JPH0545630B2 - - Google Patents

Description

[Detailed description of the invention]

(a) Industrial Application Field The present invention relates to a rat-proofing paint. (b) Conventional technology The number of rats in Japan is three times the population, or 3
It is said that there are 100,000,000 of them, and the damage caused will reach more than 100 billion yen each year. However, although the seriousness and magnitude of the damage caused by rats had been confirmed, measures to exterminate them were largely ignored, partly due to the difficulty involved. Looking back at the history of the main methods of extermination, it began with yellow phosphorus poison Dango (which is also poisonous to pets) in the 1950s, and the rodenticide Warfuarin was introduced in the 1960s and had great effects. However, living organisms always develop immunity to these drugs. Currently, some black rats are surviving for more than 100 days on poisoned food containing warfarin. Adhesive rat traps and ultrasonic rat deterrents were developed in the 1950s, but they were not sufficiently effective. The main types of rodent damage include damage to paper or cloth bags for rice and wheat grains related to packaging materials, damage to cardboard cases for packaging various foods, and damage to flexible containers made of PVC or rubber. The damage is significant and has become a problem. Furthermore, electric leakage fires caused by rats eating computers and related communication, power, optical communication cables, communication cables, and other electric wires and cables, machine down or abnormal operation, nesting or urination inside machines, Wire breakage, poor contact, and partial corrosion occur due to excrement, and the current situation is that it is difficult to detect the defective locations of poor contact and corrosion. As has been reported in newspapers and other publications in recent years, household LP gas pipes have been eaten away by rats.
Explosions caused by gas leaks have resulted in deaths and injuries, and there is a growing demand for easy rat-proof secondary processing for various processed products. As a rodent-proofing method for various molded products such as electric wires, cables, hoses, pipes, tubes, tapes, and sheets, a rat-repellent coating is added to the resin layer (e.g., cable sheath) used as a protective layer or insulating layer of these molded products. A method of kneading a rat repellent is commonly used, and such a rat repellent has, for example, the following structural formula: Cycloheximide (hereinafter abbreviated as CHI) represented by
It has been known. However, due to its nature, cycloheximide has drawbacks in terms of water resistance, various chemical resistance, and handling safety, and in addition, CHI itself is expensive, making it difficult to easily and economically obtain rat-proof processed products. Nakatsuta. (c) Problems to be solved by the invention In rat-proof paints in which CHI is directly added, dispersed, or kneaded into various paints, CHI can be absorbed by the main film-forming elements, other sub-element forming films, or pigments.
There are many cases where it disintegrates. Furthermore, even if CHI can be successfully added to paints, depending on the type of CHI, it may be decomposed during the heating process during paint film formation or deactivated due to chemical reactions, so a large amount of CHI must be added in advance to account for the loss. I need. Furthermore, a phenomenon was observed in which CHI bleeds from the coating resin layer, falls off or is absorbed by the rat-proofing object, and the concentration drops below the level at which CHI exhibits its rat-proofing effect. Furthermore, since CHI is not water resistant, when used outdoors, CHI is eluted by rain, making it impossible to obtain a product that satisfies both over time and economically. (d) Means and action for solving the problem In order to solve the problem, the present inventors have conducted extensive research and found that when CHI is microencapsulated and incorporated into a paint, the paint , exhibits strong rodent-repellent effects over a long period of time, even when subjected to various treatments.
They discovered that CHI is stable and completed the present invention. That is, in the present invention, cycloheximide is added to the microcapsules in an amount of about 0.25 to 50 W/W%, preferably about
0.5~30W/W%, more preferably about 2~
This is a rat-proofing paint containing microcapsules in which a solution containing 20 W/W% is used as a core material and the core material is covered with a wall material. In the rat-proof paint of the present invention, the paint containing CHI microcapsules is not particularly limited. For example, if we look at the classification based on raw materials, we can see oil-based paints, alcoholic paints, cellulose paints, synthetic resin paints,
There are water-based paints, lacquer-based paints, and rubber-based paints; oil-based paints include boiled oil, oil paint, oil varnish, and enamel; alcoholic paints include natural resin varnishes, synthetic resin varnishes, and cellulose paints include clear lacquer and lacquer. Car enamel, synthetic resin paints include water-based paint varnish, synthetic resin enamel, emulsion polymerization paint, water-based paint includes water-based paint, emulsion oil paint, emulsion polymerization paint, lacquer-based paint includes lacquer, cashew varnish,
Rubber paints include chlorinated rubber paint, cyclized rubber paint,
There are synthetic rubber paints such as SBR. Among these, synthetic resin varnishes can be mentioned in particular, including phenolic resin varnishes, phthalic acid resin varnishes, maleic acid resin varnishes, urea resin varnishes, melamine resin varnishes, vinyl resin varnishes, epoxy resin varnishes, and silicone resin varnishes. There are varnishes, furan resin varnishes, and polyester resin varnishes. Among these, vinyl resin varnishes are particularly useful, and include vinyl acetate resin varnishes, vinyl chloride vinyl acetate copolymer varnishes, styrene resin varnishes, acrylic acid resin varnishes, polyvinyl butyral varnishes, and the like. In practical use, these paints contain plasticizers, desiccants, hardeners, dispersants, anti-skinning agents, thickeners, flattening agents, anti-sag agents, and anti-mildew agents as film-forming subelements. A UV absorber, a UV absorber, or a pigment may be mixed or added. The rat repellent pigment, which contains CHI microcapsules by mixing and dispersing them in each of the above paints, can be used as is for communication, signal, power, electric cable coatings, PVC sheets used for flexible containers, etc., paper bags, walls, etc. It can be applied to cloth or architectural interior materials and used as rat-proof cables, rat-proof flexible containers, rat-proof paper bags, rat-proof cloth, or rat-proof interior materials, respectively. The CHI microcapsules used in the present invention are not particularly limited as long as they are microcapsules containing a CHI solution dissolved in a suitable solvent, but for example, an organic solvent that is inert to CHI and has an appropriate solubility Dissolved in, interfacial polymerization method, in
Microcapsules in which a wall film is formed by a method such as an in-situ method, a coacervation method, an in-liquid curing coating method (orifice method), an in-liquid drying method, or a spraying/granulation method are preferred. Such organic solvents include alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, and butyl alcohol; ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), ethyl butyl ketone, and cyclohexanone; ethyl ether, butyl ether, Ethers such as amyl ether, hexyl ether, ethyl vinyl ether, cellosolve, and carbitol; Aliphatic and aromatic hydrocarbons such as hexane, heptane, octane, benzene, toluene, xylene, and cyclohexane; Kerosene, light oil, paraffin oil, etc. Mineral oils; esters such as acetate, propionate, butyrate, lactic acid, oxalate, crotonate, salicylate, benzoate, phthalate, adipate, sebacate, phosphate; Examples include low molecular weight epoxy resins. Furthermore, due to the strength stability of CHI, during the capsule production process, and the usage form of CHI-containing capsules,
When the solvent is required to have a high boiling point, non-volatility, hydrophobicity, etc., the above-mentioned esters or low molecular weight epoxy resins may be used as the solvent. The esters used in this case include dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diheptyl phthalate, dioctyl phthalate, diisodecyl phthalate, butylbenzyl phthalate, dimethyl isophthalate, and di-2-phthalate.
Ethylhexyl, ditridecyl phthalate, dinormal alkyl phthalate, etc.; adipate esters such as diisobutyl adipate, dioctyl adipate, sebacic acid esters such as dibenzyl sebacate, dioctyl sebacate; triphenyl phosphate, tricresyl phosphate, trioctyl phosphate ,
Preferably, it is selected from phosphoric acid esters such as octyl diphenyl phosphate. In addition, as a low molecular weight epoxy resin, the molecular weight
Epoxy resins with a molecular weight of 400 or less are preferable, and examples of such epoxy resins include "Epicote"
There are epoxy resins such as "815, 816, 818" (product name; manufactured by Ciel Chemical Co., Ltd.). The content of CHI in the above-mentioned various solvents is suitably about 0.25 to 50 W/W%, preferably about 0.5 to 30 W/W%, based on the microcapsules. 2 to 20 W/W% is preferable. On the other hand, the capsule wall that microencapsulates the CHI solution is composed of a polymeric material formed using reactive materials such as monomers or low molecular weight prepolymers, and from the viewpoint of not losing the medicinal efficacy of CHI, urea resin, Resins such as melamine resin, urea/melamine mixed resin, phenol resin, polyamide, polyester, polyurea, polyurethane, etc. are suitable. Such a wall material is appropriately employed in consideration of various conditions, economic efficiency, etc. when the encapsulated preparation is used. To obtain a rat-proof product by applying the rat-proof paint to a rat-proof object, a commonly used coating method may be used, such as brushing, spraying, electrostatic coating, electrodeposition, or screen printing. The coating may be applied by applying a printing technique such as, or by applying various coating machines such as a blade coater, gravure coater, or air knife coater. For these rat-proof paints, the amount of CHI applied is
It is sufficient to apply about 0.05 to 2.0 g/m ² , preferably about 0.10 to 0.7 g/m ² , more preferably about 0.2 to 0.5
It is sufficient to apply g/ ^m2 , and the economical efficiency of the paint (coating amount)
Considering the function of the coating film, the CHI content of CHI microcapsules and the time when adding or dispersing them to the coating are determined as appropriate.
The CHI microcapsule content may be determined. (e) Examples The present invention will be explained in more detail below with reference to Examples and Experimental Examples. Note that the CHI microcapsules used in the examples were prepared according to the reference example. Reference Example Dissolve 12 g of CHI (trade name: Naramycin, manufactured by Tanabe Seiyaku) and 13 g of terephthalic acid chloride in 120 g of dimethyl phthalate to obtain Solution A. Emulsify Solution A in 300 g of 2% PVA (polyvinyl alcohol) aqueous solution to prepare an O/W emulsion. Meanwhile, 80g of water
4g of sodium carbonate and 8g of diethylenetriamine
Prepare solution B by dissolving g. While stirring the above O/W emulsion, the solution B was slowly added, and the stirring reaction was continued for 24 hours to obtain 8% CHI-containing microcapsules having polyamide walls. In the same manner, 15% and 1.5% CHI-containing microcapsules were obtained. Example 1 Paint for processing PVC tarpaulin for flexible containers

[Table] A polyvinyl chloride composition with the following formulation was calendered to a thickness of 1 mm using a polyester base fabric as an interlining. On one side of a flexible container tarpaulin, a rat-proofing paint with the formulation of Example 1 was applied to the tarpaulin while stirring. A tarpaulin for a rodent-proof flexible container was obtained by gravure coating 13 g per m ² of area and drying at 80° C. for 2 minutes. Vinyl chloride composition Polyvinyl chloride (average degree of polymerization 1450) 100 parts by weight Dioctyl phthalate 25 〃 Dibutyl phthalate 20 〃 Chlorinated paraffin 10 〃 Basic lead carbonate 5 〃 Lead stearate 1 〃 Experimental example 1 (1) Rodent control on PVC flexible container tarpaulin
Storage stability of CHI <Method> The same formulation as in Example 1, excluding CHI microcapsules (Control Example 1), and containing 2% CHI crystals in place of CHI microcapsules (Control Example 2) ), rat-proof PVC obtained by applying rat-proof coating in the same manner as in Example 1 for those containing 3% of the same CHI crystals (Control Example 3).
Regarding tarpaulin, storage stability on PVC tarpaulin under conditions of 50°C and 85% relative humidity was investigated. <Results> The results are shown in Table 1.

[Table] CHI provisional measurement method: Add 10 ml of acetone to 1 g of rodent-proof tarpaulin, let it stand at room temperature for 24 hours, then add 10 ml of methanol, warm it to 70°C, let it stand for 1 hour, and then use the liquid as a sample and use the official pesticide inspection method. (For preparations containing CHI as the main ingredient) (the same applies hereinafter). (2) Rat repellent effect of rat-proof PVC flexible container tarpaulin <Method> The tarpaulin obtained in (1) above was cut into 75 x 150 mm.
Wrap two pieces of solid food for rats with this and staple around the periphery to use as a sample. This sample was placed overnight in a breeding cage containing three Wistar rats weighing approximately 500 g that had been fasted for 24 hours, and then taken out and the state of feeding damage was examined. Five breeding cages were used. <Results> The results are shown in Table 2 below.

[Table] (3) Transfer of CHI to PVC flexible container tarpaulin <Method> After leaving the tarpaulin obtained in (1) above at room temperature,
The amount of CHI transferred to the tarpaulin body was measured. <Results> The results were as shown in Table 3 below.

[Table] CHI provisional measurement method: After contacting the specimen with the surface of the medium containing the test bacterium Satucharomyces cerevisiae for 5 minutes,
The amount of CHI was determined from the area of the inhibition zone generated on the surface of the culture medium after culturing for a period of time. (4) Water resistance of CHI of rat-proof PVC flexible container tarpaulin <Method> A 100 x 100 mm piece was taken from each tarpaulin obtained in (1) above, and this was cut into four pieces as samples.
Pour into a 200ml beaker and add 100ml of water to 30°C.
5 ml of immersion water was collected over time in a constant temperature water bath at 50°C, and the amount of CHI eluted into the water was measured. The amount of CHI on the tarpaulin was determined in accordance with (1) above. <Results> The results are shown in Table 4 below.

【table】 Example 2 PVC coated cable outdoor rat proof paint

[Table] Le

[Table] Three control cables each having a conductor with 7 strands and a core diameter of 3.5 mm and an insulating layer made of a polyvinyl chloride composition coated with a thickness of 1.0 mm are twisted together, and a conductor with a core diameter of 3.5 mm is twisted together.
The surface of the cable coated with a 1.5 mm protective layer of polyvinyl chloride of the following formulation was coated with a rodent-proofing paint of the formulation of Example 2 at 150 g per m ² of the cable surface.
Apply with hand spray so that (4 applications)
A rat-proof PVC coated cable was obtained. Polyvinyl chloride (average degree of polymerization 300) 100 parts by weight Dioctyl phthalate 50 〃 Polymerized organotin mercapto compound 5 〃 Lead stearate 1 〃 Experimental example 2 (1) Storage stability of CHI on rodent-proof PVC coated cable <Method> Same formulation as Example 2, excluding CHI microcapsules (Control Example 1), 8% CHI
13.4% 1.5% CHI microcapsules instead of microcapsules (Control Example 2), 8%
0.2% CHI crystals instead of CHI microcapsules
Regarding the compounded product (Comparative Example 3), rat-proof PVC coated cables obtained by applying rat-proof coating in the same manner as in Example 2 were tested at 50°C relative humidity.
on PVC coated cable under 85% condition
The storage stability of CHI was investigated. <Results> The results are shown in Table 5 below.

[Table] CHI measurement method: According to (1) of Experimental Example 1. (2) Water resistance of CHI on rat-proof PVC coated cables <Method> Cut each PVC coated cable obtained in (1) above into 30 mm lengths, put them in a 200 ml beaker, add 100 ml of water, and boil for 30 minutes.
℃、Put in a constant temperature water bath of 50℃ and soak in water 5 over time.
ml was sampled and the amount of CHI eluted into the water was measured. The amount of remaining CHI on the PVC cable was determined in accordance with (1) above. <Results> The results are shown in Table 6 below.

[Table] (3) Rat-repellent effect of rat-proof PVC coated cable <Method> Each PVC coated cable obtained in (1) above was cut into 200 mm pieces and used as samples. This sample was placed in a breeding cage containing two black rats weighing approximately 400 g along with feed and drinking water for two days, and was removed every 24 hours to observe the exposure rate of the core wire. There are 5 breeding cages
The average was calculated using a cage. <Results> The results are shown in Table 7 below.

【table】 Example 3 General spray anti-mouse paint

[Table] Methyl ether
)152g
CHI content (%) 0.20 0 0.20
0.20
* Average degree of polymerization 200-300
Experimental Example 3 (1) Stability of CHI in aerosol spray paint film on glass surface <Method> Same formulation as Example 3, excluding CHI microcapsules (Control Example 1), 8%
Compounding 13.4% CHI microcapsules instead of 1.5% CHI microcapsules (Control Example 2),
CHI crystals instead of 8% CHI microcapsules
For those containing 0.2% (Comparative Example 3), each was applied at 150 g per 1 m ² of glass plate, dried at room temperature, and then coated on the glass plate at 50°C and 85% relative humidity. The storage stability of CHI in membranes was investigated. <Results> The results are shown in Table 8 below.

【table】

[Table] (2) Rat repellent effect of aerosol spray coating applied to wood chips <Method> Each aerosol spray coating used in (1) above was
x 3 x 10 cm pieces of lauan wood, the surface of the wood piece (138 cm ² )
Approximately 2.1g of the solution was applied to the sample, dried at room temperature, and used as a sample. Three of these samples were placed in a breeding cage containing three Wistar rats weighing approximately 400 g, fed with feed and drinking water, and left for 72 hours. The cages were removed every 24 hours and the rate of weight loss due to feeding damage was measured.
Five breeding cages were used and the average was calculated. <Results> The results are shown in Table 9 below.

【table】 Example 4 Indoor rat-proof paint for PVC coated cables

[Table] On the surface of the PVC coated cable used in Example 2,
After dipping the rodent-proofing paint having the formulation of Example 4 in an amount of 80g per ^m2 of cable surface while stirring (dipping twice), the rodent-proofing PVC coated cable was dried at 80°C for 2 minutes using infrared rays. And so. Experimental Example 4 (1) Rat repellent test on rat-proof PVC coated cable <Method> Same formulation as Example 4, excluding CHI microcapsules (Control Example 1), 8%
0.5% CHI crystals instead of CHI microcapsules
The blended products (Comparative Example 2) were each treated with a rat-proof coating in the same manner as in Example 4.
For PVC coated cables, each cable is 200mm
It was cut into pieces and used as samples. This sample was placed in a breeding cage containing one brown rat weighing 500 g, together with feed and drinking water, for 2 days, and the cage was taken out every 24 hours to observe the exposure rate of the core wire. The breeding cage is
The average was calculated using 10 cages. <Results> The results are shown in Table 10 below.

【table】 Example 5 Mouse-proof paint for paper coating

[Table] Experimental Example 5 (1) Storage stability of CHI in rodent-proof paint for paper coating (Method) Same formulation as in Example 5, except for CHI microcapsules (Control Example 1), CHI micro Regarding the product containing 2% CHI crystals instead of capsules (Control Example 2), 50℃, relative humidity 85%
The storage stability of CHI in each paint was investigated under the following conditions. CHI was measured in accordance with (1) of Experimental Example. <Results> The results are shown in Table 11 below.

【table】

[Table] (2) Rat repellent effect of rat-proof paper coated with rat-proof paint (Method) Each paint used in (1) above was applied to 81 g/ ^m2 of kraft paper.
After applying 15g per ^m2 and drying at room temperature, 75 x 150
Cut into mm pieces, wrap two solid samples for rats with this, and staple the periphery to use as samples. This sample was placed overnight in a breeding cage containing three Wistar rats weighing 400 g that had been fasted for 24 hours, and then taken out and examined for feeding damage. Five breeding cages were used and the average was calculated. <Results> The results are shown in Table 12.

【table】 Example 6 Water-based emulsion rat-proof paint for indoor construction

[Table] Le

[Table] Experimental Example 6 (1) Stability of CHI in aqueous emulsion paint <Method> Same formulation as Example 6, excluding 8% CHI microcapsules (Control Example 1), 8%
1.0 CHI crystals instead of CHI microcapsules
200ml each for those containing % (Comparative Example 2)
was packed in a glass bottle and stored at 30℃, and the
The storage stability of CHI was investigated. <Results> The results are shown in Table 13 below.

[Table] (2) Stability of CHI in water-based emulsion rodent-proof paint film on glass surface <Method> Each paint used in (1) above was applied to a glass plate of 1 m ^{2 .}
After coating in an amount of 30 g per coat and drying at room temperature, the storage stability of CHI in each coating film was examined under conditions of 50° C. and 85% relative temperature. <Results> The results were as shown in Table 14.

[Table] (f) Idea of the invention The rat-proofing paint of the present invention contains a microcapsule preparation with a solution containing CHI as the core material, so the rat-proofing paint itself has an excellent rat-proofing effect. It has the following. Therefore, it can be used as a rat-proofing material or by coating or impregnating various rat-proofing objects. In addition, the core material of the microencapsulated formulation is CHI
Since it is a solution, when a mouse bites it, it diffuses into the sleeping liquid very quickly and its taste is effective, so the repellent effect itself is improved compared to the conventional ones using CHI crystals. For example, the content itself can be significantly reduced compared to when crystals are used. Furthermore, since the rodent repellent paint uses CHI's micro-encapsulated formulation, the resin varnish as the main film-forming element contained in the paint and the sub-element for film formation are absorbed when dispersed, mixed, and added to the paint. Certain additives do not cause a decrease in CHI titer. For paints that require heat treatment during the process of forming a film, CHI can be safely protected from heat. Therefore, it not only improves economic efficiency by predicting the decomposition of CHI under the conditions described above and eliminating the need for excessive preparation, but also allows it to be used in paints that could not be applied to CHI crystals until now, and its applications can be improved. spreads. In addition, since CHI microcapsules are used, there is no possibility that the rodent repellent paint will seep into the object to be coated when applying it, or that it will not leak from the paint layer after the rodent repellent paint film is formed.
Because CHI does not bleed into the object to which it is applied, it has excellent water resistance, chemical resistance, physical irritation resistance, and weather resistance, and maintains excellent rodent repellency over a long period of time. . In addition, safety is improved because CHI's microencapsulated formulation is used, which is advantageous in terms of occupational safety and health during manufacturing and handling, and furthermore, as a molded product, it is advantageous in terms of food hygiene and public health. .

Claims (1)

[Claims] 1. A rat-proof paint comprising microcapsules in which a solution containing cyclohexide is used as a core material and the core material is covered with a wall material.