JPH08193009A - Industrial antiseptic and fungicide - Google Patents

Abstract

(57) [Abstract] [Purpose] The present invention provides an emulsion paint, an oil paint, an electrodeposition paint, an organic adhesive, a paste, a clay, an ink, a cutting oil,
A new industrial antiseptic fungus to prevent the deterioration of various industrial raw materials and products such as grinding oil, wood, leather, textiles and white water during the production of paper by bacteria, yeast, filamentous fungi, algae, etc. The purpose is to provide an agent. [Structure] Two types of (±) -allyl-1- (2,4-dichlorophenyl) -2-imidazol-1-ylethyl ether and sorbic acid or a salt thereof, or dehydroacetic acid or a salt thereof. An industrial antiseptic and fungicide, characterized by containing as an active ingredient.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to emulsion paints, oil paints, electrodeposition paints, organic adhesives, pastes, clays, inks, cutting oils, grinding oils, woods, leathers, fibers and white water during paper production. The present invention relates to a novel industrial antiseptic and fungicide for preventing deterioration of various industrial raw materials and products by bacteria, yeasts, filamentous fungi, algae and the like.

[0002]

2. Description of the Related Art One of the active ingredients of the present invention is (±)-
Allyl-1- (2,4-dichlorophenyl) -2-imidazol-1-ylethyl ether (hereinafter referred to as “Compound A”) is used as a fungicide for fruit trees and the like in The Pesticide Manual (The Pestic).
ide Manual) 9th edition pp. 482-483
Page (1991) and is also known as an antifungal agent during storage of citrus fruits and banana fruits. In addition, the other active ingredient, sorbic acid or a salt thereof (hereinafter referred to as "compound B" unless otherwise specified).
And dehydroacetic acid or salts thereof (hereinafter referred to as "Compound C" unless otherwise specified) are used as fungicides (Encyclopedia of antibacterial and antifungal agents, pages 152 and 162).
Published August 22, 1986 by the Japanese Society for Antibacterial and Antifungal). Further, as the admixture similar to the present invention, a mixture of compound B or compound C and para-chlorometaxylenol (JP-A-55-87003), compound B or compound C and 2- (4-thiazolyl). ) -Bentimidazole admixture (Japanese Patent Application Laid-Open No. 55-87007) is known.

[0003]

In order to protect industrial raw materials and products from deterioration due to bacteria, yeasts, molds, it is necessary to prevent the generation of various microorganisms nonselectively and eradicated. . However, the antiseptic and fungicides that have been used so far are highly toxic to humans and animals, and their use is restricted, the effect becomes weak when the amount used is small, or the residual effect over a long period of time is poor. In addition, there are few conventional drugs that sufficiently exhibit both the antiseptic effect and the antifungal effect. Any of compound A, compound B or compound C used in the present invention has such drawbacks, and their use alone is not always satisfactory.

Therefore, the present invention is to provide a novel industrial antiseptic and fungicide for preventing the generation of various microorganisms that deteriorate industrial raw materials and products for a long period of time, in place of conventional chemical agents. .

[0005]

[Means for Solving the Problems] In order to develop a new industrial antiseptic and fungicide that meets such demands, the present inventors have conducted various tests on various chemical agents and have earnestly studied them. As a result, they have found that the compound A represented by the chemical structural formula to be described later and the compound B or the compound C are used in combination as a preservative and fungicide for various industrial raw materials and products.

Therefore, the gist of the present invention is to provide (±) -allyl-1- (2,4-dichlorophenyl) -2-imidazol-1-ylethyl ether,
An industrial antiseptic and fungicide which comprises, as an active ingredient, a mixture of two kinds of sorbic acid or a salt thereof or dehydroacetic acid or a salt thereof.

Next, the chemical name or general name and the chemical structural formula of the active ingredient of the present invention are shown.

[0008]

Embedded image Compound A [(±) -allyl-1- (2,4-dichlorophenyl) -2-imidazol-1-ylethyl ether]

[0009]

Embedded image Compound B (sorbic acid or a salt thereof) (In the formula, X represents a hydrogen atom or an alkali metal.)

[0010]

Embedded image Compound C (dehydroacetic acid or a salt thereof) (In the formula, R represents an alkali metal.)

Examples of the compound B which can be used in the present invention include sorbic acid, sodium sorbate and potassium sorbate, with sorbic acid and potassium sorbate being preferred. Compound C includes dehydroacetic acid,
Examples thereof include sodium dehydroacetate and potassium dehydroacetate, and preferred are dehydroacetic acid and sodium dehydroacetate.

[0012]

The industrial antiseptic and fungicide of the present invention, that is, the mixture of compound A and compound B or compound C is an antiseptic and antifungal agent for preventing various industrial raw materials and products from being deteriorated by microorganisms. Acts synergistically as active ingredients.

[0013]

EXAMPLES Formulation and Use of Industrial Antiseptic and Antifungal Agent The industrial antiseptic and antifungal agent of the present invention can be obtained by the following method. That is, the two active ingredients of the present invention are mixed with a suitable carrier and auxiliary agent such as a surfactant, a binder, a stabilizer and the like, and a wettable powder, an emulsion, a liquid preparation,
It may be formulated into a flowable agent (sol agent) or the like.

In the case of wettable powders, emulsions, solutions and flowable agents, the content of the active ingredient of the present invention in these preparations is
It can be contained in the range of 0.1 to 90% (weight%, the same hereinafter). In this case, for example, the mixing ratio of compound A and compound B or compound C is 1 part by weight of compound A (parts by weight,
same as below. ) To compound B or compound C
50 parts, preferably 0.2-5 parts.

The carrier that can be used is not limited to a particular one, as long as it is a commonly used one for industrial preservatives and fungicides, and it can be used as a solid or liquid.

For example, as the solid carrier, mineral powder (kaolin, bentonite, clay, montmorillonite, talc, diatomaceous earth, mica, vermiculite, gypsum, calcium carbonate, apatite, white carbon, slaked lime, silica sand, ammonium sulfate, urea, etc.), Examples thereof include vegetable powders (soybean flour, wheat flour, wood flour, tobacco powder, starch, crystalline cellulose, etc.), alumina, silicates, sugar polymers, highly dispersible silicic acids, waxes, oils and the like.

As the liquid carrier, water, alcohols (methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, ethylene glycol, benzyl alcohol, etc.), aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene) are used. , Chlorobenzene, cumene, methylnaphthalene, etc.), halogenated hydrocarbons (chloroform, carbon tetrachloride, dichloromethane, chloroethylene, trichlorofluoromethane, dichlorodifluoromethane, etc.), ethers (ethyl ether, ethylene oxide, dioxane, etc.) Tetrahydrofuran, etc., Ketones (acetone, methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone, etc.), Esters (ethyl acetate, butyl acetate, ethylene glycol acetate) , Amyl acetate, etc.), nitriles (acetonitrile, propionitrile, acrylonitrile, etc.), sulfoxides [dimethyl sulfoxide, etc.], alcohol ethers (ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 1-methoxy-2-propanol) Etc.), amines (ethylamine, dimethylamine, trimethylamine,
Isobutylamine, etc.), aliphatic or alicyclic hydrocarbons (n-hexane, cyclohexane, etc.), industrial gasoline (petroleum ether, solvent naphtha, etc.) and petroleum fractions (paraffins, kerosene, gas oil, etc.), etc. Can be mentioned.

For the preparation of emulsions, wettable powders, sol agents (flowable agents), etc., emulsification, dispersion, solubilization, wetting,
Surfactants are used for purposes such as foaming and spreading. Examples of such a surfactant include those shown below, but the surfactants are not limited to these examples. Non-ionic type (polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, polyoxyethylene sorbitan alkyl ester, sorbitan alkyl ester, etc.) Anionic type (alkylbenzene sulfonate, alkyl sulfosuccinate, alkyl sulfate, polyoxyethylene alkyl sulfate, aryl) Sulfonate, etc. Cationic type [Alkylamine salt (laurylamine, stearyltrimethylammonium chloride, alkyldimethylbenzylammonium chloride), etc.] Amphoteric type [Carboxylic acid (betaine type), sulfate ester, etc.]

In addition to these, polyvinyl alcohol (PVA) and carboxymethyl cellulose (CM
Various auxiliary agents such as C), gum arabic, polyvinyl acetate, gelatin, casein, sodium alginate and the like can be used. Further, if necessary, an antioxidant,
A suitable amount of a stabilizer such as an ultraviolet absorber can be added.

The industrial antiseptic and fungicide of the present invention is an insecticide or 2- (4-thiazolyl) benzimidazole (T
BZ), 1,2-benzisothiazolin-3-one, benzyl bromoacetate, pentachlorophenol or a salt thereof, 2,4,5,6-tetrachloro-4-methylsulfonylpyridine, para-oxybenzoic acid n-butyl ester, 1 , 2-dibromo-2,4-dicyanobutane, N
-Dichlorofluoromethyl-N ', N'-dimethyl-N
-Phenylsulfamide (Preventol A4), 2,
4,5,6-Tetrachloroisophthalonitrile, parachlorometaxylenol, 3-iodo-2-propargylbutyl carbamate (IPBC), methyl-2-benzimidazole carbamate (MBC), 5-chloro-2
-Methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one can be used as a mixture with various industrial preservatives and fungicides.

Although some examples will be given below, the mixing ratio of the active ingredient, auxiliary components and other addition amounts are not limited to the following examples.

In the examples, all parts are parts by weight.

[0023]

Example 1 (Flowable Agent) 5 parts of compound A, compound B (potassium salt) or compound C
(Sodium salt) 5 parts, lauryl sulfate 2
Part, xanthan gum 0.2 part, and water 87.8 parts are put into a ball mill and ground and mixed for 12 hours to obtain each flowable agent containing 10% of the active ingredient.

A similar flowable agent can be obtained by substituting the potassium salt of compound B with an acid or sodium salt and the sodium salt of compound C with an acid or potassium salt, respectively.

[0025]

Example 2 (Wettable powder) 20 parts of compound A, 20 parts of compound B (potassium salt) or 20 parts of compound C (sodium salt), lauryl sulfate 7
Part and clay 53 parts are mixed and pulverized to obtain 40% of active ingredient
Each wettable powder containing is obtained.

A wettable powder can be obtained in the same manner by substituting the potassium salt of compound B with an acid or sodium salt and the sodium salt of compound C with an acid or potassium salt, respectively.

[0027]

Example 3 (Emulsion) 2.5 parts of compound A, 2.5 parts of compound B (potassium salt) or compound C (sodium salt), 85 parts of diethylene glycol, Newcalgen ST60 (an emulsifier manufactured by Takemoto Yushi Co., Ltd.) 10 parts of trade name) are mixed and dissolved to obtain each emulsion.

An emulsion is similarly obtained by substituting the potassium salt of compound B with an acid or sodium salt and the sodium salt of compound C with an acid or potassium salt, respectively.

[0029]

Example 4 (Liquid) 1.0 part of compound A, 1.0 part of compound B (potassium salt) or 1.0 part of compound C (sodium salt), ethanol 49
And 49 parts of water are mixed and dissolved to obtain each liquid preparation.

A liquid preparation is obtained in the same manner by substituting the potassium salt of compound B with an acid or sodium salt and the sodium salt of compound C with an acid or potassium salt, respectively.

The industrial antiseptic and fungicide of the present invention is used as follows. That is, various formulations prepared according to the above-mentioned examples are added as they are, or diluted with water or an appropriate organic solvent, and (1) added to various industrial raw materials or during a manufacturing process or to a product. , (2) a method of coating or spraying the surface of various industrial raw materials and products, (3) a method of immersing various industrial raw materials and products in a diluted solution of the industrial antiseptic and fungicide of the present invention, etc. It can be used by various methods according to the generally used method of industrial antiseptic and fungicide, and is not limited to any particular method.

[0032]

Use of the industrial antiseptic and fungicide of the present invention brings about the following effects.

First, the drug of the present invention non-selectively and eradicates the generation of various microorganisms such as bacteria, yeasts and filamentous fungi. Therefore, it can be widely used as an industrial antiseptic agent. Second, it shows a strong antiseptic and antifungal effect even with a small dose. Thirdly, a high antiseptic and antifungal effect can be exerted for a long time even with a small dose. Fourth, there are few problems such as human toxicity. Fifthly, it can be used in various methods such as spraying, spraying, coating and mixing with industrial raw materials and products, but any method does not adversely affect the industrial raw materials and products.

Since the industrial antiseptic and fungicide of the present invention has the above-mentioned characteristics, it can be widely used as an antiseptic and fungicide for various industrial raw materials and products as exemplified below. it can. (1) Prevention of spoilage problems due to growth of bacteria, filamentous fungi, yeast, etc. during the manufacturing process of water-based or oil-based paints, during storage and during use, and contamination damage due to growth of filamentous fungi on the painted surface after painting. (2) Prevention of spoilage problems caused by growth of bacteria such as casein, polyvinyl alcohol, starch, and other adhesives or pastes, filamentous fungi, yeasts, and contamination of filamentous fungi on the coated adhesive surface. (3) Prevention of quality deterioration damage due to growth of bacteria, filamentous fungi, yeast, etc. during storage of papermaking raw materials such as wet pulp and chips. (4) Prevention of contamination and deterioration of quality of processed products and materials such as wood, plywood, bamboo and leather due to growth of filamentous fungi. (5) Natural fibers, synthetic fibers and blended products of these,
Prevention of contamination and deterioration of quality due to the growth of bacteria, filamentous fungi and yeast on materials. (6) Prevention of quality deterioration damage due to growth of bacteria, filamentous fungi, and yeast on synthetic emulsion or emulsion tax. (7) Preventing deterioration of quality due to growth of bacteria, filamentous fungi, and yeast in concrete admixtures. (8) Prevention of quality deterioration damage due to growth of bacteria, filamentous fungi, and yeast in hydraulic fluids. (9) Preventing deterioration of quality due to growth of bacteria, filamentous fungi, and yeast in plastics, rubber, etc. (10) A controlling agent for slime disorders mainly caused by bacteria, filamentous fungi, and algae during the papermaking process.

Next, test examples are shown to show the usefulness as the industrial antiseptic and fungicide of the present invention.

Test Example 1 Test for antifungal effect of filter paper Compound A and compound B (potassium salt) or compound C (sodium salt) were dissolved in ethanol to give compound A.
And the compound B (potassium salt) or the compound C (sodium salt) are mixed at a ratio of 5: 1 to 1: 5 to prepare a predetermined concentration.

1 ml of this solution was soaked in a filter paper having a diameter of 30 mm and then air-dried in a room to obtain a test piece. This test piece was attached to the center of an agar medium (composition: glucose 40 g, peptone 10 g, agar 25 g and distilled water 1000 ml) of a Petri dish, and Aspergillus niger, Penicillium funiculosum, Cladosporium cladsporioides, gliocladium virences, A mixed spore suspension of Aureobasidium pullulans is spray-inoculated on the medium surface and on the test piece in an amount of 1 ml.

The Petri dish was covered with a lid and incubated in an incubator at 28 ± 2 ° C., and 14 days later, the mold growth condition on the test piece was examined according to the following criteria.

The control section was prepared and tested in the same manner as above. The results are shown in Tables 1 and 2.

[0040]

[0041]

[Table 1]

[0042]

[Table 2]

Test Example 2 Mold resistance test of emulsion paint The test method was according to JIS Z 2911. That is, a vinyl acetate emulsion white paint is added with a reagent agent prepared according to Example 1 so as to have a predetermined concentration, and the mixture is stirred and mixed with a homogenizer for 30 seconds to prepare a paint. A filter paper (Toyo Filter Paper No. 2) having a diameter of 12.5 cm is dipped in the obtained coating liquid to uniformly apply the sample, and then air dried at room temperature for 48 hours. In this case, the thickness of the coating film is uniform, and the weight of the paint attached to the filter paper is 90 to 110% of the weight of the filter paper. This filter paper was used as a circular test piece with a diameter of 3 cm, and a beaker with a capacity of 200 ml was prepared for each test piece. 200 ml of water was added to it and kept at 20 ° C, and the test piece was immersed in it for 18 hours. Then, the test piece is taken out, hung at room temperature for 2 hours, and further hung in a dryer (80 to 85 ° C.). After 2 hours, the test piece was taken out and the agar medium of the Petri dish (composition: glucose 40 g, peptone 10 g, agar) was used.
25 g and 1000 ml of purified water) was applied to the center of the culture surface, and a mixed spore suspension of Aspergillus niger, Penicillium funiculosum, Cladosporium cladsporioides, Gliocladium virens, and Aureobasidium pullulans was added to the medium surface and the test piece. Spray inoculate evenly on top of.

The Petri dish was covered with a lid and incubated in an incubator at 28 ± 2 ° C., and 3 days, 7 days and 14 days thereafter, the mold growth state on the test piece was examined according to the criteria of Test Example 1.

The drugs in the control group were prepared and tested according to Example 1. The results are shown in Table 3.

[0046]

[Table 3]

Test Example 3 Antifungal Field Test of Emulsion Paint A predetermined amount of a flowable agent prepared according to Example 1 is added to a vinyl acetate emulsion white paint and mixed sufficiently to obtain a paint liquid. Apply this paint solution to the concrete wall,
Occurrence of mold was examined after 3 months, 6 months and 12 months according to the following criteria.

The drugs in the control group were prepared according to Example 1 and tested. The results are shown in Table 4.

[0049]

[0050]

[Table 4]

Test Example 4 Mold resistance test of starch paste 15 parts of potato starch and 85 parts of an aqueous solution prepared by diluting the emulsion prepared according to Example 3 with water to a predetermined concentration were placed in a 200 ml volume flask. While stirring, the temperature is raised to 70 ° C., and then the starch paste is prepared while gradually cooling. Place it in a 200 ml beaker, and mix the fungal mixed spore liquid (Aspergillus niger, Penicillium citrinum, Cladosporium).
Clados Polioides, Ketomium globosum) 1
Spray with ml. Cover the beaker with aluminum foil and set the temperature to 2
Incubate in an incubator at 8 ± 2 ° C and a humidity of 95 to 99%. The degree of mold resistance was evaluated every one week based on the same criteria as in Test Example 1.

The drugs in the control group were prepared and tested according to Example 3. The results are shown in Table 5.

[0053]

[Table 5]

Test Example 5 Antifungal Effect of Spray Liquid Field Test A predetermined amount of the liquid agent prepared according to Example 4 is diluted with a mixed solution of water and ethanol (1: 1) to give a spray liquid.
This spray solution was sprayed onto the wallpaper-attached surface at 100 ml / m ² and the occurrence of mold was examined based on the following criteria after 3 months, 6 months and 12 months.

The drugs in the control group were prepared and tested in accordance with the above. The results are shown in Table 6.

[0056]

[0057]

[Table 6]

Claims (1)

[Claims] 1. A method comprising: (±) -allyl-1- (2,4-dichlorophenyl) -2-imidazol-1-ylethyl ether and sorbic acid or a salt thereof, or dehydroacetic acid or a salt thereof. An industrial antiseptic and fungicide containing two kinds as active ingredients.