WO1998035552A1

WO1998035552A1 - Heat-generating agent for heating fumigant

Info

Publication number: WO1998035552A1
Application number: PCT/JP1998/000637
Authority: WO
Inventors: Kenji Takita
Original assignee: Chugai Seiyaku Kabushiki Kaisha
Priority date: 1997-02-17
Filing date: 1998-02-17
Publication date: 1998-08-20
Also published as: AU5881498A

Abstract

A heat-generating agent for heating a fumigant, containing calcium oxide having a heat generation rate of at least 5 °C/sec when 20 g of calcium oxide and 6 ml of water are allowed to react with each other. A heating method of a fumigant comprising heating a fumigant by the heat generated when calcium oxide having a heat generation rate of at least 5 °C/sec and water are allowed to react with each other (when 20 g of calcium oxide and 6 ml of water are allowed to react). A heater for a fumigant, storing the heat-generating agent in a container and a fumigant kit including the heat-generating agent and the fumigant are also provided.

Description

Specification

Exothermic agent for fumigation heating

The present invention relates to an exothermic agent for heating a smoke agent containing highly active calcium oxide and a method for heating the smoke agent using heat generated by a hydration reaction of calcium oxide with high activity. Background art

Smoke-killers are agents that smoke pest control substances by heating.

Conventionally, as one method of heating and smoking a smoker, a smoker containing a self-combustible substance such as nitrocellulose is reacted with a metal oxide and silicon (a so-called thermite reaction). A direct heating method is known, in which the smoke is itself self-burned by directly heating (igniting) at once using the heat generated by the fumes. The heating method by the thermit reaction is disclosed in Japanese Utility Model Application Laid-Open No. 62-144627 and Japanese Patent Laid-Open No. 1-288218.

However, the heating method by thermite reaction is based on the combustion reaction, so the temperature rises more than necessary at the time of heating, so that the active ingredient in the smoke agent may cause thermal decomposition. However, there was a problem in using a highly thermally degradable drug as an active ingredient.

On the other hand, smokers containing so-called organic blowing agents, which generally do not have self-combustibility, are compared indirectly from the outside due to the high heat generated by the hydration reaction between a large amount of calcium oxide and water. There is also an indirect heating method that heats gently for a long time (Japanese Patent Publication No. 59-49201). In the above-mentioned indirect heating method, in the case of a hydration reaction using calcium oxide, heat is generated per weight of calcium oxide. Because of its low volume, effective volatilization of the pesticidal components required much greater weight of calcium oxide than that of the smoke.

Furthermore, in the indirect heating method, even if a large amount of calcium oxide is used, the rate of heat generation after adding water (hydration reaction rate) is slow, and considerable time is required before smoking starts. _ It took time.

Japanese Utility Model Publication No. 5-69922 discloses that quicklime is tableted and molded into a ring or a cylinder and used as a heating element for heating cans. The heating element is merely intended to fill the container, prevent the heating agent from flying off, and uniformly heat the can. The amount of heat required to initiate smoke in a short time after adding water is insufficient.

In view of the above-mentioned problems, the present invention provides a heat generating apparatus for heating a smoking agent containing calcium oxide, which causes less thermal decomposition of the active ingredient, efficiently heats the smoking agent, and starts smoking immediately. It is intended to provide an agent.

It is a further object of the present invention to provide a heating agent for heating a smoking agent containing oxidizing power, which can be used not only for an indirect heating method for a smoking agent but also for a direct heating method. Disclosure of the invention

The present inventors have conducted intensive studies on a method of heating a smoke agent using high heat generated by a hydration reaction of calcium oxide, and as a result, the heat generation rate when 20 g of calcium oxide was reacted with 6 ml of water. Calcium oxide at a temperature of 5 ° C / sec or more is subjected to a hydration reaction. Can be heated to the desired temperature.

Furthermore, by using the above-mentioned molded body of calcium oxide, it was possible to raise the heat of hydration reaction of calcium oxide to a much higher temperature in a time than in the case of using the conventional technology. We have found that the sum reaction heat can be used not only for the indirect heating method for smokers but also for the direct heating method.

In addition, since the apparent specific gravity is increased by tableting and molding calcium oxide as described above, the size is smaller than that of a conventional smoker container that uses unformed calcium oxide as a heating agent. It has become possible to make lightweight containers.

That is, the present invention provides a heating agent for heating a smoking agent containing calcium oxide having a heat generation rate of 5 ° CZ seconds or more when 20 g of calcium oxide is reacted with 6 ml of water. Book The exothermic agent of the invention is shaped so that the maximum temperature of the surface of the exothermic agent is equal to or higher than the fuming temperature of the smoking agent to be heated by heat generated when calcium oxide is reacted with water. Good. The tableting pressure at that time is preferably from ²⁰⁰ to 400 kg / cm ² . Preferably, it is tablet-formed into a shape of a perforated molded body. Examples of the shape of the perforated molded body include a cylindrical shape, a ring shape, and a cup shape.

The present invention also provides a method for heating a smoking agent by heat generated when calcium oxide having a heat generation rate of 5 ° CZ seconds or more (when 20 g of calcium oxide is reacted with 6 ml of water) is reacted with water. And a method for heating a smoking agent. Less than 100% by weight of calcium oxide, based on the total weight of the smoke agent to be heated, may be reacted with water. Preferably, calcium oxide is reacted with water in the presence of an inorganic acid and Z or an organic acid.

Drugs that can be used as fumigation agents include insecticides, various germicides I] ^ and their mixtures according to the purpose.

Examples of the above insecticides include, for example, pyrethroids such as permethrin, allesulin, resmethrin, cyphenothrin, pralethrin, phenothrin, humvalerate, fenprono, ° trin, etofenprox, etc. Organic drugs, such as organic compounds, phennitrothion, dichlorvos (DDVP), diazinon, protifos, and vitex, and carbamates such as propoxur and methoxadiazon.

Examples of the above-mentioned fungicides include fungicides for agricultural chemicals such as isophthalonitrile, procymidone, biletone, and molestan, thiabendazole, 3-odo-2—propynylbutyl carbamate (IPBC), IF-100, etc. Environmental sanitizing germicides can be used.

The content of the above drug is preferably 2% by weight or more and 20% by weight or less based on the total weight of the smoking agent.

The heating method of the present invention can be used for both smokers heated by the direct heating method and smokers heated by the indirect heating method. Nitrocellulose, azodicarbonamide, dinitrosopentamethylene tetramamine, oxybisbenzenesulfonyl hydrazide, nitroguanidine, And a composition comprising an oxidizing agent such as chloric acid-containing realm and ammonium nitrate and a combustible substance such as sugars and wood flour. Such fumigation agents include the above-mentioned chemicals, heat generation agents for fumigation agents, heat-generating aids such as melamine and zinc oxide, and inorganic minerals such as clay, kaolin, talc, and diatomaceous earth. Addition is also possible. Furthermore, binders and fragrances such as carboquine methylcellulose, hydroxyquinepropyl methylcellulose, polyvinyl alcohol, starch, potency enhancers such as piperonyl butoxide, S-421, and oxidation of BHT, tocoprole, etc. An additive such as an inhibitor may be contained. Both smokers heated by the direct heating method and smokers heated by the indirect heating method are preferably in the form of powders, granules, tablets, pastes and the like.

Further, the present invention provides a smoker heating device in which the above-mentioned exothermic agent is housed in a container, wherein the container is capable of efficiently transmitting heat generated by a hydration reaction or the like to the smoker in contact with the container. It should be something you can do. For example, preferably, 5 W / m '° C or higher, more favorable Mashiku as container according good _c container having a 1 0 WZm · ° C or more heat conductivity (the case of 2 5 ° C), Examples include those made of a material selected from aluminum, tin, copper, iron, and the like. Further, the container further when it _c being sealed Further, the present invention provides a fumigant kit containing the above-described heating agent and smoking agents. The smoker may be either a smoker heated by a direct heating method or a smoker heated by an indirect heating method as described above.

In the present specification, the “heat generation rate” indicates an average temperature increase per second from the start time of heat generation by the hydration reaction of calcium oxide and water to the time to reach the maximum temperature. The heat generation rate is 25 ° C or room temperature.Powder or granules of calcium oxide are placed in a glass tube at 2 Og, and hydrated with 6 ml of water. Can be determined by measuring the maximum internal temperature and calculating the average temperature rise per second from the start of the hydration reaction to the maximum temperature.

The heat generation rate of calcium oxide, which has been conventionally used for heating a smoking agent, is about 3 ns or less when 20 g of oxidizing power is reacted with 6 ml of water. On the other hand, the heat generation rate of calcium oxide used in the present invention is at least 5 ° CZ seconds, preferably at least 6 ° CZ seconds when 20 g of calcium oxide is reacted with 6 ml of water. The heat generation rate when reacting 20 g of calcium oxide with 6 ml of water used in the present invention is 5 ° C / sec. The above calcium oxide is hereinafter referred to as “highly active calcium oxide”. The “perforated molded body” in the present invention is a columnar, cubic, It refers to a molded article such as a rectangular parallelepiped, polygonal column, polygon, or sphere, and the hole may or may not penetrate the molded article. When the hole does not penetrate, it is desirable that the depth of the hole is not less than 1/3 of the thickness of the molded body.

Examples of such a perforated formed body include a formed body having a cylindrical shape, a ring shape, a cup shape, and the like.

In addition, instead of the perforated molded body, highly active calcium oxide is cut into grooves on the surface of the molded body, or the molded body is formed into a star shape or the like, and is subjected to tablet compression molding to form calcium oxide units. A shape having a surface area per weight equivalent to that of the perforated molded article can also obtain the same effect as the perforated molded article of the present invention. BEST MODE FOR CARRYING OUT THE INVENTION

First, prepare highly active calcium oxide. Highly active calcium oxide is, for example, a method of dehydrating slaked lime by heating it to 550 to 770 ° C for about 10 minutes to 6 hours under conditions substantially free of carbon dioxide. (See Japanese Patent Application Publication No. 1-3088885).

When used as an exothermic agent for heating a smoking agent, the powdered granules of highly active calcium oxide produced by the above method may be used as they are, but preferably, they are compressed into tablets by a conventional method, and Into a ring, ring, cup, etc.

The tableting pressure at this time is preferably from 200 to 400 kg / cm ² . If the tableting pressure is less than ²⁰⁰ kg / cm ^2, it is difficult to obtain a good molded product, and if it exceeds 400 kg / cm ² , cracks may occur in the molded product.

It is good to mold only highly active calcium oxide for tableting, but using a lubricant such as magnesium stearate, calcium stearate, talc, or sodium lauryl sulfate further improves tableting moldability. can do.

At this time, the dimensions of the tablet diameter (ø) and hole diameter (ø) are not particularly specified. It may be determined according to the desired calorific value and the size of the storage container.

When the perforated molded body of the present invention is prepared, the ratio (ø2Z01) of the tableting diameter (ø1) to the hole diameter (ø2) is 0.1 to 0.8, preferably 0.2. ~ 0.5.

At this time, the weight of each molded article varies depending on the desired calorific value, but is generally 1 to 24 g, preferably 2 to 15 g. Further, the heat generating agent for heating a smoking agent of the present invention can be used alone, or can be used by stacking a plurality of them.

The heating agent for heating the smoker of the present invention requires much more weight than the conventional smoker for heating and smoking the calcium oxide for heating the smoker. On the other hand, the smoker can be heated and smoked with a smaller weight of calcium oxide than the smoker.

Furthermore, the exothermic agent for smokers of the present invention becomes apparently more specific by tableting, and it is possible to design a container form with a smaller heating space than before, and it is possible to make it smaller than before.・ It is possible to design a smoker container that is lighter. For example, the exothermic agent for heating the smoking agent of the present invention is sealed in a highly heat-conductive container made of aluminum, tin, copper, iron, or the like, so that the heating of the smoking agent, which has been reduced in size and weight, can be performed. Equipment can be made.

Conventionally, the method of heating a smoke agent with calcium oxide has been to heat the smoke agent from the outside of the container containing the smoke agent. In addition, it is possible to design a smoker container that heats the smoker by installing a heating device inside the container that holds the smoker, making the smoker smaller and lighter than before. It is feasible to design a smoke agent vessel. '

In addition, the above-described heating device can be used as an ignition device for directly heating a smoking agent containing a self-combustible substance, instead of an ignition device using reaction heat of a thermite reaction. By using the heating device, it is possible to suppress the thermal decomposition of the active ingredient at the time of ignition of the smoking agent, as compared with the ignition by the reaction heat of the thermite reaction.

In addition, when using the exothermic agent for heating the smoking agent of the present invention, the heating of the smoking agent is good even if the hydration reaction is performed with only water, but in the presence of an inorganic acid and / or an organic acid. , By performing the hydration reaction, the smoker can be heated more efficiently, and the time until smoke starts can be adjusted. The addition of the acid further increases the maximum surface temperature.

Examples of the inorganic acid include boric acid, nitric acid, hydrochloric acid, perchloric acid and the like. In addition, examples of the organic acid include succinic acid, oxalic acid, lingic acid, ascorbic acid, and citric acid.

It is advisable to add water to be reacted with highly active calcium oxide in such an amount that the stoichiometric ratio is 0.5. The inorganic or organic acid may be added in an amount of 0.1 to 20%, preferably 1 to 5%, based on water.

The exothermic agent for heating a smoker of the present invention can be used for any smoker conventionally used by heating by a direct heating method or an indirect heating method.

The ripening agent of the present invention can be combined with a conventional smoker to form a smoker kit. When combined with a smoke agent heated by a direct heating method, the amount of the exothermic agent is 5 to 100% by weight, preferably 10 to 50% by weight, based on the total weight of the smoke agent. Good. When combined with a smoke agent heated by the indirect heating method, the amount of the exothermic agent is 20 to 100% by weight, preferably 50 to 200% by weight, based on the total weight of the smoke agent. It is good.

In the smoker kit of the present invention, the exothermic agent and the smoker may not be in direct contact with each other but may be housed in different adjacent containers.

Further, the exothermic agent for heating a smoking agent of the present invention can be used for heating other than the smoking agent depending on the calorific value of the hydration reaction.

Hereinafter, the present invention will be described specifically with reference to Examples, but the scope of the present invention is not limited thereto. Example 1 Manufacturing method of exothermic agent for fumigation agent (granular)

According to the method described in Japanese Patent Application Laid-Open Publication No. Hei 13-80825, slaked lime was heated at 600 ° C. for about 4 hours under a condition substantially free of carbon dioxide to dehydrate it. ~ 5 fractions of granular highly active calcium oxide were obtained. -W Example 2. Production method of exothermic agent for fumigation heat generation (perforated molded product)

4 g of 1-5 mm granular high-activity calcium oxide of Example 1 was tableted at a tableting pressure of 240 kg / cm ² , tablet diameter (ø) 20 mm, hole diameter ø 6.3. It was formed into a cylinder having a thickness of 12 mm. At this time, a small amount of magnesium stearate was added to the surface of the mold to improve the tableting formability during tableting. Example 3. Manufacturing method of exothermic agent for heat generation of smoking agent (molded product without hole)

4.2 g of 1-5 mm granular highly active calcium oxide of Example 1 was tableted at a tableting pressure of 240 kg / cm ² , with a tablet diameter (ø) 2 O mm and a thickness of 12 strokes. Into a cylindrical shape. At this time, a small amount of magnesium stearate was added to the mold at the time of tableting as in Example 2. Example 4. Manufacturing method of exothermic agent for heat generation of smoking agent (molded product without hole)

In the same manner as in Example 3, 0.4 g of the granular highly active calcium oxide of 1 to 5 mm in Example 1 was formed into a columnar shape having a tablet diameter (ø) of 10 mm and a thickness of 5 mm. Comparative Example 1. Manufacturing method of exothermic agent for fumigation heat generation (perforated product)

In the same manner as in Example 2, 4 g of granular commercially available calcium oxide (manufactured by Wako Pure Chemical Industries, Ltd.) of 1 to 5 faces was formed into a cylindrical shape. Test example 1. Heat generation rate

20 g of the highly active granular calcium oxide prepared in Example 1 was placed in a 0.27 mm glass tube, and at a temperature of 25 ° C, 6 ml of water was injected with a syringe to obtain calcium oxide. The internal maximum temperature was measured with a CA thermocouple located in the center, and the heating rate was calculated from the maximum temperature arrival time. As a comparative example, 20 g of granular calcium oxide of a reagent (manufactured by Wako Pure Chemical Industries) and a conventional product were measured in the same manner. Table 1 shows the results. Table 1 Maximum internal temperature and heat generation rate

; Calcium iodide property Maximum internal temperature (° C) Heat release rate (° CZ seconds) Example 13 22 7.

Reagent form 600 .6

Obey 1 ?: Loro 2 3 6 3. 1

Test example 2. Maximum surface temperature

The exothermic agent for heating the smoker of Example 2, Example 3 and Comparative Example 1 was 3 tablets each, and the exothermic agent for heating the smoker of Example 4 was 30 tablets, inner diameter 22 mm, height 5 It was inserted into an aluminum tube having a thickness of 0 mm and a thickness of 0.75 mm, and 4 ml of water or a 1% by weight aqueous solution of boric acid was added. Thereafter, the maximum surface temperature was measured by an infrared imaging device. Table 2 shows the results.

Table 2 Results of measurement of maximum surface temperature Temperature of calcium oxide Properties Acid Maximum surface temperature (° C) Example 2 Perforated molded product No additive (water) 2 3 3

Example 2 Perforated molded product Boric acid 250

Example 3 Molded product without holes No additive (water) '7 6

Example 4 Molded product without holes No additive (water) 2 2 1

Comparative Example 1 Perforated molded product No additive (water) 4 2

Test example 3. Heat and smoke test

The actual heating test of the smoker was carried out by contacting the aluminum tubes of various calcium oxides conducted in Test Example 2 with 25 g of smoker granules. Table 3 shows the results. The formulation of the smoker granules is as follows,

Methoxadiazone 5%

Phenotrin 2%

Azodicarbonamide 40%

2 Torosenorelose 10%

Carboxymethyl cellulose 5%

Cray

Total amount 100% Table 3 Results of Heating and Smoke Tests Calcium Oxide Properties Acid Smoke Existence Example 2 Perforated Molded Product No Addition (Water)

Example 2 Perforated molded product Boric acid

Example 3 Molded product without holes No additive (water) No fuming

Example 4 Molded product without holes No additive (water)

Comparative Example 1 Perforated molded article No additive (water) fuming

Industrial applicability

According to the present invention, it is possible to heat a smoker to a desired temperature in a short time and with a small amount of calcium oxide, as compared with a conventional smoker utilizing heat of hydration reaction of calcium oxide. became.

Further, by using the exothermic agent for heating the smoking agent of the present invention, the heat of hydration reaction of calcium oxide can be used not only for the indirect heating method for the smoke agent but also for the direct heating method. In addition, the heating agent for heating the smoking agent of the present invention has a higher apparent specific gravity by tableting and molding, so that the heating agent for heating the smoking agent is smaller than the conventional container of the smoking agent using calcium oxide as the heating agent. Smaller and lighter containers can be made.

Claims

The scope of the claims.

1. An exothermic agent for heating a smoking agent containing calcium oxide, which has a heating rate of 5 ° CZ seconds or more when 20 g of calcium oxide is reacted with 6 ml of water.

2. The heat-generating agent is formed such that the maximum surface temperature of the heating agent is equal to or higher than the fuming temperature of the smoking agent to be heated by heat generated when the calcium oxide is reacted with water. The exothermic agent as described.

3. The exothermic agent according to claim 1 or 2, wherein the exothermic agent is formed at a compression pressure of 3.2 to 400 kg / cm ² .

4. The exothermic agent according to claim 1 or 2, wherein the exothermic agent is tablet-formed into a perforated molded article.

5. The exothermic agent according to claim 4, wherein the shape of the perforated formed body is any one of a cylindrical shape, a ring shape, and a cup shape.

6. The fumigation agent is heated by the heat generated when calcium oxide having a heat generation rate of 5 CZ seconds or more (when 20 g of calcium oxide is reacted with 6 mi of water) is reacted with water. The method of heating the smoker.

7. The method according to claim 6, wherein less than 100% by weight of calcium oxide is reacted with water, based on the total weight of the smoking agent to be heated.

8. The method according to claim 6 or 7, wherein the calcium oxide is reacted with water in the presence of an inorganic acid and / or an organic acid.

9. A smoker heating device containing the exothermic agent according to any one of claims 1 to 5 in a container.

10. The apparatus according to claim 9, wherein the container has a thermal conductivity of 5 WZm · ° C or more (at 25 ° C).

11. The apparatus according to claim 10, wherein the container is made of a material selected from the group consisting of aluminum, tin, copper and iron.