JPH0436203A - Industrial antiseptic and antifungal agent - Google Patents

Abstract

PURPOSE:To obtain an antiseptic and antifungal agent, containing 2-(thiocyanomethylthio)benzothiazole and tetrachloroisophthalonitrile or 2-(methoxycarbonylamino)benzimidazole and capable of exhibiting excellent synergistic antimicrobial effects. CONSTITUTION:The subject formulation containing 2-(thiocyanomethylthio) benzothiazole (A) and tetrachloroisophthalonitrile (B) in a ratio of (9:1) to (1:3) [preferably (4:1) to (3:7) weight ratio] and the subject formulation containing the compound (A) and 2-(methoxycarbonylamino)benzimidazole (C) in a ratio of (9:1) to (3:7) [preferably (9:1)-(4:6) weight ratio]. Since the aforementioned formulations are capable of exhibiting excellent synergistic antimicrobial effects with wide antimicrobial spectra, the object range of application can be extended. The compounds (B) and (C) may be mixed and the compound (A) may be used in combination. The aforementioned formulations are used for dyes, pastes, wood, leathers, fibers, pulps, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION (a) Industrial application field This invention is directed to the use of 2-(thiocyanomethylthio)benzothiazole (hereinafter abbreviated as TCMTB) and tetrachloroisophthalonitrile (hereinafter abbreviated as daconyl) or The present invention relates to a preservative and antifungal agent containing 2-(methoxycarbonylamino)benzimidazole (hereinafter abbreviated as MBC). The agent of this invention prevents various industrial raw materials and industrial products such as dyes, pastes, wood, leather, fibers, and pulp from deteriorating due to rotting or mold growth caused by microorganisms such as bacteria and fungi. It is useful as a preservative and fungicidal agent to prevent mold.

(b) Conventional Technology Many chemicals have been used as industrial preservatives and antifungal agents, such as organic mercury compounds, organic tin compounds, and chlorinated phenols. However, in recent years, the toxicity and environmental pollution of these compounds have become a problem.

It is known that TCMTB, Daconyl, or MBC are each individually low-toxic antimicrobial agents (Japanese Patent Application Laid-Open No. 57-22003, etc.). However, when used alone, each had a narrow antibacterial spectrum and was unable to completely inhibit the growth of microorganisms.

In this regard, various attempts have been made to use these antimicrobial agents in combination with other antimicrobial agents.

For example, for TCMTB, methylene bisthionoanate (MBTC), a well-known antimicrobial agent, is used.
) and Troisan Polyface (I PBC), etc., it has been reported that the antibacterial spectrum can be expanded and the antibacterial effect can be increased by 1 nil (Wood Preservation No. 14).
Volume 5, No. 5 (198g), pp. 8-18 [Research on low toxicity fungicides (3) J).

(c) Problems to be Solved by the Invention However, although the antibacterial effect exerted by the above-mentioned combination drug containing TCMTB as one component is improved compared to when used alone, it is not fully satisfactory; There were also limits to the improvement of effectiveness.

This invention was made under such circumstances, and especially T.
The purpose of the present invention is to provide a combination antibacterial agent containing CMTB as one component, particularly a preservative and antifungal agent, which exhibits a superior antibacterial effect compared to conventional antibacterial agents containing TCMTB.

(d) Means for Solving the Problems According to the present invention, the product contains 2-(thiocyanomethylthio)benzothiazole and tetrachloroisophthalonitrile in a weight ratio of 9:1 to 13. Industrial preservative and anti-mold agent, and industrial preservative and anti-mold agent containing 2-(thiocyanomethylthio)benzothiazole and 2-(methquincarbonylamino)benzimidazole in a weight ratio of 91 to 3.7. agent is provided.

This invention uses a specific inophthalonitrile compound or a specific benzimidazole compound, among many other low-toxicity antimicrobial agents, in combination with TCMTB. This was based on the discovery that it has a synergistic antibacterial effect that is significantly superior to that of combination drugs.

In the combined drug of TCMTB and Daconil in this invention, the weight ratio of these is preferably 41 to 37 from the viewpoint of synergistic antibacterial effect.

Moreover, in a combination drug of TCMTB and MBC, the weight ratio thereof is preferably 9:1 to 4.6.

Of course, TCM is a mixture of Daconyl and MBC.
It may be used in combination with TB, and the present invention also includes such a drug.

Each active ingredient of the present invention is preferably used in the form of a liquid preparation. However, the present invention is not limited thereto, and depending on the intended use, it may be used in the form of a powder or the like.

For example, when starch paste liquid or wet valve (L) is used for the preservative and anti-mold treatment of wood itself, it is suitable to use it in the form of a -liquid preparation. In this case, TCMTB is dissolved in a battering machine solvent or emulsified with a surfactant and water.
Daconyl or MBC powder can be made flowable by adding xanthan gum or a polymeric thickener.

In this case, examples of the battering machine solvent include hydrophilic solvents such as glycols such as methylformamide and phenyl glycol, and hydrophobic solvents such as mineral oil, aliphatic hydrocarbons such as kiln, and aromatic hydrocarbons.

When used as a powder, it is suitable to prepare TCMTB by holding it in a carrier such as diatomaceous earth or kaolin and mixing it with Daconyl or MBC. In addition, it is possible to make a paste using the above-mentioned solvents and surfactants, and such a paste is suitable for applying to wood for preservative and anti-mildew treatment. Of course, compounds for other uses, such as insecticides, may be used or mixed with the drug of this invention.

The amount of the industrial preservative and fungicide of this invention to be used varies depending on the object and dosage form, so there is no particular limitation, or, for example, when it is added to a wet pipe, the total concentration of active ingredients It is suitable to add it in an amount of about 50 to 300 mg/Kg (based on pulp).

(e) Examples The following examples will be described, but the present invention is not limited thereto.

[Drug example] Examples of the drugs of this invention are shown in Table 1 along with comparative examples.

The numbers in the table indicate weight percentages. Also STP
indicates a polyoxyalkylene styryl phenyl ether phosphate surfactant.

(Margin below) Table 1 The following tests were conducted using each of these formulations.

Example 1 (synergistic effect against mold) (Test method) 10 ml each of Czapek liquid medium in test tubes with Noricon stoppers.
After dispensing and sterilizing in an autoclave, the isolated bacteria Alter
naria SP, Fusarium SP, As
Each spore of pergillus SP @mixture of suspension 0.
Add 1 ml to 2 sterile test tubes containing 1 Nira Avec liquid medium. Next, after adding the drug, it was incubated at 27°C, and the inhibitory concentration (MI
C).

Zapek liquid medium composition (per medium 10,100O) Sub-loin 30g Sodium nitrate 3g Potassium hydrogen phosphate 1g Magnesium sulfate 0.5g Potassium chloride 0.5g Ferrous sulfate 0.01g Pure water 1000ml pH 6.8 This result was used as the first It is shown in Fig. 2 and Fig. 2. Like this TC
It can be seen that a remarkable synergistic antibacterial (antifungal) effect can be achieved by using MTB together with Daconyl or MBC.

Example 2 A wet pulp anti-mildew test was conducted on some of the formulation examples described above.

(Test method) H Paper Company unbleached kraft pulp (UKP) is punched out to a diameter of 5 cm, and a predetermined amount of 03% drug solution is uniformly added to one side of the pulp notebook. Press for 2 minutes at 3.5 kgz'ci' (water content of pulp 50%) to obtain a test pulp. The test pulp is placed on an inorganic salt agar medium, statically cultured at 27°C, and the state of mold development is observed orally.

No mold growth is observed on the judgment criteria sheet ・Mold growth is observed on less than 1/3 of the notebook←
Mold growth is observed on 1/3 to 2/3 of the sheet←
The results, in which mold growth was observed on 273 or more sheets, are shown in Tables 2 and 3. In addition, the fungal species is Al
ternaria SPSTricoderma SP
.

Fusarium SP.

It was Penicillium SP.

Tea Table 3 (TCMTB-District Effect) Table 2 (TCIITB-Dani lny/L,) Effect) (Left below blank) Example 3 (Mold Resistance Test of Starch Slurry) (Test Method) 3% of Cation Modified Cornstarch Make a water slurry. After standing at room temperature for 4 to 5 days, this is used as a test starch slurry. After adding the drug, the starch slurry is cultured at 30°C, and the number of mold bacteria is measured over time.

The results are shown in Table 4. In addition, the fungal species is Ce
phalosporium SP and Fusarium
It was SP.

Table 4 (Number of mold bacteria) Test starch paste. After adding the drug, the starch paste is cultured at 30°C, and 7 days later, the preservative effect is determined by the presence or absence of a putrid odor in a sensory test.

The results are shown in Table 5.

Table 5 Example 4 (Preservation test of starch paste liquid) (Test method) A 3% water slurry of cationic modified cornstarch was heated at 85°C.
Cook for 15 minutes or more to prepare a starch paste solution. After leaving it for 4 to 5 months at room temperature, serve *Total active ingredient concentration (judgment) ÷ Putrid odor is observed.

- No rotten odor observed.

Example 5 (Mold resistance test on wood) Using formulation examples 1, 2, 3, 5, 6, and 7, a fungicide test against mold that grows well on wood was conducted.

The test method is based on the Japan Wood Preservation Association standards (
According to the antifungal efficacy testing method for wood fungicides specified in JWPA) No. 2, various chemical absorption amounts shown in Table 6,
Tests were conducted at treatment concentrations.

For comparison, Table 6 also shows the cases of 2(thiocyanomethylthio)benzothiazole alone, Daconyl or MBC alone, which were prepared in the same manner as above.

The wood molds tested were as follows.

1) Aspergillus ni
ger2) Pen1cilliuIIl funiculosum
3) Aureobasidium pullulans 4)
Gliocladium vire
ns5) Rhizopus ja
vanicus (1) test piece preparation Beech sapwood pieces (20X 3x 50mm) with 0.2%
, 03%, and 05% concentrations were immersed in the drugs of Formulation Examples 1 to 7 for 3 minutes, and then air-dried for 2 days to prepare one treated specimen.

(2) Anti-mold test method Pour a 2% agar solution sterilized in an autoclave onto a sterilized Nyare (diameter 90 mm) and solidify it by placing a polypropyne net on top of it as a pedestal to prevent direct contact between the test piece and the agar.

Place three test pieces on a stand and sprinkle a spore suspension of the test mold onto each piece. The number of processed pieces is 6 l density pieces (12 pieces). The test culture was carried out at 26° C. for 4 weeks, and the evaluation was made by observing the growth of the mold on each test piece after 4 weeks for each mold species and concentration, and determining the evaluation value according to the criteria shown below.

Evaluation value Mold growth status 0 No mold growth is observed on the test piece.Mold growth is observed only on the sides of the test piece.2 Mold growth is observed on the area of the upper surface of the test piece below 173.3 Test. The damage value (D) in Table 6, where mold growth is observed over 172 areas of the body, is calculated by calculating the sum of the average evaluation values (S) for each concentration of the sample and using the following formula.

Total average evaluation (S)” A I + A t + A3
=, A4+As (A 1. A t...A, average evaluation value for each mold species) (D) = X100 S.

Table 6 So, S of untreated test specimen Sl S of treated test specimen of a certain concentration (blank below) A-: A, niger, AI: P, runiculos
um, A3 people pullulans, Ah:G, vire
nsA+: R, javan+cus S Sum of average evaluation values D Limb damage value Note that the drug treatment concentration is the total treatment concentration of active ingredients.

As is clear from Table 6, when compared with each test compound alone at a damage value of 30 or less, which is considered to have a substantial antifungal effect, TCMTB alone in the comparative example has a damage value of 0.
30 or more at 2% concentration, also Daconyl alone or MBC
Even at a single concentration of 1.0%, it has a damage value of 30 or higher, meaning no substantial antifungal effect has been obtained, whereas the chemical of this invention has a damage value of 30 or less even at a concentration of 0.2%, which is the lowest concentration tested. I understand that.

Daconil or M, which has a worse antifungal effect than TCMTB
By combining BC, the antifungal efficacy was significantly improved compared to TCMTB alone, and this superior effect is thought to be based on the synergistic effect of using each active ingredient in combination. reactor. Also, when the mixing ratio of the two components was 11, the antifungal effect was greatest.

Example 6 (wood preservative test) -1-CM T B and Daconil maf2: Yo~IBC
We conducted a preservative efficacy test on each type of wood rot fungus.

The test compound is TCMTB: Daconyl Marini is MBC=
An emulsified flowable agent containing 20% of the above two components prepared by mixing a glycol solvent, an STP surfactant, a thickening agent, and water in a ratio of 1:1 (weight ratio) is described below ( Japan Wood Preservation Association Standards (JWPA)
) Tests were conducted at various concentrations shown in Table 7 according to the method for testing the preservative efficacy of wood preservatives specified in Item 1. For comparison, the cases of TCMTB alone and Daconyl or MBC alone, which were produced in the same manner as above, are also shown in Table 7.

The wood-decaying fungi tested were as follows.

1) Versicolor 2) Versicolor (1) Preparation of test pieces Two types of sapwood pieces: cedar and beech (5 x 20 x 40 mm)
, the surface is straight-grained, and the end surface is made of room-temperature-curing evokino grain.
10! Apply it evenly by brushing to break the bond at a rate of IOg/m', and after air drying, divide it into two groups: those without weathering and those that do.
After the treatment was carried out according to the operating method, the two groups were dried at 60° C. until the sapwood had a constant weight and were used as test pieces.

(2) Preservation test (JWPA preservative efficacy test method) and results The medium is JIS modified medium (peptone - 05%, malt extract = 10%, glucose - 25%, K) l, PO, = 03%
, Mg5O, .711.0 = 0.2%), wood-decaying fungi were cultured in the medium base, and test cultures were performed using the following combinations of test pieces of two tree species and wood-decaying fungi. The test culture was carried out for C. versicolor and O. japonica at 26=2° C. for 56 days to determine the preservative efficacy value. The results are shown in Table 7. The preservative efficacy value is calculated using the following formula and is 1.

The test wood-decaying fungi applied to the sapwood pieces of the two species of wood were tested, respectively. This combination of wood preservatives prevents rotting.
When comparing the degree of wood preservatives and the amount of absorption of wood preservatives, it is possible to evaluate the preservative efficacy of wood preservatives more comprehensively by determining the high preservative efficacy values for combinations of untreated wood that result in a high weight loss. f2 et al.

(Left below) Table 7 As is clear from Table 7, the substantial preservative effect STP
l O Xanothane gum l Water 69 Using this agent (Daconyl TBZ=I:I formulation), a wet pulp anti-mold test was conducted in the same manner as in Example 2. The results are shown in Table 8, and when Daconyl was used alone In contrast, no synergistic effect was observed.

Table 8 (E) Effects of the Invention The industrial preservative and antifungal agent of the present invention exhibits synergistic antibacterial effects that are significantly superior to those obtained when each active ingredient is used alone. Therefore, even if the amount of the active ingredients used is small, in which the conventionally intended preservative and antifungal effect cannot be obtained, it is possible to obtain the preservative and antifungal effect by combining these ingredients.

When compared with each test compound alone at a preservative efficacy value of 90 or higher, which is said to have a positive effect, for example, T C
It can be seen that the lO% concentration of M T B alone was all below 90, and no substantial preservative effect was obtained, whereas in the compounds of the present application, the concentration was mostly above 90. T
The combination of Daconyl or MBC results in significantly increased preservative efficacy values than CMTB alone. This excellent effect is thought to be based on the synergistic effect of using each active ingredient in combination.

Comparative test l Instead of TCMTB, 2-(4-thiazolyl)benzimidazole (TBZ), which is a typical known fungicide, was used.
The results of testing the effect of using this in combination with Daconil in the same manner as in Example 2 will be described below.

First, the composition of the comparative drug used is as shown below.

Daconil 10 (wt%) TBZ l 0 However, since it has a strong active ingredient, it has the advantage of expanding the antibacterial spectrum and reducing the range of restrictions for application.

[Brief explanation of drawings]

FIG. 1 and FIG. 2 are graphs for explaining the synergistic effect of the industrial preservative and antifungal agent of the present invention.

Claims (1)

[Claims] 1,2-(thiocyanomethylthio)benzothiazole and tetrachloroisophthalonitrile in a weight ratio of 9:1 to 1.
An industrial preservative and antifungal agent containing a blending ratio of :3. 2. Claim 1, wherein the blending ratio is 4:1 to 3:7 by weight.
industrial preservative and anti-mold agent. An industrial preservative and antifungal agent containing 3,2-(thiocyanomethylthio)benzothiazole and 2-(methoxycarbonylamino)benzimidazole in a weight ratio of 9:1 to 3:7. 4. Claim 3, wherein the blending ratio is 9:1 to 4:6 by weight.
industrial preservative and anti-mold agent. 5,2-(Thiocyanomethylthio)benzothiazole and tetrachloroisophthalonitrile in a weight ratio of 9:1 to 1
: An industrial preservative and anti-mold method consisting of adding to the target system at an addition ratio of 3. 6. Claim 5, wherein the addition ratio is 4:1 to 3:7 by weight.
Industrial preservative and mold prevention method. An industrial preservative and anti-mold method comprising adding 7,2-(thiocyanomethylthio)benzothiazole and 2-(methoxycarbonylamino)benzimidazole to the target system at a weight ratio of 9:1 to 3:7. . 8. Claim 7: The addition ratio is 9:1 to 4:6 by weight.
Industrial preservative and mold prevention method.