JPH0466442B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Field of Application) The present invention provides a preservative and anti-mold oil agent, specifically, a benzimidazole compound used for preservative and anti-mold in the industrial field including wood, fibers, paints, etc., or in the food, agricultural field, etc. This invention relates to a soluble antiseptic and antifungal oil agent. (Prior art) In general, benzimidazole compounds have excellent antiseptic and antifungal effects, so they have already been put into practical use as disinfectants for industrial, food, and agricultural uses. It has been pointed out that it is extremely difficult to dissolve in organic solvents. For example, looking at the solubility of 2-benzimidazole methyl carbamate, a typical benzimidazole compound, it has a solubility of 7ppm in water at pH 8.
28ppm for PH4, 0.5ppm for hexane, 36ppm for benzene, 63ppm for methylene chloride, 300ppm for ethanol and acetone, 100ppm for chloroform
In addition, since it is inexpensive, it is poorly soluble in kerosene, xylene (industrial use), etc., which are generally used as solvents for disinfectants and the like. In addition, acetic acid and dimethylformamide are known as solvents with relatively high solubility, but there are difficulties in using them in terms of solvent toxicity, odor, iron corrosiveness, cost, etc., and it is difficult to put them into practical use. ing. From this point of view, formulations of disinfectants containing benzimidazole compounds (hereinafter also referred to as active ingredients) as active ingredients are limited to powders, wettable powders, flowables, etc. It is used by spraying, scattering, or dispersing onto objects. However, if such a dosage form is used alone, the dispersion of the active ingredient into the object to be treated will be uneven, and the bactericidal effect will not be fully demonstrated. Depending on the purpose of use, solvents may be required to obtain a satisfactory effect. There is a need for solubility, particularly in solvents such as kerosene and xylene (industrial), which are commonly used as solvents for disinfectants and the like. For example, when the raw material is used for wood preservative, it can be dissolved in a solvent and subjected to dipping treatment, coating treatment, etc.
Since it is necessary to perform pressure injection treatment, etc., the active substance solution itself must be stable for a long period of time, have excellent adhesion and permeability to the wood surface, and the active substance that has adhered and penetrated must not fall off easily. is required. However, in the formulations that have been put into practical use,
Since the active substance is used in the form of fine particles dispersed in the liquid used, it precipitates and separates in a short period of time, resulting in a lack of stability of the active substance dispersion liquid, as well as poor adhesion to wood.
It has poor permeability, and when the wood after treatment is exposed to wind and rain, the raw material falls off considerably, making it difficult to maintain the sustainability of the effect over a long period of time. Furthermore, when using the active substance to sterilize fibers, it is desirable that the active substance be completely dissolved in the liquid used in order to improve permeability and retention of the active substance into the fibers. . Furthermore, even when mixing raw materials into paints, it is difficult to mix uniformly with conventional formulations, so a solvent-soluble formulation is desired. Furthermore, when the raw material is used in combination with other oil-based preservatives and antifungal agents, it is required to be soluble in commonly used solvents. (Problems to be Solved by the Invention) The present invention was made by focusing on the above-mentioned drawbacks and demands of the benzimidazole compound, which originally has excellent effects as a preservative and antifungal agent. A stable solvent-soluble preservative and anti-mold oil agent that dissolves benzimidozole compounds at a sufficient concentration for general-purpose organic solvents such as kerosene and xylene, without using solvents, which are difficult in terms of price. The purpose is to provide As a result of conducting various studies to achieve this objective, the present inventor has found that by blending oil-soluble phosphoric acid and alcohol mono- or diester into a benzimidazole compound, the compound can be made solvent-soluble. This discovery led to the present invention. (Means for Solving the Problems) That is, the present invention uses a benzimidazole compound as an active ingredient, blends with the compound singly or a mixture of at least an oil-soluble molar or diester of phosphoric acid and alcohol, and It is a preservative and anti-mold oil agent that is dissolved in. In the present invention, examples of the benzimidazole compound include the following compounds conventionally known as antiseptic and antifungal compounds. Namely, methyl 2-benzimidazolecarbamate (hereinafter abbreviated as BCM), 2-(4-thiazolyl)benzimidazole (hereinafter abbreviated as TBZ), and bethyl 1-butylcarbamoyl-2-benzimidazolecarbamate (hereinafter referred to as benomyl). ), 5-butyl-2-benzimidazole methyl carbamate (hereinafter abbreviated as PBZ),
One or a mixture of two or more of 4,5,6,7-tetrachloro-2-trifluoromethylbenzimidazole, 2-thiocyanomethylthiobenzimidazole, 2-benzimidazole ethyl carbamate (hereinafter abbreviated as BCE), etc. can be mentioned. Further, the mono- or diester of phosphoric acid and alcohol needs to be at least oil-soluble, and there is no problem with it being water-soluble at the same time. Esters other than mono- or diesters of phosphoric acid and alcohol, such as triesters, are excluded because they have little ability to dissolve benzimidazole compounds in solvents. Note that oil-soluble in the present invention means compatible with organic solvents other than water. Examples of the mono- or diester of phosphoric acid (H ₃ PO ₄ ) and alcohol include hexyl phosphate, dihexyl phosphate, 2-ethylhexyl phosphate, di-2-ethylhexyl phosphate, phenoxyethyl phosphate, and diphenoxyl phosphate. Examples include ethyl, nonylphenyl phosphate, dichlorohexyl phosphate, mono- or diester of phosphoric acid and polyethylene glycol, and these may be used alone or in combination. Next, the benzimidazole compound raw material contained in the preservative and antifungal oil of the present invention is about 0.03 to 5.0% (in this specification, % represents weight %) based on the oil composition. If it is less than 0.03%, the antiseptic and antifungal effect will be reduced, and if it is more than 5.0%, the amount of phosphoric acid ester that must be added for dissolution will be excessive, which is not preferable. In addition, the blending ratio of the phosphoric acid ester depends on the type of raw material used in the oil composition and the solvent to be dissolved;
Although it cannot be specified uniformly because it varies depending on the dissolved concentration, etc., it is necessary to mix it at about 2.0% or more in order to ensure a drug substance concentration of about 0.03% or more. Next, the solvent in which the drug substance is to be dissolved includes, for example, kerosene, xylene (industrial use), toluene, ethyl acetate, methyl isopropyl ketone, etc., which are commonly used as solvents for disinfectants, insecticides, etc.
Preferred examples include methyl isobutyl ketone, cyclohexanone, ethylene glycol monomethyl ether, isopropanol, and aromatic mixed solvents (for example, Ipsol, a trade name manufactured by Idemitsu Oil Co., Ltd.). Furthermore, there is no problem in using the antiseptic, antifungal oil of the present invention in combination with other agents having bactericidal, insecticidal, or anticidal effects, and rust preventives, surfactants, oil-based dyes, oil-based fragrances, etc. It is also possible to increase the additional effect by appropriately blending. That is,
Examples of bactericidal agents and insecticides and termiticides that can be used in combination with the preservative and antifungal oil of the present invention are as follows, but it is needless to say that they are not limited to these. Fungicide ●Haloallylsulfhorn For example, G-Yodo P
-Trisulfone●Iodopropargyl system For example, P-chlorophenyl-3-iodo-2-propanyloxymethane●N-Haloalkylthio system For example, N,N-dimethyl-N'-fluorodichloromethylthio-
N'-Phenylsulfamide●Nitrile system For example 2,3,5,6-tetrachloroisophthalonitrile●8-oxyquinoline system For example 8-oxyquinoline copper●Benzothiazole system For example 2-mercaptobenzothiazole●Isothiazoline system For example 1,2-benzothiazolin-3-one●Organic tin-based e.g. bis-tributyltin-oxide●Phenol-based e.g. p-chloro-m-xylenol●Quaternary ammonium-based e.g. dimethyldidecyl ammonium fluoride insecticide and termiticide●Organic Chlorine-based e.g. chlordane ●Organic phosphorus-based e.g. diethyl-2,3-dihydro-3-oxo-2-phenyl-6-pyridazinylphosfluorothionate (Example) Example 1 Various benzimidazole-based substances as raw materials Using a compound, blending a seed phosphate ester with it,
The preservative and anti-mold oil agent of the present invention was prepared by dissolving it in various general-purpose solvents. Preparation examples are listed below. No.1 ●BCM 0.1% ●Equimolar mixture of hexyl phosphate and dihexyl phosphate 7.5 ●Kerosine 92.4 No.2 ●BCM 0.1 ●No.1 phosphate ester 5.0 ●Industrial xylene 94.9 No.3 ●BCM 0.1 ● No.1 phosphate ester 5.0 ●0-xylene 94.9 No.4 ●BCM 0.1 ●No.1 phosphate ester 5.0 ●Ipsol 94.9 No.5 ●BCM 0.1 ●2-ethylhexyl phosphate and di-2-ethylhexyl phosphate, etc. Molar mixture 7.5 ● Kerosene 92.4 No. 6 ● BCM 0.1 ● Phosphate ester of No. 5 5.0 ● N,N-dimethyl-N'-phenyl-N'-fluorodichloromethylthiosulfamide 0.5 ● Industrial xylene 94.4 No. 7 ●BCM 0.1 ●No.5 phosphate ester 5.0 ●Ipsol 94.9 No.8 ●BCM 0.1 ●Equimolar mixture of phenoxyethyl phosphate and diphenoxyethyl phosphate 7.5 ●P-chlorophenyl-3-iodo-2-propynyl Oxymethane 0.5 ●Kerosine 91.9 No.9 ●BCM 0.1 ●No.8 phosphate ester 5.0 ●Industrial xylene 94.9 No.10 ●BCM 0.1 ●No.8 phosphate ester 5.0 ●Ipsol 94.9 No.11 ●BCM 0.1 ●No.8 phosphate ester 5.0 ●Isopropanol 94.9 No.12 ●BCM 0.1 ●Nonyl phenyl phosphate 7.5 ●Kerosine 92.4 No.13 ●No.12 phosphate ester 5.0 ●BCM 0.1 ●Industrial xylene 94.9 No.14 ● BCM 0.1 ●Dicyclohexyl phosphate 10.0 ●Industrial xylene 89.9 No.15 ●BCM 0.2 ●No.1 phosphoric acid ester 5.0 ●N-Trichloromethylthiotetrahydrophthalimide (bactericide) 0.8 ●Toluene 94.0 No.16 ●BCM 0.25 ●No. .5 phosphate ester 5.0 ●Ethyl acetate 94.75 No.17 ●BCM 0.5 ●No.1 phosphate ester 15.0 ●Kerosine 84.5 No.18 ●BCM 0.5 ●No.1 phosphate ester 7.0 ●Industrial xylene 92.0 No. .19 ●BCM 0.5 ●No.1 phosphate ester 7.5 ●Diheptyl phthalate (plasticizer) 25.0 ●Industrial xylene 67.0 No.20 ●BCM 0.5 ●No.1 phosphate ester 7.5 ●Isopzol 92.0 No.21 ● BCM 0.5 ●No.5 phosphate ester 15.0 ●0,0-dimethyl-0-(3-methyl-4-nitrophenyl) thiophosphate (insecticide and termiticide) 4.0 ●Kerosine 80.5 No.22 ●BCM 0.5 ●No.5 phosphate ester 7.5 ●Industrial xylene 92.0 No.23 ●BCM 0.5 ●No.5 phosphate ester 7.5 ●Ipsol 92.0 No.24 ●BCM 0.5 ●No.8 phosphate ester 15.0 ●Kerosine 84.5 No.25 ●BCM 0.5 ●No.8 phosphate ester 10.0 ●Industrial xylene 89.5 No.26 ●BCM 0.5 ●No.8 phosphate ester 10.0 ●Methyl isobutyl ketone 89.5 No.27 ・BCM 0.5 ・No.12 15.0 ●Industrial xylene 84.5 No.28 ●BCM 0.5 ●No.14 phosphate ester 15.0 ●Industrial xylene 84.5 No.29 ●BCM 2.5 ●No.5 phosphate ester 20.0 ●Industrial xylene 77.5 No.30 ●BCM 5.5 ●No.5 phosphoric acid ester 30.0 ●Mixture of polyoxyethylene nonyl phenyl ether and dodenbenzene sulfonate (surfactant) 10.0 ●Industrial xylene 55.0 No.31 ●BCM 1.0 ●Phosphorus Equivalent mixture of acids and mono- and diesters of polyethylene glycol 30.0 ●Oil yellow (oil-based dye) 3.0 ●Industrial xylene 66.0 No.32 ●TBZ 0.5 ●No.1 phosphate ester 15.0 ●Kerosine 84.5 No.33 ●TBZ 0.5 ●No.1 phosphate ester 7.5 ●Industrial xylene 92.0 No.34 ●TBZ 0.5 ●No.1 phosphate ester 7.5 ●Ipsol 92.0 No.35 ●TBZ 0.5 ●No.5 phosphate ester 7.5 ●Fluorodichloro Methylthiophthalimide (bactericide) 0.5 ●Ipsol 91.5 No.36 ●TBZ 2.5 ●No.5 phosphate ester 20.0 ●Ipsol 77.5 No.37 ●Benomyl 0.25 ●No.8 phosphate ester 5.0 ●Industrial xylene 94.75 No. 38 ●Benomyl 1.0 ●No.8 phosphate ester 15.0 ●Mixture of polyoxyethylene nonyl phenyl ether and dodecylbenzenesulfonate (surfactant) 10.0 ●Industrial xylene 74.0 No.39 ●PBZ 0.1 ●No.5 Phosphate ester of 5.0 ●Ipsol 94.9 No.40 ●PBZ 0.25 ●Phosphate ester of No.8 7.5 ●Tetrachloroisophthalonitrile (bactericide)
2.5 ●Ethylene glycol monomethyl ether 89.75 No.41 ●PBZ 0.5 ●Phosphate ester of No.14 15.0 ●Ipsol 84.5 No.42 ●4,5,6,7-tetrachloro-2-trifluoromethylbenzimidazole 0.25 ●No. Phosphate ester of .12 10.0 ●Industrial xylene 89.75 No.43 ●2-Thiocyanomethylthiobenzimidazole
0.5 ●No.5 phosphate ester 10.0 ●Industrial xylene 89.5 No.44 ●BCE 0.5 ●No.1 phosphate ester 15.0 ●Kerosine 84.5 No.45 ●BCE 0.5 ●No.1 phosphate ester 7.5 ●Industrial Commercial xylene 92.0 No.46 ●BCE 0.5 ●No.5 phosphate ester 7.5 ●Industrial xylene 92.0 No.47 ●BCE 0.5 ●No.8 phosphate ester 7.5 ●Tri-n-butylteine oxide (bactericide)
0.2 ●Ipsol 91.8 No.48 ●BCE 0.5 ●No.12 phosphate ester 10.0 ●Cyclohexanone 89.5 No.48 ●BCE 2.5 ●No.5 phosphate ester 10.0 ●No.31 phosphate ester 15.0 ●Industrial xylene 72.5 Example 2 For four types of drug substance, BCM, TBZ, Benomyl, and BCE, the type of phosphate ester to be blended was changed, and the concentration of drug substance that can be dissolved in various solvents and the blending ratio of phosphate ester were determined. The results were as shown in Tables 1 to 4. All solubility tests were conducted at room temperature.

【table】

【table】

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[Table] As is clear from the results in Tables 1 to 4, it is important to increase the blending ratio of phosphate ester to the drug substance, and that above a certain blending ratio, the drug substance dissolves and becomes a transparent solution. Furthermore, it can be seen that the lower the concentration of the drug substance in the composition, the more it can be dissolved at a smaller blending ratio. As a comparative example, the drug substance shown in Example 2 was tested for solubility in xylene at a concentration of 0.1% with tri-2-ethyl-hexyl phosphate added, but at a blending ratio of 30% to the composition. However, it did not dissolve, indicating that the phosphoric triester does not have the solvent dissolving power of the original substance. Test Example 1 The oils of the present invention prepared in No. 1, No. 17, and No. 30 of Example 1 with partially different compositions were tested for their antiseptic and antifungal effects on wood. As a control, untreated and BCM commercially available hydrating agents were also tested. That is, as a wood test piece, 3×3×
0.6cm particle board (3 pieces repeated)
The samples were immersed in each drug for 3 minutes according to the classification in the left column of Table 5, and then dried overnight. A mixed spore solution of the test molds consisting of Aspergillus niger, Trichoderma viride, Alternaria titri, Penicillium titrinum, and Rhizopus nigricans was sprayed onto the specimen placed on PDA medium in a Petri dish at 26°C. The test piece was stored for 4 weeks, and the growth status of the bacterial cells on the test piece was observed and evaluated.
The evaluation values are values determined based on the bacterial growth status standards in the table below, and the number of test pieces corresponding to each evaluation value is
Shown in the table.

【table】

[Table] From the results in Table 5, it can be seen that the test pieces treated with the oil of the present invention had better antifungal effects than the test pieces treated with the BCM hydrating agent at the same effective concentration, as well as the untreated one. You can see that This is presumably because the oil agent of the present invention had better permeability into the test piece and more of the active ingredient was absorbed than the active ingredient dispersion type hydrating agent. Test Example 2 The oil agents of the present invention prepared in Nos. 37 and 38 of Example 1 were tested for their antifungal effects on polyester nonwoven fabrics. In addition, as a control, untreated and Benomyl commercially available hydrating powders were also tested. That is, a 3 x 3 x 0.2 cm polyester nonwoven fabric (Spunboard 4252P manufactured by Toyobo Spunbond Co., Ltd.) (repeated number of sheets: 3) was used as a test piece, and it was treated in the same manner as in Test Example 1 with the chemicals in the categories in the left column of Table 6. After processing,
An anti-spinning mold test was conducted in a similar manner. however,
The evaluation values based on the growth status of bacterial cells were as shown in the following table.

【table】

[Table] The results are shown in Table 6, and the same antifungal effect as in the wood treatment of Test Example 1 was obtained. Test Example 3 The oil agent of the present invention prepared in No. 19 of Example 1 was tested for its antifungal effect on vinyl chloride resin. As a control, xylene suspensions of untreated and BCM were also tested. That is, a 5 x 5 x 0.1 cm steel plate covered with a vinyl chloride resin sheet (repeated number of sheets: 3) was used as a test piece, and the BCM concentration was varied so that each drug was 50 g/ ^m2 . It was applied and dried for 2 days. In the anti-mold test, the mold growth on the PVC surface was observed in the same manner as in Test Example 1, except that the mold was left for 3 months in an environment with a room temperature of 25°C and an equivalent humidity of 97%, which is highly conducive to mold growth. However, the evaluation values based on the growth status of bacterial cells were as shown in the following table.

[Table] The results are shown in Table 7, and it can be seen that the antifungal effect is excellent when the active ingredient is completely dissolved in the solvent.

[Table] (Effects of the Invention) As explained in detail above, the antiseptic and antifungal oil agent of the present invention has almost no solubility in conventionally inexpensive and versatile solvents, so it can be used as a powder, wettable powder, or Benzimidazole compounds, which were previously limited to the form of flowable agents, can now be used in a solvent-soluble form. Therefore, it is not only possible to further improve the workability and effects when applying the compound to existing purposes, but also to apply it to objects for which conventional dosage forms have not been sufficiently effective. It becomes possible to significantly expand the range. Furthermore, according to the present invention, an oil agent can be obtained by dissolving the oil agent in an inexpensive and versatile solvent to a high concentration that can sufficiently exhibit the antiseptic and antifungal effect, and is stable over a long period of time and is effective against wood, fibers, etc. On the other hand, it has good adhesion, permeability and retention, and therefore has the advantage that it is possible to significantly improve the antiseptic and antifungal effect and its sustainability.

Claims (1)

[Claims] 1. A preservative and antifungal oil agent comprising a benzimidazole compound as an active ingredient, which is blended with at least an oil-soluble mono- or diester of phosphoric acid and alcohol, either singly or in a mixture, and dissolved in a solvent.