JPH0684284B2 - Pest control material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial field of application) The present invention is applicable to a gap such as a cockroach, a fly, or other harmful insects, a drainage port of a sink, or a precision instrument such as an electronic weighing machine or a vending machine. The present invention relates to a paste-like pest control material which can prevent pests from entering by being applied to the periphery of a device where there is a risk of pests entering.

(Prior Art) In recent years, a pest control sheet or a pest repellent sheet obtained by impregnating paper, synthetic resin, or the like with a chemical has been widely used. These sheets are usually used by laying them around the lower part of the sink, precision equipment, vending machines, etc. However,
The work of laying these sheets under the sink or the above equipment requires a considerable amount of labor, and is particularly troublesome especially for heavy objects and highly accurate equipment. Moreover, after the effectiveness of the drug on these sheets disappears, the same labor is required to remove these sheets.

(Object of the invention) The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a caulking material or a sealing material in a gap around a sink or a drainage outlet of a kitchen where pests can easily enter. An object of the present invention is to provide a pest control material which can be packed, can be applied around precision instruments and vending machines, and can be easily peeled off after use.

(Means for Achieving the Purpose) In order to achieve the above object, the present invention is a kneaded pesticide and a diisocyanate prepolymer having an ether bond or an ester bond, which is in the form of a paste. It is designed to be cured by contact with water.

The pest control material of the present invention is in a paste form, and it is desirable to cure it after a certain period of time. Practically, it is desirable to cure the coating within a few hours after coating, so the proportion of the terminal isocyanate groups in the diisocyanate prepolymer after coating is preferably 3 to 15% by weight. If it is 3% by weight or less, it takes a long time to cure, and if it is 15% by weight or more, the ratio of the segment chains becomes too small, which causes a problem in the release property of the pest control agent described later.

Further, the segment chains of the diisocyanate prepolymer need to have appropriate hydrophilicity. If the degree of hydrophilicity is too large, the chances of the isocyanate group coming into contact with water become too large, and thus crosslinking proceeds at once and causes foaming. On the other hand, if the degree of hydrophilicity of the segment chains is too small, the opportunity for the isocyanate group to come into contact with water becomes extremely small and the time required for curing becomes long, which is not practical.

Now, it is desirable that the pest control material of the present invention releases the pest control agent for a relatively long time. The so-called sustained release principle of gradually releasing the pest control agent will be described below. That is, the release of the pest control agent is greatly affected by the chemical affinity between the pest control agent and the segment chain, and the release rate can be controlled by adjusting the chemical affinity. Here, the solubility coefficient is a factor that controls the strength of the chemical affinity between the two substances. Substances with similar solubility coefficient values generally have good solubility and compatibility,
On the contrary, there is no solubility or compatibility between substances whose solubility coefficient values greatly differ. Therefore, when the solubility coefficient values of the pest control agent and the segment chains are very close and the compatibility is good, a uniform paste can be obtained. However, if the chemical affinity between the two becomes too strong, the pesticide will be retained in the segment chains and will not be released.

On the contrary, when there is a large difference in solubility coefficient between the two and there is no compatibility or extremely low compatibility, a uniform paste-like product cannot be obtained.

The pest control material of the present invention is the result of intensive research on the above theory,
It was able to be utilized practically, and coexisting units having different compatibility with the pest control agent stepwise in one segment chain, and making a difference in chemical affinity between the unit and the pest control agent. The release rate of the pest control agent is controlled appropriately so that the pest control agent can be released.

Further, the pest control material of the present invention is in a paste form, and its ease of use is also an important factor for practical use. That is, the quality of the coating property is determined by its viscosity and hardness. In order to control the viscosity and hardness, the melting point of the diisocyanate prepolymer, that is, the degree of polymerization for adjusting the melting point is a problem. That is, when the degree of polymerization of the segment chains is too high, the melting point becomes high, and the segment becomes solid at the time of use. For this reason, for example, when the paste-like material is placed in the closed tube, it becomes difficult to squeeze out and it becomes impossible to apply it. On the other hand, when the degree of polymerization of the segment chains is low, the melting point is low, the liquid becomes liquid at the time of use, and the viscosity becomes low at the time of application. Considering also that the diisocyanate prepolymer is plasticized to some extent when mixed with a liquid pesticide, the diisocyanate prepolymer has a melting point of 40 ° C to 45 ° C which is slightly higher than the temperature at the time of use.
It is desirable to use a polymer having a segment chain and the degree of polymerization of the segment chain needs to be adjusted.

As the diisocyanate prepolymer used in the pest control material of the present invention, it is desirable to use the following compounds alone or in a mixture of two or more kinds.

1) A diisocyanate prepolymer having an ether bond represented by the general formula of the segment chain of (CH _{2) m} —O _n , wherein m is 3 to 5 and n is 10 to 25, and the molecular weight is
Diisocyanate prepolymer in the range 700-2000.

2) A diisocyanate prepolymer having an ester bond represented by the general formula of the segment chain of (CH ₂ ) _m —COO _n , wherein m is 3 to 5, n is 10 to 25, and molecular weight is 1200 to 2500.
Diisocyanate prepolymers in the range of.

Further, the amount of such a diisocyanate prepolymer blended is 60 to 95% by weight in consideration of the efficacy of the drug, the curing time and the like.
It is desirable to set the range to. However, as will be described later, when the filler and the plasticizer are added, the compounding amount of the diisocyanate prepolymer may be 40 to 60% by weight.

The pest control material of the present invention is mainly an amide repellent alone or as an amide repellent and an insecticide, which is used as a pest control agent in combination, and is particularly an amide repellent and is dissolved in the repellent. When a combination of insecticides and fungicides is used, the repellent acts as a carrier for these agents and a small amount of insecticide or fungicide can be constantly exuded. At this time, most of the pests do not approach due to the repellent effect of the amide repellent, but a small amount of approaching pests can be killed by the pesticide.

In addition, a bactericidal agent may also be used in the same manner to provide a bactericidal effect.

In addition, when only the insecticidal or bactericidal effect is required without the repellant effect, the insecticidal effect can be obtained by using a solvent having a solubility coefficient similar to that of the repellant and having a function as a carrier agent instead of the repellant. Agents and fungicides are constantly released little by little to exert a remarkable insecticidal and bactericidal effect.

Next, as the amide repellent, for example, N.N-diethyl-m-toluamide, N-butylacetanilide, N.
N-diethinisuccinamate and the like can be mentioned, and these are used alone or in admixture of two or more.

Examples of insecticides include 3-allyl-2methylcyclopent-2-en-4-one-1-yl-dl-cis / trans-chrysanthemate, 3-allyl-2-methylcyclopenta-2. -En-4-on-1-yl-d-
Cis / trans-chrysanthate, d-3 allyl-2
-Methylcyclopent-2-en-4-one-1-yl-d-trans-chrysanthemate, 3-allyl-2-
Methylcyclopent-2-en-4-one-1-yl-
d-trans chrysanthemate, 5-benzyl-3-furylmethyl-d-cis / trans-chrysanthemate,
5- (2-Probagyl) -3-furylmethyl chrysanthemate, 3-phenoxybenzyl-2,2-dimethyl-
3- (2 ', 2'-dichloro) vinylcyclopropanecarboxylate, 3-phenoxybenzyl-d-cis / trans-chrysanthemate, O, O-isopropoxyphenylmethylcarbamate, O, O-dimethyl -O- (3-
Methyl-4-nitrophenyl) thionophosphate,
N- (3,4,5,6-tetrahydrophthalimide) -methyl-d
l-cis / trans-chrysanthemate, O, O-dimethyl-S (1,2-dicarboetoquinethyl) -dimethiophosphate, α-isopropyl-4-chlorophenylacetate, O- (4-bromo-2) , 5-dichlorophenyl)
-O, O-dimethyl phosphorothioate and the like can be mentioned.

Further, as a bactericide, 2,4,4'-trichloro-2'-
Hydroxydiphenyl ether, 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine, alkylbenzyldimethylammonium chloride, benzylmethyl-2- [2- (P-1,1,3,3-tetramethylbutyl) Phenoxy) atoxy] -ethylammonium chloride, 4-isopropyltrobolone, N, N-dimethyl-N
-Phenyl-N- (fluorodichloromethylthio) sulfonamide, 2- (4'-thiazolyl) benzimidazole, N- (fluorodichloromethylthio) phthalimide, 6-acetoxy-2,4-dimethyl-m-dioxyethylene Zinc bis (dithiocarbamate), manganese ethylene bis (dithiocarbamate), zinc manneb complex compound, bis (dimethyldithiocarbamate) ethylenebis (dithiocarbamate) dizinc, bis (dimethylthiocarbamoyl) disulfite, crotonic acid 2 , 6-Dinitro-4-octylphenyl reaction isomer mixture, N-trichloromethylthiotetrahydrophthalimide, 2,3-
Dicyano-1,4-dithiaanthraquinone, 2,4-dichloro-6- (P-chloroaniline) S-toluazine, Sn
-Butyl S'-P-tert-butylbenzyl N-3,
-Pyridyldithiocarboxylic imitate, N- (3 ', 5'
-Dichlorophenyl) -1,2-dimethylchloropropanedicarboximide, bis (chlorophenyl) trichloroethanol, 6-methylquinoxaline-2,3-dithiocarbonate, tetrachloroisophthalonitrile, methyl-1- (butylcarbamoyl) -2- Examples thereof include benzimidazole carbamate, plastoidin S-benzylaminobenzenesulfonate, stobutomycin hydrochloride, kasugamycin hydrochloride and cycloheximide.

As described above, pest control agents comprising repellents, insecticides, bactericides and the like can generally exhibit a remarkable pest control effect when blended in an amount of 1% by weight or more, but in consideration of the sustainability of the effect and cost, etc. It is appropriate that the range is 5 to 30% by weight.
However, 40 to 50% by weight may be blended depending on the application. The pest control material of the present invention, as described above, is kneaded with a pest control agent and a diisocyanate prepolymer to form a paste, in order to adjust the viscosity and hardness thereof, and the peelability of the coating film. In order to increase the amount, a proper amount of filler or plasticizer may be added. For example, as the filler, an inorganic filler such as aluminum hydroxide or magnesium hydroxide is preferably used. Also, as a plasticizer,
A fatty acid ester of glycerin such as triacetin is used. By appropriately adjusting the viscosity and hardness of the pest control material with such a filler or plasticizer, workability during construction is improved, and peelability after use is further improved.

If too much such a filler or plasticizer is added, the pest control effect will be extremely poor.
It is desirable to use up to 75% by weight.

(Function) The pesticidal material of the present invention is a paste-like product obtained by kneading a pesticidal agent and a diisocyanate prepolymer having an ether bond or an ester bond, and the isocyanate group of the diisocyanate prepolymer has a moisture content in the air. It reacts, crosslinks and hardens. Therefore, the pest control material of the present invention is packed in a tubular closed container, and when necessary, it is extruded from the tube and injected into the gap around the sink, or when it is applied around the precision equipment, it is cured by moisture in the air. To do.

In the cured pest control material of the present invention, the drug inside the drug gradually migrates to the surface and is released in appropriate amounts for a long period of time, so that the drug effect lasts for a long time. It is because the segment chain of the diisocyanate prepolymer contains units whose compatibility with the drug is gradually different,
Each unit has a different chemical affinity with the drug,
The drug is released while being controlled appropriately, and the pest control effect is exerted for a long period of time. Further, since it has the above configuration after use, it can be peeled off.

(Example) Example 1 10% by weight of NN diethyl-m-toluamide as a repellent was added to a diisocyanate prepolymer having a molecular weight of 2370 having a polycaprolactone chain as a segment chain (Sample No. 1), 15 The mixture added with wt% (Sample No. 2) was kneaded into a paste and immediately put in a closed container.

These were coated on a glass plate in a heat of about 3 mm and the curing time was measured. After about 12 hours, it was completely cured. Table 1 shows the results of measuring the time-dependent drug residual ratio of each of the cured coatings.

The residual ratio was measured by extracting the drug with acetone and quantifying it by gas chromatography.

From Table 1, it can be seen that the pest control material of the present invention controls the release of the drug over a long period of time.

Example 2) NN-diethyl-m-toluamide was added as a repellent to a diisocyanate prepolymer having a molecular weight of 2000 and having a polytetramethylene glycol chain in the segment chain.
10 wt% was added and kneaded to form a paste, which was packed in a tube to obtain a pest control material. The repellent effect of this pest control material on cockroaches was examined by the following method. A 1 m x 20 cm vinyl chloride plate was coated with this pest control material to a thickness of 2 mm, and used as a test sample. On the other hand, a 1 m × 20 cm vinyl chloride plate coated with a heat of 2 mm was prepared for comparison by using a paste containing no repellent. And the bat shown in the figure (1m x 1m x 80cm depth)
A plate (T) coated with a repellent-containing paste and a plate (C) coated with a repellent-free paste were set on both ends of (A).

A partition (B) was provided at the center of the bat, and a passage (b) having a width of 10 cm and a height of 5 cm was provided below the center.
Leave 30 cockroaches in the center of the bulkhead (B).
% Of cockroaches on the plate (C) side after time
It is expressed as and is the repellent rate. The test results are shown in Table 2.

As is clear from the above results, the pest control material of the present invention has a long-lasting repellent effect on cockroaches.

Example 3) A diisocyanate prepolymer having a molecular weight of 1250 having a tetramethylene glycol polymer in a segment chain and a diisocyanate prepolymer having a molecular weight of 2300 having a polycaprolactone chain in a segment chain are used in a weight ratio of 2
Mixed at a ratio of 1: 1. Next, add N-N.diethyl-m-toluamide as a repellent and dimethyl-4-nitro-m-tolylphosphorothioate as an insecticide in an amount of 10% by weight and 2% by weight, respectively, to make a paste, and put it in a closed container. Stuffed.

The insecticidal effect of this paste on the mites, Plutella xylostella, was examined by the following method.

First, add the mite to a mite breeding medium and the density is about 70
Adjust to 0 medium / g medium. 50 g of this is collected in a petri dish (250 ml). Two petri dishes were prepared, and one of the petri dishes was coated with the above paste-like material to a thickness of about 0.5 mm. The other petri dish is used as a comparative example without being treated. Each petri dish was placed at 25 ° C.-75% RH-dark place, and after 2 weeks and 1 month, the taken-out mite density was examined. The results are shown in Table 3.

As is clear from the above results, the pest control material of the present invention can maintain a remarkable insecticidal effect for a long period of time. As described above, from Examples 1 and 2, the pest control material of the present invention can sustain the release of the pest repellent for a long period of time by gradually changing the degree of compatibility between the diisocyanate prepolymer and the pest repellent. , Its repellent effect is also effective for a long period of time. Furthermore, from Example 3, the pest control material of the present invention, when added with an insect repellent or a pesticide that dissolves in a carrier material, the pesticide acts as a carrier for the pesticide or fungicide, Since a small amount of insecticide or fungicide can be constantly exuded, a remarkable insecticidal effect can be exerted for a long period of time. In addition, all the pest control materials used in the examples cure within 12 hours after application. Furthermore, what was stored in a closed container and stored did not cure even after 6 months, and no change with time was observed.

(Effect) As described above, since the pest control material of the present invention is in the form of a paste, it is easy to fill in the gaps where cockroaches and other pests come in and go out, and it is necessary to apply it under or around precision equipment or vending equipment. Easy and extremely easy to handle. And the pest control material that is applied or filled in a small gap reacts with moisture in the air and hardens over time, so
Even if a hand or an object touches it later, there is an advantage that the control material does not stick to the surface.

In addition, since a suitable amount of the drug is released for a long period of time, the controlling effect is long, but if the thickness of the coating film is increased, the controlling effect can be maintained for a longer period of time. Further, since the pest control material of the present invention is excellent in the peeling property of the coating film, it can be easily removed after use, and there is an advantage that the re-application work can be easily performed.

[Brief description of drawings]

 The drawing is a plan view of the bat. A: bat, B: bulkhead, b ... passage, C, T ... plate.

Claims (4)

[Claims] 1. A paste-like pest control material obtained by kneading a pest control agent and a diisocyanate prepolymer having an ether bond or an ester bond. 2. A diisocyanate prepolymer in which a segment chain of the diisocyanate prepolymer has an ether bond represented by the general formula (CH ₂ ) _m —O _n and m is 3 to 5, n
Is 10 to 25 and the molecular weight is in the range of 700 to 2000. The paste-like pest control material according to claim 1. 3. A diisocyanate prepolymer in which a segment chain of the diisocyanate prepolymer has an ester bond represented by the general formula (CH ₂ ) _m —COO _n and m is 3 to 5,
The paste-like pest control material according to claim 1, wherein n is 10 to 25 and the molecular weight is 1200 to 2500. 4. The paste according to claim 1, wherein the diisocyanate prepolymer is a mixture of the diisocyanate prepolymer according to claim 2 and the diisocyanate prepolymer according to claim 3. Pest control material.