JPH0578527B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a new industrial disinfectant composition. (Prior Art) Water ( Water-containing compositions such as so-called process water (e.g. white water) and flat water used for secondary recovery have the disadvantage that they are susceptible to attack by various microorganisms such as bacteria, molds or yeast, and are susceptible to spoilage and mold. are doing. A large number of bacterial agents are used to control microbial attack of these water-containing compositions. (Problem to be solved by the invention) In the past, heavy metal fungicides such as organomercury compounds and organotin compounds were used to prevent microbial attack on water-containing compositions, but due to their strong toxicity, Replaced by non-metallic disinfectants.
However, non-metallic disinfectants may have insufficient bactericidal effects against certain types of microorganisms, or may be unstable in the target industrial products or materials.
It has drawbacks such as lack of long-lasting effects,
It is not satisfactory as an industrial disinfectant. (Means for Solving the Problem) The present inventor has conducted various studies in order to provide a useful industrial fungicide that exhibits excellent antiseptic and antifungal effects on water-containing compositions that are prone to rot and mold. However,
2-Bromo-2-, which belongs to the above non-metallic fungicides
Nitropropyne-1,3-diol (hereinafter referred to as
(sometimes abbreviated as BNPD) is also known to have bactericidal and fungicidal effects.
A composition containing iodo-2-propynylbutyl carbamate (hereinafter sometimes abbreviated as IPBC) or (and) 2,3,3-triiodoallyl alcohol (hereinafter sometimes abbreviated as TIAA) is , latex emulsions, in much smaller quantities than if each were used alone.
It exhibits excellent antiseptic and anti-mold effects on water-containing compositions such as fiber emulsions, emulsion paints, emulsion waxes, spinning oils, industrial cooling water, spinning white water, oil recovery flat water, etc.
It has been found that there is no risk of residual toxicity or pollution, there is no adverse effect on the target water-containing composition, and it has a simple, inexpensive, and highly adaptable preservative and anti-mold effect, making it extremely useful as an industrial fungicide. death,
The present invention was completed based on these findings. That is, the present invention uses 2-bromo-2-nitropropyne-1,3-diol (BNPD) and 3-iodo-2-propynylbutyl carbamate (IPBC).
or (and) 2,3,3-triiodoallyl alcohol (TIAA) as an active ingredient. The composition of the present invention is manufactured by containing BNPD and IPBC or/and TIAA as active ingredients. These active ingredients are each represented by the following formula.

[Formula] IPBC: I-C≡C-O -CONHCH ₂ CH ₂ CH ₂ CH ₃

[Formula] Specifically, the composition of the present invention combines BNPD and
IPBC, BNPD and TIAA, or BNPD and
IPBC and TIAA are dissolved or dispersed in suitable liquids (e.g. common solvents) or in suitable solid entities (e.g. diluents, bulking agents).
It can be produced by mixing with or adsorbing on these. If necessary, in addition, for example emulsifying agents, dispersing agents, suspending agents, vegetable oils,
It can also be produced by appropriately adding mineral oil, higher alcohol, surfactant, stabilizer, etc. The composition of the present invention is used in an appropriate dosage form such as an oil solution, an emulsion, a wettable powder, an aqueous solution, a suspension, a powder, a granule, a fine powder, or a paste. These formulations can be prepared by methods known per se. BNPD as an active ingredient in the composition of the present invention
When using IPBC, the usage ratio of both is BNPD1
It ranges from about 0.01 to 1 part by weight, preferably about 0.1 to 0.5 part by weight of IPBC to parts by weight.
When using TIAA, the usage ratio of both is BNPD1
It ranges from about 0.1 to 10 parts by weight, preferably about 0.5 to 2 parts by weight of TIAA, based on the weight of BNPD.
When using IPBC and TIAA, the ratio of the three is about 0.01 to 1 part by weight of IPBC and about 0.1 to 10 parts by weight of TIAA, preferably about 1 part by weight of IPBC to 1 part by weight of BNPD.
0.1 to 0.5 parts by weight, and about 0.5 to 1 part by weight of TIAA. Also, the amount of total active ingredients in the composition of the invention,
i.e. BNPD and IPBC or (and) TIAA
Although the total amount used will vary depending on the dosage form and purpose of use, it is generally appropriate to have a concentration of about 5 to 50% by weight based on the total composition. For pastes, suspensions, powders, etc., the appropriate amount is about 5 to 20% by weight, and about 5 to 50% by weight. Each active ingredient of the composition of the present invention may be dissolved or dispersed separately in a suitable liquid carrier or added to a suitable solid carrier and then mixed, or may be pre-mixed and then dissolved or dispersed in a suitable liquid carrier. It may be separated into liquids or added to a suitable solid carrier. Suitable liquid carriers for use in the present invention include, for example, alcohols (eg, methyl alcohol, ethyl alcohol, ethylene glycol, etc.), ketones (eg, acetone, methyl ethyl ketone, etc.), ethers (eg, dioxane, tetrahydrofuran, cellosolve, etc.),
Aliphatic hydrocarbons (e.g., gasolin, kerosene, kerosene, fuel oil, machine oil, etc.), aromatic hydrocarbons (e.g., benzene, toluene, xylene,
(solvent naphtha, methylnaphthalene, etc.),
Other halogenated hydrocarbons (e.g., chloroform, carbon tetrachloride, etc.), acid aminos (e.g., dimethylformamide, etc.), esters (e.g., methyl acetate, ethyl acetate,
butyl acetate, fatty acid glycerin ester, etc.) or nitriles (e.g., acetonitrile, etc.) can be used, but examples include glycols (e.g., ethylene glycol, propylene glycol, trimethylene glycol, etc.), cellosolves (e.g., ethylene glycol monoethyl ether, Water-soluble solvents such as ethylene glycol monomethyl ether, etc.) or galbitols (eg, diethyl glycol monoethyl ether, diethylene glycol monomethyl ether, etc.) are suitable. Examples of solid carriers include clays (such as kaolin, bentonite, acid clay, etc.), talcs (such as talc powder, waxite powder, etc.), silicas (such as diatomaceous earth, silicic anhydride, mica powder, etc.), alumina, and sulfur. Powder, activated carbon, etc. are used, and these may be used alone or in combination of two or more. Examples of emulsifiers, dispersants, etc. used in the composition of the present invention include soaps, sulfuric esters of higher alcohols, alkyl sulfonic acids, alkylaryl sulfonic acids, quaternary ammonium salts, fatty acid esters, polyalkylene oxides, and anhydrocarbons. Surfactants such as sorbitol are used, and it is generally preferable to include them in the composition in an amount of about 0.5 to 10% by weight. In addition, alginic acid, agar, carboxymethyl cellulose, polyvinyl alcohol, vegetable oil, bentonite, cresol soap, etc. can also be used in place of these surfactants or as an adjuvant thereof, if necessary. Furthermore, other types of fungicides (e.g., organic iodine fungicides, organophosphorus fungicides, benzimidazole fungicides, organic sulfur fungicides, phenolic fungicides, antibiotics, etc.) and insecticides may be used as necessary. (natural insecticides, carbamate insecticides, organic phosphorus insecticides, etc.), fragrances, low-molecular to high-molecular phosphates, and the like may be mixed as appropriate. When using the composition of the present invention, methods such as coating, spraying,
Appropriate known methods such as a dipping method, a mixing method, and a kneading method may be applied. Generally, it is preferable to add the active ingredients to the target water-containing composition so that the total content of the active ingredients is about 1 to 500 ppm in final concentration. To explain in more detail, for example, in the case of white water, this active ingredient (BNPD and
IPBC, BNPD and TIAA, BNPD and IPBC and TIAA
The final concentration is 0.5
It is preferable to contain it so that it is about 20 ppm.
For example, when applied to a paper factory, the water-soluble liquid of the composition of the present invention is applied to a process where slime is likely to be generated.
In other words, it is best to add it to machine chests for raw materials, to screens, head boxes, white water pits, etc. for white water systems, and to shower water.
When applying the continuous addition method, make sure that the final concentration of the sum of the contents of the above active ingredients in white water is about 0.5 to 10 ppm, preferably about 1 to 5 ppm, and when applying the impact addition method, It is preferable to add each active ingredient intermittently so that the final concentration of the total content of the active ingredients is about 2 to 20 ppm, preferably about 4 to 10 ppm. When added to paints, water-soluble polymer compounds such as casein and formalin copolymers, water-soluble vinyl and acrylic polymers, water-soluble vegetable oils, and polyester resins, or, for example, methyl acrylate-styrene The composition of the present invention can be used as an active ingredient for paints based on latexes such as , vinyl acetate-methyl methacrylate, vinyl acetate-maleic anhydride, styrene-butadiene, vinyl acetate-methyl acrylate, vinyl chloride-vinyl acetate, etc. The final concentration of the content sum is 20
It is preferable to add it to about 500 ppm. In addition, when adding it to spinning oil, for example, mix mineral oil, higher alcohol, etc. with vegetable oil such as olive oil, castor oil, and fallen seed oil, and add a nonionic or anionic surfactant as necessary, so that it is evenly distributed. The final concentration of the total content of active ingredients of the composition of the present invention in spinning oil mixed with
It is preferable to add it to about 100 ppm. In this case as well, intermittent addition is effective, and if necessary, it may be used in combination with other fungicides or not alternately. (Effect of the invention) The composition of the present invention can be used for general industrial products or materials,
For example, water-containing compositions such as latex emulsions, textile emulsions, emulsion paints, emulsion waxes, spinning oils, industrial cooling water, papermaking white water, oil recovery flat water, wood and bamboo products, leather, textiles, and walls. It can be applied to industrial products or materials made of all organic materials, such as materials and ceiling materials, to effectively prevent quality deterioration caused by microorganisms such as bacteria, yeast, and mold at low concentrations. Such excellent effects may be due to the fact that the stability of each active ingredient is enhanced through blending. Furthermore, the bacterial composition of the present invention has very low toxicity to humans and animals, and is an excellent industrial sterilizing composition that can be used extremely safely, so that it can provide an extremely useful industrial sterilizing material. (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 BNPD10%, IPBC2%, Hitenol NF-13
(manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) 5% and propylene glycol 83% are mixed and dissolved to make a product. When used, it is added as is or diluted with water to a predetermined concentration. Example 2 BNPD10%, TIAA5%, Hitenol NF-13
(manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 5% and diethylene glycol 80% are mixed and dissolved to make a product. When used, it is added as is or diluted with water to a predetermined concentration. Example 3 BNPD10%, IPBC2%, TIAA3%, Hitenol NF-13 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 5%,
The product is made by mixing and dissolving 80% diethylene glycol. When used, it is added as is or diluted with water to a predetermined concentration. Test Example 1 The solvent prepared in Examples 1, 2, and 3 (composition of the present invention), 15% each of the active ingredients BNPD, IPBC, or TIAA, and 5% Hitenol NF-13 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and a solvent mixed and dissolved with 80% diethylene glycol (hereinafter referred to as BNPD15% solvent, IPBC15% solvent, and TIAA15%)
A preservative and anti-mold test was conducted on vinyl acetate-based base putty. Add each test chemical to 100g of putty at a concentration of 0.1, 0.2, 0.3, and 0.4% and mix uniformly. Then, inoculate 1% of a 100-fold diluted solution of rotten putty, knead uniformly again, and then Immediately after storage and after storage at 33°C for 4 weeks, the number of viable bacteria was determined by the pour method using a glucose broth agar medium. Then, calculate how many times the number of viable bacteria has increased using the formula: Number of viable bacteria measured after 4 weeks at 33°C (number of viable bacteria/g)/Number of viable bacteria measured immediately after preparation (number of viable bacteria/g) = (multiple) If the multiple is 10 times or more, it is judged as +, 10 ² times or more, 10 ³ times or more, or 1 after the decimal point (reduction in the number of viable bacteria), and the results are summarized in Table 1.

[Table] Example 2 The solution obtained in Example 1, BNPD 15% solution and IPBC 15% solution were placed in a spinning oil bath at a textile factory.
It was added 600ppm and used for circulation. As a result, on the 14th day of cyclic use, the number of viable bacteria in the spinning oil bath containing 600 ppm of BNPD15% solvent was 35 x 10 ⁶ (cells/g).
In the spinning oil bath to which 600 ppm of IPBC 15% solvent was added, the number of viable bacteria was 26 × 10 ⁷ (cells/ml), and slime generation was observed in both cases. The number of viable bacteria in the spinning oil bath containing 600 ppm of the resulting solvent was 93 even after one month of cyclic use.
×10 (pieces/ml), no slime formation was observed. Test Example 3 The solvent prepared in Example 3 (sterilizing composition of the present invention), BNPD 15% solution, IPBC 15% solution, and
The anti-deterioration effect of TIAA15% solvent on cotton canvas was investigated using the soil burial test method. The cotton canvas was dipped in each solvent to a concentration of 0.1% and 0.2% based on the weight of the canvas, dried, and then cut into strips of 3 x 20 cm to prepare cotton canvas samples. On the other hand, 35×
Fill a 25 x 20 cm plastic container with sand to a thickness of 3 cm, spread a polyethylene sheet with many holes on top of it, and then add 5 cm of a mixture of field soil and sand in a ratio of 8:2. , and place the sample on top of it.
Furthermore, after burying the sample in a 7 cm thick mixture of farm soil and sand (8:2), the sample was stored at approximately 25°C while being sprinkled with water every week, and the state of deterioration caused by microorganisms in the sample was examined after one month. Ta. The results are -, +,,
The results are shown in Table 2 based on the 4-level evaluation. −: No deterioration observed in the sample piece. +: Slight deterioration is observed in the sample piece. : Sample piece is severely deteriorated but retains its original shape. : Sample pieces have deteriorated so much that they do not retain their original shape.

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Claims (1)

[Claims] 1 2-bromo-2-nitropropane-1,3-
An industrial disinfectant composition comprising a diol and 3-iodo-2-propynylbutyl carbamate or (and) 2,3,3-triiodoallyl alcohol as active ingredients.