JPH037213B2 - - Google Patents

Description

[Detailed description of the invention]

(a) Industrial Application Field The present invention relates to a rat-proofing resin composition. (b) Conventional technology The number of rats in Japan is said to be three times the population, or 300 million rats, and the damage caused by rats is approximately 1,000 per year.
It is said that the amount will reach over 100 million yen. However, although the seriousness and magnitude of the damage caused by rats was recognized, measures to exterminate them were largely ignored, partly due to the difficulty involved. 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. In addition, machines may be down or malfunction due to rodent ingestion of computers and related communication/power/optical communication cables, signal cables, and other electric wires/cables, or due to nesting or urinating/defecating inside the machine. Disconnection/poor contact/
Partial corrosion occurs, and the current situation is that it is difficult to detect defective locations, especially when it comes to poor contact and corrosion. As a rodent-proofing method for various molded products such as electric wires, cables, hoses, pipes, tubes, tapes, sheets, etc., it is recommended that the resin layer (for example, cable coating resin layer) used as a protective layer or insulating layer of these molded products be coated with rodents. A method of kneading rat repellents is widely used, and such rat repellents include, for example, the formula () Cycloheximide (CHI) is known. (c) Problems to be solved by the invention However, in rodent-proof molded products in which CHI is directly kneaded into the resin layer constituting the surface of the molded product, the heat (for example, 150 to 200°C) during coating with the resin layer
Due to the influence of by-products (for example, liberated hydrogen chloride when vinyl chloride resin is used), the amount of CHI decomposed is large, and the amount of CHI in the resin layer is
However, due to the action of the plasticizer, the resin bleeds onto the surface of the resin layer over time and is likely to fall off or be chemically decomposed, resulting in a problem in that the rodent repellent effect cannot be maintained for a sufficient period of time. In addition, in the case of vinyl chloride resin that is commonly used for various molded products or their protective layers, if the surface is resin coated or kneaded only into the surface layer, the vinyl chloride resin layer will be damaged by the action of the plasticizer. There was also the problem that it migrated to the inside, making it difficult to retain an effective amount of CHI on the surface. Furthermore, if it is mixed into the entire coating resin layer, a large amount of CHI
This, together with the fact that CHI itself is expensive, was disadvantageous from an economic standpoint. (d) Means and action for solving the problems The present inventors have conducted extensive research to solve the problems, and have found that when CHI is microencapsulated and contained in a resin, the resin lasts for a long period of time. They discovered that CHI exhibits a strong rat-proofing effect and is stable even when subjected to various treatments, leading to the completion of the present invention. That is, the present invention is a rodent-proofing resin composition containing microcapsules in which a solution containing cycloheximide is used as a core material and the core material is covered with a wall material. The resin containing CHI microcapsules in the rodent-proofing resin composition of the present invention is not particularly limited, but includes, for example, thermoplastic resins, thermosetting resins,
There are synthetic rubbers, natural resins, etc. Among thermoplastic resins, vinyl resins include polyvinyl chloride, polyvinyl acetate, and polyvinylidene chloride, and petroleum-based resins include polyethylene, polypropylene, prebutene, and acrylic resins. Examples of such resins include methacrylic resin, polyacrylonitrile, and styrene resins such as polystyrene, ABS resin, and polyamide resin. In particular, considering the field of application of rodent-proof resin compositions, polymers or copolymers made of monomers having vinyl groups, such as polyvinyl chloride, polyvinyl acetate, polyvinyllidene chloride, polyvinyl formal, and ethylene-vinyl acetate copolymers etc.,
Further examples include crosslinked polyethylene, polystyrene, polyethylene, and ethylene-acrylic acid copolymer. In addition, as the thermosetting resin, phenol resin,
Examples include urea resin, melamine resin, polyester, polyurethane, and epoxy resin. Synthetic rubbers include diene, olefin, acrylic, urethane, silicone, fluorine, etc. More specifically, polybutadiene, SBR,
Examples include NBR, butyl rubber, chloroprene rubber, polyisobutylene rubber, ethylene rubber, propylene rubber, silicone rubber, etc. Further, examples of natural resins include copal, rosin, and the like. Plasticizers, stabilizers, lubricants, colorants, flame retardants, fillers, antioxidants, and other desired additives may be mixed or added to these resins to improve their processability and stability. good. The CHI microcapsules used in the present invention may be those obtained by the method described below, and the content in the resin will vary slightly depending on the place of use, whether or not it has been processed, and the type of resin, but usually it is ,
Approximately 0.1~25w/w% is suitable and approximately 0.17~20w/w
%, especially about 0.5-6.0w/
Preferably, it is w%. Mix CHI microcapsules with each of the above resins.
The rodent-proof resin composition containing CHI microcapsules can be used as various pellet compounds. In addition, CHI microcapsules are dispersed in resin and appropriate additives, plasticizers,
A paste-like rodent-proofing resin composition containing CHI microcapsules by adding a dispersant etc. can be used as it is or by coating, impregnating or filling it on a rodent-proofing object.
It is available. In addition, a rodent-proofing resin composition prepared by heating and melting a resin and kneading CHI microcapsules therein can be used by molding it into a desired shape. As described above, the rodent-proofing resin composition containing CHI microcapsules has an excellent rodent-proofing effect by itself, so it can be used as it is, in the form of a paste, or molded into a desired shape for various rodent-proofing fillings. It can be used as a rodent repellent material. The CHI microcapsules used in the present invention may be microcapsules made of a CHI solution dissolved in an appropriate solvent, and are not particularly limited. Dissolution and interfacial polymerization method, in
Microcapsules in which a wall film is formed around the CHI solution 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 spray/granulation method are preferred. The CHI content in the microcapsules is about 0.25 to 50 w/w%, especially about 0.5 to 50 w/w%, based on the capsule.
30 w/w% is preferred, and about 2-20 w/w% is most preferred. Examples of organic solvents for dissolving the CHI include alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol;
Ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), ethyl butyl ketone, cyclohexanone; Ethers such as ethyl ether, butel ether, amyl ether, hexyl ether, ethyl vinyl ether, cellosolve, carbitol; hexane, heptane Hydrocarbon solvents such as aliphatic hydrocarbons and aromatic hydrocarbons such as , octane, benzene, toluene, xylene, and cyclohexane; Mineral oils such as kerosene, light oil, and paraffin oil; Acetate ester, propionate ester, butyrate ester, and lactic acid ester , oxalic acid ester, crotonic acid ester, salicylic acid ester, benzoic acid ester, phthalic acid ester, adipic acid ester, sebacic acid ester, phosphoric acid ester, and other esters; and 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.
Phthalate esters such as ethylhexyl, ditridecyl phthalate, and dinormal alkyl 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" (trade name manufactured by Ciel Chemical Co., Ltd.) are preferred. The content of CHI in the above various solvents is suitably about 0.25 to 50 w/w%, preferably about 0.5 to 30 w/w%, and about 2 to 20 w/w% from the viewpoint of economy and effectiveness. It is preferable to set it as w%. On the other hand, as mentioned above, 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, so that it does not lose the medicinal efficacy of CHI. , urea resin, melamine resin, urea/melamine mixed resin, phenol resin, polyamide, polyester, polyurea, polyurethane, and other resins are suitable. Such a wall material is appropriately employed in consideration of various conditions, economic efficiency, etc. when the encapsulated preparation is used. When the rat-proofing resin composition of the present invention is used as a rat-proofing material, it can be carried out by molding the rat-proofing resin composition itself, or by coating a resin molded product with the rat-proofing resin composition. Can be done. In either case, the molding can be done using conventional methods and existing equipment in this technical field.
For example, the processing method can be extrusion processing, injection processing, calendar processing, etc., and the conditions can be changed and used as appropriate within a range that does not reduce the potency of CHI microcapsules. Examples of such rodent-proof resin molded products include linear bodies such as electric wires and cables, hollow molded products such as pipes, hoses, and tubes, and rolled molded products such as tapes and sheets. In these rat-proof molded products, if CHI microcapsules are contained in the molded product in an amount of about 0.1 to 25 w/w%, the rat-proof effect can be exhibited. To explain this in more detail, for example, when the rodent-proof molded product is an electric wire or cable, approximately 0.1 to 25 w/w% of CHI microcapsules are usually added to the insulating layer of the electric wire or the sheath of the cable. Preferably from about 0.17 to 20 w/w%, particularly preferably from about 0.5 to 20% w/w
A rodent-proof electric wire or rodent-proof cable can be made by containing the rod at a concentration of 6.0 w/w% or by forming a coating layer of a rodent-proofing resin composition on the outside of the insulating layer or cable. Even when forming a coating layer, the content of CHI microcapsules may be within the same range as when the microcapsules are directly contained in an insulating layer or sheath. In any of the above cases, the wire coating itself can be carried out by a method commonly used in the field of wire coating. In addition, when the rodent-proof molded product is a tarpaulin, sheet, tape, etc. for flexible containers, the rodent-proofing resin composition can be directly rolled or laminated to form rodent-proof flexible containers, rodent-proofing tapes, and rodent-proofing sheets. It can be done. In the case of such sheet-like rodent-proof molded products,
CHI microcapsules may be adjusted to contain about 0.1 to 25 w/w%, preferably about 0.17 to 20 w/w%, particularly preferably about 0.5 to 6 w/w%. In addition to these, the rodent-proofing resin composition of the present invention can be suitably used in rodent-proofing molded products such as various films (particularly agricultural films), vinyl leather, and vinyl tiles. (d) Examples Hereinafter, the present invention will be explained in more detail with reference to Examples and Experimental Examples. CHI microcapsules used in 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. On the other hand, prepare Solution B by dissolving 4 g of sodium carbonate and 8 g of diethylenetriamine in 80 g of water.
While stirring the O/W emulsion, a slow-stretched solution B was added, and the stirring reaction was continued for 24 hours to obtain 8% CHI-containing microcapsules having a polyamide wall and an average particle size of 10 μm. In the above, 5% CHI-containing microcapsules, 10
% CHI-containing microcapsules and 15% CHI-containing microcapsules were obtained. Example 1 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 thickness of 1.0 mm is placed on top of the control cable. Co-extrusion coating to a thickness of 0.5 mm using a rat-proof vinyl chloride composition consisting of the following formulation on top of the protective layer [simultaneous multilayer extrusion coating, conditions: 160°C]
5 minutes] to obtain a rodent-proof vinyl chloride coated cable. <Formulation example> Polyvinyl chloride (average degree of polymerization 1300) 100 parts by weight Dioctyl phthalate 50 parts by weight Polymerized organotin mercapto compound 5 parts by weight Lead stearate 1 part by weight 8% CHI microcapsules (Content in prescription as CHI 0.25%) ) 5 parts by weight Example 2 A ratproof resin composition was obtained using the following formulation. Sheet-shaped rodent-proof polyethylene resin <Formulation> Low-density polyethylene (specific gravity 0.92) 100 parts by weight 5% CHI microcapsules 4 parts by weight The processing method was to form a sheet by hot pressing. Sheet-shaped rodent-proof silicone resin <Formulation> Silicone rubber compound for general extrusion
100 parts by weight KE550-U (manufactured by Shin-Etsu Silicone) 10% CHI microcapsules 2.1 parts by weight <Processing method> Formed into a sheet by hot pressing. Sheet-shaped rodent-proof polystyrene resin <Formulation> Polystyrene (Styron 495 manufactured by Dow Chemical)
100 parts by weight 8% CHI microcapsules 2.5 parts by weight <Processing method> Formed into a sheet by hot pressing. Sheet-shaped rodent-proof phenolic resin <Formulation> Phenol resin PR50247 (manufactured by Sumitomo Bakelite) 100 parts by weight 15% CHI microcapsules 1.4 parts by weight <Processing method> Formed into a sheet by hot pressing. Example 3 A 1 mm thick PVC composition was calendered on both sides using a polyester base fabric with a density of 17 vertically and 18 horizontally 1000 d polyester threads (conditions: warming at 140°C, 20 minutes, pressing) 170℃,
One side of the flexible container tarpaulin prepared (for 5 minutes) was laminated to a thickness of 0.5 mm using a rat-proof vinyl chloride composition having the following formulation to obtain a rat-proof vinyl chloride flexible container tarpaulin. <Formulation example> Polyvinyl chloride (average degree of polymerization 1450) 100 parts by weight DOP (dioctyl phthalate) 25 parts by weight DBP (dibutyl phthalate) 20 parts by weight Chlorinated paraffin 10 parts by weight White lead (basic lead carbonate) 5 parts by weight Part lead stearate 1 part by weight 8% CHI microcapsules 5 parts by weight (0.24% as CHI) Example 4 Rat-proof rubber pipes for city gas made of natural rubber were manufactured by manufacturing gas rubber pipes using the following formulation. Obtained. <Formulation example> Natural rubber 100 parts by weight Sulfur 3 parts by weight Dibenzothiazole disulfide 1 part by weight Diphenylguanidine 0.3 parts by weight Zinc white 5 parts by weight Stearic acid 1 part by weight 4,4'-thiobis(6-tert-butyl) -3 methyl-phenol) 1 part by weight Paraffin 1 part by weight Activated calcium carbonate 100 parts by weight Carbon black 30 parts by weight Mineral oil 10 parts by weight 8% CHI microcapsules 6.5 parts by weight (Theoretical potency as CHI 0.20%) Examples 5 In Example 4, 100 parts by weight of styrene butadiene rubber (SBR-1502) was substituted for natural rubber, 2 parts by weight was substituted for 3 parts by weight of sulfur, 1.5 parts by weight was substituted for 1 part by weight of dibenzothiazole disulfide, and 0.3 parts by weight of diphenylguanidine. A rodent-proof rubber pipe for city gas made of SBR was obtained by carrying out the same procedure as in Example 4 using 0.5 parts by weight instead of 0.5 parts by weight. Example 1 (1) Stability of CHI during rodent-proof coating processing of PVC cable <Method> The same formulation as in Example 1, excluding CHI microcapsules (Control Example 1), CHI
Rat-proof polyvinyl chloride was prepared in the same manner as in Example 1 for the product containing 0.7% CHI crystals instead of microcapsules (Control Example 2) and the product containing 0.5% CHI crystals instead of CHI microcapsules (Control Example 3). The stability of CHI was investigated after coating. <Results> The results are shown in Table 1 below.

[Table] CHI measurement method: Peel off the rat-proof coating layer containing cycloheximide, add 10 ml of acetone to 1 g of rat-proof coat, and let it stand at room temperature for 24 hours.
Leave it for an hour, then add 10ml of methanol and
Using a sample of the solution that has been heated to ℃ and left for 1 hour, it is measured in accordance with the official testing method for agricultural chemicals [preparations containing CHI as the main ingredient] (hereinafter the same). (2) Storage stability of CHI in PVC rat-proof cable <Method> Cut out the rat-proof coating layer from each cable obtained in (1) above, and store it in the coating layer under conditions of 50°C and 85% relative humidity. Stability was investigated. <Results> The results are shown in Table 2.

[Table] (3) Rat-repelling effect of PVC rat-proof cable <Method> Cut each cable obtained in (1) above into 20 cm pieces and place them in a breeding cage containing 2 male Wistar rats and 3 female Wistar rats. After giving feed and drinking water and leaving it for 24 or 48 hours, each cable was taken out and the status of feeding damage by rats was observed. <Results> The results are shown in Table 3.

[Table] (4) To the inner sheath (protective) layer of the PVC cable
Transfer of CHI <Method> The cable obtained in (1) above was left at room temperature (23° C.), and the amount of CHI transferred to the inner protective layer was measured. <Results> The results are shown in Table 4 below.

[Table] (5) Bleed CHI from PVC cable <Method> Each cable obtained in (1) above was heated at 50℃ and relative humidity 85℃.
%, and the amount of CHI bled onto the cable surface was measured. <Results> The results are shown in Table 5 below.

【table】

[Table] CHI measurement method After rolling a specimen into contact with the surface of a medium containing the test bacterium Satucharomyces cerevisiae for 5 minutes, culturing at 32°C for 16 hours, the amount of CHI was determined from the area of the inhibition zone generated on the surface of the medium. Ta. (6) CHI water resistance of PVC cable <Method> Cut each cable obtained in (1) above into 3 cm pieces,
ml beaker, add 100ml of water, 30℃, 50℃
Put it in a constant temperature water tank and take it out after a certain period of time.
The amount of CHI in the cable was measured. <Results> The results are shown in Table 6 below.

[Table] Experimental Example 2 (1) Stability of CHI during production of tarpaulin for PVC flexible containers <Method> The same formulation as in Example 3, excluding CHI microcapsules (Control Example 1), One in which 1.6 parts by weight of CHI crystals were added instead of capsules (Control Example 2) and one in which 0.8 parts by weight of CHI crystals were added in place of the microcapsules (Control Example 3).
were carried out in the same manner as in Example 2.
A tarpaulin for PVC flexible containers was manufactured and the stability of CHI was investigated. <Results> The results are shown in Table 7 below.

[Table] CHI measurement method Peel off the rat-proof vinyl chloride layer containing cycloheximide, add 1g of acetone to the layer, leave it at room temperature for 24 hours, then add 10ml of methanol and heat to 70℃ for 1 hour. Using the soaking liquid left as a sample, measure according to the official agricultural chemical testing method [preparations containing CHI as the main ingredient]. (2) Rat-repellent effect of PVC tarpaulin Cut each tarpaulin obtained in (1) above to 75 x 150 mm, wrap two pieces of solid food for rats with it, and staple the surrounding area to use as a sample. This sample
After being placed overnight in a breeding cage containing a wild black rat weighing approximately 500 g that had been fasted for 24 hours, the cage was removed and the state of feeding damage was examined. <Results> The results are shown in Table 8 below.

【table】

[Table] (e) Effects of the invention Since the rodent-proofing resin composition of the present invention contains a microcapsule preparation whose core material is a solution containing CHI, the rodent-proofing resin composition itself is It has an excellent rat-proofing effect. Therefore, it can be widely used as a rat-proofing material or by kneading, coating, filling, impregnating, etc. into various rat-proofing objects. In addition, the core material of the microencapsulated formulation is CHI
Because it is a solution, when a mouse bites it, it diffuses extremely quickly into saliva, and the taste is effective, so the repellent effect itself is improved compared to conventional CHI crystals. As a result, for example, the content itself can be significantly reduced compared to when crystals are used.

Claims (1)

[Claims] 1. An organic solvent solution containing cycloheximide is used as a core material, and the core material is a group consisting of urea, melamine, urea/melamine mixed resin, phenolic resin, polyamide resin, polyester resin, polyurea resin, and polyurethane resin. A rodent-proofing resin composition comprising a resin composition containing microcapsules coated with a wall substance consisting of at least one selected from the following. 2 Microcapsules are added to the resin composition at a rate of approx.
The rodent-proofing resin composition according to claim 1, containing 0.1 to 25% W/W. 3. The rodent-proofing resin composition according to claim 1 or 2, which is a rodent-proofing resin composition formed into an electric wire, cable, hose, pipe, tube, tape, or sheet. 4. The rodent-proofing resin composition according to claim 1, 2 or 3, which is a resin composition comprising a vinyl resin.