JPS5940125B2 - Termite-controlling coating composition - Google Patents

Description

[Detailed description of the invention] The present invention relates to a coating composition having termite control properties.

Termites not only cause damage to buildings, etc., but recently they have also been attacking cables, especially the synthetic resins and synthetic rubbers used to cover underground cables, causing fatal damage such as deterioration of insulation.

Insulating materials such as polystyrene (styrofoam) and polyurethane (urethane rubber) are also damaged by termites.

Conventionally, 1 to 2% (by weight) of chlordane, DDT, dieldrin, etc. have been blended with synthetic resins or synthetic rubbers to obtain a certain degree of termite control effect, but such amounts are not effective for long term termite control.

Moreover, if a large amount of these is blended, there is a risk that the insulation resistance of cables etc. will be reduced.

Furthermore, the above compounds are toxic and undesirable for workers.

As a result of various studies, the inventors discovered a compound that has a termite control effect for a long period of time even when mixed in a small amount.

That is, the present invention is a termite-controlling coating composition comprising a synthetic resin or natural or synthetic rubber mixed with a tricyclohexyltin compound as an active ingredient.

In the present invention, the I.licyclohexyltin compound to be kneaded into the synthetic resin or natural or synthetic rubber includes simple compounds and polymer compounds.

As a simple compound, for example, the general formula (where m is 1 or 2
an integer of

When m-1, X is a chlorine atom, bromine atom, fluorine atom, hydroxyl group, carboxyl group, or alkylmercaptide group; when m-2, X is an oxygen atom, sulfur atom, or sulfate group) Examples include tricyclohexyltin compounds.

These compounds include, for example, tricyclohexyltin chloride, bromide, fluoride, hydroxide, carboxylate, methylmercaptide, ethylmercaptide, butylmercaptide, octylmercaptide, laurylmercaptide, bis(tricyclohexyltin) oxide. , sulfide, sulfate, etc.

Further, as a polymer compound, for example, a polymer having the general formula (wherein R1 is a hydrogen atom, a halogen atom, a lower alkyl group, or a group -COOQ, and R2 is a hydrogen atom, a halogen atom,
lower alkyl group or group -CH2COOQ', Q, Q' represents an alkyl group, alkenyl group, aryl group, aralkyl group, cycloalkyl group or tricyclohexyltin group having 1 to 18 carbon atoms; It is a polymer in which one or more cyclohexyltin bonding units are present.

The tricyclohexyltin-containing polymer represented by the above general formula Cm) is obtained by homopolymerizing the tricyclohexyltin compound represented by the general formula (wherein R1 and R2 have the same meanings as above) or by polymerizing this compound with other polymers. It is obtained by copolymerizing one or more types of sexually unsaturated compounds.

It can also be obtained by reacting a pre-obtained polymer having a carboxyl group, an acid anhydride group, or an alkali salt thereof in a side chain with a tricyclohexyltin compound by a conventional method.

Examples of the tricyclohexyltin compound represented by the above general formula CIII) include tricyclohexyltin acrylate, tricyclohexyltin methacrylate, tricyclohexyltin α-bromoac! JL/-I', screw (
Tricyclohexyltin) malate, tricyclohexyltin crotonate, bis(tricyclohexyltin) itaconate, tricyclohegycyltin butyl itaconate, tricyclohexyltin octyl maleate, tricyclohexyltin itaconate, and the like.

Other polymerizable unsaturated compounds to be copolymerized with these tricyclohexyltin compounds include, for example, styrene, α
-methylstyrene, vinyltoluene, cyclohexene,
Unsaturated hydrocarbons such as butadiene, vinyl compounds such as vinyl chloride, vinyl acetate, vinylidene chloride, methyl vinyl ether, butyl vinyl ether, acrylic acid, methacrylic acid or their esters, acrylic compounds such as acrylamide and acrylonitrile, maleic acid, fumar Examples include acids, itaconic acid, vinylbenzoic acid, crotonic acid, and esters thereof.

The l-'J cyclohexyltin-containing polymer, which is the active ingredient of the present invention, is a tricyclohexyltin compound represented by the above general formula [111], or by adding other polymerizable unsaturated compounds thereto to form a suitable vinyl polymerization catalyst. It can be easily obtained by polymerization methods such as bulk, solution, emulsification, and suspension, preferably in the presence of a radical catalyst.

In other methods, a carboxyl group, an acid anhydride group, or an alkali salt thereof is added to the side chain obtained in advance by homopolymerization of a polymerizable unsaturated carboxylic acid or its derivative or by copolymerization of it with other polymerizable unsaturated compounds mentioned above. The polymer which is the active ingredient of the present invention can be obtained by reacting a polymer having the following with bis(tricyclohexyltin) oxide, tricyclohexyltin hydroxide, or tricyclohexyltin halide.

Examples of the synthetic resin or natural or synthetic rubber into which the active ingredient of the present invention is to be kneaded include synthetic rubbers such as polyvinyl chloride, polyethylene, polyamide, polyurethane, natural rubber, butyl rubber, neoprene, and silicone rubber.

In addition to the active ingredients of the present invention, other termite control agents such as chlortene, dieldrin, chlornaphthalene, dendrolazine, and wood preservatives such as creosote oil, tentenate metal salts, tributyltin compounds, triphenyltin compounds, etc. may be used as necessary. Can be added.

In the present invention, the active ingredient can be kneaded into the synthetic resin or natural or synthetic rubber in an amount of usually 0.01 to 10% by weight.

Kneading into the synthetic resin is carried out using a commonly used kneader, and the resulting mixed wire can be coated onto electric wires, etc., using an extruder using a crosshead, for example.

In addition, when kneading into natural or synthetic rubber, first strands are rolled for several minutes using a high-speed (over 20 phr) and cooled roll, and then a softener, reinforcing agent, process oil, vulcanizing agent, accelerator, etc. The mixture is mixed with anti-oxidants, anti-aging agents, pigments, etc., and mixed with a roll.

In order to thoroughly knead the mixture, it is once passed through an extruder, and the resulting kneaded product can be coated onto electric wires and the like in the same manner as the synthetic resin described above.

After coating, vulcanization is performed by heating. Since the active ingredients of the present invention are incorporated into cables and other coatings obtained from the termite-controlling coating composition of the present invention, they have increased resistance to rain and wind, and can prevent termites for a long period of time with a relatively small amount. It can be prevented.

In addition, the acute toxicity of tricyclohexyltin compounds to rats is, for example, tricyclohexyltin hydroxide with an LD5o of 650, and chlordane with an LD5o of 335 to 4.
30 and dieldrin LD5846 (more than m9/kg
), the present invention can be carried out advantageously.

Next, production examples, working examples, and test examples will be shown, in which the middle part of each example indicates parts by weight, and % indicates weight %.

Production example 1 200g of tricyclohexyltin methacrylate, 100g of xylene? and 1.01 of azobisisobutyronitrile were added, and the mixture was heated and stirred at 75 to 85°C for 7 hours in a nitrogen stream.

During this time, 65 g of catalyst O was added 3 hours after the start of polymerization.

After raising the internal temperature to 120° C. and allowing the reaction to continue for another hour, 100 g of xylene was added and the mixture was cooled to room temperature.

The produced polymerization solution has an almost colorless and transparent viscosity (25℃)
6.2-voice viscous liquid, non-volatile content test (diameter 60
2 grams of sample was placed in a mm tin plate, and the percentage of remaining amount after 3 hours at 110°C.

(same below) showed 49.6%. The xylene was removed from the polymerization solution and used as the homopolymer of Example 4.

Production example 2 Maleic anhydride 16.3P, styrene 101, octyl acrylate 30g, benzoyl peroxide 0.8
and 80 g of xylene at 85-90°C in a nitrogen stream for 50 minutes.
Polymerized for hours.

Tricyclohexyltin hydroxide 126.7? dissolved in xylene 101 in the obtained polymerization solution? was added, and reflux dehydration was performed at 80° C. for 2 hours under reduced pressure (60 to 707 nrILHg).

The amount of dehydration during that time was 2.8 mA (theoretical amount 2.99 ml).

The resulting polymerization solution was a slightly cloudy liquid with a temperature of 7.2 poise (at 25° C.), and a nonvolatile content test showed 497%.

The polymer obtained by distilling off xylene from this polymerization solution has acid anhydrides of 1790 and 1870C in the infrared absorption spectrum.
absorption of rrL-1 disappears, tin carboxylate) 16
It showed strong absorption at 50 cm.

This polymer is used as a copolymer in Example 5.

Production Example 3 Tricyclohexyltin acrylate 160g, vinyl acetate 40g, benzene 1602 and methyl ethyl ketone 4
Add 1.01 of azobisisobutyronitrile to 0g,
The reaction was carried out at 75-80°C for 5 hours.

The resulting polymerization solution was a clear, colorless liquid of 9.8 poise (at 25° C.) with a non-volatile content test of 49.8%.

Benzene was removed from this polymerization solution and used as the copolymer of Example 6.

Production example 4 Bis(tricyclohexyltin) itaconate 160L?
, methyl methacrylate 201, butyl acrylate 2
1.0 liters of benzoyl peroxide was added to 01 and benzene 2001, and the mixture was polymerized under reflux for 4 hours.

After that, add 1.0' of catalyst? was added, and the reaction was continued for 3 hours.

The resulting polymerization solution was a clear, colorless liquid with a temperature of 8.7 voices (25° C.) and a non-volatile content test of 49.9%.

Benzene was removed from this polymerization solution and used as a copolymer in Example 9.

Production Example 5 140 g of tricyclohexyltin methacrylate, 40 g of methyl methacrylate, 2 Of octyl acrylate, and 100 g of xylene were mixed with 1.1 g of azobisin butyronitrile.
0 was added and the reaction was carried out at 75-85°C for 3 hours, then 0.51 of the catalyst was added and the reaction was continued for 4 hours.

Furthermore, the internal temperature was raised to 120° C., kept for 1 hour for reaction, and then 100 g of xylene was added and cooled to room temperature.

The resulting polymerization solution was a colorless and transparent liquid of 84 poise (25° C.) and had a non-volatile content test of 49.8.

This polymerization solution was used as a copolymer in Example 12 by removing xylene.

Production example 6 Tricyclohexyltin itakone) 180P, styrene 20L? Then, 1.01 l of benzoyl peroxide was added to 201' of benzene, and the mixture was polymerized under reflux for 4 hours.

Thereafter, an additional 1.01 liters of catalyst was added, and the reaction was continued for 3 hours.

The resulting polymerization solution was a colorless and transparent liquid of 8.7 poise (at 25° C.), with a non-volatile content test of 49.9%.

Benzene was removed from this polymerization solution and used as a copolymer in Example 13.

Examples 1 to 9 50 parts of dioctyl phthalate, 3 parts of tribasic lead sulfate, and 1.0 or 2.0 parts of the active ingredients shown in Table 1 below were added to 100 parts of vinyl chloride resin (degree of polymerization 1'1OO), A termite-controlling vinyl chloride resin composition was prepared.

Each composition was kneaded with rolls at 150°C for 3 minutes, and then four sheets were stacked and pressed at 170°C and 100 kg/ca for 20 minutes to obtain a vinyl chloride resin plate with a thickness of about 2 mm.

Examples 10 to 14 1.0 or 2.0 parts of the active ingredients shown in Table 2 below were added to 100 parts of polyethylene resin (molecular weight 20,000) to prepare a termite-controlling polyethylene resin composition.

After kneading each composition for 3 minutes with a roll at 140°, two sheets were stacked at 160°C, 50 kg/cr;
Pressing was performed for a minute to obtain a polyethylene resin plate with a thickness of about 1.0 mm.

(Efficacy test) 400 P of dry sand (particle size 0.5 to 1 mm) that has been previously sterilized at a temperature of 115° C. for 2 hours or more and 8 C1 of sterilized distilled water are added to a cylindrical glass insect rearing bottle with a diameter of 1 Ocn and a capacity of 500 I711.

A large number of these bottles were prepared, and a disk cut into a diameter of 3Q mm from each resin plate made by kneading the active ingredients of Examples 1 to 14 and Comparative Examples 1 to 6 was placed in each bottle.
Take the fish out of the nest and put it in.

The breeding conditions are a temperature of 25±2°C and a humidity of 75% in a dark place for several months to two years.

Dead termites were removed, and live termites were added one after another to visually observe whether the termites caused feeding damage.

The results are shown in Tables 3-1 and 3-2. The indication of feeding damage in the table is as follows.

−: No feeding damage +: Slight feeding damage ++: Feeding damage +++: Hole

Claims (1)

[Claims] 1. A termite-controlling coating composition comprising a synthetic resin or natural or synthetic rubber mixed with a tricyclohexyltin compound as an active ingredient.