JPS61260002A - Antiseptic, mildewproofing oil agent - Google Patents

Abstract

PURPOSE:The titled solvent-soluble type oil agent dissolved in a sufficient concentration in a general purpose solvent such as herosine, xylene, etc., comprising a benzimidazole compound as an active ingredient, made solvent-soluble by blending the compound with a specific compound having oil solubility. CONSTITUTION:A benzimidazole compound which has improved antiseptic and mildewproofing effects and is put to practical use as a germicide is used as an active ingredient, the compound is blended with one of a mixture of a mono- or a diester of phosphoric acid and an alcohol, having oil solibility, so that the blend becomes solvent-soluble. The agent is useful in an industrial field such as wood, fiber, coating compound, etc., food field and agricultural field. EFFECT:The titled agent is not limited to a preparation such as dust, wettable powder, flowable agent, it is dissolved in an inexpensive solvent having general purpose, it can show sufficient antiseptic, mildewproofing effects, it is stable for a long period, it has high adhesivity, permeability and maintenance on wood, fiber, etc., and it can extremely improve antiseptic, mildewproofing effect and its durability.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention is a preservative and anti-mold oil agent, specifically, an oil agent which is used for preservative and anti-mold in industrial fields including wood, fibers, paints, etc., or in the food and agricultural fields. The present invention relates to a preservative and anti-mold oil containing a solvent-soluble benzimidazole compound.

(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, as a typical benzimidazole compound, 2
- Looking at the solubility of methyl benzimidazole carbamate, it is 7 ppm in water at pH 8 and 2 ppm at pH 4.
8ppm, 0.5ppm for hexane, 3ppm for benzene
6ppm 1 in methylene chloride 681) pH 11 300ppm in ethanol and acetone, 1100 in chloroform
pp, etc., and because 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, dimethylformamide, etc. are known as solvents with relatively high solubility.
Practical use has been difficult due to the toxicity of the solvent, odor, corrosion resistance to iron chips, and cost.

From this point of view, benzimidazole compounds (hereinafter referred to as
Disinfectant preparations containing active ingredients (also called active ingredients) are limited to powders, wettable powders, and flowable formulations, and these formulations can be sprayed, sprinkled, or dispersed onto the object to be treated. It is used in such a way.

However, with only such a dosage form, the dispersion of the active ingredient into the object to be treated becomes uneven, and the sterilizing effect is not sufficiently exerted. In particular, it is required to dissolve them in solvents such as kerosene and xylene (industrial use), which are commonly used as solvents for disinfectants and the like.

For example, when using the active ingredient for wood preservation, it is necessary to perform dipping, coating, pressure injection, etc. in the form of a solution dissolved in a solvent, so the active ingredient solution itself must be stable for a long period of time and It is required that the material has excellent adhesion and permeability to the wood surface, and that the adhered and permeated base material does not easily fall off.

However, in the formulations that have been put into practical use to date, the drug substance is used in a state in which it is dispersed in the form of fine particles in the liquid used, so it precipitates and separates in a short period of time, resulting in a lack of stability of the drug substance dispersion. In addition, it has poor adhesion and permeability to wood, and when the treated wood is exposed to the wind and rain, the raw material is likely to fall off, making it difficult to maintain its effects 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. Kerosene, without using solvents, which have disadvantages in terms of price, etc.
The purpose of the present invention is to provide a stable solvent-soluble preservative and anti-mold oil agent in which a benzimidazole compound is dissolved in a sufficient concentration in a general-purpose organic solvent such as xylene.

As a result of various studies to achieve this objective, the present inventor has discovered 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 agents. Namely, 2-benzimidazole methyl carbamate (hereinafter abbreviated as BGM), 2-(4-thiazolyl)benzimidazole (
(hereinafter abbreviated as TBZ), 1-butylcarbamoyl-2
-Methyl benzimidazole carbamate (hereinafter abbreviated as benomyl), 5-butyl-2-benzimidazole methyl carbamate (hereinafter abbreviated as PBZ), 4.5
, 6.7-tetrachloro-2-trifluoromethylbenzimidazole, 2-thiocyanomethylthiobenzimidazole, 2-benzimidazole ethyl carbamate (hereinafter abbreviated as BCE), etc., or a mixture of two or more thereof. I can do it.

Further, the mono- or diester of phosphoric acid and alcohol needs to be at least oil-soluble, and may be 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 that it is compatible with organic solvents outside water.

Examples of the mono- or diester of phosphoric acid (83PO4) and alcohol include hexyl phosphate, dihexyl phosphate, 2-ethylhexyl phosphate, di-2-ethylhexyl phosphate, phenoxyethyl phosphate, diphenoxyethyl phosphate, Examples include nonylphenyl, dicyclohexyl phosphate, mono- or diester of phosphoric acid and polyethylene glycol, and these can be used alone or in combination.

Next, the benzimidazole compound raw material contained in the preservative and anti-mold oil of the present invention is about 0.03
~5.0% (in this specification, % represents weight %). If it is less than 0.03%, the antiseptic and mold-preventing effect will decrease, 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.

The blending ratio of the phosphoric acid ester cannot be uniformly defined because it varies depending on the raw material used in the oil composition, the type of solvent to be dissolved, the dissolved concentration, etc., but the raw material concentration is about 0.
In order to ensure 0.3% or more, it is necessary to mix approximately 2.0% or more.

Next, the solvent in which the drug substance should be dissolved is commonly used as a solvent for disinfectants, insecticides, etc., such as kerosene, xylene (industrial use), toluene, ethyl acetate, methyl isopropyl ketone, and methyl isobutyl. Suitable examples include ketones, cyclohexanone, ethylene glycol monomethyl ether, isopropanol, and aromatic mixed solvents (for example, Ibuzol, 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 bactericides and insecticides and anticides that can be used in combination with the preservative and anti-mold oil of the present invention are as follows, but it is needless to say that they are not limited to these.

Bactericidal agent/Haloallylsulfone type (e.g. di-iodo-P-)
Lysulfone/iodopropargyl system For example, P-chlorophenyl-3-iodo-2-propargyl/N-haloalkylthio system For example, N,N-dimethyl-N'-fluorodichloromethylthio-N'-phenylsulfamide/nitrile system For example, 2, 3,5゜6-titrachloroisophthalonitrile/8-oxyquinoline system For example, 8-oxyquinoline copper/benzothiazole system For example, 2-mercaptobenzothiazole/inthiazoline system For example, 1,2-benzothiazoline-3-one/organic Tin-based e.g. bis-tributyltin-oxide/phenol-based e.g. p-chlorotoxylenol/quaternary ammonium-based e.g. dimethyldidecylammonium fluoride insecticide/organic chlorine-based e.g. chlordane/organic phosphorus-based e.g. diethyl-2゜3 -Sibide Draw 3 Monooxo 2-phenyl-6-pyridazinyl phosfluorothionate (Example) Example I Using various benzimidazole compounds as raw materials,
Seed phosphoric acid ester was blended with this and dissolved in various general-purpose solvents to prepare the preservative and anti-mold oil agent of the present invention. Preparation examples are listed below.

No. 1 ・BGM 0.
1%・Equimolar mixture of hexyl phosphate and dihexyl phosphate 7.5・Kerosine
92.4NO02・B G M
0.1・No.1 phosphoric acid ester 5.0・Industrial xylene
94.9No.3 ・BGM
0.1・No.1 phosphoric acid ester 5.
0.O-xylene 94.9No.4
・BGM 0.1・No
, Phosphate ester of 1 5.0 Ibusol
94.9 No. 5 ・BGM
0. Equimolar mixture of 2-ethylhexyl triphosphate and di-2-ethylhexyl phosphate 7.5 Kerosene
92.4 No. 6 ・BGM
0.1・No.5 phosphoric acid ester 5.0・N,N-dimethyl-N′-phenyl-N′-fluorodichloromethylthiosulfamide 0.5・Industrial xylene 94.4No.7・B GM ,
0.1・No.5 phosphate ester 5.0・Ibusol
94.9 No. 8 ・BGM
0. Equimolar mixture of phenoxyethyl triphosphate and diphenoxyethyl phosphate 7.5 P-chlorophenyl-3-iodo-2-propynyloxymethane 0.5 Kerosene 91.9 No. 9
・BGM 0.1・No. 8
Phosphate ester of 5.0/industrial xylene
94.9No, 10-B GM
0.1・No.8 phosphoric acid ester
5.0・Ibuzol 94.
9No, 11 ・B GM
0.1・No.8 phosphoric acid ester 5.0・
Isoproper tool 94.9No, 12 ・
B GM 0.1・nonylphenyl phosphate 7.5・kerosene
92.4No, 13 ・B GM
0.1・No.12 phosphoric acid ester 5.0・Industrial xylene 94.
9No, 14 ・B GM
0. Dicyclohexyl triphosphate 10.0・Industrial xylene 89.9No, 15・B
GM 0.2・No.1 phosphoric acid ester 5.0・N-trichloromethylthiotetrahydrophthalimide (bactericide) 0.8・Toluene 94. ONo, 16
・BGM 0.25・No,
Phosphate ester of 5 5.0 Ethyl acetate
94.75No, 17 ・BGM
0.5・No.1 phosphoric acid ester 15.0・kerosene 8
4.5No, 18 ・B GM
0.5・No.1 phosphoric acid ester 7.
0. Industrial xylene 92. ONo, 19
・BGM 0.5・No
, 1 phosphoric acid ester 7.5 Diheptyl phthalate 25.0 (plasticizer) Industrial quince 67, ONo, 20
・BGM 0.5・No, 1
Phosphate ester of 7.5 Ibusol
92. ONo, 21-B GM
0.5・No.5 phosphoric acid ester
15.0・0.0-dimethyl-〇-(3-methyl-4-nitrophenyl) thiophosphate (insecticide and termiticide) 4.0・Kerosine 80.5No, 22-
B GM 0.5・No,
Phosphate ester of No. 5 7.5・Industrial xylene 92. ONo, 23-B CM
0.5・No,5 phosphate ester 7,5・Ibusol 9
2. ONo, 24 ・B GM
0.5・No.8 phosphoric acid ester 15.
0. Kerosene 84.5 No. 25
・BCM O, 5・No
,8 phosphoric acid ester 1O90・Industrial xylene 89.5No.26・B GM
0.5・No.8 phosphoric acid ester 10.0・Methyl isobutyl ketone
89.5No, 27 ・B CM
0.5・No, 12 phosphoric acid ester 15
．． 0. Industrial xylene 84.5 No. 2
8. BGM
0.5・No, 14 phosphate ester 1
5. O・Industrial xylene 84.5No.
29 ・B GM 2.5・
No. 5 phosphoric acid ester 20.0/industrial xylene 77.5 No. 30-B GM
5.5・No.5 phosphoric acid ester 30.0・Mixture of polyoxyethylene nonylphenyl ether and dodenbenzene sulfonate (surfactant) 10.0・Industrial xylene 55. ONo, 31 ・B GM
1.0 - Equivalent mixture of mono- and diesters of phosphoric acid and polyethylene glycol 30.0 - Oil yellow (oil-based dye) 3.0 - Industrial xylene 66, ONo., 32
・TBZ O, 5・No, 1
Phosphate ester of 15.0・kerosene
84.5No, 33・TBZ
Phosphate ester of O,5・No,1
7.5・Industrial xylene 92. O
No, 34 ・TB Z O
,5・N001 phosphate ester 7.5・Ibusol 92゜ONo, 35・T
BZ O,5・No.5 phosphate ester 7.5・Fluorodichloromethylthiophthalimide (bactericide) 0.5・Ibuzol 91.5No.36
・TB Z 2.5・No
, phosphoric acid ester of 5 20.0 Ibusol
77.5No, 37 ・Benomyl
0.25・No.8 phosphoric acid ester 5.0・Industrial xylene
94.75No, 38 ・Benomyl
1.0・No.8 phosphoric acid ester
15.0・Mixture of polyoxyethylene nonylphenyl ether and dodecylbenzene sulfonate (surfactant>10.0・Industrial xylene 74.ONo, 39・PBZ
Phosphate ester of O,1・No,5 5.0・Ibusol
94.9No, 4O-PBZ
Phosphate ester of O, 25・No, 8 7
．． 5. Tetrachloroisophthalonitrile (bactericide) 2.5 ・Ethylene glycol monomethyl ether 89.75 No. 41
・PBZ O, 5・No,
14 Phosphate Ester E5.0 Ibusol
84.5No, 42 ・4, -5,
6, 7-titrachloro 2-trifluoromethylbenzimidazole 0.25・No, 12
Phosphate ester of 10.0/industrial xylene
89.75No, 43 ・2-Thiocyanomethylthiobenzimidazole 0.5・No
, 5 phosphoric acid ester 10.0・Industrial xylene 89.5No. 44・BCE
0.5・No.1 phosphoric acid ester 15.0・kerosene 8
4.5 No, 45 ・BCE
0.5・No.1 phosphoric acid ester 7.5
・Industrial xylene 92. ONo, 46
・BCE 0.5・No, 5
Phosphate ester of 7.5・Industrial xylene
92. ONo, 47 ・BCE
0.5・No.8 phosphoric acid ester
7.5 ・Tree n-butyltin oxide (bactericide) 0.2 ・Ibusol 91.8 No. 48
・BCE 0.5・No, 1
Phosphate ester of 2 10.0・Cyclohexanone 89.5No, 49・BCE
2.5・No.5 phosphoric acid ester 1000・No.31 phosphoric acid ester
15.0・Industrial xylene 72.5 Example 2 For four types of raw materials, BGM, TBZ, benomyl, and BCE, the type of phosphate ester to be blended was changed,
The results of determining the concentration of the drug substance soluble in various solvents and the blending ratio of the phosphate ester are shown in Tables 1 to 4. Note that all solubility tests were conducted at room temperature.

As is clear from the results in Tables 1 to 4, as the blending ratio of phosphate ester to the drug substance increases, the drug substance dissolves above a certain blending ratio to form 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 blended with tri-2-ethyl-hexyl phosphate and tested for solubility in xylene at concentrations of 0 and 1%, but at a blending ratio of 30% to the composition. However, since it did not dissolve, it was found that the sulfuric acid triester does not have the solvent dissolving power of the original substance.

Test Example 1 Oils of the present invention prepared in Example 1 No. 1, No. 17, and No. 30 with some different formulations were tested for their antiseptic and antifungal effects on wood. As a control, untreated and BGM commercially available hydrating agents were also tested. That is, as a wood test piece, 3 x 3 x Q, 5
A particle board (3 sheets) was used, which was immersed in each chemical for 3 minutes according to the categories shown in the left column of Table 5, and then dried day and night. A mixed spore solution of test molds consisting of Aspergillus niger, Trichoderma viride, Alternaria plover, Penicillium titrinum, and Rhizopus nigricans was added to the PDA in a Petri dish.
It was sprayed onto a test piece placed on a medium, stored at 26°C for 4 weeks, and the growth status of bacterial cells on the test piece was observed and evaluated.

The evaluation values are numerical values determined based on the bacterial growth status criteria shown in the following table, and the number of test pieces corresponding to each evaluation value is shown in Table 5.

■Evaluation A: ■-■ From the results in Table 5, it can be seen that the test pieces treated with the oil of the present invention were not only untreated, but also had better protection than the test pieces treated with the BCM hydrating agent at the same effective concentration. It can be seen that the mold effect is excellent.This is thought to be because the oil agent of the present invention has better permeability into the test piece and more of the active ingredient was absorbed compared to the active ingredient dispersion type hydrating agent. Ru.

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. As a control, untreated and commercially available benomyl hydrating powders were also tested. In other words, as a test piece, 3
X3XQ, 2cm polyester nonwoven fabric (Spunbond 4252P manufactured by Toyobo Spunbond Co., Ltd.) (repeated number of sheets: 3) was treated in the same manner as in Test Example 1 with the chemicals listed in the left column of Table 6, and then treated in the same manner as in Test Example 1. An anti-mold test was conducted using the method. However, the evaluation values based on the growth status of bacterial cells were as shown in the following table.

Table 6 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 agents of the present invention prepared in Example 1 No. 19 were tested for their antifungal effect on vinyl chloride resin. As a control, untreated and BGM xylene suspensions were also tested. That is, 5 x 5 x as a test piece
A steel plate of O.1 am coated with a vinyl chloride resin sheet (repeated number of sheets: 3) was used, and each drug was coated at 50 g/1rd with varying BGM concentration, 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 DEG C. and a relative 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.

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.

(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 flowable agent. Benzimidazole compounds, which were previously limited to the following dosage form, can now be used in a solvent-soluble form. Therefore, it is not only possible to further improve the workability and effectiveness when applying the compound to existing purposes, but also the range of application to targets for which sufficient effects could not be obtained with conventional dosage forms. can be expanded significantly.

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 anti-mold 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 as a mixture, and dissolved in a solvent.