JPH0127042B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an insect repellent for clothing. Conventionally, insect repellents such as paradichlorobenzene, naphthalene, and camphor have been commonly used as insect repellent measures for clothing. Such insect repellents are usually put into a suitable form and put into clothing storage furniture, etc., but their effective period is at most 3 to 4 months, and they must be replaced with new insect repellents every time this period. It has the fatal disadvantage that the insect repellent effect cannot be sustained and that insect control management requires complicated steps. In addition, all of the above-mentioned known insect repellents have a strong, irritant odor, which has the disadvantage of staining stored clothing, and furthermore, the problem of toxicity cannot be ignored. In addition, pyrethroid insect repellents are widely used as general household insect repellents, but known pyrethroid insect repellents generally have low vapor pressure and are difficult to use as insect repellents for clothing that utilize gas effects. must be formulated into a dosage form with a huge surface area, making it impractical. In view of the above-mentioned current situation, the present inventors aimed to obtain an insect repellent that is safe, long-lasting, and odorless, exhibits an excellent gas effect at room temperature, and can be effectively used as an insect repellent for clothing. For this purpose, various studies have been conducted on a wide range of compounds. As a result, although it belongs to the category of synthetic pyrethroids, it has never been used as an insect repellent of this kind, and of course, the following specific esters, which have no known insect repellent effect against clothing pests, are highly effective and meet the above purpose. It has been found that it has a vapor pressure (usually on the order of ×10 ^-3 mmHg/30°C), a fast-acting and excellent insect repellent effect, extremely low toxicity, and odorlessness. The present invention was completed based on this new discovery. That is, the present invention is based on the formula (A) 1-ethynyl-2-methyl-2-
Pentenyl alcohol and (b) 2,2,3,3-tetramethylcyclopropanecarboxylic acid, 2,2-dimethyl-3-(2',
at least one ester with an acid selected from the group consisting of 2'-diclobinyl)cyclopropane-1-carboxylic acid and 2,2-dimethyl-3-(2'-methyl-1'-propenyl)cyclopropanecarboxylic acid; This invention relates to an insect repellent for clothing characterized by containing seeds as an active ingredient. The insect repellent for clothing of the present invention can exhibit an excellent insect repellent effect against various clothing pests such as bur moth, carp moth, Japanese carp beetle, Japanese carp beetle, etc., and the active ingredient compound has an extremely high vapor pressure. It can be expected to be fast-acting due to the gas effect, and it also has excellent performance such as being virtually odorless and having extremely low toxicity. In particular, the effective insect repellent concentration of the insect repellent of the present invention is about 1/1000 to 1/200 of that of paradichlorobenzene, naphthalene, and camphor, which are known representative insect repellents, as shown in the test examples described below. This is a low concentration. Therefore, it can exhibit a sufficient insect repellent effect even when used in an extremely small amount, and can dramatically extend the effective period when used in the same amount. Specifically, the esters used as active ingredients in the present invention are represented by the following chemical structures and chemical names. 1-ethynyl-2-methyl-2-pentenyl 2,2,3,3-tetramethylcyclopropanecarboxylate (hereinafter referred to as "Compound No. 1") 1-ethyl-2-methyl-2-pentenyl 2,
2-dimethyl-3-(2',2'-dichlorvinyl)
-Cyclopropane-1-carboxylate (hereinafter referred to as "Compound No. 2") 1-Ethynyl-2-methyl-2-pentenyl 2,2-dimethyl-3-(2'-methyl-1'-propenyl)cyclopropane-1-carboxylate (hereinafter referred to as "Compound No. 3") The above chemical structure The esters represented by (1) to (3) have steric and optical isomers, and any of these isomers can be used in the same manner in the present invention. The insect repellent for clothing of the present invention can be applied directly to places where an insect repellent effect is required, such as in various storage furniture used for storing clothes such as Japanese dance rooms, wardrobes, wardrobes, and costume boxes. However, it is usually preferable to use suitable carriers and other excipients, for example, in solid forms such as powders, granules, tablets, rods, and plates, or in emulsions, dispersants, suspensions, and sprays. It is prepared in the form of a liquid such as an aerosol, an oil, etc., and applied to control insect pests on clothing by a method according to each form. Examples of carriers (diluents) that can be used in preparing liquid formulations include water, alcohols such as ethyl alcohol, esters such as ethyl acetate, halogenated hydrocarbons such as dichloroethane, and ketones such as acetone and methyl ethyl ketone. Examples include ethers such as , tetrahydrofuran and dioxane, aliphatic hydrocarbons such as hexane, kerosene, paraffin and petroleum benzene, and aromatic hydrocarbons such as benzene and toluene. In addition, ordinary emulsifiers, dispersants, spreading agents, wetting agents, stabilizers, propellants, etc. can be added to the liquid agent, and ordinary film forming agents can also be added to form paints, adhesives, etc. You can also. Examples of the additives used include cellulose derivatives such as nitrocellulose, acetylcellulose, methylcellulose, and acetylbutylcellulose, vinyl resins such as vinyl acetate resin, alkyd resins, urea resins, epoxy resins, polyester resins, Urethane resin,
Silicone resins, acrylic resins, rubbers such as chlorinated rubber, various film forming agents such as polyvinyl alcohol; soaps, polyoxyethylene fatty alcohol ethers such as polyoxyethylene oleyl ether, polyoxyethylene nonyl phenyl ether, etc. Surfactants such as polyoxyethylene alkyl allyl ether, polyoxyethylene fatty acid ester, fatty acid glyceride, sorbitan fatty acid ester, sulfuric ester of higher alcohol, alkyl allyl sulfonate such as sodium dodecylbenzenesulfonate; Liquefied petroleum gas (LPG) ), dimethyl ether, and fluorocarbon; examples include casein, gelatin, alginic acid, and CMC. In addition, carriers used in preparing the solid form include various mineral powders such as silicic acid, kaolin, activated carbon, talc, calcium carbonate, and ceramic powder, as well as wood powder, bean powder, and wheat flour. , various vegetable powders such as starch, and clathrate compounds such as cyclodextrin. Furthermore, when preparing it in the form of a solid agent, for example, tricyclodecane,
Cyclododecane, 2,4,6-triisopropyl-1,3,5-trioxane, trimethylenenorbornene, paradichlorobenzene, naphthalene,
A sublimable solid agent can also be obtained by using a sublimable carrier such as camphor, and molding the carrier and the active ingredient compound by melt-mixing or grinding. In addition, the above solid agent includes
It also includes the form of a resin molded product in which the active ingredient compound is kneaded into plastic. In addition, the insect repellent for clothing of the present invention can be microencapsulated using a spray drying method using polyvinyl alcohol, CMC, etc., an in-liquid curing method using gelatin, polyvinyl alcohol, alginic acid, etc., a coacelvation method, etc. It can also be prepared in the form of a gel using a gelling agent such as benzylidene-D-sorbitol or carrageenan. The insect repellent for clothing of the present invention having various forms prepared in this manner is not particularly limited and can be determined as appropriate depending on each form, but usually the active ingredient compound is within a range of up to about 80% (by weight, the same hereinafter). , more preferably in the range of 0.1 to 65%. Furthermore, the insect repellent of the present invention may contain various synergists, antioxidants for improving stability, and other additives that are blended into known pyrethroid insecticides, if necessary. Here, preferred synergists include piperonyl butoxide, isobornyl thiocyanate, Riesene, S-421
Examples of antioxidants include butylated hydroxyanisole, dibutylated hydroxytoluene, tocopherol, and γ-oryzanol. The amount of these added is not limited, but it is appropriate to add up to 10 times the amount of the active ingredient compound, usually 1/50 to 10 times the amount. Other additives include PCMX, d-BCA, salicylic acid, benzoic acid,
Examples include volatile antibacterial and antifungal agents such as sorbic acid, 1-oxy-3-methyl-4-isopropylbenzene, OPP, and hinokitiol, and coloring and flavoring agents. The amount of the volatile antibacterial/antifungal agent additive is usually up to 70%, preferably 0.1 to 50%, of the formulation. Furthermore, the insect repellent of the present invention can also be used in combination with a known clothing insect repellent. When using the insect repellent of the present invention, it should be placed in places where insect repellent effects are required, such as inside clothing storage furniture.
Wrapping with suitable packaging materials, such as various known raised, crepe, net, layered papers, non-woven fabrics, cloth, etc., or applying without wrapping, by pouring, scattering, spraying, coating, pasting, etc. can do. In particular, since the active ingredient compound of the present invention is substantially odorless, it can also be applied in such a way that it comes into direct contact with clothing. In addition, the insect repellent for clothing of the present invention can be applied, for example, to a suitable sheet-like base material in advance by applying, impregnating, spraying, dropping, kneading, etc., and then transferring the insect repellent to the desired location in a form that is retained on the base material. It can also be applied to Examples of sheet-like base materials used in this case include polyethylene, polypropylene, nylon,
Synthetic resin sheets such as polyvinyl chloride, polyvinylidene chloride, polyester, etc., animal/plant or inorganic fiber sheets (paper, cloth, non-woven fabric, leather, etc.), mixed sheets or blended fabrics of synthetic resins and inorganic fibers or powders. Examples include blended fabrics or nonwoven fabrics of the above synthetic resins and animal and plant fibers, and laminated sheets of the above various sheets. Furthermore, the insect repellent for clothing of the present invention can be applied to wood used as a storage furniture member, such as thorn, pencil fern, camphor tree, yew, fir, fir, hemlock, japonica, zierton, agathis, cedar, Japanese walnut,
Beech, Quercus oak, Zelkova, Japanese elm, Mizume, etc.
It can be used by applying it to plastics such as vinyl chloride resin, chlorinated polyethylene, polyethylene, polypropylene, vinyl chloride-vinyl acetate copolymer, corrugated cardboard, etc. by applying, impregnating, spraying, dropping, kneading, etc. in advance. As a suitable holding means in the above, for example, a method of impregnating the furniture member with the active ingredient compound and a liquid that gels, crystallizes, or solidifies at room temperature separately or after mixing them in advance under normal pressure, reduced pressure, or increased pressure is exemplified. can. The liquid that gels at room temperature is a common gelling agent such as dibenzylidene-D-sorbitol, and the liquid that crystallizes or solidifies at room temperature includes, for example, acetanilide, dimethyl isophthalate, magnesium acetate, dimethyl terephthalate,
Maleic anhydride, lauric acid, stearyl alcohol, petroleum-based solid paraffin, animal and plant solid wax, sodium tetraborate (decahydrate), sodium aluminum sulfate, magnesium sulfate (hexahydrate),
Examples include 2,4,6-triisopropyl-1,3,5-trioxane, tricyclodecane, cyclododecane, trimethylenenorbornene, and disodium hydrogen phosphate (pentahydrate). The insect repellent for clothing of the present invention applied in this manner has strong efficacy and appropriate volatility, and the duration of the effect can be varied as necessary. It can easily maintain its efficacy for years, and when it is made into powder, granule, sublimation preparations, etc., it can be effectively volatilized in small amounts for short-term use.
Furthermore, there is almost no smell, it is odorless or can be scented to your liking, and clothes that have been in the drawer for a long time can be put on immediately after being taken out of the drawer.
It has many advantages and is of high industrial value. Next, the present invention will be specifically explained with reference to Examples. Example 1 Single-sided polyethylene laminate nonwoven fabric (PE80μ
A mixture of compound No. 3 and butylhydroxyanisole = 5:1 parts by weight was applied to the non-woven fabric (thickness) so that compound No. 3 was 5 g/m ² , and then polyethylene (80 μ thick) was heat-sealed to the non-woven fabric side. A three-layer insect repellent sheet was manufactured. Example 2 Compound No. 2 was applied to 0.9 m ² tattoo paper at a concentration of 2 g/m ² to produce an insect repellent sheet for a Japanese dance bon. Example 3 Compound No. 1 was placed on 100 mmφ x 3 mm pulp cardboard.
A pine-like insect repellent sheet was produced by applying the product at a concentration of mg/cm ² . Example 4 Compound No. 3: Silicic acid: Cyclododecane = 1:
After sufficiently crushing and mixing 1:98 parts by weight, the mixture was compressed into 10 g/tablet under a pressure of 300 Kg/cm ² and wrapped in nonwoven fabric to obtain an insect repellent. Example 5 Compound No. 1: dimethyl terephthalate: cyclododecane = 3:50:47 parts by weight was dissolved by heating at 100 to 120°C. x 20mm) and pressure treated at 15Kg/ ^cm2 , approximately 50% of the weight of the wood, approximately 1Kg as impregnated amount.
Impregnated with. Next, an extract was produced using these two side plates and one facing plate, and the extract was placed in a chest of drawers for use. Example 6 Compound No. 8: Cyclododecane = 1:19 parts by weight was extracted according to the treatment in Example 5, and the side plate and facing plate were impregnated to produce a processed extract of about 1 kg in total, and placed in a chest of drawers. there was. Example 7 Compound No. 1: Aerosil #200 = 1:4 parts by weight were sufficiently stirred and mixed and pulverized, and 10 g of the mixture was filled into a non-woven fabric bag and used. Example 8 Compound No. 3: Hydrocarbon solvent (bp200-280
An insect repellent aerosol for clothing having a composition of 5:35:60 weight percent of LPG was produced and subjected to the test described below. Example 8 Compound No. 2: Nitrocellulose (5-7 seconds):
Dibutyl phthalate: Thinner = 3.8: 5: 2.8:
A paint of 910 parts by weight was prepared and applied to the inside of the extractor drawer and the lower part of the receiving plate so as to have a thickness of 50 μm after the solvent was distilled off. Example 10 A cardboard paper with vinylidene chloride coated nylon/polyethylene laminated to a thickness of 20 μm on one side was treated with a dichloromethane solution containing 10% Compound No. 3 at 110 ml/m ² from the other side, and after the solvent was distilled off, the size was 500 x 800 x 200.
A costume box with a lid of mm was manufactured and used. Test Example 1 A predetermined amount of the active ingredient compound was placed in a shear dish at the bottom of a 10-volume glass container in stages, and then 20 carp moth larvae, 30 days old, and ^{a 2}
Place a 60-mesh nylon bag containing mg) in the container so that it does not come into contact with the above compound, and after sealing.
Leave it in a dark place at 25℃. After a week, open the container and
Measure the amount of feeding damage (mg) on muslin cloth. Calculate the feeding damage rate (%) from the above amount of feeding damage using the formula below. Feeding damage rate (%) = Amount of fabric feeding damage after the end of the test (mg) / Fabric weight before starting the test (mg) × 100 Amount of active ingredient compound when the above feeding damage rate (%) shows 2% (mg per container) , hereinafter referred to as LC _0.02 ), the results are shown in Table 1 below as the average value of the same test conducted twice. For comparison, Table 1 also shows the results of the same test using paradichlorobenzene and naphthalene. Table 1 Active ingredient compounds LC _0.02 (mg/) Compound No. 1 0.04 Compound No. 2 0.02 Compound No. 3 0.01 Paradiclobenzene 8 Naphthalene 6 Test Example 2 Efficacy tests of the formulations shown in Examples 1 to 9 were conducted. The procedure was carried out according to Example 1. The container contains 60 pieces of clothing.
Larvae were placed using water extraction two weeks after the preparation, and the test period was two weeks. Also, Example 6,
Regarding No. 7, similar tests were conducted over time. The results are shown in Table 2 below in the same manner as Test Example 1 (Table 1). For comparison, Table 2 also shows the results of a similar test using a commercially available naphthalene preparation.

[Table] Test Example 3 The effectiveness test of the costume box shown in Example 10 was conducted according to Test Example 1. The larvae were placed two weeks after the clothes were placed, and the test period was two weeks. Similar tests were also conducted over time. The results are shown in Table 3 below in the same manner as Test Example 2 (Table 2).

[Table] Test example 4 Glass chiare (diameter 8cm, height 4cm, capacity
10 bur larvae and a piece of wool (2 x 2 cm) that had not been treated with chemicals were placed in a 200 ml solution. A net was placed over the top of the shear tray, and paper (2 x 2 cm) impregnated with the active ingredient was placed in the center of the net. Furthermore, a glass of the same capacity was placed on top of it with the lid on, so that the content became 400 ml. The wool pieces were exposed to the chemical for 24 hours using the method described above, and the feeding damage rate and mortality rate of the wool pieces were observed, and the feeding damage repelling effect was observed.

【table】

[Table] The compound of the present application showed a good feeding damage repelling effect while keeping lethal efficacy at a low level, whereas d-allethrin did not show the same effect. On the other hand, the control paradichlorobenzene showed 100% lethal efficacy at the above dose, but the feeding damage rate was higher than that of the compound of the present invention. Test example 5 A triangular prism box made of plywood (3 cm on each side, 7.5 cm in height)
cm, with both sides sealed with cardboard. However, one side comes with a 0.5 x 1 cm booth. ) to release 10 test larvae. A sheet of chemically treated glass wool paper (2 cm ² ) with varying amounts of application was hung inside this triangular prism box, and these triangular prism boxes were placed in a glass shear (diameter 12 cm, height 6 cm), and after 4 hours. The expulsion effect was evaluated.

[Table] * Known transpiration insecticides

[Table] The compound of the present invention expelled bur moths and Japanese cutworms at extremely low doses, and a clear repellent effect was observed. On the other hand, no significant effect was observed with d-allethrin using this test method. Furthermore, 2, which is known as a heating type repellent,
As a result of comparison with t-butyl-4-hydroxyanisole and paradichlorobenzene, which is known as an insect repellent for clothing, the compound of the present invention has a sufficient effect of repelling clothing pests at a lower application rate than these. I found out that I have it. Test Example 6 A test was conducted using carp moth according to the method of Test Example 4. However, the drug exposure period was 7 days. The results are shown in the table below.

【table】

[Table] As shown in the above table, Compound No. 3 exhibited superior feeding damage effects compared to tetramethrin, resmethrin, and comparative compounds A, B, and C described in JP-A-49-132230.

Claims (1)

[Claims] 1 (A) Formula 1-ethynyl-2-methyl-2-
Pentenyl alcohol and (b) 2,2,3,3-tetramethylcyclopropanecarboxylic acid, 2,2-dimethyl-3-(2',
at least one ester with an acid selected from the group consisting of 2'-dichlorovinyl)cyclopropane-1-carboxylic acid and 2,2-dimethyl-3-(2'-methyl-1'-propenyl)cyclopropanecarboxylic acid; An insect repellent for clothing characterized by containing seeds as an active ingredient.