin CY177 were excluded from the components used in Example 4.

Comparative Example 12 The same components as in Example 4 were placed in a grinder, mixed and stirred to obtain a powder.

Comparative Example 13 Granules having a diameter of about 2.5 mm were produced in the same manner as in Example 5 except that 49 parts of calcium carbonate was used except that epicron 830: 1 part was removed from the components used in Example 5.

Comparative Example 14 The same components as in Example 5 were mixed and stirred in a crusher,
About 20 parts of water was added and kneaded, and the obtained kneaded product was formed into a rod shape having a diameter of 10 mm and a length of 100 mm by an extruder. Next, this was dried at about 60 ° C. to obtain a stick-shaped smoke agent.

Comparative Example 15 The components of Example 5 were removed from Epicron 830: 1 part,
Granules having a diameter of about 2.5 mm were produced in the same manner as in Example 5, except that 1 part of 2,6-di-tert-butyl-4-methylphenol was added.

Comparative Example 16 Granules having a diameter of about 2.5 mm were produced in the same manner as in Example 5, except that 1 part of epichlorone (epoxy equivalent: about 90) was added to the components used in Example 5 except that epicron 830: 1 part was removed.

Comparative Example 17 Granules having a diameter of about 2.5 mm were produced in the same manner as in Example 6 except that epichlorone 3050: 2 parts was excluded from the components used in Example 6, and 56 parts of diatomaceous earth was used.

Comparative Example 18 The components used in Example 6 were removed except for Epicron 3050: 2 parts.
Granules having a diameter of about 2.5 mm were produced in the same manner as in Example 6 except that 2,6-di-tert-butyl-4-methylphenol: 2 parts was added.

Comparative Example 19 Granules having a diameter of about 2.5 mm were produced in the same manner as in Example 7 except that 3 parts of talc was used instead of Epicoat 828: 3 parts from the components used in Example 7.

Comparative Example 20 Granules having a diameter of about 2.5 mm were produced in the same manner as in Example 8, except that the components used in Example 8 were replaced with 52 parts of kaolin except for 152: 4 parts of Epicoat.

Comparative Example 21 The same ingredients as in Example 8 were taken in a grinder, mixed and stirred, and then formed into tablets having a diameter of 22 mm using a tableting machine.

Comparative Example 22 The same components as in Example 8 were placed in a grinder and mixed and stirred to obtain a powder.

Comparative Example 23 Granules having a diameter of about 2.5 mm were produced in the same manner as in Example 9 except that the component used in Example 9 was replaced with 52 parts of clay except that 5 parts of Epicron 7050 was used.

Comparative Example 24 In the same manner as in Example 10, except that the component used in Example 10 was replaced with 33 parts of clay except for epicuron N665: 4 parts, the diameter was reduced.
2.5 mm granules were produced.

[Test Example]

30 g of each of the preparations of Examples 1 to 10 and Comparative Examples 1 to 20 was filled in a can and packaged to prepare a sample.

The content of the active ingredient in the sample and the sample stored in a thermostat at 60 ° C. for a certain period was determined by gas chromatography.

Next, the content after storage with respect to the content before the start of storage was determined, and this was defined as the residual ratio of the active ingredient.

 The smoke rate was determined as follows.

A 50 g sample was smoked at room temperature with an internal volume of 5800, the room air was stirred by a fan, and about 20 room air was passed through a glass tube filled with silica gel for chromatography using a vacuum pump, and the active ingredient was adsorbed on the silica gel. Let it. Next, the active ingredient is eluted and recovered with acetone, quantified by gas chromatography, and the amount of the active ingredient (Ag) in the collected indoor air is determined. On the other hand, the content (B%) of the active ingredient in the sample is determined by a gas chromatography method in a conventional manner.

 Based on these values, the smoke conversion rate was determined by the following equation.

Table 1 shows the test results.

[Effects of the Invention] As is clear from the test results shown in Table 1, the smoking agent containing the organic iodine-based bactericide of the present invention as an active ingredient is excellent in stability over time and the rate of smoking, and It is satisfactory as an agent. Therefore, the smoke suppressant of the present invention has made it possible to prevent the generation of molds in buildings and the like and to remove the molds, which have been conventionally desired, in a more labor-saving and safer manner.

Claims (1)

(57) [Claims] (1) 4-chlorophenyl-3-iodopropargyl formal, 1-[(diiodomethyl) sulfonyl] -4-methylbenzene, 2,4,5-trichloroiodopropargyl ether, 2,3,3-triethyl Iodoallyl alcohol, 1-bromo-3-ethoxycarbonyloxy-
1,2-diiodo-1-propene, 3-iodo-2-propynylbutylcarbamate and phenyl-11-iodo-
At least one organic iodine compound selected from 10-undecenoate, a compound containing 1 gram equivalent of an epoxy group, a compound having an epoxy group having a weight (gram) of 150 to 2500, nitrocellulose, potassium chlorate and azo compound; An organic iodine-based bactericidal smoker comprising one or more exothermic bases selected from dicarbonamides and having a diameter of 0.5 to 5.0 mm.