JP2917484B2 - Pest control molded product - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention provides an effect of controlling indoor dust mites obtained by molding and processing a resin composition obtained by blending a specific agent with a thermoplastic resin. Fiber that has a repellent effect on mosquitoes,
The present invention relates to a pest-controlling molded article such as a film and a sheet.

[Conventional technology]

In recent years, indoor dust mites frequently occur due to changes in the living environment,
Since it causes not only discomfort but also insect bite and allergic asthma, there is a strong health and hygiene interest in such mites control measures.

As control measures, conventional insecticides for sanitary insect pests are mainly sprayed on carpets and tatami mats inhabiting mites, applied or press-fitted, or mixed with a latex composition for carpet backing, etc. It is done to adhere. Further, it has been practiced to lay a paper or a sheet to which an insecticide is attached below to expect a mite control effect.

Further, as a physical method, the extermination operation is performed by sunlight mist or heat treatment with high frequency or hot air.

[Problems to be solved by the invention]

 However, these methods have the following disadvantages.

1) Since the effect is short-term, it is necessary to repeat the processing.

2) There is a bad smell or pungent smell.

3) The effect is not certain unless a large amount of drug is used.

4) Objects that come into direct contact with the human body or animals cannot be treated with drugs or have severe restrictions.

5) The efficacy is easily lost by washing or other treatments.

6) Kneading into high melting point resin is not possible.

7) Physical processing cannot be easily performed on a daily basis.

In recent years, it has been desired to impart an effect of repelling mosquitoes to clothing such as pantyhose, socks, and shirts.

[Means for explaining the problem]

Under such a background, an object of the present invention is to provide a tick that is safer, has a long-lasting effect without washing out, and has a long-lasting effect, and can be used safely in applications that directly contact the human body. It is an object of the present invention to provide fibers, films, sheets, and the like having an effect of controlling pests such as blood-sucking pests such as mosquitoes and mosquitoes, and clothing, rugs, daily necessities, sporting goods, and the like obtained by processing them.

The present inventors have conducted a diligent search for compounds that are compatible with thermoplastic resins that can be melt-processed into fibers and films, withstand processing temperatures, and have a high effect of controlling ticks and mosquitoes. Phthalate, dialkyl adipate and dialkyl fumarate (hereinafter sometimes abbreviated as dialkyl phthalate, adipate and fumarate, or simply referred to as drug) are found to be excellent,
The present invention has been reached.

That is, the gist of the present invention is to provide a thermoplastic resin selected from the group consisting of a polyolefin resin, a polyamide resin and a polyester resin, as a pest-controlling component, dialkyl phthalate, dialkyl adipate and dialkyl fumarate (provided that these alkyl groups A pest control composition containing 0.1 to 10% by weight of a resin composition, which is obtained by melt-molding a resin composition containing only one or more agents selected from carbon numbers 1 to 8). In the goods.

 Hereinafter, the present invention will be described in more detail.

The thermoplastic resin applied to the present invention has a melting point of 130 ° to 270 °.
And a thermoplastic resin selected from the group consisting of a polyolefin resin, a polyamide resin and a polyester resin. Typical examples include polyolefin resins such as polyethylene and polypropylene; polyamide resins such as nylon 6 and nylon 12; and polyester resins such as polybutylene terephthalate and polyethylene terephthalate. These thermoplastic resins are film or fiber-forming polymers. Among them, polyamide resins such as nylon 6 and nylon 66 are particularly preferable for clothing such as pantyhose and socks. Further, those resins having a melting point of 260 ° C. or less are preferable because the emission of dialkyl phthalate, adipate and fumarate is small.

Dialkyl phthalate, adipate and fumarate, which are agents applied to the present invention, have an alkyl group having 1 to 8 carbon atoms, and specific examples of the alkyl group include methyl, ethyl, propyl (normal and iso). Butyl, pentyl, hexyl, heptyl and octyl groups. Examples of the dialkyl phthalate include ortho (o-) dialkyl phthalate, isodialkyl phthalate, and teredialkyl phthalate.

The content of the agents dialkyl phthalate, adipate and fumarate is 0.1 to 10% by weight, preferably 1.3 to 5.0% by weight in the molded article.

If the content is less than this range, the pest control effect is small, and if it is large, when molding a molded article containing such a large amount of drug, molding becomes difficult because the scattering of the drug during melt molding becomes large, and furthermore, Is not preferable because bubbles are generated in the molded article and the strength of the molded article is reduced.

Many of the conventional chemicals used for controlling insect pests have large scattering during melt molding, and even if a predetermined amount is added, the actually measured content after molding is reduced, and there are problems such as insufficient effects being exhibited.
The specific drug of the present invention is characterized by a small decrease in the content after molding. The drug content of the resin composition to be subjected to melt molding is determined in consideration of a decrease in the content after molding.

The present composition can be prepared by mixing the present drug by any method in a step before melt-molding into a fiber or the like. The compounding method can be carried out by a well-known method, for example, a method of attaching the present drug to the surface of a resin pellet is simple, but if the amount of attachment is large, the content of the drug in the molded article tends to vary, In addition, the biting of the extruder tends to be unstable. In such a case, the resin and the drug may be dry-blended to a predetermined concentration and melt-mixed and extruded to form pellets. Alternatively, a master pellet in which a predetermined amount or more of the drug is kneaded may be prepared and blended with the resin pellet for dilution.

When a relatively large amount of the drug is contained, the drug is impregnated in advance into a carrier powder, for example, a fine powder of white carbon (amorphous silicic anhydride), talc, magnesium oxide, clay or the like, and then kneaded into a resin and molded. Is preferred.

The composition of the present invention may further contain known additives such as a heat stabilizer, a weather resistance improver, a lubricant, a dye / pigment, an antistatic agent, a reinforcing agent, and a flame retardant.

The insect-controlling molded article of the present invention is obtained by melt molding at a temperature of 120 to 300 ° C, and specific examples include fibers, films, sheets and the like.

The toxicity of dialkyl phthalate, adipate and fumarate used in the present invention has been reported as follows, and is considered to be very high in safety because it does not come into contact with a resin in a large amount when mixed.

[Action] When the agent of the present invention is compounded and kneaded into a thermoplastic resin,
The active ingredient, which is a compounded drug, sequentially moves to the surface of the resin and exerts its effect, while the active ingredient existing inside is protected and does not flow off even if it is washed. Since the amount of the active ingredient appearing on the resin surface can be adjusted to a small amount, the safety is high.

However, in general, when melt-molded into fibers or films, heat treatment at 200 to 250 ° C. or higher is required.Conventionally, since the insecticide having high safety to withstand this step is unknown, the fibers and films of the present invention are Could not be obtained. However, dialkyl phthalates, adipates, and fumarates have good compatibility with thermoplastic resins, and have high safety per se and little scattering when kneaded into the resin. The validity of the period is recognized.

In the present invention, a fiber or a primary molded article such as a film or a sheet is further processed into a thread, a cloth, clothing, a carpet,
It can withstand processing operations such as heating, washing, dyeing, and rubbing in the process of processing into blankets, bedding, tents, and various other daily necessities, and can maintain a pest control effect as a final product.

〔Example〕

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples unless departing from the gist thereof. In addition, the test method used for evaluation of Examples 1-9 of this Example and Comparative Examples 1-7 is as follows.

 Acaricidal efficacy was determined by the following two methods.

(1) Screw tube method For a film sample, cut the sample into 1 mm width, weigh 400 mg of the fiber as it is and pack it in a screw tube with a capacity of 5 ml. Stir so that the specimen and medium (mite) are well mixed. After that, it is placed under the condition of 25 ° C and 75% RH and taken out after a predetermined time,
It was spread on a petri dish and examined directly for life and death under a stereoscopic microscope. In addition, the thing which did not respond even if a stimulus was given was made into the dead and dead.

(2) Planting method A film sample is cut into a disc having a diameter of 6 cm and placed on the bottom of a glass petri dish of the same diameter. Next, test mites were collected at a rate of 300
The seeds are uniformly inoculated with the culture medium on the specimen so as to reach ~ 500 heads, placed under 25 ° C and 75% RH, and taken out after a predetermined time. Were counted, and then judged as alive or dead. The mortality was averaged by changing the visual field six times, and the death was observed directly under a stereoscopic microscope.

As a method for quantifying the drug content, methylene chloride was used as an extraction solvent, extraction was performed by an ultrasonic extractor, and gas chromatography was checked by a conventional method.

The details of the method for quantifying the drug (dialkyl phthalate, dialkyl adipate, dialkyl fumarate) in the resin are as follows.

1) Quantification of drug A drug-containing resin sample of about 0.1 to 10 g is precisely weighed, 200 ml of methylene chloride is added thereto, and extraction is performed for 30 minutes by an ultrasonic cleaner. The extract was collected by filtration, and the residue was washed three times with a small amount of methylene chloride.
Accurately add 10 ml, concentrate on a water bath, add acetone to the residue to make exactly 25 ml, and use it as a sample solution.

For this sample solution, the amount of the drug is determined by gas chromatography under the same operating conditions as when the calibration curve was prepared.

2) Preparation of calibration curve Precisely weigh out about 300 mg of the drug standard, add acetone to make exactly 100 ml, take exactly 10 ml of this solution, add exactly 10 ml of the internal standard solution, add acetone, and add exactly Add 25 ml to make a standard curve standard solution. 1 μl of this solution was injected into a gas chromatograph under the following conditions, and a calibration curve was created from the obtained gas chromatograph.

Internal standard solution: di-isobutyl phthalate 300mg / 100ml
(Acetone) Gas chromatograph operating conditions Function: Shimadzu GC-8APF Carrier gas: Nitrogen gas 0.5kg / cm ² Temperature: Separator tube 165 ° C Vaporization room 200 ° C Detector 220 ° C Separation tube: Inner diameter 3mm, length 1m Hard glass Filler: 3% silicon XE-60 Chromosolve W (Chromosolve is a trademark) AW DMCS 60-80 mesh Recording paper feed: 2.5 mm / min Detector: Flame ionization detector Injection volume: 1.0 μl Sensitivity: 10 ² MΩ recorder: Shimadzu C-R3A Next, the durability test method for washing is shown. Performed for neutral detergents and organic solvents.

(A) Neutral detergent: Immerse 3 g of nylon spun fiber specimen in 100 cc of a 1% solution of a commercially available neutral detergent, extract with an ultrasonic cleaner for 5 minutes, thoroughly wash with running water, and then dry at 130 ° C for 5 minutes. It was subjected to a post-screw tube efficacy test.

(B) Organic solvent: Similar to a neutral detergent, 3 g of a sample is added to 100 cc of n.
-The sample was placed in hexane and perchlorethylene, extracted with an ultrasonic cleaner for 5 minutes, dried at 130 ° C for 5 minutes, and subjected to an efficacy test.

Examples 1 to 9 and Comparative Examples 1 to 2 Nylon 6 (manufactured by Mitsubishi Kasei Corporation; relative viscosity 3.5), polyethylene (manufactured by Mitsubishi Kasei Corporation; MI ≒ 1) and polypropylene (manufactured by Mitsubishi Kasei Corporation; MI-0.8) pellets were separately blended with o-dimethyl phthalate, o-diethyl phthalate, o-di-n-butyl phthalate, diisobutyl adipate, o-dioctyl phthalate, and dibutyl fumarate in the amounts shown in Table 1. Thereafter, nylon was kneaded at a temperature of 240 ° C., and polyethylene and polypropylene were kneaded at a temperature of 200 ° C. in a single screw extruder to obtain drug-containing pellets. The pellets were formed into a film having a thickness of 25 μm by an extruder equipped with a T-die. The extrusion temperature at that time was 240 ° C. and 200 ° C., respectively, and the temperature of the cooling roll was 30 ° C.

Comparative Examples 3 to 7 In the same manner as described above, except that dialkyl phthalate, adipate and fumarate were replaced by N, N-diethyltoluamide, isobornyl thiocyanoacetate, diazinon, and phthalthrine, respectively. A film was obtained. The same procedure was performed for the case where no drug was added (Comparative Example 7). Table 1 shows the results of measuring the drug content in each film. The films obtained in Examples 1 to 9 of the present invention and Comparative Examples 2 to 7 were used as specimens, and the results of the efficacy test on Dermatophagoides farinae by the screw tube method are shown in Table 2, and the results of the efficacy test on Dermatophagoides farinae by the screw tube method. Table
Table 3 shows the results of the potency test on Dermatophagoides farinae by the planting method. With these results,
It can be seen that the molded product of the present invention has a high initial efficacy in the anti-mite effect.

Example 10, Comparative Example 8 A mixture of nylon 6 (manufactured by Mitsubishi Kasei Corporation, relative viscosity 2.3) and 3% of o-diethyl phthalate mixed with 25%
Melt spinning was performed at 0 ° C., and then a three-fold drawing was performed.
A fiber having a filament of 90 denier was obtained. The drug content in this fiber was 2.1%. A durability test was performed on the fibers with respect to a detergent. The test was performed as an efficacy test for Dermatophagoides farinae by the screw tube method. For comparison, a 90% emulsion of a fiber obtained from a non-drug-containing nylon was used as a drug in a post-processing to obtain a drug amount of 2%.
%, And dried at 130 ° C. for 5 minutes, and subjected to the same durability test for detergents. Table-
It is shown in FIG. In the table, "1" and "2" are the results of conducting each experiment twice.

In the example, it is shown that even if the temporary effect is reduced by the washing process, the effect is restored after a while, but in the comparative example, the effect is hardly restored.

Example 11 Next, an example in which the molded article of the present invention is used for nylon stockings will be described below.

The nylon 6 (O-diethyl phthalate 2.0% by weight) pellets used in Example 2 was
A fabric consisting of denier 24-filament fiber was used as a treated sample.

For comparison, a stocking cloth made of nylon 6 containing no O-diethyl phthalate (an untreated sample) was used.

(1) Repellent test for mites Test method: One petri dish at the center and six petri dishes around it so as to be in contact with it. The cloth of each sample is cut into a circular shape having a diameter of 3 cm, and three sheets are laid every other one of six surrounding petri dishes. In the meantime, three sheets are laid on the petri dish with the cloth of the untreated sample as a control. In the center of each sample, place 500 mg of a clean medium containing no ticks in a mountain shape, and in the middle petri dish, put a medium in which the test ticks have sufficiently propagated (2,000 or more as ticks) at 25 ° C / 75% After 3 days, the number of mites that had entered the culture medium of each petri dish after 3 days was counted (in 25 mg), and the repellent rate was calculated by the following formula. (Control group = medium on untreated sample, test group = medium on sample) In addition, the test was performed on the processed sample and the unprocessed sample as the above samples.

Test results: The repellent test results for Dermatophagoides farinae are shown in Table-6.

(2) Blood sucking repellent test against Aedes albopictus in the field Test method: This test took the form of a semifield test. In an area where Aedes albopictus frequently occurs in Takasago City, Hyogo Prefecture, both arms of an adult were used as a blood sucking source. First, without wearing the sample, the area from the tip of the hand to the upper arm was exposed, and it was confirmed that Aedes albopictus sucked blood. After confirming the state of sucking blood, the sample was covered from the hand to the upper arm, and the number of mosquitoes sucking blood for 20 minutes was counted. In the same manner, the control sample and the naked state were checked, and the repellent effect was evaluated based on the number of mosquitoes that sucked blood. This test was performed every other week for a total of three days.

Test results: The results of the repellent test for Aedes albopictus are shown in Tables 7 and 8.

(Effects of the Invention) Melt molded products such as fibers and films containing a specific amount of the dialkyl phthalate, adipate and fumarate of the present invention have a strong effect of inhibiting the growth of dust mites and repelling mosquitoes, and have good washing resistance. It is intended to provide a safe and effective pest control product for a long period of time.

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁶ Identification code FI // A01N 37/00 A01N 37/00 (72) Inventor Eiichi Kamoshida 370 Enzo, Chigasaki-shi, Kanagawa Prefecture Mitsubishi Chemical Corporation Chigasaki Business (56) References JP-A-58-129040 (JP, A) JP-A-61-176502 (JP, A) (58) Fields studied (Int. Cl. ⁶ , DB name) C08K 5/00-13 / 08 A01N 37/00-37/16

Claims (1)

(57) [Claims] A thermoplastic resin selected from the group consisting of a polyolefin resin, a polyamide resin and a polyester resin, wherein the insect-controlling components include dialkyl phthalate, dialkyl adipate and dialkyl fumarate (provided that the number of carbon atoms of these alkyl groups is A pest-controlling molded article containing 0.1 to 10% by weight of a resin composition obtained by melt-molding a resin composition containing only one or more drugs selected from 1 to 8).