JPS6197204A - Industrial fungicide composition - Google Patents

Abstract

PURPOSE:To provide a fungicide composition containing a 2-benzimidazolecar bamic acid lower alkyl ester, etc., and 3-iodo-2-propynyl N-n-butylcarbamate, etc., as active components, and applicable to paint, leather, textile, etc. CONSTITUTION:The titled fungicide composition contains (A) one or more compounds selected from 2-benzimidazolecarbamic acid lower alkyl ester, 2-(4- thiazolyl)-benzimidazole and 2-n-octyl-4-isothiazolin-3-one and (B) one or more compounds selected from 3-iodo-2-propynyl N-n-butylcarbamate and 2,3,3- triiodoallyl alcohol at a weight ratio of 1:0.2-5. The fungicidal composition is applied to industrial products or materials made of various organic materials, e.g. paint, wood and bamboo product, leather, textile, wall material, ceiling material, etc., and is effective to prevent the degradation of the material with fungi, yeasts, bacteria, etc., at a low concentration.

Description

[Detailed description of the invention] (Industrial application field) The present invention relates to a new industrial disinfectant composition.

(Prior Art) The above benzimidazo-p-based compounds and 2-n-octyl-4-isothiazolin-3-one are generally used in industrial products and materials, such as paints, pastes, wood and bamboo products, textiles, or paper products. Aspergillus grows on plants and causes changes such as contamination and substrate deterioration.
lus), Penicillium
) It exhibits excellent antibacterial activity against molds such as Trichoderma and Cladosporium using the agar medium dilution method. However, when used in a wide variety of practical situations, such as coating oil-based paints or emulsion paints, or mold-proofing wood and bamboo products, cotton canvas, etc., the practical concentration (50 to 500
It often has drawbacks such as no effect at all (ppm).

(Problems to be Solved by the Invention) The present inventor has solved these problems and created an excellent industrial disinfectant and antifungal composition that can be used in industrial products and materials and has a wide range of disinfectant and antifungal effects. As a result of conducting various studies to provide the above-mentioned benzimidazole-μ fungicides, namely 2-benzimidazole carbamic acid lower acyl ester/I/ (hereinafter sometimes abbreviated as BICA), 2-
(4-thiacyly/I/)-benzimidazo-/L/ (hereinafter sometimes abbreviated as TBZ) and 2-n-octyl/l/-4-isothiazolin-3-one (hereinafter sometimes abbreviated as 01T) 3-iodo- in at least one of the
2-propynyl N--n-butyl carbamate (hereinafter referred to as I
A composition containing at least one of 2.3.3-) lyodoallyl alcohol/L/ (hereinafter also abbreviated as TIAA) (sometimes abbreviated as PBC) and 2.3. Resistance test method, Tl5-Z-2911
Not only does it show excellent efficacy in tests, but it also shows in practical tests that it is effective at a concentration significantly lower than that of single agents such as BICA, TBZ, OIT, IPBC, or TIAA, and has a wide range of antibacterial properties. They discovered that it has a spectrum μ, and after further research, they completed the present invention.

(Means for solving the problem) The present invention provides 2-benzimidazo-ρ carbamic acid lower 7A
'Jl'! , xF# (BICA), 2-(4-thiacyly/I/)-benzimidazo-1v (TBZ) and 2-
n-octyl/I/-4-isothiazolin-3-one (O
IT ) and 3-iodo-2-zoroviny A/N-n-butyl carbamate (IPBC) and 2
, 3.3-Trimmed Ali A〃Co-A/(TIAA)
It relates to an industrial sterilizing composition characterized by containing at least one of the following as an active ingredient.

Examples of BICA include lower alkyl esters of 2-benzimidazo-bamic acid having about 1 to 4 carbon atoms, such as methyl ethyl, n-propylene A/, 1-propyμ, n-glutyl, 1- Butyl.

(3)-Butyl, t-butyl ester μ, etc. are used. Regarding BICA and TBZ, their #L classes are also included in this specification. BICA and TB
Salts of Z include hydrochloride and sulfate.

Inorganic acid addition salts such as nitrates and p-)/L/ence
Examples include organic acid addition salts such as phonate.

Depending on the purpose of use, the sterilizing composition of the present invention can be directly retracted, dispersed in a suitable liquid carrier, or mixed with a suitable solid carrier, and if necessary, further added with an emulsifier, 9 dispersing agents, suspending agents, spreading agents, etc. Adhesives, penetrants, wetting agents, mucilage agents, stabilizers, etc. are added to produce irrigation agents, 1 powder, 2 M granules, and paste J! ! It can be used in the form of a clouding agent, a spray agent, etc., and when mixed with other fungicides, insecticides, deterioration inhibitors, etc., and used in the same manner as known industrial fungicides. I can do that. The composition of the present invention is produced by mixing the above-mentioned active ingredients, carriers, and auxiliary ingredients by a known method or an analogous method.

Although the mixing ratio of the above (BICA, TBZ, and OIT groups and the engineering PBC and TIAA groups) differs depending on the purpose, usually the IPBC and TIAA groups are α02~ 50 weight ratio,
Preferably the weight ratio is 0.2 to 5. BICA, TBZ
When two compounds of the group OIT and OIT are used, BIC
Mixing ratio of BICA and TBZ in A+TBZ, BICA
4-Mixing ratio of BICA and OIT in OIT, 'I'B
The mixing ratio of TBZ and OIT in Z+0IT is 1:0.1 to 10 (preferably 1:0.2 to 5) by weight.
is within the range of When using all three compounds of the group BICA, TBZ and 0T, BICA, TBZ, O
The mixing ratio of IT is 1:0.1 to 10:0.1 by weight.
10 (preferably 1:12 to 5:0.2 to 5). Further, when both compounds of the group IPBC and TIAA are used, the mixing ratio of IFBC and TIAA is in the range of 1:0.1 to 10 (preferably 1:0.2 to 5) in terms of weight ratio.

The liquid carrier used in the sterilizing composition of the present invention may be any liquid as long as it does not react with the active ingredient. Recall, propylene glyco-μ, etc.), ketones (e.g. acetone, methyl ethyl ketone, etc.), ethers (e.g. dioxane,
tetrahydrofuran, cellulose, diethylene glycol dimethyl ether, etc.], aliphatic hydrogenated compounds (e.g. gasoline, Kelsene, kerosene, fuel oil 9 machine oil, etc.),
Aromatic hydrocarbons (e.g. benzene, toluene, xylene, solvent naphtha, methylnaphthalene, etc.), other organic bases (e.g. pyridine, aldehyde collidine, etc.), halogenated hydrocarbons (e.g. chloroform, carbon tetrachloride, etc.) , acid amides (e.g. dimethylformamide), esters (e.g. ethyl acetate)
Examples of the solvents that can be used include acetic acid, butyl acetate, glycerin ester of fatty acid, etc.), nitric acid (eg, acetonitrile, etc.), diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, etc.

In addition, soaps are used as emulsifiers and dispersants.

Higher alcohol 1μ acetate ester, alkyl sulfonic acid,
A~K~Ary-〃Sulfonic acid, quaternary ammonium salt,
Oki! /7/I/ Surfactants such as amines, fatty acid esters, boria-y-kylene oxides, and anhydrosolbi-1v systems are used, and general Kll! 0.5 in the drug
It is preferable to contain about 50% by weight. In addition, if necessary, alginic acid, cold
Cellulose (CMC), polyvinyl alcohol, vegetable oil, bentonite, cresol soap, etc. may also be used. In addition, other types of fungicides (e.g., organochlorine fungicides, organophosphorus fungicides, organic sulfur fungicides, organic nitrogen fungicides, organic nitrogen sulfur fungicides, pheno-μ fungicides, etc.) may be used as necessary. , organic acid ester fungicides, antibiotics, etc.), insecticides (natural insecticides, carbamate insecticides,
Organic phosphorus insecticides, etc.), fragrances, low-molecular or high-molecular phosphates, etc. may be mixed as appropriate.

Among these, preferred ones are more specifically shown as 1.2
-benzisothiazolin-3-one, 2°4.5.6-
Tetowo chloroisophthalinitri~.

4-Chlorometaxyleno-〃, Tetofhydro 3.5-
dimethyfi/-211-1,3,5-thiazoazone-2
- Examples include thione.

The content ratio of the active ingredient in the industrial sterilizing composition of the present invention varies depending on its dosage form and purpose of use, but it is generally appropriate to add it to a concentration of about 5 to 100% by weight. In the case of wettable powders, it is preferably about 10 to 803% by weight, in the case of powders, about 10 to 100% by weight, and in the case of suspensions, about 5 to 50% by weight. In addition, during actual use, depending on the purpose of use, appropriate solvents, diluents, fillers, etc. may be added to the disinfectant compositions in these dosage forms, or they may be added to industrial products or materials to which these disinfectant compositions are applied. By adjusting the addition capsule of approximately α0
It is preferable to operate the active ingredient at a concentration of about 0.05 to α1% by weight, preferably α0f-0.05% by weight.

(Effects of the Invention) The sterilizing composition of the present invention can be used for general industrial products or materials, such as paints, wood and bamboo products, leather, and textiles.

It can be applied to industrial products or materials made of all kinds of materials such as wall materials, ceiling materials, etc. to prevent mold and mildew. It effectively prevents quality deterioration caused by microorganisms such as bacteria or bacteria at low concentrations.

In addition, the fungicidal composition of the present invention has very low toxicity to humans and animals;
It is an excellent industrial disinfectant composition that is extremely safe to use.

(Examples) Hereinafter, the present invention will be explained in more detail with reference to Examples and Test Examples, but the scope of the present invention is not limited by these in any way. Note that % in Examples and Test Examples indicates weight percentage.

Example 1 2-benzimidazo-ycarbamic acid methyl ester/1
15%, IPBC5%, Day 1! A 1% aqueous solution of Celogen VS-C (J manufactured by Dai-Kogyo Seiyaku Co., Ltd.) was added at 88% to 2% Knee A/N (manufactured by Kao Atophus Co., Ltd.), and mixed and atomized using a sand mill to obtain a product (suspension agent). When used, it is added as is or diluted with water to a predetermined concentration.

Example 2 2-benzimidazo-μ force y pamic acid ethyl ester w
ans%, IPBC5%, Hitenoh 11F-13 (
Dai-Kogyo Seiyaku Co., Ltd.) 5%, diethylene glycol/
Mix and dissolve L'85% to obtain a product (solution). When used, it is added as is or diluted with water to a predetermined concentration.

Example 3 To 5% TBZ and 5% IPBCIO, add 82% aqueous solution of 3% Damo-A/IP (Kao Atofunu Co., Ltd.) and 1% Celogen WS-C, mix in Sandomi and atomize to form a product (suspension agent). ). When used, it is added after being diluted with t- or water to a predetermined concentration.

Example 4 2-benzimidazo-μ force〃bamic acid methyl μ-ester/S
Add 88% of 15% TIA, 5% TIA, 2% K De4-A/m (manufactured by Kao Atlas Co., Ltd.), and 1% aqueous solution of Celogen WS-C (manufactured by Dai-Kogyo Seiyaku Co., Ltd.), and mix in a Sandomi. Atomize it into a product (suspension agent). When used, it is added after being diluted with t'- or water to a predetermined concentration.

Example 5 2-benzimidazo-ycarbamic acid ethylester μ hydrochloride 5%, TIAA 5%, Hitenor μ*r-13 (manufactured by Dai-Kogyo Seiyaku Co., Ltd.) 5%, diethylene glycol: f-/
Mix and dissolve I/85% to make a product (solution). When used, it is added as is or diluted with water to a predetermined concentration.

Example 6 To 125% T and TIAAIO%, 82% aqueous solution of 3% De4-IWEP (Kao Atfus Co., Ltd.!A) and 1% Celogen WS-C was added, mixed in a sand mill and atomized to form a product (suspension agent). do. When used, it is added as is or diluted with water to a predetermined concentration.

Example 7 0IT40% diethylene glycol solution 3%, IPB
C5%, Nonipo A/85 (manufactured by Sanyo Chemical Industries) ts%,
Mix and grind 2% sodium lignin sulfonate and 8% and 5% clay to make a product (water use agent).

Example 8 01T40% diethylene glycol solution 3%, TIA
5% of people, Nonipou A/85 (Sanyo Chemical Industries 1it)
15%, sodium lignin sulfonate 2%, clay 8 & 5
% is mixed and pulverized to make a product (water use agent).

Test Example 1 For each single agent having the same active ingredient content as the compositions prepared in Examples 1 to 6, 74S standard (Z-2
The antifungal effects on paints were compared according to the paint mold resistance test method of 911, Section 7). Table I shows the test results.
Show K. However, the test bacteria are vinyl acetate Ema/I/V
Gun paints include vinyl acetate Y series and acrylic μ series Emma/I/VW.
The first paint was a suspension of mold [Aspergillus (A
sper-gillus sp, ), Penicillium sp-, ) Ricode
Trichoderma sp.

Alternaria 8fL 4
Species coexistence] was tested. However, water immersion and 80-85℃
Drying was omitted.

Two types of test paints were used: a vinyl acetate emulsion paint (ViniPaint manufactured by Kansai Paint Co., Ltd.) and an acrylic emulsion paint (Vini Deluxe No. 100 manufactured by Kansai Paint Co., Ltd.). The results show the extent of mold growth on the sample surface:
+, +), bands in five levels, and the indication (1, 2, 3) according to the TI8 standard mold resistance indication method is also written.

−: No mold growth observed on the sample surface.

±: Very slight growth of mosquitoes is observed around the test slope.

+: Mold growth is observed on the sample surface below about 173 cm.

+: Mold growth is observed on the sample surface from about 173 to about v3.

Citrus: Mold growth is observed on approximately 273 to the entire surface of the sample.

BICA-CII3: 2-benzimidazolecarbamic acid methyμ ester B Engineering CA -C2115.HCl: 2-Benzimidazo-μcarbamic acid ethyl ester tv hydrochloride B Engineering CA -
C113,B X CA-C2115・flcl,T
A composition consisting of BZ, IPBC and Tlmumu as single agents was produced as follows.

BICA-CH3 (10% suspension agent): BIC of Example 1
KBI instead of A-CH5 (5%) + 1PBC (5%)
It was produced in the same manner as in Example 1 using CA-CH3 (10%).

B I CA-C2115・IICI (10% solution)
:9! Example 2 B construction CA-C2H5・MCI (5%)
+ IPBC (5%) Kawashi B I CA-C211
It was produced in the same manner as in Example 2 using 5.l1C1, (10%).

TBZ (15% suspending agent) and IPBC (15% suspending agent): Example 317) TIIZ (5%) + IPBC (10
%) respectively TBZ (15%), IPBC
(15%) and produced in the same manner as in Example 3.

TIAA (15% suspending agent): TIIZ of Example 6 (5%
) 4-TIAA (10%) to 'r engineering AA (15
%) in the same manner as in Example 6.

Addition amount (%) in Table IK refers to the amount of vinyl acetate emulsion material added to the compositions of Examples 1 to 6 and the above compositions consisting of single agents in such a way that the amount of active ingredient becomes the value in the column of addition amount. It is diluted with acrylic emulsion.

Table 1 Test Example 2 For each single agent having the same active ingredient content as the compositions prepared in Examples 7 and 8, fiber wall material JI8
The antifungal effect on three types of K (those mainly consisting of filamentous fibers (manufactured by Fuji Shokai)) was investigated.

The test results are shown in Table 2.

Fiber wall material 3.39.69 and 129% of the test chemicals were added to 1 bag (620f) for 3112 coating, and 3.9% of water was added to each.
Add to 5j, mix well, then paint evenly on Toyo-Kami 2 to a thickness of about 1 mysK, and after air drying, 3X3cI1
The sample pieces cut in Step 1 were pasted on a SAGLOW agar plate, and the molds [Penioillium s
p, ), ) Trioho-derm
a sp, ) *Mucor ap
), Curvularia (Curvularia sp,
) was spray inoculated with a suspension of 4 types of specimens, cultured at 28°C, and the degree of mold growth on the sample surface was observed on the 7th and 144th day, as in Test Example 1. ”
Displayed in t+'e''l+05 steps.

01T, a2 consisting of single agent PBC and TIAA
% irrigation agent was added to the water of Example 7, "0T40% diethylene glycol solution 3%, IPBC 5%", respectively.
O engineering T (6,2%) + diethylene glyco-/L' (1,
8%) J, [pBC(6,2%) 1+diethyleneglyco-/L/(1,s%)Jtr'rxAA(6,
2%) + diethylene glycol (18%)" in the same manner as in Example 7.

The amount added (f/bag) in Table 2 is 5 in Examples 7 and 8.
It represents the amount of each water use agent added to one bag (6201F) for painting in the anti-mold test of the above water use agents consisting of hydrating powders and single agents.

Table 2 Procedural amendment (voluntary) Patent application 2 filed on October 15, 1980 Name of invention Industrial germicidal composition 3 Relationship with the case by the person making the amendment Address of patent applicant 2-27 Doshomachi, Higashi-ku, Osaka City Name (2
93) Takeda Pharmaceutical Co., Ltd. Representative: Kanetai Iku 4, Agent address: 2-17-85-5 Jusohonmachi, Yodoyou-ku, Osaka City, Japan
Column 6 of the detailed description of the invention in the specification subject to amendment, page 15, lines 14 to 18 of the specification of the contents of the amendment: ``It is... in Table 1.'' should be corrected to ``The amount added (%) in Table 1 is indicated by.''

that's all

Claims (1)

[Claims] 2-benzimidazole carbamic acid lower alkyl ester, at least one of 2-(4-thiazolyl)-benzimidazole and 2-n-octyl-4-isothiazolin-3-one and 3-iodo-2-propynyl N-
An industrial disinfectant composition comprising at least one of n-butyl carbamate and 2,3,3-triiodoallyl alcohol as active ingredients.