JP3414469B2 - Acaricide composition - Google Patents

Description

Detailed Description of the Invention

[0001]

The present invention relates to relates Boda Western over preparative formed by applying Boda two compositions and the same. More particularly, tatami, carpets, walls, ceiling, floor or as a spread cloth, further building materials, anti <br/> da formed by applying Boda two composition and it that can be used as a packaging material on Nishi over door.

[0002]

2. Description of the Related Art In recent years, due to changes and advances in housing structures and equipment, indoor airtightness has improved, and with the spread of cooling and heating, living spaces for residents have become comfortable. However, it is at the same time insurance health unfavorable, a condition suitable for growth of da two of which micro-organisms.

[0003] In addition, many mites occur on tatami mats and jutan
However, the number of cases of damage is increasing. Furthermore, there is no underfloor and ventilation
Molds on the tatami mats in poorly-built houses, and as a result, mites
It is an unfavorable environment for hygiene that increases the occurrence of
There is.

[0004] Conventionally, against these damages, pyrethroid insecticides (resmethrin, permethrin, phenothrin, etc.) and organophosphorus insecticides (diazinon) are applied to house dust mites such as house dust mites, mosquito mites, Dermatophagoides farinae, mites and dust mites. , Fenitrothion, etc.), Carbamate insecticides (Proboxur, etc.)
, Etc. have been used, but they had the drawback that only specific mites were effective. In addition, there is a problem that a large amount is required because the effect is weak as a whole.

Recently, in order to eliminate such a situation ,
Mite growth, drugs that are effective in both preventing breeding have been reported.

4-Chlorophenyl-3-iodopropargyl formal (Japanese Examined Patent Publication No. 3-76282) is a compound which is known as a fungicide but also has a high effect as an anti-mitic agent.

3-Bromo-2,3-iodo-2-propenylethyl carbonate (Japanese Patent Laid-Open No. 63-93702) is also known as a fungicide, but it is also a highly effective compound as an anti-mitic agent.

2,3,3-Triiodoallyl alcohol (JP-A-1-125303) is also known as a fungicide, but it is also a highly effective compound as an anti-mitic agent. These iodine compounds are generally vulnerable to light, are unstable over time such as discoloration, and are relatively liable to volatilize and lack long-term sustainability.

In order to solve this problem, the present inventors have added an antioxidant and a light stabilizer to improve the stability over time, form a coating film, and mix it with an adhesive. ,
Attempts have been made to improve the persistence of efficacy.

However, although the above-mentioned methods were able to improve the respective objectives to some extent, practically satisfactory effects were obtained, such as a delay in developing the tick- proof effect and a decrease in efficacy. Not.

Accordingly, it is an object of the present invention is excellent <br/> is the mite effect, sustained stable efficacy over a long period of time, further Boda double composition with a stable quality without unevenness and it the object of the present invention is to provide a Boda Western over door formed by coating. And to provide a Boda western over preparative that are expected to contact effects a sheet or spatial effect utilizing the properties of the drug, respectively.

[0012]

That is, the gist of the present invention is as follows: (1) 4-chlorophenyl-3-iodopropargyl formal, 3-bromo-2,3-iodo-2-propenylethyl carbonate and 2, An anti-da, which contains at least two compounds selected from the group consisting of 3,3-triiodoallyl alcohol as an active ingredient.
Two- agent composition, (2) 4-chlorophenyl-3-iodopropargyl formal, 3-bromo-2,3-iodo-2-propenylethyl carbonate and / or 2,3,3-triiodoallyl alcohol The mixing ratio is 1:20 by weight.
1: the in the first range (1) Boda double adhesive composition according, (3) fixing agent and / or further comprising said humectant (1) or (2) above, wherein the Boda two agents composition, (4) the (1) to (3) either ing by applying a Boda two agents <br/> composition according to the porous substrate to explosion d'Nishi over preparative, (5) coating is the mixing ratio of the active ingredient and binder in Boda double adhesive composition, a weight ratio of 1: 0.5 to 1: wherein the range of 5 (4) Boda Western over preparative described, (6) mixing ratio of humectant in the applied as Boda double adhesive composition, with respect to basis weight of 100 g / m ² sheets, 3
Wherein a to 10 g (4) Boda Western over preparative described, (7) the binder is a vinyl-based resin (4) Boda Western over preparative described, and (8) humectants polyalkylene glycol there wherein (4) Boda Western over preparative described relates.

[0013] Boda two compositions of the present invention, 4-chlorophenyl-3-iodopropargyl formal, 3-bromo-2,3-iodo-2-propenyl-ethyl carbonate and 2,3,3-triiodo It is characterized in that it contains at least two compounds selected from the group consisting of allyl alcohol as active ingredients. in this way,
By containing these two or more kinds of compounds, a synergistic effect on the tick-preventing effect, which was not observed in the conventional single use, was observed. While in sheet material, the spatial effect and contact specific Boda two effects are obtained simultaneously (see Test Example). In the present invention, the combination of these active ingredients is not particularly limited, but a combination containing at least 4-chlorophenyl-3-iodopropargyl formal as one of the active ingredients is preferable.

In this case, these compounding ratios are 4-chlorophenyl-3-iodopropargyl formal and 3-chlorophenyl-3-iodopropargyl formal.
The weight ratio of bromo-2,3-iodo-2-propenylethyl carbonate and / or 2,3,3-triiodoallyl alcohol is preferably in the range of 1:20 to 1: 1 and more preferably It is in the range of 1:15 to 1: 1. If it is less than 1:20, the mites-preventing effect is particularly likely to decrease
When it exceeds 1: 1, 4-chlorophenyl-3-iodopropargyl formal has high volatility and is easily decomposed with time, which is not preferable.

The composition of the present invention has various forms depending on the purpose of use, such as oil, emulsion, wettable powder, powder, granules, aerosol, paint, or a preparation obtained by impregnating paper or non-woven fabric with the composition. Can be used as

The amount of the composition of the present invention used and the amount of the active ingredient are appropriately determined depending on the formulation, application method, application site and the like. The throughput of these active ingredients is usually 0.1 per m ^2.
Is about 20 g, preferably 1.0 to 10 g.

[0017] Boda two compositions of the present invention, other active ingredients of the solvent, binder, humectant, stabilizer, ultraviolet inhibitor, perfume, can additionally contain a synergist, and the like. In this case, to contain fixing agents and / or humectants, excellent mite effect, also preferred for sustaining and stable efficacy over a long period of time.

The composition of the present invention may be one which does not contain a fixing agent and / or a moisturizing agent as long as it contains the above-mentioned active ingredient. You may mix and use it. When the composition of the present invention contains a fixing agent and / or a moisturizing agent in advance, the content of the fixing agent is usually 0.2 to 25 g / m ² , preferably 1 to 2
It is 0 g / m ² , and the content of the moisturizer is usually 1 to 10 g.
/ M ² , preferably 2 to 6 g / m ² .

The role of the sticking agent is to hold the active ingredient stably and, moreover, to release the active ingredient gradually with time. Therefore, examples of the adhesive used include vinyl resins, cellulose derivatives, alkyd resins, urea resins, epoxy resins, polyester resins, urethane resins, silicone resins, chlorinated rubber, PVA, and the like, Considering the stability of the active ingredient, the solubility in a solvent, the degree of sticking to a sheet, etc., a vinyl resin is preferable. Examples of vinyl resins include vinyl acetate resins, vinyl acetate-vinyl chloride copolymer resins, polyvinyl butyral, and acrylic resins. In use, the viscous type is preferable to the solidified type. Usually 15-5
It is used as an emulsion of 0% by weight, preferably about 30% by weight.

Most commonly used moisturizers are surfactants, and the types thereof are soaps, polyoxyethylene fatty acid alcohol ethers, polyoxyethylene alkyl ethers, polyoxydiethylene fatty acid esters, fatty acid glycerides, sorbitan fatty acid esters and the like. There is. These surfactants are not preferable because they have a strong ability to elute active ingredients when the sheet is exposed to water. Further, higher alcohols often generate an unpleasant odor, which is not preferable in an environment where humans inhabit. In addition, fungi and other nutrient sources should be avoided as much as possible. Therefore, in the present invention, considering these various conditions, moreover, it is a high-boiling-point liquid that easily adheres to the feet such as mites,
Examples of the substance that facilitates the supply of the active ingredient to the sheet surface include room temperature liquids of polyalkylene glycol, solids, waxes, and the like, and room temperature liquids of polyalkylene glycol are most suitable as a moisturizer.

Among the polyalkylene glycols, those which are liquid at room temperature include polyethylene glycols 200, 300, 400 and 600 (trade name PEG-20).
0, 300, 400, 600, Sanyo Chemical Industry Co., Ltd.)
And polyoxypropylene glycol (trade name, Sannix PP-400, 1000, 3000, Sanyo Chemical Industry Co., Ltd.), polyoxyethylene polyoxypropylene glycol (trade name, Newpol PE-61, 62,
64, manufactured by Sanyo Chemical Industry Co., Ltd. and polyalkylene glycol derivative (trade name, Calarin 102, 104, 20)
2, Sanyo Chemical Industry Co., Ltd., and the like.

[0022] Boda Western over preparative of the present invention is characterized by comprising applying a more Boda two agents <br/> composition to the porous substrate. Examples of the porous substrate used include paper such as filter paper and kraft paper, non-woven fabric, woven fabric, and porous membrane.
As a coating method, brush coating, spraying, dipping, a coating machine, gravure printing, or the like can be used.

[0023] Boda Western over the door of the present invention, the anti-mite effect
Considering, it is preferable that the fixing agent and humectants and amounts as follows.

That is, regarding the compounding ratio of the adhesive, the compounding ratio of the above-mentioned active ingredient and adhesive is 1: 0.2 by weight.
It is preferably in the range of 5 to 1: 2.5, and 1: 0.
It is more preferably in the range of 5 to 1: 2. The blending ratio of the binder is 1: 0.25 to decrease is smaller than a mite effect, contrary to 1: 2.5 mite effect as well beyond the lowered.

The blending ratio of the humectant is preferably ³ to 10 g, and more preferably 5 to 9 g, based on the basis weight of the sheet of 100 g / m ² . Mite effect is reduced to be less than 3g, ing to feel too wet and more than 10g. Here, the basis weight of the sheet means the thickness or weight of the sheet, and the weight of the sheet per 1 m ² .

Examples of the solvent used include a mixed solvent of alcohols and water, a mixed solvent of ketones and water, and the like. Here, as alcohols, ethyl alcohol,
Examples include normal propyl alcohol and isopropyl alcohol. Acetone etc. are mentioned as ketones. Alcohol and water ratio is 1: 1 when making the sheet
~ 9: 1 is preferred.

[0027]

EXAMPLES The present invention will be described in more detail with reference to test examples, but the present invention is not limited to these test examples.

Test Example 1 IF-1000, Sampras, TIA were used as reagents.
Each sample was prepared by using A and diluting it with acetone to adjust the concentration of the reagent agent so that the coating amount shown in Table 1 was obtained.
The composition of the present invention is a mixture of two or more of the above, and the comparative product is used alone.

The general compound name of the reagent is IF-
1000 is 4-chlorophenyl-3-iodopropargyl formal, Sampras is 3-bromo-2,3-iodo-2-propenylethylcarbonate, TIAA is 2,
3,3-triiodoallyl alcohol.

2 ml of the obtained sample was applied to Toyo filter paper No. 5A having a diameter of 12.5 cm and dried in air for 3 hours. After air-drying, it was cut into a size of 6 cm × 12 cm, folded into two, and about 50 test mites were put in the inside as a guide, and the three sides were sealed with clips. Kona moth mites are stored in a container (humidity 84% RH) whose humidity is adjusted with a saturated potassium chloride aqueous solution at room temperature (25 ± 4 ° C.), and H. mites are humidified with a saturated sodium chloride aqueous solution at room temperature (25 ± 4 ° C.) It preserve | saved in the adjusted container (humidity 75% RH). After 24 hours, the clip was opened, and the number of test mites and the number of dead mites were examined with a stereoscopic microscope.

This test was repeated three times, and the mortality rate was calculated from the following formula. The test results are shown in Table 1.

[0032]

[Equation 1]

[0033]

[Table 1]

As is clear from Table 1, the composition of the present invention has a higher mite mortality rate than the comparative product used alone, and it is clearly recognized that the respective reagent agents have a synergistic effect.

Test Example 2 Each sample having the composition shown in Table 2 was applied to a nonwoven fabric (manufactured by Teijin UNICEF, BT-040EW) (total amount of active ingredient: 2 g).
/ M ² ) to produce a test sheet, and the test sheet immediately after production and stored at room temperature for 12 months after production,
The following test was carried out to check the effect of preventing ticks (miticide) and mold.

(1) Mite control test In the test, acarid mite was used as a test insect. A mini tatami mat (20 × 20 cm) was prepared, and a test sheet and a chemical-free sheet (as a control) were put inside the tatami mat and stored for 2 weeks at a temperature of 25 ° C. and a humidity of 75%. After storage, 2 g (approximately 20,000) of mites were planted together with the breeding medium at room temperature (25
It was left for 3 weeks in a container (humidity 84% RH) whose humidity was adjusted with a saturated potassium chloride aqueous solution at ± 4 ° C.

After 3 weeks, 10 × 10 cm on this mini tatami mat
Two black paper sheets of No. 3 were placed for 10 minutes, and the number of ticks active on the front and back of the black paper sheet was examined, and the growth inhibition rate was calculated from the following formula. Two weeks after the mite planting, 2 g of powdered feed serving as a mite feed was added to the tatami mat.

[0038]

[Equation 2]

(2) Antifungal test In the test, a mixed bacterium consisting of the following test bacteria was used. 1. Aspergillus niger IA
M 3001 2. Penicillium citrinu
m) IFO 6026 3. Gliocladium vire
ns) IFO 6355 4. Clados Polium
porium cladosporioides) IFO 6368 5. Aureobasidiu
m pullulans) IFO 6353

The test method was as follows: 1 ml of each of the test bacteria cultivated in malt broth medium at 25 ° C. for 3 days was inoculated in a Petri dish (diameter 9 cm) containing 20 ml of potato dextrose agar medium and mixed with 5 species. Place the test sheet (25 cm ² ) on this medium as bacteria and 2
The width of the growth inhibition zone for the bacteria was measured after 1 week at 5 ° C. The above results are shown in Table 2.

[0041]

[Table 2]

As is clear from Table 2, the compositions of the present invention (Sample Nos. 14 to 16) were used alone (Sample No. 14).
Compared with 11 to 13), the 12-month-old sheet has a higher mite growth inhibitory rate and an excellent antifungal effect, and it is clearly recognized that the stable effect lasts for a long period of time.

Test Example 3 As shown in Table 3, 10% by weight of a reagent agent containing various active ingredients and 8% by weight of PEG-400 (humectant)
And fixing agent (vinyl acetate resin 50% emulsion) 20
A sample solution prepared by diluting and mixing a drug solution consisting of 60 wt% with 62 wt% of isopropyl alcohol and water (weight ratio 9: 1) was applied to kraft paper to prepare a sheet (active ingredient amount 2 g / m ² ). Further, this sheet was stored at room temperature for 12 months to prepare a test sheet. The mite-preventing effect of this test sheet was examined. In this test, the properties of the sample liquid before coating were observed. The test method for tick prevention is as follows.

Each test sheet was cut into a size of 6 × 12 cm and folded in two, and about 50 test mites were put in the inside of the test sheet as a guide, and the three sides were sealed with clips. This was stored at room temperature (25 ± 4 ° C.) in a container (humidity 84% RH) whose humidity was adjusted with a saturated potassium chloride aqueous solution. After 24 hours, the clip was opened and the mortality rate was examined with a stereoscopic microscope. The repetition was repeated 3 times each. The mortality rate was calculated according to Test Example 1.

[0045]

[Table 3]

As is clear from Table 3, in the composition of the present invention, when the weight ratio of IF-1000: Samplus was less than 1:20 (Sample Nos. 20 and 21), the lethality was decreased. Was given.

Test Example 4 ( Effect of Adhesive Amount) IF-1000: Sampras: TIAA (2: 5: 3)
7% by weight of the active ingredient of PEG-400 (humectant)
A chemical solution consisting of 10% by weight and a fixing agent (vinyl acetate resin 50% emulsion) X% by weight (X is a value shown in Table 4) is mixed to 100% by weight with a mixed solvent of isopropyl alcohol and water (weight ratio 9: 1). Apply the sample to kraft paper (3
0 g / m ² ) to prepare a sheet. Further, this sheet was stored at room temperature for 12 months to prepare a test sheet.

With respect to this test sheet, the anti-mite effect and the anti-mold effect were examined. The effect of preventing mites was the same as in Test Example 3. The antifungal test method is as follows. Place the wallpaper on the test sheet so that it fits the actual situation, stop with clips, spread the filter paper on a glass petri dish 9 cmφ, add sufficient sterilized water, and leave it on the filter paper with the wallpaper surface of each sheet facing up. , Aspergillus niger
100 μl of spore suspension (bacterial density 1.00 × 10 ³ )
After dripping and culturing at 25 ° C. for 1 week, the density of Aspergillus niger was measured. The results are shown in Table 4 .

[0049]

[Table 4]

As is clear from Table 4 , in the composition of the present invention, when the mixing ratio of the active ingredient and the fixing agent is out of the range of 1: 0.25 to 1: 2.5 by weight, the anti-corrosion effect is not obtained. reduction of the two effects were observed.

Test Example 5 (Effect of amount of moisturizer) IF-1000: 7% by weight of active ingredient of TIAA (1: 4), adhesive (vinyl acetate resin 50% emulsion) 1
A drug consisting of 8% by weight and X% by weight of humectant (PEG-400) (X is a value shown in Table 5) was mixed to 100% by weight with a mixed solvent of isopropyl alcohol and water (weight ratio 9: 1). Applied sample to kraft paper (30g / m ² )
Then, a sheet was prepared. In addition, this sheet at room temperature for 12
It was stored for a month and used as a test sheet.

With respect to this test sheet, the effect of preventing mite and fungus was examined. The effect of mites was the same as in Test Example 3, and the fungicidal effect was the same as in Test Example 2. The results are shown in Table 5 .

[0053]

[Table 5]

As is clear from Table 5 , in the composition of the present invention, the blending ratio of the moisturizing agent is 10% by weight of the sheet.
If it goes out of the range of ³ to 10 g with respect to 0 g / m ² , dust prevention
Reduction of the two effects were observed. When the amount of humectant was small, the drug transfer to the surface of the sheet was incomplete and the efficacy was lowered. On the other hand, if the moisturizing agent is too much, the drug on the surface of the sheet comes into contact with the hand or the wrapped packaging material, and the drug is exposed. Further, when the amount of the moisturizing agent is large, the sheet itself has a moist feel, which causes a problem in the commercial property.

[0055]

Boda Nishi over bets Boda formed by two compositions and applying it to the present invention exhibits excellent mite effect and its effect is immediate, and stable over a long period of time It has a long-lasting effect and a stable quality with no variations.

Continuation of front page (51) Int.Cl. ⁷ Identification code FI A01N 47/06 A01N 47/06 A (56) References JP-A-63-41405 (JP, A) JP-A-63-44504 (JP, A) ) JP-A-2-304003 (JP, A) JP-A-5-112406 (JP, A) JP-A-5-117105 (JP, A) JP-A-60-239401 (JP, A) JP-A-56- 123907 (JP, A) JP 61-97204 (JP, A) JP 1-125303 (JP, A) JP 60-218301 (JP, A) JP 2-47360 (JP, A) JP 63-93702 (JP, A) Lee, Dong Heub, "Fungal detoxificatione of organodiodes, preservatives, 1994, No. 1p p.81-86, 81-86 Lee, Dong Heub, "Fungal detoxificatio n of organodiodine wood preservatives. Fungal metabolis in the decomposition o, Holzforschung, 1992, Vol. 46, No. 6, pp. 467-469 Lee, Dong Heub, "Photostability of or ganiodine wood preservatives. II. The Photophysical processes, of preservi vikas. 37, No. 3, pp. 261-265 Lee, Dong Heub, "Photostability of or ganoiodine wood preservatives. I. Prog less degrai pla. Lee, Dong Heub, "Application of the crossed-paper technique to the evaluation of the synergistic is, 1990, 1990. 36, No. 12, pp. 1095-1099 (58) Fields surveyed (Int.Cl. ⁷ , DB name) A01N 31/14 A01N 25/10 A01N 25/24 A01N 25/34 A01N 31/02 A01N 47/06 CA (STN) REGISTRY (STN )

Claims (8)

(57) [Claims] 1. At least one selected from the group consisting of 4-chlorophenyl-3-iodopropargyl formal, 3-bromo-2,3-iodo-2-propenylethyl carbonate and 2,3,3-triiodoallyl alcohol. Boda two composition characterized by containing the two compounds as an active ingredient. 2. 4-Chlorophenyl-3-iodopropargyl formal and 3-bromo-2,3-iodo-2-
Propenylethyl carbonate and / or 2,3,3-
The compounding ratio of triiodoallyl alcohol is 1: by weight.
1:20 Boda double composition of claim 1, wherein in the first range. 3. A fixing agent and / or further comprising a humectant claim 1 or 2 Boda double agent composition. 4. Anti d'Western over preparative ing by applying a Boda two agents <br/> composition according to the porous substrate in any one of claims 1-3. 5. The compounding ratio of the active ingredient and binder in the coating is the Boda double adhesive composition, a weight ratio of 1: 0.25
1: Boda Western over preparative according to claim 4, wherein in the range of 2.5. 6. A mixing ratio of humectant in the applied as Boda double adhesive composition, with respect to basis weight of 100 g / m ² sheets, Boda Western over preparative according to claim 4, wherein a 3 to 10 g. 7. sticking agent Boda Western over preparative according to claim 4, wherein the vinyl resin. 8. Boda Western over preparative according to claim 4, wherein the humectant is a polyalkylene glycol.