JPH0542991B2 - - Google Patents

Description

[Detailed description of the invention]

(a) Industrial Application Field The present invention relates to a rat-proofing adhesive. (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, even though the seriousness and scale of the damage caused by rats was recognized, measures to exterminate them were largely ignored, partly due to their inconvenience. 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, black rats that can survive for more than 100 days on warfarin-poisoned bait are also being threatened. In the 1950s, adhesive rat traps and ultrasonic rat deterrents were developed, but they were not fully satisfactory. The main types of rodent damage are damage to packaging materials such as paper or cloth bags for rice and wheat grain, damage to cardboard cases for packaging various foods, and damage to flexible containers made of PVC or rubber. has become a prominent problem. In addition, electric leakage fires due to rat ingestion of computers and related communication/power/optical communication cables, signal cables, and other electric wires/cables, machine down or abnormal operation, or business or urination inside the machine. Derailment due to excrement, poor contact, partial corrosion, etc. occur, and the current situation is that it is particularly difficult to detect the defective parts of poor contact and corrosion. In recent years, as has been frequently reported in newspapers and other publications, household LP gas pipes have been eaten by rats and people have been killed or injured due to explosions caused by gas leaks. The demand for products that can be used is also increasing. As a rodent-proofing method for various molded products such as electric wires, cables, hoses, pipes, tubes, tapes, and sheets, rat repellents are added to resin layers (e.g., cable sheaths) used as protective layers and insulating layers for these molded products. A method of kneading a rat repellent is commonly used, and examples of such rat repellents include the following structural formula: Cycloheximide (hereinafter abbreviated as CHI) represented by
It has been known. However, due to its properties, cycloheximide has drawbacks in terms of water resistance, resistance to various chemicals, and handling safety.Additionally, CHI itself is expensive, so it is difficult to obtain rat-proof processed products easily and economically. I couldn't do it. (c) Problems to be solved by the invention In rodent-proof adhesives in which CHI is directly added, dispersed, or kneaded into various adhesives or pressure-sensitive adhesives, the main component of the adhesive or pressure-sensitive adhesive or other various additives or curing In many cases, CHI is degraded by the agent. Furthermore, even if they can be successfully added to adhesives or adhesives, depending on their type, they may be decomposed during the heating process during curing or deactivated due to chemical reactions, so excess CHI required. Furthermore, CHI may bleed through the adhesive or adhesive resin layer and fall off or be absorbed by the rodent-proof object.
There is a phenomenon in which the concentration of CHI drops below the level at which it exhibits its rat-proofing effect. Also, since CHI is not water resistant, when used outdoors, rain may damage CHI.
is eluted, and it has not been possible to obtain a product that is satisfactory both over time and economically, and has not been commercialized. (d) Means and action for solving the problem In order to solve the problem, the present inventors, as a result of intensive research, have made CHI into microcapsules.
It has been discovered that when incorporated into an adhesive or pressure-sensitive adhesive, the adhesive or pressure-sensitive adhesive exhibits a strong rodent-repelling effect for a long period of time, and that CHI is stable even when subjected to various processing, and the present invention I was able to complete it. That is, in the present invention, cycloheximide is applied to microcapsules at a rate of about 0.25 to 50 W/W, preferably about
0.5~30W/w%, more preferably about 2~
This invention relates to a rat-proofing adhesive comprising microcapsules whose core material is a solution containing 20 W/W% and whose core material is covered with a wall material. In the rodent-proof adhesive of the present invention, the adhesive containing CHI microcapsules is not particularly limited. For example, there are synthetic adhesives by composition, including resin adhesives such as urea resin, phenol resin, resorcinol resin, epoxy resin,
Polyurethane, polyamide, vinyl acetate resin, vinyl chloride resin, polyvinyl alcohol, acrylic resin, and rubber adhesives include chloroprene,
There are nitrile rubber, SBR, natural rubber, recycled rubber, butyl rubber, polysulfide, and silicone rubber. In addition, starch can be used as a natural adhesive. Further examples include polyisobutylene, polyvinyl ether, chlorinated rubber, cellulose, and asphalt adhesives. Among these, Uniar resin, melamine resin, and phenol resin adhesives, which are produced in large quantities, as well as vinyl acetate resin adhesives and synthetic rubber adhesives, are particularly suitable. In practical use, solvents, plasticizers, resins, thickeners, fillers, pigments, preservatives, anti-aging agents, antifoaming agents and other desired additives are mixed or added to these adhesives. It's okay. The CHI microcapsules used in the present invention may be those obtained by the method described below. The rat-proof adhesive, which contains CHI microcapsules by mixing and dispersing CHI microcapsules in each of the above adhesives, can be used as is for adhering wall cloths and other architectural interior materials, pasting paper bags together, flexible containers, etc. Glue the PVC sheet that will be
It can be used as a rat-proof bag or a rat-proof container, and it can also be used as a rat-proof adhesive tape by kneading it into an adhesive that is normally sticky and coating it on a PVC sheet. Furthermore, the product dispersed or impregnated in a sealant can be used as it is for crack repair and as a rodent-proofing sealant for joints. The CHI-containing 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 CHI was dissolved in and a wall film was formed by methods such as interfacial polymerization method, in situ method, coacelbasian method, in-liquid curing coating method (orifice method), in-liquid drying method, and spray/granulation method. Microcapsules are preferred. Examples of 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, and amyl. Ethers such as ether, hexyl ether, ethyl vinyl ether, cellosolve, and carbitol; Aliphatic and aromatic hydrocarbons such as hexane, heptane, octane, benzene, toluene, xylene, and cyclohexane; Mineral oils such as kerosene, diesel oil, and paraffin oil ; Esters such as acetate, propylonate, butyrate, lactic acid, oxalate, crotonate, salicylate, benzoate, phthalate, adipate, sebacate, phosphate; low Examples include molecular weight epoxy resins. Furthermore, due to the stability of CHI's potency and/or the capsule production method and/or the form of use of CHI-containing capsules, the solvent must have a high boiling point, non-volatility,
When hydrophobicity is a requirement, 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.
Phthalate esters such as ethylhexyl, ditridecyl phthalate, and dinoraralkyl phthalate; adipate esters such as diisobutyl adipate and dioctyl adipate; dibenzyl sebacate;
Sebacic acid esters such as dioctyl sebacate;
It is preferable to select from phosphoric acid esters such as triphenyl phosphate, tricresyl phosphate, trioctyl phosphate, and 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 815,
Low molecular weight epoxy resins such as "816, 818" (manufactured by Ciel Kagaku Co., Ltd., trade name) are preferred. The content of CHI in the above various solvents is approximately 0.25 to 50 W/W%, preferably approximately
A suitable amount is 0.5 to 30 W/W%, and preferably about 2 to 20 W/W% from the viewpoint of economy and effectiveness. On the other hand, the capsule wall that microencapsulates the CHI solution is made of a polymeric material formed using reactive materials such as monomers or low-molecular-weight prepolymers. Resins such as melamine resin, urea, melamine mixed resin, phenolic 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. When using the rodent-proof adhesive of the present invention as a regular material, the main component of the adhesive may be selected depending on the material to be bonded, and may be dispersed and mixed during the adhesive preparation process, or CHI microcapsules may be added during use. It may be used by adding it. In addition, when using it in the form of an adhesive layer such as tape or tack paper, apply it to the adhesive in advance.
After kneading a predetermined amount of CHI-containing microcapsules, form an adhesive layer or heat-adhesive layer on a material such as plastic paper by coating, form it into a tape shape or tack paper shape, and wrap it around a desired object. It can be used by pasting it on. If these are used, rodent-proof electric wires and rodent-proof hoses can be easily made by wrapping them around electric wires, gas rubber hoses, etc. that have not been subjected to rodent-proofing treatment in advance.
Additionally, wrapping young trees with tape treated with rodent-repellent adhesive is a perfect way to prevent orchards from being eaten by rodents during snowfall. Furthermore, when using it as a sealant, for example, the main raw materials are liquid coloring agents such as oil, polybutene, and alkyd resin, and mineral fillers such as calcium carbonate asbestos, and these are thoroughly mixed with CHI microcapsules. I can do that. For these rodent-proof adhesives, the amount of CHI applied is approx.
It is sufficient to apply 0.05 to 3 g/m ² , preferably about 0.1 to 1.7 g/m ² , more preferably about 0.3 g to 0.7 g/m ² , depending on the CHI concentration of CHI microcapsules, the amount of adhesive applied, and the adhesive strength. The content of CHI microcapsules may be determined appropriately by taking these into consideration. (E) Examples The present invention will be explained in more detail below using Examples and Experimental Examples. Note that the CHI microcapsules used in the Examples were prepared according to Reference Examples. Reference Example 12 g of CHI [trade name: Naramycin, manufactured by Tanabe Seiyaku Co., Ltd.] and 13 g of terephthalic acid chloride are dissolved 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 water 80
Prepare Solution B by dissolving 4 g of sodium carbonate and 8 g of diethylenetriamine in g. Above O/W
Slowly adding liquid B to the emulsion while stirring, the stirring reaction was continued for 24 hours to obtain 8% CHI-containing microcapsules having polyamide walls. Similarly, 15%, 10%, and 2% CHI-containing microcapsules were obtained. Example 1 CHI microcapsules were added to a natural rubber adhesive for sealing bags and paper containers based on the following formulation, and thoroughly stirred and mixed to obtain a rat-proofing adhesive. Prescription weight part Esdyne natural rubber adhesive for sealing bags and paper containers
114'' (manufactured by Sekisui Chemical Co., Ltd., trade name, solid content 44%) 100 8% CHI microcapsules 28 Example 2 Based on the following formulation, CHI microcapsules and curing agent were added to a synthetic rubber adhesive for soft PVC. Add
The mixture was sufficiently stirred and mixed to obtain a rat-proofing adhesive. Prescription weight part Synthetic rubber adhesive for soft PVC "ESDINE"
277MPU” (manufactured by Sekisui Chemical Co., Ltd., product name, solid content 18%)
100 Curing agent (for Esdyne 277MPU) 3 15% CHI microcapsules 14 Example 3 A rat-proofing adhesive was obtained in the same manner as in Example 1 based on the following formulation. Prescription weight part Vinyl acetate resin adhesive for paper "ESDINE 5100"
(Manufactured by Sekisui Chemical Co., Ltd., trade name, solid content 45%) 100 10% CHI microcapsules 20 Example 4 A rat-proofing adhesive was obtained in the same manner as in Example 2 based on the following formulation. Part by weight of prescription Epoxy resin adhesive for leather bonding "ESDINE"
3120'' (manufactured by Sekisui Chemical Co., Ltd., trade name, solid content 97%) 100 Hardening agent (for Esudine 3120) 100 10% CHI microcapsules 50 Example 5 Based on the following formulation, butyl rubber architectural sealer, CHI microcapsules were added and sufficiently dispersed to prepare a rat-proof building sealer. Prescription weight: Butyl rubber architectural sealer “ESDINE 680”
(Manufactured by Sekisui Chemical Co., Ltd., trade name, solid content 75%) 100 2% CHI microcapsules 15 Example 6 CHI microcapsules were dispersed and mixed in an acrylic resin adhesive for adhesive processing according to the following recipe, Obtained a rat-proof adhesive. Part by weight of prescription Acrylic resin adhesive for adhesive processing "ESDINE"
395c'' (manufactured by Sekisui Chemical Co., Ltd., trade name, solid content 40%) 100 15% CHI microcapsules 20 Comparative Examples 1 to 6 CHI crystals were used in place of the CHI microcapsules used in Examples 1 to 6, respectively. 1.78, 1.87, 1.70,
Added 4.08, 0.26, and 2.56 parts by weight, and as in the example,
We obtained a rat-proofing adhesive, a rat-proofing sealer, and a rat-proofing adhesive. Experimental example 1 CHI stability in cured rodent-proof adhesive film. (Method 1) A cured film of the rat-proof adhesive of Examples 1 to 4 and Comparative Examples 1 to 4 was formed, and after being left at 50°C and 85% relative humidity for 3 weeks, about 1 g of the film was crushed in an agate mortar. Further, it is pulverized using a cell disruptor. Approximately 0.5g of this sample
Add 10 ml of acetone to the water, leave it for 24 hours, add 10 ml of methanol, heat it at 70℃ for 1 hour, and use the filtrate as a sample according to the official pesticide inspection method (for drugs containing CHI as the main component). The amount of CHI was measured.

[Table] (Method 2) A cured sealer and adhesive layer of the rodent-proof adhesives of Examples 5 and 6 and Comparative Examples 5 and 6 were formed, and the temperature was 50°C and the relative humidity was 85°C.
After leaving it for 3 weeks under %, add about 1g of the sample to 10ml of acetone.
was added and left for 24 hours, then 10 ml of methanol was added, heated to 70°C, and left to stand for 1 hour.The filtrate was used as a sample and tested using the official pesticide testing method (preparations containing CHI as the main ingredient).
The amount of CHI was measured according to the following.

[Table] Experimental Example 2 Mouse-repelling effect of rat-proofing adhesive processed products (Method 1) Using the rat-proofing adhesives of Examples 1 to 4 and Comparative Examples 1 to 4, rat-proofing sheets were prepared in the following manner. ,50℃
After standing under a relative humidity of 85%, the sheet was cut into 75 x 150 mm, wrapped around two pieces of solid food for rats, and stapled around the edges to be used as a sample. This sample is 24
The cage was placed overnight in a breeding cage containing three wild black rats weighing around 500 g that had been fasted for an hour, and then taken out and examined for feeding damage. <Preparation of rat-proofing sheet> Rat-proofing adhesives prepared in Examples 1 and 3 and Comparative Examples 1 and 3 and bags/paper container seals used in Examples 1 and 3 and Comparative Examples 1 and 3 as Controls 1 and 3 A natural rubber adhesive for paper and a vinyl acetate adhesive for paper were applied wet to high-quality paper (50 kg) using a wire bar to a coating amount of 30 g/ ^m2 , respectively, and then air-dried. A rat-proof treated paper and a control treated paper were prepared by pressure bonding. The rodent-proof adhesive prepared in Example 2 and Comparative Example 2 and the synthetic rubber adhesive for soft PVC used in Example 2 and Comparative Example 2 as Control 2 were coated with a wire bar at a coating amount of 30 g/m ^{2 .} The solution was applied to a soft PVC sheet with a thickness of 0.5 mm, and after air-drying for 30 minutes, a soft PVC sheet with the same thickness of 0.5 mm was attached to prepare a rat-proof PVC sheet and a control PVC sheet. The rat-proofing adhesive prepared in Example 4 and Comparative Example 4 and the epoxy resin adhesive for leather adhesion used in Example 4 and Comparative Example 4 as Control 4 were coated with a wire bar at a coating amount of 25 g/m ^{2 .} A rat-proof leather sheet and a control leather sheet were prepared by applying pressure to cowhide having a thickness of 0.5 mm, and applying pressure to the cowhide having a thickness of 0.5 mm.

【table】

[Table] (Method 2) Rodent-proof adhesive of Example 5, Comparative Example 5 and Control Example 5
The butyl rubber construction sealer used in Example 5 and Comparative Example 5 was used to fill the holes in three aluminum partition plates, each with a circular hole through which a mouse could pass.
Leave for 3 weeks at 50℃ relative temperature 85%. Example 5,
Partition plates created for Comparative Example 5 and Target 5 sealer are referred to as A, B, and C, respectively. The partition plate is placed inside the mouse cage, and the space between the mouse and the sample is partitioned in series with the mouse and the food. At that time, the order in which partition plates A, B, and C are left in place is changed, and the state of barrier destruction when heading toward the feed is examined. The black rats used in the test, weighing around 500g, were made to learn to go through the holes in the partition plate to eat food, and were kept fasted for 24 hours before the test.

[Table] (Method 3) The rodent-proofing adhesives of Example 6 and Comparative Example 6 and the acrylic resin adhesive for adhesive processing used in Example 6 and Comparative Example 6 as Control 6 were coated with a wire bar until the applied amount was solid. The mixture was applied to a 0.1 mm soft PVC sheet at a concentration of 20 g/m ^{2 per} minute, and air-dried for 10 minutes or more to prepare rat-proof adhesive tape and adhesive tape. Using that tape,
It was wrapped around a PVC cable and left at 50°C with a relative humidity of 85% or less for 3 weeks before being used as a sample. This sample was placed overnight in a breeding cage containing one wild rat weighing around 500 g that had been fasted for 24 hours, and then removed from the PVC
Checked the cable for damage.

[Table] Experimental Example 3 Results of rat-proof adhesive processed products prepared in Method 1 of Example 2, Method 2 of Example 6, Comparative Examples 2 and 6, and soft PVC sheets and adhesive tapes that are adhesive processed products.
Storage stability of CHI. (Method) The above PVC sheet and adhesive sheet were heated at 50℃ relative humidity.
CHI was quantified under the condition of 85% in accordance with the method shown in Experimental Example 1 in order to examine the storage stability in the adhesive layer or adhesive layer.

[Table] (F) Effects of the Invention Since the rodent-proofing resin adhesive of the present invention contains a microcapsule preparation whose core material is a solution containing CHI, the rodent-proofing adhesive itself is excellent. It has a rat-proofing effect. Therefore, it can be used as a rat-proof material or applied to various rat-proof objects.
It can be widely used by impregnating it and pasting it together, filling gaps, or wrapping it around objects in the form of adhesive tape. In addition, the core material of the microencapsulated formulation is CHI
Since it is a solution, when a mouse chews it, it diffuses into the saliva extremely quickly and the taste is effective, so the repellent effect itself is improved compared to the conventional one using CHI crystals. For example, the content itself can be significantly reduced compared to when crystals are used. Furthermore, since the rodent-proof adhesive uses CHI's microencapsulated formulation, it can be dispersed into the adhesive and
During mixing and kneading, the titer of CHI does not decrease due to volatile water and other solvents contained in the adhesive. Furthermore, the CHI can be safely protected from the curing agent in adhesives where a curing agent must be added or from heat in adhesives which must be heat cured. Therefore, there is no need to predict the decomposition of CHI under the conditions mentioned above and to prepare an excessive amount, which not only improves economic efficiency, but also allows use in adhesives that have not been applicable to CHI crystals until now.

Claims (1)

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