JPH0615446B2 - Industrial antiseptic and fungicide - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION 1) Object of the invention Industrial field of application The present invention is an emulsion paint, an oil paint, an electrodeposition paint, an organic adhesive, a paste, a clay, an ink, a cutting oil, a grinding oil, a wood, The present invention relates to a novel industrial antiseptic and fungicide for preventing deterioration of various industrial raw materials and products such as leather, textiles and white water at the time of paper production by bacteria, yeast, filamentous fungi, algae, etc. .

2. Description of the Related Art Up to now, various industrial antiseptic and fungicides have been developed and used. Examples thereof include 2- (4-thiazolyl) benzimidazole (TBZ), 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 (platinum butyl),
1,2-dibromo-, N- dichlorprop-fluorobenzyl methyl -N ', N'-dimethyl -N- phenyl sulfamide (Purenbentoru _A 4), 2,4,
5,6-Tetrachloroisophthalonitol and para-chlorometaxylenol (PCMX), which is one of the compounds represented by the general formula (II) of the present invention, are known. These are usually used alone, but in some cases, they may be used as a mixture of two or more kinds.

On the other hand, some of the pyridinium tetraphenylborate compounds represented by the following general formula (I) used in the present invention are known as active ingredients for underwater antifouling paints (Japanese Patent Publication No.
No. 1571) and others are novel fungicides found by the present inventors (Japanese Patent Application No. 62-2131).
No. 00 specification). Further, it is known that the following compounds similar to these have antiseptic and antifungal activity (JP-A-60-
155185).

In the formula, R ₁ represents a hydrogen atom, a halogen atom or a lower alkyl group, R ₂ represents a halogen atom, a lower alkyl group or a lower alkenyl group, and R ₃ is a heterocyclic amine.

Problems to be Solved by the Invention 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 in a non-selective and eradicative manner. However, the antiseptic and fungicides that have been used so far are highly toxic to humans and animals, and their use is regulated.If the amount used is small, the effect becomes weak, or there is little residual effect over a long period of time. Many. In addition, there are few conventional drugs that sufficiently exhibit both the antiseptic effect and the antifungal effect. Both the pyridinium tetraphenylborate compound and the substituted phenol compound used in the present invention have such drawbacks, and their use alone is not always satisfactory.

Therefore, the present invention provides a novel industrial antiseptic and fungicide that can prevent the generation of various microorganisms that deteriorate industrial raw materials and products for a long period of time by using a small amount of the drug instead of the conventional drug. The purpose is to do.

2) Structure of the invention Means for solving the problem The inventors of the present invention have conducted various tests on many chemical agents in order to develop a new industrial antiseptic and fungicide that meets such demands, and earnestly studied them. did. As a result, the general formula (I)
Represented by One kind of pyridium tetraphenylborate compound,
Represented by general formula (II) It has been found that a mixture with one of the substituted phenol compounds represented by the formula (1) is extremely useful as an antiseptic and fungicide for various industrial raw materials and products.

However, in the formula, R represents a hydrogen atom, a lower alkoxycarbonyl group or a carbamoyl group, and m represents an integer of 1 to 2.

Examples of preferable compounds contained in the general formula (I) or (II) are as follows.

Compounds A to E are also referred to in the following examples, test examples and the like.

"Compound A" "Compound B" "Compound C" "Compound D" "Compound E" Some of the compounds of the general formula (I) of the present invention are novel compounds and can be produced by the method detailed in Japanese Patent Application No. 62-213001. The outline of the manufacturing method will be described.

The compound of the general formula (I) is obtained by reacting tetraphenylboron sodium of the following formula (III) with the hydrohalic acid salt of the substituted pyridine of the following general formula (IV), based on the following reaction: Can be manufactured.

In the above reaction formula, R has the same meaning as described above, and X represents a halogen atom.

That is, tetraphenylboron-sodium (III) and a substituted pyridine hydrohalide of the general formula (IV),
The reaction is completed by dissolving in an inert solvent such as lower alkanol such as methanol, ethanol and isopropanol, ketones such as acetone, water and the like and mixing and stirring at a temperature of 10 to 60 ° C. for 30 minutes to 2 hours. As the reaction solvent, the above solvents may be used alone, or may be used in combination. When the reaction product is precipitated in the solvent as crystals, it can be filtered off, but usually, the solvent is distilled off and the mixture is concentrated, and then the crystals are filtered off and washed with water to remove inorganic salts. Removed and dried to give the product as a pure product.
The complex of (I) is obtained. The tetraphenylboron-onium complex of the general formula (I) thus obtained can be further purified by recrystallizing it with a solvent such as methanol, ethanol, chloroform or dimethylformamide, if necessary.

Reference examples show production examples of compounds represented by the general formula (I).

Other compounds included in the general formula (I) can be produced by the method according to Reference Example 1 and used in the present invention.

Reference Example 1 Synthesis of tetraphenylboron-2-methoxycarbonylpyridinium complex (Compound No. 2) In a 100 ml flask, 1.7 g (5 mmol) of tetraphenylboron sodium was dissolved in 20 ml of ethanol, which was stirred. On the other hand, a solution prepared by dissolving 0.868 g (5 mmol) of nicotinic acid methyl ester hydrochloride in 5 ml of ethanol was added dropwise. After completion of dropping, the reaction was completed by stirring for 30 minutes. The solvent of the reaction solution was distilled off, and 10 ml of water was added to the precipitated crystals to loosen them, and the crystals were filtered. The crystals were dried to obtain 2.2 g (yield 96%) of a tetraphenylboron-2-methoxycarbonylpyridinium complex having a melting point of 166 to 168 ° C. (decomposition) as white crystals.

In the industrial antiseptic and fungicide of the present invention, pyridinium tetraphenylborate compounds such as compounds A and B,
A mixture of C and a substituted phenolic compound, for example, compounds D and E, acts synergistically as an antiseptic and antifungal active ingredient for preventing various industrial raw materials and products from being deteriorated by microorganisms.

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: two active ingredients of the present invention and a suitable carrier and auxiliary agent. An agent, for example, a surfactant, a binder, a stabilizer and the like may be mixed and formulated into a wettable powder, an emulsion, a liquid agent, a flowable agent (sol) and the like by a conventional method.

The content of the active ingredient of the present invention in these formulations is a wettable powder,
In the case of an emulsion, a liquid agent, and a flowable agent, the content can be in the range of 1 to 90% (weight%: the same hereinafter). In this case, for example, the mixing ratio of Compound A and Compound D is
To 1 to compound D 0.3 to 5, preferably 0.5
~ 1. The same applies to the mixing ratio of other compounds.

In the above, the carrier that can be used may be either solid or liquid as long as it is commonly used for industrial preservatives and antiseptics, and is not limited to a particular carrier.
For example, as a 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., vegetable powder (soybean flour, wheat flour, wood flour, tobacco powder, starch, crystalline cellulose, etc.), alumina, silicates, sugar polymers, highly dispersible silicic acid, waxes, oils, etc. .

Further, as the liquid carrier, water (ion-exchanged water, organic acid or inorganic acid aqueous solution, alkaline aqueous solution, etc.), alcohols (methanol, ethanol, n-butanol, iso)
-Propanol, n-butanol, ethylene glycol, benzyl alcohol, etc., aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, chlorobenzene, cumene, methylnaphthalene, etc.), halogenated hydrocarbons (chloroform, carbon tetrachloride) , Dichloromethane, chloroethylene, trichlorofluoromethane, dichlorodifluoromethane, etc.), ethers (ethyl ether, ethylene oxide, dioxane, 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.), sulfoxide [Dimethylsulfoxide (D
MSO), alcohol ethers (ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, etc.), aliphatic or alicyclic hydrocarbons (n-hexane, cyclohexane, etc.), industrial gasoline (petroleum ether, solvent naphtha, etc.) ), And petroleum fractions (paraffins, kerosene, gas oil, etc.) and the like. Also, emulsions, wettable powders, flowable agents (sols),
In the case of formulation such as, a surfactant (or emulsifier) is used for the purpose of emulsification, dispersion, solubilization, wetting, foaming, lubrication, spreading and the like. Examples of such a surfactant include those shown below, but of course the present invention is not limited to these examples.

Non-ionic type (polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, polyoxyethylene sorbitan alkyl ester, sorbitan alkyl ester, etc.) Anionic type (alkyl benzene sulfonate, alkyl sulfosuccinate, alkyl sulfate, polyoxyethylene alkyl sulfate, aryl) Sulfonate, etc. Cationic type [alkylamines (laurylamine, stearyltrimethylammonium chloride, alkyldimethylbenzylammonium chloride), etc.] Amphoteric type [carboxylic acid (betaine type), sulfate ester, etc.] Alcohol (PV
Various auxiliary agents such as A), carboxymethyl cellulose (CMC), gum arabic, polyvinyl acetate, gelatin, casein, sodium alginate, and tragacanth gum can be used. Further, if necessary, an appropriate amount of a stabilizer such as an antioxidant and an ultraviolet absorber can be added.

The industrial antiseptic and fungicide of the present invention can be used as a mixture with various other industrial antiseptic and antifungal agents as described above.

Some examples will be given below, but the blending ratio of the active ingredient, the auxiliary component and the addition amount thereof are not limited to the following examples.

In the examples, “parts” means “parts by weight”.

Example 1 Emulsion Compound A 1 part, Compound D 1 part, Solpol 800A
[Toho Chemical Industry Co., Ltd. product name of emulsifier] 2 parts, DMSO
An emulsion was obtained by mixing and dissolving 50 parts and 46 parts of methyl socerolbe.

Example 2 Flowable Agent Compound B 20 parts, Compound D 20 parts (both compounds have a particle size of 10 μ or less), lauryl sulfate 2 parts, alkylnaphthalene sulfonate sodium 2 parts,
A flowable agent was obtained by uniformly mixing 1 part of hydroxypropyl cellulose and 55 parts of water.

Example 3 Wettable powder 20 parts of compound C, 20 parts of compound E, 5 parts of lauryl sulfate and 55 parts of clay were ground and uniformly mixed to obtain a wettable powder.

Example 4 Dust 40 parts of compound A, 20 parts of compound E, and 40 parts of clay were crushed and uniformly mixed to obtain a powder.

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 used as they are or diluted with water or a suitable organic solvent, and added to various industrial raw materials, and applied to the surface of various industrial raw materials and products. Or by various methods according to the generally used industrial antiseptic and fungicide methods such as spray treatment, immersion of various industrial raw materials and products in a diluting solution of the agent of the present invention However, the method is not limited to a specific method.

3) Effects of the Invention The use of the industrial antiseptic and fungicide of the present invention brings about the following effects.

First of all, since the drug of the present invention has a broad antibacterial spectrum, it non-selectively and eradicates the generation of various microorganisms such as bacteria, yeasts and filamentous fungi. Therefore, it can be widely used as an antiseptic and fungicide.

Secondly, it exhibits a strong antiseptic and antifungal effect even when a small amount is used.

Thirdly, even if a small amount is used, a high antiseptic and antifungal effect is exerted for a long time. The effect is exerted as a synergistic effect as compared with the effect of each single agent.

Fourth, there are no problems such as animal toxicity.

Fifth, the agent of the present invention is applied to industrial raw materials and products,
It can be used by various methods such as mixing, but any method does not have any adverse effect on industrial raw materials and products.

Since the industrial antiseptic / antifungal agent of the present invention has the characteristics as described above, it can be widely used as an antiseptic / antifungal agent for various industrial raw materials and products as exemplified below.

(1) Control agents for slime disorders mainly caused by bacteria, filamentous fungi, and algae during the papermaking process (2) Spoilage due to growth of bacteria, filamentous fungi, yeast, etc. during the production process, storage, and use of water-based or oil-based paints Prevention of problems and contamination damage caused by the growth of filamentous fungi on the painted surface after coating (3) Rotation damage caused by the growth of bacteria, yeast, filamentous fungi, etc. on adhesives or pastes coated with casein, polyvinyl alcohol, starch, etc. And prevention of contamination damage due to growth of filamentous fungi on the coated adhesive surface (4) Prevention of quality deterioration damage due to growth of filamentous fungi, yeast, and bacteria during storage of papermaking raw materials such as wet pulp and chips (5) Wood, Prevention of contamination and deterioration of quality of processed products and materials such as plywood, bamboo, leather and plastics due to growth of filamentous fungi (6) Natural fibers, synthetic fibers and their blends Prevention of contamination due to growth of filamentous fungus on product materials and deterioration of quality (7) Prevention of deterioration of quality due to growth of yeast, bacteria and filamentous fungi in synthetic emulsion or emulsion tax. Test examples are shown to show the usefulness of the fungicide.

Test Example 1 Antibacterial activity test 1 ml of a chemical solution diluted with 10% acetone water and a medium cooled to 50 ° C. [For filamentous fungi, potato decoction agar (PH5.
8) is used, and broth agar (PH7.
0) is used] 9 ml are mixed in a sterilized petri dish having a diameter of 9 cm, and an agar plate containing a drug solution having a predetermined concentration is prepared. Preliminarily cultured in slant medium (for filamentous fungi
A spore suspension of the test bacterium, which has been subjected to 7 days at 0 ° C and 2 days at 30 ° C for bacteria, is streaked on a drug-containing medium with a platinum loop. In the case of filamentous fungi, after culturing at 28 ° C for 72 hours and at 30 ° C for 48 hours in each case, the presence or absence of growth of each bacterium is investigated, and the medium in the medium necessary for completely inhibiting the growth of the bacterium is examined. Minimum drug concentration [Minimum bacterial growth inhibitory concentration (pp
m)]. The results are as shown in Tables 1-6.

Test Example 2 Mold resistance test of emulsion paint (1) The test method was according to the method of JIS Z-2911. That is, a reagent solution prepared according to Example 1 was added to a vinyl acetate emulsion white paint so as to have a predetermined concentration, and the mixture was stirred and mixed with a homogenizer for 30 seconds to prepare a paint solution. A filter paper having a diameter of 12 cm (Toyo Filter Paper No. 2) was dipped in the obtained coating liquid to evenly apply the sample, and the sample was placed in a room at a temperature of about 20 ° C. and a humidity of about 75%.
Air dry for 8 hours. In this case, the thickness of the coating film is uniform and the weight is adjusted to 90 to 110% of the weight of the filter paper. Using this filter paper as a circular test piece with a diameter of 3 cm, prepare one beaker with a capacity of 200 ml for each test piece, add 200 ml of water to it and keep it at about 20 ° C., immerse the test piece in it for 18 hours, The test piece is removed, hung in the room for 2 hours, and further hung in a dryer (80-85 ° C). After 2 hours, remove the test piece, attach it to the center of the culture surface of the agar plate (4% glucose, 1% peptone, 2.5% agar) in a Petri dish, and culture it separately in 2% glucose-added potato decoction agar medium. Tested bacteria (Alpergillus niger ATCC 9642, Penicillium rutheum ATCC 9642, Turkish Derma T-1 ATCC
The mixed spore suspension of 9645) (mixed in equal amounts of single cell spore suspensions of three fungi) is spray-inoculated evenly on the surface of the medium 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 3 days, 7 days and 14 days thereafter, the mold growth state on the test piece was examined according to the following criteria. The results are shown in Table 2.

In the table, comparative drug (1) is a commercially available drug (emulsion) containing tributyltin oxide, and
(2) is a commercially available drug containing methylbenzimidazole carbamate.

(Survey Criteria) Mycelial growth state Mycelial growth is not observed in the mold-inoculated test piece or the inoculated part 3.

 The area of mycelial growth observed in the inoculated part of the test piece or sample does not exceed one-third of the total area.

 The total area of the hyphae developing part found in the inoculated part of the test piece or sample exceeds 1/3.

Test Example 3 Fungus resistance test of emulsion paint (Part 2) Except that the reagent agent of Test Example 2 was replaced by the same flowable agent and wettable powder as shown in Examples 2 and 3, exactly the same as Test Example 2 And tested. The results are shown in Table 8.

Test Example 4 Fungus resistance field test of emulsion paint A predetermined amount of the reagent agent prepared according to Example 1 is added to a vinyl acetate emulsion white paint and sufficiently pulverized to obtain a paint liquid. Apply this paint solution to the concrete wall and apply 3
Months, 6 months, 12 months, 18 months and 24 months
Occurrence of mold after months was investigated according to the following criteria. At the same time, the deterioration state of the coating liquid stored in tinplate was investigated.

(Survey Criteria) 3 No mold generation 2 Mold generation was found on a part of the coated surface, the area of which did not exceed one-third of the total 1 Mold generation was recognized on the whole, and the area was Three
The results, which are more than one-third, are as shown in Table 9.

In addition, when a flowable agent and a wettable powder were prepared according to Examples 2 and 3 and carried out in the same manner as this test, the same results as shown in Table 9 were obtained.

Test Example 5 Mold resistance test of starch paste 150 parts of tapioca starch, 84.9 parts of water and 0.1 part of the reagent prepared according to Example 2 were put in a 200 ml flask and heated to 70 ° C. with stirring, and then Cool slowly to prepare starch paste. Place it in a Petri dish 9 cm in diameter. Mixed spore suspension (Aspergillus niger ATCC 6275, Penicillium
Citrinum ATCC 9849, Rhizopus niglycans S. N. 32, Cladosporium Herbalum I
AMF517, Ketomium gloposum ATCC62
05) is sprayed in 1 ml portions. And the temperature 28 ± 2
Cultivation was carried out in an incubator at a temperature of 95 ° C and a humidity of 95 to 99%, and the degree of mold resistance was evaluated every one week based on the same criteria as in Test Example 2.

A commercially available organic nitrogen-sulfur fungicide was prepared and tested in the same manner as the drug of Example 1 as a comparative drug.

The results are as shown in Table 10.

Test Example 6 Mold resistance test to cotton cloth A cotton cloth is immersed in an aqueous solution of a reagent agent prepared according to Example 2 at a predetermined concentration. After the immersion, the water content is reduced to about 100% and air-dried.

After air-drying, make a test piece of 4 cm x 4 cm and make it JISZ-2911.
The mold resistance was measured according to the paint test.

That is, the test piece was put on an agar plate (dextrose 4) of a Petri dish.
%, Peptone 1%, agar 2.5%) attached to the center of the culture surface, and separately cultivated separately in 2% grape sugar added potato decoction agar medium (Aspergillus niger A)
TCC9642, Penicillium luteum ATCC9
642, Trichoderma T-1 ATCC 9645) mixed spore suspension (mixed with equal amounts of single spore suspensions of 3 kinds of bacteria) sprayed and inoculated evenly on the surface of the medium and on the test piece in an amount of 1 ml each. To do. The petri dish was covered with a lid and incubated in an incubator at 28 ° C. ± 2 ° C., and 3 days, 7 days, and 14 days thereafter, the mold growth state of the test piece was examined according to the same criteria as in Test Example 2.

The results are shown in Table 11.

Next, an example of the antiseptic effect test of the industrial antiseptic and fungicide of the present invention is shown.

Test Example 7 Preservative effect test of casein solution To 10.0 parts of casein and 88.0 parts of water, the reagent agent prepared according to Example 2 was added, and the mixture was put into a 200 ml flask and heated with stirring to 80 ° C. And Put this casein solution in a beaker and cover with aluminum foil, 30 ℃
It was stored in an incubator. After 3 days and 10 days, 1 ml of the casein solution was taken out, and the increase in bacteria was measured by the agar dilution method.

The results are shown in Table 12.

Claims (1)

[Claims] 1. A pyridinium tetraphenylborate compound (I) represented by the following chemical structural formula as an active ingredient:
Industrial antiseptic and fungicide containing a mixture of one of the above and one of the substituted phenolic compounds (II) [Wherein, R represents a hydrogen atom, a lower alkoxycarbonyl group or a carbamoyl group, and m represents an integer of 1 to 2]