JPH10167906A - Molding product for pest control - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin molding product for controlling pest excellent in safety, not decreasing the efficiency by thermal degradation, not generating a malodor when adding and kneading the pesticidal agent with a resin, hardly causing coloration and physical change of the resin, and capable of providing an excellent pest-repellence for a long period. SOLUTION: This molding product for controlling pest is obtained by adding 0.01-10wt.% preparation comprising chemicals comprising one or more kinds of a dialkyl ester of a dibasic acid of the formula, ROOC(CH2 )n COOR [R is a 1-8C saturated alkyl, (n) is an integer of 5-18] and chemicals comprising 1-50 pts.wt. synthesis pyrethroid-based pesticide in combination to a thermoplastic resin and kneading the preparation with the thermoplastic resin in a molten state. One or more kinds of piperonylbutoxide, N,N-diethyl-3- methylbenzamide, octachlorodipropyl ether, isovornyl thiocyanoacetate and N-octylbicycloheptene-dicarboximide can be added thereto in an amount 2-10 times as much as that of the pyrethroid-based persticide.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin molded article which imparts excellent pest control properties to a thermoplastic resin. Further, in detail, a dibasic acid-saturated dialkyl ester and a synthetic pyrethroid-based insect repellent alone or in combination with an efficacy enhancer are mixed with a thermoplastic resin to form a drug that has a synergistic effect on insect repellency. Pest-controlling resin molded product that has a pest-controlling property and is applied to clothing and many other textiles, films, sheets, and other resin-molded products, and exhibits a safe and long-term control effect. About.

[0002]

2. Description of the Related Art The most common and simple method for controlling pests is the application of insect repellents. However, drugs used as insect repellents have a problem in safety.
Recently, due to advances in chemistry, efforts have been made to increase the efficacy of insect repellents and reduce harm as much as possible.
The effect is also appearing. At the beginning of the development of insect repellents, the insect repellent effect was prioritized, and harmful insect repellents such as phosphorus compounds were widely used in households.

[0003] The use of these insecticides has come to be applied in various fields. In particular, emphasis has been placed on household use and the amount of use thereof has also been increased, so that the harmfulness of the compounds has been concerned, and insecticides with lower toxicity have been required. The insect repellent at the beginning of development was used in large quantities as a raw material for Katori incense and the like by applying natural pyrethrum. Studies on the synthesis of pyrethrin, the main component of pyrethrum, have been actively conducted. The synthetic product is a homologue of synetrin 1 having an allyl group, and a synthetic pyrethrin which is not inferior to natural products has been completed, and a number of pyrethroid-based compounds have been announced as derivatives thereof.

As a synthetic pyrethroid insect repellent, for example,
2,2-dimethyl-3- (2-methyl-1-propenyl) cyclopropanecarboxylic acid-2-methyl-4-oxo-3- (2-propenyl) -2-cyclopentene-1
-Yl-ester (generic name arrestrin), 2,2-dimethyl-3- (2-methyl-1-propenyl) cyclopropanecarboxylic acid (1,3,4,5,6,7-hexahydro-1,3- Dioxo-2H-isoindol-2-yl) methyl ester (generic name tetramethrin), 5-benzyl-3-freelmethyl-(+)-trans-chrysanstate (generic name resmethrin), 2,2-dimethyl- 3- (2-methyl-1-propenyl) cyclopropanecarboxylic acid (3-phenoxyphenyl) methyl ester (generic name phenothrin), 3- (2,2-dichloroethynyl) -2,2-dimethylcyclopropanecarboxylic acid ( 3-Phenoxyphenyl) methyl ester (generic name permethrin) is on the market.

Further, with the completion of various pyrethroids, a large number of potency enhancers that can be added to this compound to further enhance the insecticidal efficacy have been developed, and the efficacy as well as the safety of the insecticide have been enhanced. Examples of the potency enhancer include one or two of piperonyl butoxide, N, N-diethyl-3-methylbenzamide, octachlorodipropyl ether, isobornyl thiocyanoacetate, and N-octylbicycloheptene-carboximide. The insect repellent effect can be enhanced by adding 2 to 10 times the above.

The thermoplastic resin has a very wide range of applications as fibers, cotton, films, sheets, and other various molded products because of its easy processing. In particular, textile products include beddings such as clothes, futons, blankets, sheets, curtains,
In addition to rugs such as upholstery, carpets and tatami mats, they are also used in large amounts as synthetic cotton and cushioning materials.

[0007] When these finished products are used, processing of repellent chemicals for the purpose of inhibiting the propagation of pests can be suppressed by suppressing the propagation of pests. In the past, surface treatment of these resin molded products was common, but the insect repellent used in the processing was reduced in effectiveness due to oxidation by air or the influence of ultraviolet rays, or surface friction during use or A stable insect repellent effect cannot be maintained for a long period of time due to the dropping of the drug due to washing or the like. As a method of improvement, a method of directly kneading the resin has been studied.

However, problems with the method of adding an insect repellent during the heating and melting of a thermoplastic resin include, for example, a decrease in efficacy due to thermal decomposition, coloring of the resin, generation of a bad smell during operation, change in physical properties of the resin, and the like. . In particular, when the melting temperature is 200 ° C. or higher, the insect repellent is also susceptible to the influence.

Many of the insect repellent components have excellent performance in those containing sulfur, nitrogen, phosphorus, and halogen atoms in their chemical structural formulas, but these compounds have the disadvantages described above. Many have. Among these compounds, compounds having good heat stability and excellent insect repellency were found.

[0010]

DISCLOSURE OF THE INVENTION The present invention relates to a method for kneading an insect repellent during the melting of a thermoplastic resin to obtain various pest control molded products. It is an object of the present invention to obtain a resin molded product having less odor during operation and having excellent repelling performance over a long period of time against pests.

[0011]

Means for Solving the Problems The present inventors have studied the application of saturated dialkyl ester derivatives of aliphatic dibasic acids in order to solve the above problems. As a result, oxalic acid, malonic acid, and succinic acid have been studied. The effect was observed in dibasic acid-saturated dialkyl esters such as glutaric acid, adipic acid, pimelic acid, cornic acid, azelaic acid, sebacic acid, nonane-dicarboxylic acid and undecane-dicarboxylic acid. In the compound represented by the following general formula (1), ROOC (CH ₂ ) nCOOR (1): pimelic acid with n = 5, corkic acid with n = 6, azelaic acid with n = 7, and n = 8 JP-A-7-176905 discloses that compounds having 1 to 8 carbon atoms in the alkyl group of the dialkyl ester such as sebacic acid are excellent in insect repellency. However, for two insecticidal synergies and C ₈ or more alkyl groups obtained by compounding a medicament aliphatic dibasic acid saturated dialkyl esters and synthetic pyrethroid compounds for the present invention, not yet viewed announcement.

[0012] The present invention relates to a dibasic acid-saturated dialkyl ester represented by one or more pyrethroid compounds.
By combining 1 to 50 parts of the above species, a synergistic effect excellent in pest control properties was discovered, and the present invention was completed. Further, the insect repellent effect can be further enhanced by using a pyrethroid-based compound used together with an efficacy enhancer.

Both the dibasic acid saturated dialkyl ester and the pyrethroid compound are excellent in compatibility with a thermoplastic resin and thermal stability, and hardly decompose when kneaded into the resin.

The thermoplastic resin used in the kneading of the present invention includes polyolefin resins such as polyethylene and polypropylene, styrene resins such as polystyrene resins and ABS resins, vinyl acetate, vinyl chloride resins, and methyl methacrylate. It exhibits excellent insect repellency when used for polyamide resins, polyester resins, polyether resins, polycarbonate resins, polyurethane resins, etc. in addition to polyvinyl resins.

As an application example depending on the composition of the thermoplastic resin, as a resin used for a film or a fiber product, a polyester resin, a polyamide resin, a polyolefin resin or the like is suitable. The dibasic acid saturated dialkyl ester of the insect repellent used in the present invention has 1 to 18 methylene groups. The alkyl group of the fatty acid has 1 to 8 carbon atoms, and the alkyl group includes methyl, ethyl, propyl (including normal and iso isomers, the same applies hereinafter), butyl,
Pentyl, hexyl, heptyl, octyl and undecane groups. In the present invention, an antioxidant, an ultraviolet absorber, a coloring agent, a flavoring agent, a plasticizer, a surfactant, an antibacterial agent, a fungicide, and the like can be used in combination.

[0016]

[Action] An insect repellent compound kneaded into a thermoplastic resin and used in combination with a dibasic acid saturated dialkyl ester as a compound, a synthetic pyrethroid-based insect repellent and an efficacy enhancer to provide a synergistic effect on insect pests. is there. This concomitant drug has an excellent insect repellent effect, has good compatibility with resins, and shows no alteration, coloring, decomposition, etc. due to the melting temperature. In addition, there is no problem with regard to the solubility of many resin molded products during heating and melting. Thereby, the resin molded product can maintain the insect repellent effect for a long period of time.

[0017]

The present invention will be described below in more detail with reference to examples, but the present invention is not limited to these examples. Insect repellents and thermoplastic resins used in the examples are as shown below. In addition,% shown in the Examples
Are all% by weight.

Insect repellent, potency enhancer and solvent used in Examples (1) Dibutyl sebacate (trade name: product of DBS Daihachi Chemical Co., Ltd.) (2) Pyrethroid insect repellent (phenothrin) (3) Efficacy Enhancer (piperonyl butoxide) (4) Solvent (ethanol)

As a synergistic effect of the dibasic acid saturated fatty acid dialkyl ester and the pyrethroid insecticide and an efficacy test using the pyrethroid efficacy enhancer in combination, Table 1 shows the simple substance and the compounding ratio of each. In addition, the solvent was used as a shaping agent.

[Table 1]

Thermoplastic resin used in the experiment (1) Nylon 6 (trade name: Kanebo Nylon MC11)
2 Kanebo Corporation products) (2) Low density polyethylene (trade name Mirason NE Co., Ltd.)
O23H Mitsui Chemicals Co., Ltd. product)

Method of kneading insect repellent prepared in Table 1 into resin and trial manufacture of film (1) Nylon 6 was kneaded at a heating temperature of 220 to 250 ° C. (2) Low density polyethylene has a heating temperature of 150 to 170
The kneading was carried out at a temperature of ° C. The amount of insect repellent added is 0.05% for each resin,
0.1%. The prototype of the film is a 30 micron-thick film, each manufactured by Labo Plast Mill (Toyo Seiki Seisakusho) using an extruded film production tester.
Used for insect repellency test. Using the above insect repellent film,
An insect repellent test was performed on the house dust mite, Dermatophagoides pteronyssinus, by the invasion prevention method. The test method is as follows.

As shown in FIG. 1, a sample 3 was placed on a plastic petri dish 2 having a diameter of 4 cm and a height of 0.6 cm, and a powder sample 5 containing no mites was placed thereon. Put 05g. This is placed at the center of a plastic petri dish 1 having a diameter of 9 cm and a height of 1.5 cm. Between the large and small petri dishes, a well-propagated tick culture medium (approximately 10,000 living mite population) is uniformly spread. Put this on the adhesive sheet 6,
Put the adhesive sheet together with the adhesive sheet in a 27 x 13 x 9 cm plastic container for food preservation, cover with saturated saline, cover the container, keep the humidity in the container at about 75%, and store it in a thermostat at 25 ° C ± 1 ° C. Breed one day and night. On the next day, the powdered feed on the sample was collected by the saturated saline floating method and the sample was collected by the water washing method, and the ticks were collected and counted.

[0023]

(Equation 1)

Tests of repellency of insecticide-kneaded resin film against Dermatophagoides pteronyssinus (Table 2) and Table 3 show the results of a test for preventing penetration of a nylon film containing a pesticide and a method of preventing penetration of a low-density polyethylene film containing a pesticide. The test results are shown in Tables 4 and 5. The test was repeated three times in consideration of variations.

Mite repellent test results by intrusion prevention method

[Table 2]

[0026]

[Table 3]

[0027]

[Table 4]

[0028]

[Table 5] When the test results according to Tables 2 to 5 are combined, the effects are as follows. Mite repellent rate: E>D>B>A> C

[0029]

According to the present invention, the thermoplastic resin is selected from dibasic acid saturated dialkyl esters represented by the general formula (1):
1 to 50 parts of a synthetic pyrethroid-based insect repellent is used in combination with one or more kinds of drugs, and one or two or more of potency enhancers are added to the pyrethroid-based insect repellent in a 2 to 10-fold amount. 0.01 to 10.0% by weight of the compounded drug which has an improved pest control effect and a mutually synergistic effect
Is kneaded during the melting of the thermoplastic resin and then molded to obtain a resin molded product having excellent insect repellency against pests for a long period of time.

[Brief description of the drawings]

FIG. 1 is a layout diagram of a petri dish used in an intrusion prevention method in a mite repellent test according to the present invention.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 Petri dish (9 cm in diameter) 5 Powder feed 2 Petri dish (4 cm in diameter) 6 Adhesive sheet 3 Test sample 4 Tick culture medium

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08K 5/103 A01N 31/02 // A01N 31/02 37/18 37/18 43/30 43/30 43/38 43/38 47/48 47/48 53/00 508A (A01N 53/08 37:04)

Claims (3)

[Claims] 1. The following general formula (1): ROOC (CH ₂ ) nCOOR (1) wherein R is a saturated alkyl residue having 1 to 8 carbon atoms, and n is 5
Represents an integer of ~ 18. )), A synergistic effect on pest control can be obtained by using 1 to 50 parts of a synthetic pyrethroid insect repellent in combination with one or more drugs selected from dibasic acid saturated dialkyl esters shown in A pest control molded product characterized in that a drug is kneaded when a thermoplastic resin is melted. 2. An amount of a drug having a synergistic effect on insect pest control obtained by the combined use of the drug shown in claim 1 to a thermoplastic resin is 0.01 to 10.0% by weight. Item 1. A pest control molded product according to Item 1. 3. A synthetic pyrethroid-based insect repellent, as a potency enhancer, piperonyl butoxide, N, N-diethyl-3-.
One or two of methylbenzamide, octachlorodipropyl ether, isobornyl thiocyanoacetate, N-octylbicycloheptene-dicarboximide
The pest control molded product according to claim 1, wherein 2 to 10 times the amount of the seed or more is added.