JPS61225101A - Volatile mildew-proofing agent - Google Patents

Abstract

PURPOSE:To provide the titled mildew-proofing agent containing camphor and diphenylene oxide as active components, having high safety to human body, exhibiting excellent mildew-proofing effect for a long period, and applicable to a body or place unsuitable to the direct treatment. CONSTITUTION:Camphor is combined with diphenylene oxide acting as a synergist, and the mixture is used as an active component of the titled agent. The amount of diphenylene oxide is preferably 1-10wt% based on camphor. Both compounds are mixed with each other or packed separately in air- permeable nonwoven cloth, etc., and placed close to each other. If necessary, the agent may contain binder, colorant, fungicide, insecticide, etc. Diphenylene oxide used as the mildew-proofing agent is a colorless crystal having a melting point of 83 deg.C and a boiling point of 287 deg.C and high safety and stability.

Description

[Detailed description of the invention] Industrial applications The present invention relates to volatile fungicides.

More specifically, the present invention relates to an inexpensive and practical volatile fungicide that is highly safe for the human body, has an excellent fungicidal effect, and has an excellent long-lasting effect.

BACKGROUND OF THE INVENTION Molds exist everywhere in the natural world, and if environmental factors such as temperature, humidity, and nutrient sources are suitable, they can occur anywhere and cause various types of damage. For example, mold can grow not only in clothing and leather, but also in plastics such as vinyl chloride resin, using plasticizers as a nutrient source.In recent years, there has been an increase in the number of houses with moderate temperatures and high airtightness, such as ceilings, floors, toilets, etc. Mold can be found in the bathroom, kitchen, and sometimes even on the walls of living rooms.

The occurrence of mold in this way impairs the appearance, deteriorates the quality of the product, and can even have a negative effect on the human body.In particular, mold contamination is absolutely unacceptable in pharmaceutical and food factories. Therefore, thorough anti-fungal measures are being taken. Against this background, the need for fungicides has increased in recent years, and research and development to develop excellent fungicides has been actively conducted.

By the way, many fungicides have been known so far, such as copper-based, organotin-based, chlorinated phenol-based, quaternary ammonium salt-based, thiazole and isothiazole-based, and organic bromine-based agents.

However, these drugs are usually applied by surface treatment or internal treatment such as spraying, coating, injection, or mixing, but it is difficult to directly treat the target object or location. The drawback is that it cannot be used for certain substances, such as food packaging materials, pharmaceutical packaging materials, textile products such as clothing, leather raw materials and their products, agricultural products, etc. due to problems of contamination and toxicity. There is.

Therefore, volatile fungicides are usually used when contamination or toxicity is a concern. Conventionally, p-dichlorobenzene has been widely used as a volatile fungicide because it is inexpensive and also has an insect repellent effect.
It has also been proposed that other fungicidal substances such as p-dichloro-m-xylenol are added to p-dichlorobenzene to improve the anti-fungal effect (Japanese Patent Publication No. 55
-2403).

However, p-dichlorobenzene is a type of organic chlorine-based drug, and there is a risk that it may accumulate in living organisms and cause harm, and may also combine with the ocular mucosa and cause clouding of the crystalline lens (industrial poisoning). (Handbook), its use is likely to be regulated.

Therefore, in recent years, many compounds and combinations thereof have been proposed as volatile fungicides to replace p-dichlorobenzene. For example, a sublimable fungicide containing adamantane, a sublimable hydrocarbon, and a sublimable or volatile fungicidal substance (Japanese Unexamined Patent Publication No. 55-4313), t-
It contains a butylphenol compound as an active ingredient, and at least one synergist selected from naphthalene, dichlorobenzene, di-t-butylbenzene, acetaldehyde trimer, propylaldehyde trimer, and isobutyraldehyde trimer. A volatile fungicide containing a sublimable compound (Japanese Patent Publication No. 59-29161) has been proposed.

However, all of these fungicides are more expensive than p-dichlorobenzene, and their antifungal effects, durability, and odor are not necessarily satisfactory. I can't say that.

Problems to be Solved by the Invention Under these circumstances, the purpose of the present invention is to provide an inexpensive method that is extremely safe for humans, has an excellent antifungal effect, and has an excellent long-lasting effect. The object of the present invention is to provide a practical volatile fungicide.

Means for Solving the Problems The present inventor has focused on gunfer, which has a relatively low fungicidal effect, but has extremely low toxicity to mammals, and has conducted intensive research into synergists that increase its antifungal effect. As a result of repeated research, we found that diphenylene oxide is extremely effective as a synergist, is highly safe for the human body, and has properties that are stable and provide a long-lasting antifungal effect. The present inventors have discovered a scale that is suitable for the above purpose, and have completed the present invention based on this knowledge.

That is, the present invention provides a volatile fungicide containing a combination of gunfer and diphenylene oxide as an active ingredient.

Diphenylene oxide used in the fungicide of the present invention is a colorless crystal with a melting point of 86°C and a boiling point of 287°C, and has no mutagenicity regardless of the presence or absence of metabolic activation. The toxicity T-, +D5o values for both sexes were 9 or more per 10 fl/1, making it a highly safe and stable compound.

This diphenylene oxide vapor has almost no antifungal effect, and is a substance that has never been used in combination with an antifungal component.

However, when this was combined with Ganfer, the fungicidal effect was significantly enhanced, the effect was sustained, and it was possible to provide a highly practical fungicidal agent that was safe for the human body. This was a completely unexpected discovery. That is, the present invention is based on the discovery of an extremely effective synergist that can significantly enhance the antifungal effect of Ganfer, which has a weak antifungal effect but is extremely safe, and can maintain the effect for a long period of time. be.

In the fungicide of the present invention, the ratio of diphenylene oxide to gunfer is appropriately selected depending on the desired duration, but if it is too small, the effect of the invention will not be exhibited, and if it is too large, the Since the volatilization rate of gunfer and the volatilization rate of diphenylene oxide are considerably different, after the gunfer is completely volatilized, diphenylene oxide remains, which is not preferred in practice. Usually diphenylene oxide is 1 to 1
Used in the 0 weight range.

In addition, diphenylene oxide and caffar should not be mixed, but should be wrapped separately in breathable non-woven fabric, etc.
However, when mixed, they exhibit almost the same effect.

The fungicide of the present invention may also contain binders, colorants, flavoring agents, other fungicidal substances, bactericidal substances, insecticidal substances, and the like, if necessary.

Effects of the Invention The volatile fungicide of the present invention contains a combination of gunfer and diphenylene oxide as a synergist as an active ingredient, is highly safe for the human body, and is a fungicide. It is an inexpensive and practical fungicide that is highly effective and has a long-lasting effect.

Since the fungicide is volatile, it is particularly suitable for objects and places where direct treatment with chemicals such as surface treatment and internal treatment is not suitable, such as food packaging materials, pharmaceutical packaging materials, textile products such as secondary products, etc. It is useful for preventing mold on leather raw materials and their products, agricultural products, etc., indoors in cupboards, drawers, closets, bathrooms, furniture, clothing cases, etc., and outdoors in warehouses, greenhouses such as vinyl houses, etc.

Example Next, the present invention will be explained in more detail with reference to Examples.

Example 1, Comparative Example i A Saburo agar medium was poured into a glass Petri dish with a diameter of 50 πM and a depth of 5 mm, and allowed to cool to form a flat medium. The spore suspension (
(Airborne bacterial spores suspended in physiological saline) 5μ
inoculate with a microsyringe.

Place this petri dish in a glass bottle (No. 11), place a chemical mixed with five portions of dife heavy oxide (I told Ganfer) next to it, seal it tightly, and culture it for a certain period of time in a constant-temperature warehouse at 30 degrees Celsius. The growth status of the plants was observed.

= 7- Also, as a comparative example, for the drug-free version, for the drug, gunfer alone, diphenylene oxide alone, trioxane alone, and trioxane mixed with 5 weight classes of diphenylene oxide. A similar experiment was conducted using each.

To judge the antifungal effect, evaluate the growth status of fallen bacteria as follows.
The test was conducted in stages, and the results are shown in the table below.

Judgment Criteria: No mold growth observed, 10, 10, 10, 10, 10, 10, 10, 10, 10, 10, 10, 10, 10, 10, 10, 10, 10, 10, 10, 10, 10, 10, 10, 20, 20, 20, 20 and 30 mildew found to occur.
110 recognized across the board = From this table, even if diphenylene oxide is combined with a sublimable substance that has no anti-mold properties, such as trioxane,
Although the antifungal effect is not exhibited, it is found that the antifungal effect is exerted when combined with Ganfer.

Example 2 The procedure was exactly the same as in Example 1, except that instead of using a drug mixed with 5 parts by weight of diphenylene oxide for Ganpher, 4 m2 of diphenylene oxide and 46 m9 of Ganfer were placed separately without being mixed. Similarly, an experiment was conducted on (~).As a result, no mold growth was observed even after 6 days had passed.

Patent applicant Tatsu Todoroki, Director of the Agency of Industrial Science and Technology, designated agent
Ryozo Hayami, Director of Osaka Industrial Technology Laboratory, Agency of Industrial Science and Technology

Claims (1)

[Claims] 1. A volatile fungicide containing a combination of gunfer and diphenylene oxide as an active ingredient. 2. The fungicide according to claim 1, wherein the ratio of gunfer to diphenylene oxide is in the range of 100:1 to 100:10 on a weight basis.