JPH026402A - Termite-preventing agent and preparation thereof - Google Patents

Abstract

PURPOSE:To provide a highly excellent termite-preventing agent by impregnating a cellulosic base material with a slightly water soluble compound prepared by converting a constant amount of a water-soluble molybdic or tungstic acid salt with an inorganic acid or a salt thereof. CONSTITUTION:After a cellulosic base material is impregnated with one or both of a water-soluble molybdic acid salt and a water-soluble tungstic acid salt, an inorganic acid (e.g., nitric acid or hydrochloric acid) or a salt thereof (e.g., calcium chloride or silver nitrate) is added to the cellulosic base material in an amount of >=0.5 times equivalent based on one or both of the molybdate and the tungstate to convert 50-100% of one or both of the water soluble salts into one or both of a slightly water soluble molybdenum compound and a slightly water soluble tungsten compound having water solubilities of <=1wt.%, respectively, thereby providing a highly excellent termite-preventing agent. The agent penetrates into the inner portions of the base material and is highly effective.

Description

[Detailed description of the invention] vinegar.

An aqueous solution of an inorganic acid or an inorganic salt is added in order to form a termite control agent in the cellulose base material.

An inorganic acid or inorganic salt is produced by sequentially adding an aqueous solution of molybdenum and tungsten in which a:c=0 to 0 to contain a weight composition ratio of 50:50 to 100 in a cellulose base material. Ant control agent.

molybdenum, As tungsten a:c=0~50 b.

The present invention relates to a termite control agent characterized in that it contains an aqueous solution containing an inorganic acid or an inorganic salt in a weight composition ratio of 250 to 1000 so that b/a=Q, 5 times equivalent or more, and a method for producing the same.

[Conventional technology]

In recent years, damage caused by pests that damage wood, such as termites, sea bream beetles, and wood beetles, has become a problem.In order to prevent damage from these pests, the wood has traditionally been treated with insect repellents suitable for this purpose. for,
Organochlorine insecticides such as chlordane and didulin have been used as insecticidal and insect repellent ingredients.However, these insect repellent ingredients all have problems in terms of persistence, toxicity, irritation, and environmental pollution. There have been 94 attempts to develop low-toxicity insect repellents.

By the way, according to the disclosure of Japanese Patent Laid-Open No. 59-82309, it has been proposed that an effectively soluble compound of an element selected from the group consisting of molybdenum and tungsten inhibits animals from fixing nitrogen. This discovery is as follows: 1. Molybdenum and tungsten are cheap.

2.It is safer than chromium and other metals.

3. Molybdenum and tungsten are not toxic to pests other than nitrogen-fixing animals, such as termites and crucian beetles, and are highly selective.

4. It is slow-acting, so it is not repelled by termites etc.

5. Stable in various forms.

It is useful as a bottled insect repellent for wood, but when used alone as a water-soluble compound, it does not kill insects in practical situations.
The insect repellent effect was not necessarily sufficient. [Problems to be solved by the invention] The present inventors investigated mixtures of molybdenum and tungsten compounds from a practical standpoint, and found that molybdenum,
It was discovered that a remarkable synergistic effect was observed at a composition ratio of 65-15:35-85 for tungstic acid, and a patent application has already been filed (Japanese Patent Application No. 39157/1983).

Although there are many unknowns about the mechanism of this synergistic effect, it is thought to be due to the difference in the mechanism of insecticidal action of molybdenum compounds and tungsten compounds against termites.

That is, the tungsten compound is disclosed in Japanese Patent Publication No. 59-8.
As described in No. 2309, the main insecticidal mechanism of molybdenum compounds is that the main insecticidal mechanism of molybdenum compounds is that their oxides contribute greatly to the inhibition of nitrogen fixation by protozoa that live symbiotically in the intestines of termites. It is almost confirmed that the termites accumulate in the bodies of termites, and it is presumed that both effects work together to synergistically enhance the insecticidal effect.

However, in the case of termite control agents obtained by the conventional manufacturing method of termite control agents, that is, by impregnating water-soluble salts of molybdic acid and tungstic acid into cellulose base materials such as wood and then drying them, molybdenum and tungsten are Because they are not sufficiently fixed in the cellulose base material, when used outdoors, molybdenum and tungsten sometimes leached out due to rain, etc., resulting in a decrease in efficacy.

On the other hand, methods have been attempted in which powders of molybdenum compounds and tungsten compounds, which are poorly soluble in water, are directly mixed with cellulose base materials and then molded, but the distribution to the cellulose base materials is only unevenly distributed on the surface of the base materials. Sufficient insecticidal efficacy could not be expected, so uniform immobilization of molybdenum and tungsten was an important issue.

[Means and effects for solving the problem] In view of the current situation, the present inventors have developed a product that is excellent in immobilization on cellulose base materials, and therefore there is no danger of molybdenum and tungsten being leached or washed away during outdoor use. , and a termite control agent containing molybdenum and tungsten with high insecticidal and insect repellent effects, and in the cellulose base material, 50 to 100% of the fossa-soluble salts are added to the water solubility at 20°C, making it extremely useful. The present invention was completed after discovering that a termite control agent can be obtained.

Several products are provided by salt exchange in amounts corresponding to 50 to 100% of the amounts of lipden and tungsten, respectively.

After uniformly distributing the liquid on the cellulose base material, preferably wood, in the same way, soluble compounds are generated and deposited by aqueous solution treatment, so the fixation of molybdenum and tungsten penetrates into the base material at the cellular tissue level. It is characterized by being extremely strong.

Water-soluble molybdates and tungstates used in the present invention include, for example, sodium molybdate [:Na2M0O4; 39.4 (28°C)] ammonium molyftate ((NH4)6Mo7024; 43 (25°C) ] Potassium molybdate [K2MOO4; 64.6 (25°C)] Magnesium molybdate [MgMoO4; l 5.9 (25°C)] Sodium tungstate [Na2WO4: 57.6 (0' C)] Ammonium tungstate [5(NH4)20.12WO3:] Examples include, but are not limited to, potassium tungstate (K2WO4).

The number after the chemical formula is the water solubility (g/1
00m/).

In addition, examples of inorganic acids and inorganic salts that make the above water-soluble salts hardly soluble include inorganic acids - mono-nitric acid, hydrochloric acid, sulfuric acid, etc. - salts of alkaline earth metals (calcium chloride, barium chloride, nitric acid) Examples include salts of aluminum group metals (such as aluminum nitrate), salts of copper group metals (such as silver nitrate), and Vi of iron group metals (ferrous chloride, ferric chloride, cobalt chloride, etc.). As a result, molybdic anhydride 1jJo03; 0.049 (28°C)] molybdic acid (H2MOO4; 0.133 (18°C)) calcium molybdate (CaMo04; 0.005 (25°C)) iron molybdate [FeMOO4 ; 0.0076 (25°G)] Barium molybdate 1:BaMoo4 ; 0.0058 (25°C)]
Molybdate salts such as silver molybdate, aluminum molybdate, and tungstic anhydride (WO3) Tungstic acid (H2WO4) Calcium tungstate [: (cawo4) ; 0.0032 (25°C)] Iron tungstate (FeWO4) Tungsten Barium acid [(Bawo4'); 0.001 (25°c)]
It can lead to useful poorly soluble compounds of tungstates such as silver tungstate, aluminum tungstate, etc.

The number after the chemical formula is the water solubility (g/1
00go).

To explain in more detail the method for producing the mortar ant control agent of the present invention,
The composition ratio of 7μ loin and tungsten of wood, paper, cardboard, etc. is 65 to 15:35 to 85, and the total amount is 0.5 to 20% with respect to the cellulose base material. is impregnated by a method such as injection (injection, reduced pressure), spraying, dipping, etc., and preferably subjected to a drying process, and injected with an aqueous solution of an appropriate concentration of an inorganic acid or inorganic salt in an amount of 0.5 to 1.0 times equivalent (
After drying the cellulose-based product, it can be added by methods such as injection (pressure injection, reduced pressure), spraying, and dipping, and then, if necessary, molded into a desired dosage form to obtain a non-exploitable and obvious ant control agent.

By the way, the termite control agent of the present invention contains molybdenum and tungsten as insecticidal and insect repellent ingredients of 50% each.
It is characterized in that it contains ~100% of the water-soluble compounds obtained by salt exchange, and the remainder consists of water-soluble salts.

It is generally known that poorly soluble salts of molybdenum and tungsten, such as salt and salt, have a slower effect on termites than water-soluble salts, but the production method of the present invention The pheasant-soluble compound obtained by this method exhibited relatively quick efficacy and exhibited behavior similar to water-soluble salts.

Furthermore, it has been found that the initial efficacy and residual efficacy are synergistically enhanced by mixing the above-mentioned water-soluble compound with a water-soluble salt. It has become possible to provide a useful termite control agent that is both effective and effective.

Furthermore, a termite attractant is suitably added in order to more efficiently exhibit insecticidal and insect repellent effects.

As a termite attractant, for example, rotten material of Physcomitrella sp. It is also possible to add.

Furthermore, the termite control agent of the present invention may include organic phosphorus agents such as chlorpyrifos, phoxim, and pyridafenthione;
Pyrethroids such as permethrin, fuvalinate, fenvalerate, fenprobatrin, or other insecticides such as tripropylisocyanurate, or s-421, piveroni
Adding synergists such as butoxide, or adding various types of preservatives and CCA compounds such as CCA, CCE, etc.
μ-based compounds - pentachlorophenyl laurate, p-promo-2,6-dichlorophenol and other O-iodopropyl-based compounds - Engineering F-1000.

O quaternary ammonium compounds and amine salts such as 3-iodo-2-propynylbutyp-carbamate-benzaμ
Organotin compounds such as conium chloride, dialkyldimethylammonium chloride, etc. - bis(n-)butyltin) oxide, tributylnuz terephthalate, etc. O Others - zinc naphthenate, xyligen aluminum salt, etc. can be appropriately mixed to form a useful multipurpose composition. You can also get it.

The formulation of the unexploited clear ant control agent may be in various forms, such as tablets, pellets, plywood, or construction materials, depending on the properties of the control agent and the purpose of use, and any of the formulations can be prepared by conventional methods. Particularly, treated wood chips molded into wood chips using a press are suitable as termite control baits, and are suitably combined with a surfactant or casein.

Gelatin, starch m. cMc. polyvinyl alcohol be done.

The common method of applying unexploded obvious termite control agents is to treat the soil under and around houses or to bury treated pieces. Preventative plywood and construction material applications are also useful.

The effects of molybdenum and tungsten compounds against termites are slow-acting and non-repellent compared to general insecticides.Therefore, the termite control agent of the present invention utilizes the gumming phenomenon or cannibalism phenomenon of ingested termites. can eradicate the entire nest.

〔Example〕

Next, the present invention will be explained in detail with reference to test examples and examples, but it goes without saying that the present invention is not limited to these.

Test Example 1 An aqueous solution IMl containing 3.15% of sodium molybdate and 6.73% of sodium tungstate was injected into a piece of pine wood of 1XIX2crIK using Pivey, ). The post-dried treated wood chips were divided into 3 μm groups, the first group was treated with 1 g of a 3.7% aqueous solution of μm chloride, and the second group was treated with 1 g of a 1.9% aqueous solution of psium chloride. was injected using a pipette to form a force μsium salt of molybdenum and tungsten (the third group was not treated to make it difficult to dissolve).
. After drying each sample, it was immersed in water for 2 days in a beaker, and the amount of molybdenum and tungsten eluted into the water was measured by J
The dissolution rate was determined by quantitative determination according to the method described in IS a 1218, and the results were as follows.

As a result of the test, water-soluble sodium molybdate and sodium hytungstate were converted to poorly soluble calcium molybdate and psium tungstate by treatment with an aqueous calcium chloride solution, and water leaching of molybdenum and tungsten was significantly reduced. It was confirmed that

Test Example 2 According to Test Example 1, after injecting aqueous M l mA' containing 3.15% sodium molybdate and 6.73% sodium tungstate into a piece of pine wood of lXlX2 (?l11), various equivalents of calcium chloride were injected. It was treated to make it less soluble with an aqueous solution.

In order to investigate the effect of leaching on the insecticidal efficacy assuming rainfall, we performed a cooling operation in which wood chips were immersed in water for 30 minutes once every 3 days, and the samples after 2W, 1 month, and 3 months of 1 month were insecticidal. Tested.

Place each sample on the bottom of a deep-bottomed petri dish, release 20 worker ants of the house termite, cover the dish, and heat at 25±1°C.
The insects were reared under conditions of 5EH or higher, and the mortality rate and the degree of damage to wood chips (weight loss rate) were examined at regular intervals, and the results were as follows.

*The results of a molding test by mixing calcium molybdate powder with wood chips and pressing revealed that the present invention - an ant control agent, that is, calcium molybdate and tungsten acid power p obtained by treating sodium molybdate and sodium tungstate with calcium chloride. Those containing 50 to 100% Si in composition ratio showed high anticide effect and anti-corrosion effect regardless of the weathering period. In contrast, a control with a high proportion of water-soluble salts -
The effectiveness of the ant control agent (Mu4.A5) decreased rapidly as the weather resistance period became longer, and the effect of leaching in practical situations was at risk. However, the usefulness of the production method of the present invention was confirmed, although there were problems in terms of physical properties and efficacy of the sample.

Furthermore, by mixing a water-soluble salt and a poorly soluble salt, a synergistic enhancement effect was observed in terms of initial efficacy development and residual efficacy.

Next, examples of the present invention will be shown, but the present invention is of course not limited to these examples. Example 1 Sodium molybdate 3.15 g to 100 g of wood chips
% and sodium tungstate containing 6.73%'
Spray using M 100x/e hand sprayer,
After air-drying for 2 days, 100 m/p of a 2.5% aqueous solution of p-chloride was sprayed. After air drying for 2 days, 7.2 g of isocyanate adhesive was applied to the treated wood chips 728 at 30 c.
C dissolved in acetone was added, mixed well, molded using a tabletop press machine, and then cut to the size of 1X2X2C debris to obtain a termite control bait. When this was placed under the house and in the surrounding soil at a ratio of 10 ants/termite, it was able to prevent termite damage to the house for over two years, and eventually the entire termite nest was exterminated by cannibalism of the termites. I was able to do that.

On the other hand, when a control bait containing only sodium molybdate and sodium tungstate was used, it was not possible to completely eradicate the entire nest, but some of the houses suffered feeding damage from about 6 months after the treatment.

Example 2 According to Example 1, 2.8% of potassium molybdate and 15% of benzyconium water Y8 liquid were sprayed, and then molded into a V-type to obtain a bait agent.

A set of 20 pellets of fine ice and the above was placed at 6 locations around a nest of termites in the field, and the conditions of the fine ice and the nest were observed every month. It was confirmed that feeding damage had decreased dramatically and nest activity had slowed down.

Similar high effects were obtained with termite control agents containing ammonium molybdate, ammonium tungstate, and molybdic acid and tungstic acid obtained from nitric acid treatment, but control baits containing barium phosphate and barium borate were found to be highly effective. could not suppress the damage caused by thin ice.

Example 3 Ammonium molybdate and ammonium tungstate aqueous solution were applied to a lauan veneer with a thickness Q of 7 mm and a moisture content of 14 to 15%, with 2.0% molybdenum per weight of the veneer.
It was injected under pressure to contain 2.0% tungsten.

After drying, a barium chloride aqueous solution was injected under pressure to convert 100% of the molybdenum and tungsten amounts into barium molybdate and barium tungstate, respectively, followed by washing with water to remove the generated ammonium chloride and drying.

The thus obtained veneer had a thickness of 1.4 mm and a moisture content of 10.
% on both sides of lauan veneer at room temperature.
After compressing for 20 minutes at a pressure of 10 kg/c1iL, it was inserted into a hot press kept at a temperature of 120°C and weighed 9 kg.
Hot pressing was performed for 1 minute at a pressure of /crA to obtain plywood.

When this plywood was subjected to a termite damage test, it showed high effectiveness in preventing damage even after one year.

〔Effect of the invention〕

The termite control agent of the present invention has superior safety, control efficacy, and leaching prevention effect compared to conventional termite control agents, and provides an extremely useful termite control agent.

[Brief explanation of the drawing]

Figure 1 is a plot of the mortality rate after 20 days of termite release for samples of each of the control agents 7111, 3, and 5 of Trial Example 2 after the weathering period. This indicates that sex is synergistically enhanced. Figure 1

Claims (2)

[Claims] (1) In a termite control agent containing one or both of molybdenum and tungsten, a, a water-soluble salt of one or both of molybdic acid and tungstic acid, b, and an aqueous solution of an inorganic acid or an inorganic salt are added to the cellulose base material in this order. , c generated in the cellulose base material, one or both of a molybdenum compound and a tungsten compound having a water solubility of 1% by weight or less at 20° C. as molybdenum and tungsten, a:c=0 to 50:50 to
A termite control agent characterized in that it is contained in a weight composition ratio of 100. (2) Add a water-soluble salt of one or both of molybdic acid and tungstic acid to the cellulose base material, and add an aqueous solution of an inorganic acid or an inorganic salt in order so that b/a = 0.5 times equivalent or more, and In the cellulose base material, c, one or both of a molybdenum compound and a tungsten compound having a water solubility at 20° C. of 1% by weight or less as molybdenum and tungsten, a:c=0 to 50:50 to
A method for producing a termite control agent, characterized in that it is produced at a weight composition ratio of 100.