KR100787957B1 - Composition for wood preservative and insecticide - Google Patents

Abstract

A wood preservative and insecticide composition is provided which shows significantly improved antiseptic and insecticidal effect with low toxicity and has excellent stability. A wood preservative and insecticide composition comprises an antiseptic and insecticidal ingredient, a blending stabilizer and the remaining amount of an organic solvent, wherein the antiseptic and insecticidal ingredient consists of 3-iodo-2-propynylbutyl carbamate and 2-(4-ethoxyphenyl)-2-methylpropoxybenzyl ether. The composition further comprises an oxidation preventing agent such as phenyl diisodecyl phosphite.

Description

Composition for wood preservative and insecticide

The present invention relates to a wood preservative insect repellent, and more particularly used in conjunction with 3-iodo-2-propynylbutylcabamate (hereinafter referred to as 'IPBC') which is an organic iodine-based compound O, O-diethyl-O- (3,5,6-trichloro-2-pyridyl) -phosphothioate (O, O-diethyl-O- (3,5,6) -trichloro-2-pyridinyl) phosphorothioate (hereinafter referred to as 'chlorpyrifos'), but also to provide an improved antiseptic insect repellent effect as well as to a new wood preservative insect repellent composition with excellent stability.

Recently, as the standard of living of the people has improved significantly, interest in the nature-friendly living environment has been greatly increased. As a result, the use of natural wood as a material for building materials such as interior and exterior materials, structural materials, door frames and floorboards, as well as outdoor furniture, parks, recreation facilities, and log cabin facility materials is on the rise.

However, natural wood has a great problem in terms of preservation of wood because biodegradation is inevitably progressed by various fungi, blue fungus or fungi, insect pests such as Hirada powder or termite.

To prevent this problem, various preservatives used in wood have been developed, especially 4-chlorophenyl-3-iodo propargyl formal, 3-bromo-2,3- Diiodo-2-propenylethyl carbonate (3-bromo-2,3-diiodo-2-prophenyletyhl carbonate), 2,3,3-triyodoallyl alcohol (2,3,3-triiodoallyl alcohol), IPBC, etc. Organic iodine preservatives are widely used.

Among the organic iodine-based antiseptic agents, IPBC represented by the following Chemical Formula 1 blocks the supply of organic substances and inorganic substances necessary for bacterial growth by interacting with chitin, and inhibits the growth inhibitory activity of cell units such as interfering with the metabolism of extracellular fluid. In addition, it has a wide range of antibacterial effects, has no accumulation in the natural environment, is low in toxicity (LD ₅₀ = Rat 1580 mg / Kg), and its use is gradually increased as it is relatively strong in target organisms.

As a technology related to the IPBC, the present applicant has more than 1% by weight of chloropyriphos as an organophosphorus compound and 0.25% to 0.5% as an organic iodine compound based on 100% by weight of the total in Korean Patent No. 326767. Has disclosed a technique for a wood preservative composition composed of a stabilizer for wood preservatives and an organic solvent.

However, the wood preservative insecticide containing the IPBC as an active ingredient is to break down the IPBC when exposed to a light source as shown in Scheme 1 to generate a radical having a strong oxidizing power. The generated radicals cause problems such as corrosion of steel in the building structure.

In order to solve the above problems, the applicant of the present invention in the Republic of Korea Patent No. 441428, IPBC 0.25 to 0.5% by weight, chloropyriphos 1% by weight, antioxidant 0.02 to 0.2% by weight, stabilizers 1 to 5 with respect to 100% by weight total antiseptic There has been suggested an antiseptic insecticide comprising a weight% and a residual amount of an organic solvent.

As described above, the antiseptic agent disclosed in Korean Patent No. 326767 and Korean Patent No. 441428, previously filed and registered by the present applicant, has an excellent antiseptic and insect repellent effect by using chloropyriphos together with IPBC. It can be seen.

However, due to its toxicity to humans and the environment, chloropyriphos is classified by the Ministry of Environment as a toxic substance 97-1-290, and the US Environmental Protection Agency has reported that it damages the brains of pups in the placenta of rats in mice. Due to human toxicity, the US Environmental Protection Agency prohibits the production, distribution, and use of chlorpyriphos and its products for all household and children's facilities until 31 December 2001. Japan has also banned the use of building materials containing chlorpyrifos in accordance with the July 2002 Revised Building Standards Act and the July 2003 Sick House Syndrome Measure. In particular, chloropyrophore is pyrolyzed when heated, releasing toxic chlorides, nitrogen oxides, sulfur oxides, and phosphates.It is very irritating to the eyes and skin, causing exposure to symptoms such as headache, dizziness, vomiting, diarrhea and sweating. There is a problem that can be.

Accordingly, the present inventors have completed the present invention after studying a preservative insect repellent for wood of a novel composition having excellent stability as well as showing excellent anti-toxic insect repellent effect without using chloropyriphos.

Therefore, the present invention has a purpose to provide a wood preservative insect repellent excellent in stability as well as exhibit an excellent antiseptic insect repellent effect is excellent.

In order to achieve the above object, the present invention provides an antiseptic insecticide composition for wood comprising an antiseptic insecticide component, a miscible stabilizer and a residual amount of organic solvent, wherein the antiseptic insecticide component is 3-urido-2-propynylbutylcarbamate (3 -iodo-2-propynylbutyl carbamate (hereinafter referred to as 'IPBC') and 2- (4-ethoxyphenyl) -2-methylpropyl 3-phenoxybenzyl ether (2- (4-ehthoxyphenyl) -2-methylpropoxybenzyl ehter; It provides a wood preservative insect repellent composition, characterized in that consisting of `` Etofenprox (ehtofenprox) '').

Hereinafter, the wood preservative insect repellent composition according to the present invention will be described in detail.

According to the present invention, it is characterized by using IPBC and etofenprox as preservative components in a conventional wood preservative composition containing an antiseptic component as an active ingredient.

Here, IPBC is a component commonly used in conventional antiseptics, and IPBC is 0,0-diethyl-0- (3,5,6-trichloro-2-pyridyl) -phosphothioate Has been used in combination with " chloropyrophosph ". However, as described in the prior art, chloropyriphos exhibits a very strong problem for humans and the environment, and its use is limited because it may be discontinued in the future.

Accordingly, in the present invention, in order to lower the toxicity of the wood preservative composition, etofenprox having a structure of the following Chemical Formula 2 was used together with IPBC instead of chloropyriphos used in the wood preservative.

Table 1 below shows the results of toxicity comparison between etofenprox used in the antiseptic agent of the present invention and chloropyriphos widely used in the conventional antiseptic agent.

Product Name Etofenprox Chloropyrifoss CAS No. 80844-07-1 2921-88-2 Ecotoxicity Pisces Amphibians, Crustaceans, Cyclops, Fishes, Insects, Aquatic Plants, Veterans, Nematodes, Molluscs, Echinoderm, Zooplankton, Phytoplankton Acute Toxicity (LD ₅₀ ) > 42,880 mg / kg Medium 250 mg / kg Neurotoxicity no highly toxic

Where (LD ₅₀ ) represents the amount necessary for 50% of the rats to die, the higher the value, the safer.

As can be seen in Table 1, it can be seen that etofenprox has a very low toxicity compared to chloropyriphos. In particular, since the value of (LD ₅₀ ) of etofenprox is much higher than that of (LD ₅₀ ) of IPBC, it can be seen that it is a very low toxicity material.

However, as is well known, etofenprox is a substance that is not used at all for wood preservatives because it has a very weak antibacterial activity as well as a weak antiseptic effect in spite of being used as a pesticide. In spite of this weak antiseptic effect, when used in combination with IPBC, the etofenprox shows strong antibacterial and antiseptic effect by complementary action. In addition, the antiseptic spindle mixed with etofenprox and IPBC also inhibits the photolysis of IPBC without the use of antioxidants.

As a result, the antiseptic composition for wood according to the present invention having IPBC and etofenprox as an effective antiseptic component is low toxic and excellent antiseptic insects compared to the conventional wood antiseptic insecticide composition having chloropyriphos and IPBC as an effective antiseptic component. Not only can the effect be obtained, but also has an excellent photolysis inhibition effect.

At this time, when the IPBC and etofenprox are 100% by weight of the total antiseptic composition, IPBC is added to be contained at 0.25 to 0.5% by weight, and etofenprox is preferably added to be contained at 0.1 to 1.0% by weight.

If the content of IPBC is 0.5% by weight, 100% of the representative brown fungi Tyromyces palustris and Serpula lacryman s, and the representative white fungus Coriolis In the case of Colicus versicolor ( Coriolus versicolor ) it is not necessary to add more than 0.5% by weight because it shows more than 99% antiseptic effect, there is a problem that the antiseptic effect is lowered when the content of IPBC is less than 0.25% by weight. Therefore, the IPBC is preferably added so as to contain 0.25 to 0.5% by weight relative to 100% by weight of the total composition.

In addition, when the content is less than 0.1% by weight of the insect repellent effect is not only the insect repellent effect of the IPBC to prevent the effect of complementing the antiseptic effect is insufficient, if the content exceeds 1.0% by weight more insect repellent effect Since the above improvement does not improve, it is preferable to add etofenprox so that 0.1 to 1.0 weight% may be contained with respect to 100 weight% of total compositions.

The solvent of IPBC and etofenprox is primarily dissolved in conventional organic solvents such as acetone and techsol, but again in a non-aqueous, nonpolar solvent such as kerosene in order to increase the dissolution efficiency of IPBC. It can be dissolved and used. When the organic solvent is 100% by weight of the total composition, the remaining amount is added except for the added weight of components other than the organic solvent.

In addition, to the wood preservative composition of the present invention, an emulsion stabilizer added to a general wood preservative composition is added. Herein, the emulsion stabilizer may be added within the usual addition range. In the present invention, when the total composition is 100% by weight, the emulsion stabilizer is added so as to contain 1 to 5% by weight.

As described above, the wood preservative insecticide composition according to the present invention composed of IPBC and etofenprox, an emulsion stabilizer, and an organic solvent not only shows excellent antiseptic insects by the complementary action of IPBC and etofenprox but also has an excellent photolysis inhibitory effect. .

In order to obtain a better photolysis inhibitory effect, an antioxidant may be further added, which is stabilized by receiving radicals having strong oxidizing power that are produced by decomposition when IPBC is exposed to a light source.

The antioxidant may be selected from those commonly used, preferably phenyldiisodecyl phosphite.

In addition, the antioxidant may be added so as to contain 0.02 to 0.2% by weight when the total antiseptic composition is 100% by weight. Here, when the addition amount of the antioxidant is less than 0.02% by weight it is not possible to obtain a sufficient anti-corrosive effect, and when the addition amount exceeds 0.2% by weight since the anti-corrosive effect is no longer enhanced, the antioxidant is contained within the above range. It is preferable to add so that.

As a method of applying the preservative composition of the present invention to the wood as described above, a spraying method or a dipping method, which is usually performed, may be used, which may be variously changed according to a user's selection according to a working environment.

Hereinafter, the present invention will be described in more detail with reference to the following examples, which are only presented to aid the understanding of the present invention, but the present invention is not limited thereto.

<Examples 1 to 10>

20 g of acetone (about 25.3 ml) was dissolved by adding IPBC and etofenprox in the amounts shown in Table 2 below, and 40 g of polyoxyethylene sorbitan monooleate was added as an emulsion stabilizer. Taxol was added until the total weight was 1000 g to prepare a wood preservative composition.

Comparative Example 1

20 g of acetone (about 25.3 ml) was dissolved by adding IPBC and chloropyriphos in the amounts shown in Table 2 below, and 40 g of polyoxyethylene sorbitan monooleate was added as an emulsifying stabilizer. Taxol was added until the total weight was 1000 g to prepare a wood preservative composition.

Experimental Example 1 Antibacterial Test

 39.0 g of Potato-Dextrose Agar (hereinafter PDA, Hardy Diagnostics, USA) was dissolved in 1000 ml of secondary distilled water (agar 1.0% w / v) and sterilized by autoclaving. Sterile PDA was poured into the culture dish by 20 ml and hardened. This is prepared by the number of the antiseptic composition prepared in Examples 1 to 10 and Comparative Example 1. The preservative composition for wood preservatives was applied three times using a cotton swab to the prepared PDA medium.

Inoculated with the antimicrobial yeast fungus ( Aspergillus niger ) in a separate PDA medium without any treatment and incubated for 5 days, the mycelia were cut into 5 × 5 mm to treat the wood preservative composition It was placed in the middle of one PDA medium and fresh untreated PDA medium and incubated at 27 ° C. for 5 days.

 The diameter of the hyphae grown in each test piece was measured, and the area of the hyphae was determined using the diameter of the hyphae. Thereafter, as shown in Equation 1 below, the area where hyphae were grown in the PDA medium treated with the wood preservative insect repellent composition was divided by the area where the hyphae were grown in the untreated PDA medium to obtain the percentile, as shown in Equation 1 below. .

Experimental Example 2 Post-test

Fresh untreated PDA medium prepared in the same manner as in Experimental Example 1 was inoculated with fingerling mushrooms ( Coriolus velcicolor ; Coriolus versicolor ) and fluff fungus ( Ketomium globosum ; Chaetomium globosum ) and incubated for 15 days. .

 As a test wood piece, pine sapwood was prepared in a size of 20 × 20 × 10 mm (± 0.5 mm), and the preservative insecticide composition prepared in Examples 1 to 10 and Comparative Example 1 was applied to wood pieces three times using a brush, and then 60 times. Dry at ± 2 ° C. Two pieces of wood for each composition were treated to measure the weight of each to 0.01g units, one was inoculated with fingering mushrooms, the other was inoculated with fluff fungi and incubated at 27 ℃ for 12 weeks.

 The mold was removed from the finished wood pieces, dried at 60 ° C., and weighed to 0.01 g. The fungicidal inhibition was determined by the ratio of the weight of the wood remaining after the test to the weight of the wood before the test.

Experimental Example 3 Insecticidal

As a test wood piece, pine sapwood was prepared in 20 × 20 × 10 mm (± 0.5 mm), and the preservative insecticide composition prepared in Examples 1 to 10 and Comparative Example 1 was applied to the wood pieces three times using a brush and then 60 ±. It dried at 2 degreeC, and measured the weight of each processed wood piece to 0.01g unit.

Termites (10 soldier ants, 100 ants) were placed in an insect culture dish prepared as many as the number of compositions and incubated at 26 ° C. for 14 days.

The death rate (%) was calculated by measuring the number of dead individuals in the culture plate after the incubation, and the weight of the wood pieces after the test was measured to 0.01 g units, and calculated as shown in Equation 3 below to determine the inhibitory power.

Experimental Example 4 Light Stability

20 ml of the antiseptic insecticide compositions prepared in Examples 1 to 10 and Comparative Example 1 were placed in 8 transparent glass bottles, respectively, and then sealed, and then 60, respectively, in a sunlight (Toshiba DR 400 / T) and an ultraviolet lamp (Toshba GL 15). 120, 180, 240, 300, 360, 420, 480 hours were exposed. After unsealing the transparent glass bottle, 10 ml of the light-irradiated solution was taken, concentrated to 2 ml, and dissolved in 0.5 ml of chloroform, which was then gas chromatograph (GA-15A) manufactured by Shimazu, Japan. The remaining amount of IPBC was measured with. The decomposition rate was calculated by dividing the measured residual amount by the initial content, and the results are shown in Table 3 below.

The analysis conditions of the chromatography were the initial temperature of 80 ° C., the final temperature of 320 ° C., the temperature increase rate of 10 ° C./min, and the sample injection and detector temperature of 250 ° C. The carrier gas was 40 cm / sec using helium, and the nonpolar column CBP1. -S25 was used.

division IPBC (g) Etofen Prox (g) Antimicrobiality (%) Antibacterial ability (%) Insecticidal (eating power;%) Fingering mushroom Fluff fungus Example 1 2.0 5 73.7 42.5 58.7 92.3 Example 2 2.5 5 92.3 94.9 92.6 93.8 Example 3 4.0 5 99.6 98.4 95.2 94.5 Example 4 5.0 5 99.9 99.9 99.9 95.4 Example 5 5.5 5 99.9 99.9 99.9 95.6 Example 6 4.0 0 77.7 88.3 89.5 0.0 Example 7 4.0 0.9 86.3 89.8 91.4 79.7 Example 8 4.0 One 98.1 91.1 92.6 90.6 Example 9 4.0 10 99.8 98.8 98.9 96.9 Example 10 4.0 11 99.8 98.7 98.9 96.9 Comparative Example 1 5.0 10 g (chloro pyphos) 99.9 97.5 99.3 92.6

division Light stability (IPBC decomposition rate) 60 hours 120 hours 180 hours 240 hours 300 hours 360 hours 420 hours 480 hours Example 1 0.1 0.3 0.7 1.3 1.8 2.2 2.7 3.1 Example 2 0.1 0.4 0.9 1.3 1.7 2.0 2.4 2.7 Example 3 0.1 0.4 0.8 1.0 1.5 2.0 2.2 2.3 Example 4 0.1 0.3 0.7 1.2 1.4 1.7 2.3 2.7 Example 5 0.1 0.4 1.0 1.7 2.5 3.2 3.8 4.4 Example 6 42.3 43.2 44.7 45.1 48.8 48.9 49.2 49.5 Example 7 27.2 27.5 27.6 27.6 27.7 27.7 27.9 27.9 Example 8 4.7 4.9 5.2 5.1 5.3 5.2 5.4 5.3 Example 9 0.1 0.3 0.8 1.1 1.5 1.7 1.9 2.0 Example 10 0.2 0.3 0.6 0.7 0.9 1.3 1.5 1.6 Comparative Example 1 40.5 43.5 43.8 44.9 48.5 48.6 50.0 50.1

As shown in Table 2, it can be seen that an excellent antiseptic insect repellent effect is obtained when IPBC and etofenprox are mixed and used. In particular, it can be seen that in Examples 2 to 4, Examples 8 and 9 in which etofenprox and IPBC were mixed within the preferred range of the present invention, antimicrobial activity, fungi suppression, and insecticide were very excellent.

More specifically, in Examples 1 to 5 in which the content of IPBC was changed while the content of etofenprox was fixed, the amount of IPB was less than the range of the present invention. It can be seen that it exhibits inhibition and insecticidal properties. This shows that when a mixture of IPBC and etofenprosper at a predetermined component ratio shows a significantly increased effect by the complementary action. Similarly, in Examples 6 to 7, wherein the content of etofenprox was changed to less than the scope of the present invention in Examples 6 to 10 in which the content of etofenprox was fixed while the content of IPBC was fixed, compared to Example 8 It can be seen that it shows significantly low antibacterial, fungal inhibition and insecticidal. In Example 5 and Example 10, but excellent antibacterial, fungal inhibition and insecticidal properties, it can be seen that it does not show a significantly enhanced effect compared to Examples 4 and 9.

As described above, the present invention is a toxic organophosphorus insecticide used with 3-iodo-2-propynylbutylcabamate, which is an organic iodine compound, as an antiseptic component used in the related art. Phosphorus O, O-diethyl-O- (3,5,6-trichloro-2-pyridyl) -phosphothioate (O, O-diethyl-O- (3,5,6-trichloro-2- pyridinyl) phosphorothioate) instead of 3-ureo-2-propynylbutylcarbamate and 2- (4-ethoxyphenyl) -2-methylpropyl 3-phenoxybenzyl ether (2- (4-ehthoxyphenyl) -2 The use of -methylpropoxybenzyl ehter) is not only very low toxicity but can also provide an improved insect repellent effect, and has a useful effect of providing a new composition of preservative insect repellents having excellent stability.

Claims (5)

In the wood preservative composition comprising an antiseptic component, a miscible stabilizer and a residual organic solvent, The antiseptic component is 3-iodo-2-propynylbutyl carbamate and 2- (4-ethoxyphenyl) -2-methylpropyl 3-phenoxybenzyl ether (2- (4-ehthoxyphenyl) -2-methylpropoxybenzyl ehter) wood preservative composition, characterized in that consisting of. The method according to claim 1, The 3-urido-2-propynylbutyl carbamate is contained in an amount of 0.25 to 0.5% by weight based on 100% by weight of the total antiseptic agent composition, and the 2- (4-ethoxyphenyl) -2-methylpropyl 3-phenoxy Sibenzyl ether is preservative composition for wood, characterized in that containing 0.1 to 1.0% by weight. The method according to claim 1, 0.25 to 0.5 wt% of 3-ureo-2-propynylbutylcarbamate, and 0.1 to 2- (4-ethoxyphenyl) -2-methylpropyl 3-phenoxybenzyl ether, based on 100 wt% of the total preservative composition 1.0% by weight, 1 to 5% by weight of a misc stabilizer, and a residual amount of an organic solvent. The method according to any one of claims 1 to 3, The preservative insect repellent composition for wood, characterized in that it contains 0.02 to 0.2% by weight of an antioxidant that is stabilized by receiving radicals that are photodegradation products of 3-urido-2-propynylbutyl carbamate. The method according to claim 4, The antiseptic composition for wood, characterized in that the antioxidant is phenyldiisodecyl phosphite.