KR100343537B1 - Composition of preservatives for wooden structural assets - Google Patents

Abstract

The present invention relates to a preservative for wood containing sulfamic acid amine salts and cationic surfactants as an active ingredient, the preservative for wood of the present invention is a flame retardant at the same time to the wood structure, including wooden cultural properties, in addition to It can provide antiseptic and insect repellent effect.

Description

Preservatives for wood {COMPOSITION OF PRESERVATIVES FOR WOODEN STRUCTURAL ASSETS}

The present invention relates to a wood preservative. More specifically, the present invention relates to a wood preservative for imparting flame retardant, anti-fog, antiseptic, and insect repellent effect to wooden structures including wooden cultural assets.

Wood is a widely used material for manufacturing construction, furniture, furniture, etc., but due to the nature of the material, it is very vulnerable to deterioration by fire, microorganisms, or various insects. In particular, in the case of wooden structures, most of them have reached the end of their life due to such fires or biodegradation. Therefore, it is possible to significantly improve the lifespan and performance of various structures made of wood by treating the wood with flame and insect repellent. Do.

Korea has many wooden cultural and stone cultural assets, which is called the country of wooden and stone cultural assets, among which the number of wooden cultural assets is overwhelmingly large. Although many wooden cultural assets have been lost due to various wars, some of them still remain, and some of them have been designated as World Cultural Heritage by UNESCO. The Daewoong Temple of Sudeoksa Temple (1308, National Treasure No. 49) was built in the Goryeo Dynasty, including the Bulguksa Temple of Buseoksa (National Treasure No. 18) and Bongjeongsa's Paradise Exhibition (National Treasure No. 15), the best wooden cultural assets in existence. ), Buseoksa Temple (1377, National Treasure No. 19), Eunhaesa Geojoam Yeomsangjeon, Gangneung Shrine Gate, etc. The early buildings of Joseon Dynasty include Muwisa's Paradise Exhibition, Gwanryongsa's Pharmacist's Exhibition, Janggoksa's Relative War, and Bongjeongsa's Daeungjeon (Treasure No. 55), and in the middle of Joseon Dynasty, there is Palgsangjeon Temple in Beopjusa (1624, National Treasure No. 55).

As can be seen from the existing Korean wooden cultural properties, if the proper preservation methods are taken, the life of the wood is over 1,000 years, but there is no preservation technique for such excellent wooden cultural properties.

Wooden cultural properties are made of wood, which is very vulnerable to fire, and has been a problem due to its weak resistance to mold, insects, and the like. Therefore, the wooden cultural property is very high risk of fire and biodegradation if it is not effective flame retardant, anti-fog, antiseptic, insect repellent treatment.

In recent years, major cultural assets such as Bongbongsa Daeungjeon (Treasure No. 163) and Geumsansa Daegukwangjeon (Treasure No. 476) were lost in 1984, and the damage caused by biodegradation was not significant. Gangneung guesthouse (National Treasure No. 51), Gaeamsa Temple in Buan, Jeonbuk (Treasure No. 292), Daeheungsa Temple Cheonbuljeon (Type Cultural Property) in Haenam, Haenam, Jeonnam, Tongdosa Pharmacist Dictionary (Type Cultural Property) in Yangsan, Gyeongnam, Daeungjeon (Type Cultural Property) in Sunam, Suncheon, Jeonnam, Korea It is known to suffer from the termite and wood corrosion, and there is a strong need for a preservative that provides proper flame retardant, anti-corrosive, antiseptic and insect repellent performance.

Wood, which has been widely used as a material of Korean wooden cultural properties, including pine, is suitable as a building material because of its excellent strength, bending resistance, and durability.However, the wood is strong and the surface is rough and cracks are generated when it is dried. It is easy to be infringed, and has been decorated with monochromatic surfaces. Dancheong is painted with greenish green as the ground color, and then uses various pigments such as Yangnok, Changdan, Guncheong, Samcheong, Lime Liquor, Yellow, Scarlet, True Powder, Lower Leaf, Multi-Purpose, Meat Color, and Ink on it. to be.

Conventional wood fire treatment agents have been used in water-soluble inorganic salts such as phosphates such as ammonium phosphate, sodium phosphate, sulfates such as ammonium sulfate, sodium sulfate and borax or boric acid. These water-soluble inorganic salts are excellent in flame retardant effect, but when these general wood flame retardants are applied to wooden cultural properties, they are insoluble and insoluble such as calcium sulfate or calcium phosphate by reacting with calcium carbonate of elutrium contained in cerebral green for a long time. It turned into a salt, causing whitening, which not only damaged the appearance of mono, but also reduced the flame resistance.

In addition, conventionally used as an antiseptic and preservative, as a water-soluble agent, a mixture of fluorides such as sodium fluoride, arsenic compounds, dichromic acid compounds and phenols such as dinitrocresol, and CCA-based agents known as PF-based (phenol fluoride) Known mixtures of chromium, copper, and arsenic compounds are known, and as an oil-soluble agent, pentachlorophenol and its derivatives, PCP-laurate, PCP-dihydroabiethylamine, trichlorophenol, and dinitrool cresol, are known as PCP. Phenolic compounds such as tribromophenol, tin compounds such as tributyltin oxide, tributyltin fumarate, and the like, and naphthenic acid metal salts such as copper naphthenate and zinc naphthenate. In addition, as a conventional insect repellent, a mixture of borax and boric acid is known as a water-soluble agent, and as the oil-soluble agent, dolphin, crowten, succinone, carbamate-based compounds, pyrethroid-based compounds and the like are known.

However, among these drugs, for example, PCP, Dallin, PF, tin, etc. have a bad effect on the environment and are currently prohibited to use, and drugs such as CCA or copper naphthenate differ in color after treatment. The mixture of borax and boric acid, which is a water-soluble agent, generates whitening after treatment in mono, and the oil-soluble agent is extremely insoluble in water and cannot be used in an aqueous solution.

In addition, the conventional methods for flame retardant, insect repellent, and antiseptic treatment for wooden structures are impregnated with a drug having a flame retardant performance first, and then dried and impregnated with a drug having a repellent, antiseptic property or, conversely, insect repellent and antiseptic performance. It has been prepared by impregnating a drug having a first and then dried by impregnating a drug having a flame retardant performance. However, these methods require two or more impregnation processes and two or more drying processes, which require a lot of processing time and drying costs, and may lead to the leaching of the first treatment agent in the second treatment process. It was difficult to obtain sufficient impregnation amount because the dried drug blocked the pores in the wood. Therefore, as an economical impregnation method, there is an urgent need for a method of preparing a one-component type of a drug having a flame retardant and an insect repellent and an antiseptic property in one-component form. However, in general, drugs having a flame retardant component are mostly inorganic salts as described above, and agents having an antiseptic and insect repellent component, on the contrary, are organic substances, and thus are incompatible with these drugs, making it difficult to manufacture them in one-part form, and thus they are not practical. There is a situation.

Accordingly, one object of the present invention is to overcome the disadvantages of the prior art described above, to provide a one-component wood preservative that can simultaneously impart flame retardant performance and anti-fog, antiseptic, insect repellent effect to various wooden structures, including wood, in particular wooden cultural assets To provide.

In order to achieve the above object, the inventors of the present invention have found that when the amine salt of sulfamic acid is used as a drug having a flame retardant performance, and a cationic surfactant is used as a drug having antifungal, antiseptic, and insect repellent performance, two components It is excellent in the miscibility of the one-component type, which can not only impart fire-proof, anti-fog, antiseptic, and insect repellent effect to wood at the same time, but more surprisingly, it has been found that no whitening phenomenon appears on the surface after treatment on wood. .

In the present invention, the term "finish" means mainly the effect of suppressing the surface contaminants of wood. Surface contaminants, depending on the type of surface contamination by bars, these surface contaminants representing different colors Aspergillus seusok (Aspergillus: black), Rizzo crispus in (Rhizopus: black), Fusarium genus (Fusarium: Red, Purple) there may be mentioned microorganisms of: (Monilia orange) glow Cloud Stadium in (Glocladium: green), in Trichoderma (Trichoderma:: green), Penny chamber ryumsok (Penicillium green), in monilriah. Because surface contaminants of wood do not degrade cellulose, which is a component of the wood cell wall, it does not involve changes in the strength of the wood, but contaminates the surface of the wood, which significantly lowers the aesthetic and commodity value of the wood.

On the other hand, "preservative" performance refers to the effect of suppressing the fungi of wood. Wood fungi include brown fungi that degrade cellulose, white fungi that degrade lignin, and soft fungi that differ slightly in their morphology. Unlike surface contaminants, these fungi accompany the strength of wood of any kind.

In the present invention, the term "wooden cultural property" refers to all other wooden buildings and wooden structures that have a preservation value, as well as cultural assets designated as national treasures, treasures, and tangible cultural properties managed by the Cultural Property Protection Act.

Amines of sulfamic acid amine salts in the components of the present invention may use ammonium, guanidine, guanyl urea and aliphatic amines, cycloaliphatic amines or heterocyclic amines.

Examples of aliphatic amines include any of primary amines, secondary amines and tertiary amines such as methylamine, dimethylamine, ethylamine, diethylamine, propylamine, dipropylamine, monoethanolamine, diethanolamine or triethanolamine. Amines can also be used, and examples of alicyclic amines include morpholine or cyclohexylamine, and heterocyclic amines such as imidazole, methylimidazole or 1-benzyl-2-methylimidazole, or benzotria Sols and the like.

Cationic surfactant which is another component of this invention can mention long-chain alkyl quaternary ammonium salt or long-chain alkyl amine salt etc. which have 8 or more and 22 or less carbon atoms.

Examples of long-chain alkyl quaternary ammonium salts having 8 to 22 carbon atoms include alkyl trimethyl ammonium salts, alkyl dimethyl ammonium salts, alkyl dimethyl benzyl ammonium salts, and mixtures thereof, and the form of the salt is applicable to hydrochloride or bromate. .

Examples of the long chain amine salt having 8 to 22 carbon atoms include alkyl dimethyl amine salts and mixtures thereof, and ethylene oxide adducts of long chain alkylamines. The salt may be used in the form of hydrochloride, bromate, acetate or formate.

The weight ratio of sulfamic acid amine salt and cationic surfactant is 1: 0.01 to 1.0, preferably 1: 0.05 to 0.50, and the content of the mixture is 1 to 80% by weight, preferably 5 to 40% by weight. %to be. When the weight ratio of sulfamic acid amine salt and cationic surfactant is 1: 0.01 or less, it is difficult to expect sufficient flavor and antiseptic properties, and when 1: 1 or more, miscibility between sulfamic acid amine salt and cationic surfactant is poor. In addition, when their content in the total mixture is 1% by weight or less, it is difficult to expect sufficient flame resistance, anti-corrosion, antiseptic, and insect repellency, and at 80% by weight or more, it is difficult to prepare a uniform one-component type due to the solubility of each component. Do.

As can be seen in the examples below, only the mixing of sulfamic acid amine salts and cationic surfactants as components of the present invention can impart sufficient flame retardant, anti-fog, antiseptic, and insect repellent properties to wooden cultural properties including wood. As long as it does not depart from the intended scope of the invention, other agents may be added to further enhance the desired performance of the present invention. Other drugs herein include boric acid, borax, ammonium monophosphate, ammonium diphosphate, ammonium sulfate, or ammonium hydrochloride as agents having flame retardant performance. Examples of agents having antiseptic and insect repellent properties include copper hexafluoride (CuSiF ₆ ), Hexafluoride silicate (ZnSiF ₆ ), ammonium dichromate [(NH ₄ ) ₂ Cr ₂ O ₇ ], sodium dichromate (Na ₂ Cr ₂ O ₇ ), copper sulfate, copper naphthenate, zinc naphthenate, boric acid , Borax, poultry, chlorophyllose or 3-iodine-2-propynylbutylcarbamate (IPBC).

These drugs can be used in a concentration of 5% or less, and when applied to 5% or more, for example, it is not only difficult to obtain whitening resistance to mono, but also difficult to produce a uniform one-component type.

Application method of the preservative treatment agent for wood according to the present invention can be treated directly on the wooden surface, for example, with a brush or sprayer in the case of the existing wooden cultural properties, in this case, after treating the preservative agent on the wood first may be coated with mono, It is also possible to apply the preservative agent of the present invention to the monochromatic monocoated and then to the monochromatic painted. In addition, in the case of general wood, the preservative can be used semi-permanently by penetrating deep into the wood by a decompression method, a pressurization method, or a pressure reduction method.

The present invention will be described in more detail with reference to the following Examples, but the protection scope of the present invention is not limited to these Examples.

Example 1

Preservative solution 1 was prepared by adding 5.5% of didecyl dimethyl ammonium chloride cationic surfactant and 3.0% of boric acid to an aqueous solution of triethanolamine sulfamate, which is 15% as a solid.

The preservative solution 1 was sprayed three times with a simple sprayer on the lumber of 19cm long, 29cm long, and 1.0cm thick, and dried at room temperature. Specimen 1 was made by coating cerebrum green with the ground color on the dried lumberwood, and again applying the flesh color on it.

Example 2

Preservative solution 2 was prepared by adding 1.0% of distearyl dimethyl benzyl ammonium bromide cationic surfactant to an aqueous solution of guanidine sulfamate having a solid content of 30%.

The preservative solution 2 was sprayed three times with a simple sprayer on the same size of lumberjack timber as in Example 1 and dried at room temperature. Specimen 2 was made by coating cerebrum green with the ground color on the dried lumber, and multi-purple on it.

Example 3

Preservative solution 3 was prepared by adding 5.0% of stearyl trimethyl ammonium bromide cationic surfactant to an aqueous solution of ammonium sulfamate, which is 20% in solid content.

On the lumber pine wood of the same size as in Example 1 was painted cerebrum green as a background color, and then dried by coating a multi-purple. Test green 3 and multi-purple painted pine wood was pretreated with preservative solution 3 three times with a simple atomizer and dried at room temperature to make specimen 3.

Example 4

A preservative solution 4 was prepared by adding 3.0% of lauryl dimethyl amine acetate cationic surfactant and 0.1% of chlorophyllose to an aqueous solution of ethylamine sulfamate, which is 10% solids. In the pressure impregnation impregnated with the same timber as in Example 1 and reduced the pressure to -76cmHg for 1 hour, preservative solution 4 was injected into the impregnator. After the injection of the preservative solution 4 was finished, pressurized again at 3 kgf / cm ² for 1 hour to dry the meat wood impregnated with the preservative overnight at 60 ℃. Specimen 4 was prepared by coating cerebrum green with dried ground pine wood as the base color.

Example 5

Preservative solution 5 was prepared by adding 1.5% of myristyl dimethyl amine formate cationic surfactant to an aqueous solution of sulfamic acid methylamine salt which was 15% in solid content.

In the same manner as in Example 4, impregnated with preservative 5, dried dried pine wood was coated with cerebrum green as the ground color, and then deep blue was applied to make specimen 5.

Example 6

Preservative solution 6 was prepared by adding 4.0% of distearyl dimethyl benzyl ammonium bromide cationic surfactant to an aqueous solution of sulfamic acid morpholine salt of 15% in solid content.

In the same manner as in Example 4, impregnated with preservative 6, dried green pinewood was coated with cerebrum green as the ground color, and then the color was painted to make specimen 6.

Example 7

Preservative solution 7 was prepared by adding 2.5% of didecyl dimethyl ammonium chloride cationic surfactant to an aqueous solution of 12% sulfamic acid imidazole salt as a solid.

After impregnating the preservative 7 in the same manner as in Example 4, dried green pinewood was coated with cerebral green as the ground color, and then scarlet was applied to make specimen 7.

Comparative Example 1

Test specimen 8 was prepared by coating cerebrum green with the ground color on the same size of lumber pine used in Example 1, which was not treated with a preservative.

Comparative Example 2

A 15% ammonium phosphate aqueous solution was sprayed three times with a simple atomizer to the same sized lumberwood used in Example 1, which was not treated with a preservative, and dried at room temperature. Specimen 9 was made by coating cerebrum green with dried green pine wood, and multi-purple on it.

Comparative Example 3

The green pine wood of the same size used in Example 1, which was not treated with a preservative, was painted with greenish green color in the background color, and then dried by applying multi-purple color thereon. A test specimen 10 was prepared by spraying three times a 10% ammonium sulfate aqueous solution on a green pine and multi-purple painted pine wood with a simple atomizer and drying at room temperature.

Comparative Example 4

In the depressurization and pressurization impregnator of Example 4, 15% ammonium phosphate aqueous solution was impregnated with the same size as that used in Example 1, which was not treated with a preservative in the same manner, followed by coating the greenish green color after drying. Trial blue was painted to make specimen 11.

Comparative example

In the reduced pressure and pressure impregnator of Example 4, a 10% ammonium sulfate aqueous solution was impregnated with a 10% ammonium sulfate aqueous solution in the same size as that used in Example 1, which was not treated with a preservative in the same manner. The dried test piece was put in the same pressure-reduction and pressure impregnator and impregnated with 3% aqueous solution of lauryl dimethyl amine acetate cationic surfactant, followed by drying. The two-stage treatment was performed. Specimen 12 was prepared by coating cerebrospin green on the treated specimens, and then applying blue-green on it.

Comparative Example 6

A 5.5% aqueous solution of didecyl dimethyl ammonium chloride cationic surfactant was added to the same size of lumberwood used in Example 1, which was not treated with a preservative in the same manner in the vacuum and pressure impregnator of Example 4. Impregnated to dryness. The dried test piece was placed in the same pressure-reduction and pressure impregnator again, and impregnated with 10% aqueous ammonium sulfate solution, followed by drying to treat the preservative first, followed by drying, followed by two-stage treatment. The treated specimens were coated with cerebral green and then painted with blue-blue on them to make specimen 13.

Flameproof performance test

Flameproof performance test was conducted on the three specimens produced in the Examples and Comparative Examples, "Fireproof Performance of Flame Retardant, etc.", Article 7 "KOFIS 1001," The average value was obtained after performing a flame retardant test according to "Measurement Standards and Methods". According to the Enforcement Decree, the time from the sample burner to the sample burner for 2 minutes and then the flame from the burner is removed and the time from burning to burning is over, the time from burning to flame without burning up. The remaining time, the carbonized area is carbon screen, and the carbonized length is defined as carbonized road. The acceptance criteria for KOFEIS 1001 are less than 10 seconds of residual flame time, less than 30 seconds of residual time, less than 20 seconds of carbonization distance and less than 50cm of carbon screen area.

Whitening resistance test

The specimens prepared in Examples and Comparative Examples were cut to a size of 5 cm in width and 15 cm in length, and after 120 hours were tested according to the accelerated weather resistance test method of KSM-5000, the surface of the specimen was visually inspected and examined for whitening. The evaluation value was calculated | required according to Table 1.

Evaluation Whitening outbreak situation 0 No whitening occurs in the specimen. One Mild whitening occurs on the surface of the test specimen. 2 Whitening strongly occurs on the surface of the test specimen.

Anti-Foaming Test

After 4 weeks of testing with the fungus R. nigricans and A. pullulans according to the method of Forestry Preservation Laboratory Standard No. 2 (1997), the cell development status of each specimen was observed. Evaluation values were obtained according to Table 2 below.

Evaluation Developmental Status of Cells 0 There is no mold development in the test body. One Mold development appears only on the side of the specimen. 2 The development of mold appears below the upper surface of the specimen. 3 The development of mold appears on the upper surface of the specimen.

Antiseptic effect test

According to the test method defined in KS M-1701 wood preservative (1997), the test body was tested for 3 weeks using brown fungus T. palustris and white fungus T.versicolor . The average mass reduction rate of was obtained. In KS, the average mass reduction rate is 3% or less.

Insect repellency test

According to the method set forth in the Forestry Preservation Laboratory Standard No. 10 (1997), after 3 weeks of testing using Japanese termites (Reticulitermes speratus) and termites (Coptotermes formosanus), the mortality rate and average mass reduction rate of the specimens were determined. In this case, the average mass reduction rate is 3% or less to evaluate the insect repellent effect.

The test results are shown in Table 3 below.

Flameproof Whitening resistance Anti-microbial effect Antiseptic effect (%) Insect repellent Afterglow time (sec) Remaining time (sec) Carbonization length (cm) Surface area (cm ² ) Weight loss rate (%) % Mortality Example 1 2 5 12 28 0 0 2.5 1.8 100 Example 2 0 0 7 21 0 0 1.9 1.3 100 Example 3 2 7 8 33 0 0 2.1 1.5 100 Example 4 3 4 10 24 0 0 1.8 1.8 100 Example 5 2 5 9 30 0 0 2.3 1.9 100 Example 6 0 3 10 25 0 0 1.8 1.6 100 Example 7 One 2 11 28 0 0 2.0 1.5 100 Comparative Example 1 450 470 26 284 0 3 31 29 27 Comparative Example 2 4 6 13 35 2 3 25 21 37 Comparative Example 3 2 5 11 43 2 2 29 22 28 Comparative Example 4 One 4 8 29 One 3 22 18 33 Comparative Example 5 80 110 25 69 2 One 2.7 15 25 Comparative Example 6 65 96 28 77 2 3 7.8 20 26

As can be seen from the experiments of the examples and comparative examples, the comparative examples not treated with the preservative agent of the present invention were not all failed in the standard test in flame retardant, defense, antiseptic, and insect repellent, but also whitening occurred on the surface of monochromatic. However, in the specimens treated with Examples 1 to 7 treated with the preservative treatment agent of the present invention, not only did they pass the standard test in flame retardancy, anti-fog, antiseptic, and insect repellent, but also showed that no whitening phenomenon occurred on the mono surface. Can be.

Wood preservatives of the present invention can not only give the flame retardant, anti-fog, antiseptic, insect repellent effect at the same time to the wood, such as various wooden structures, including wooden cultural properties, but also does not cause whitening phenomenon. Furthermore, the one-part liquid solution saves wood processing time and costs and is easy to use.

Claims (6)

A wood preservative, containing sulfamic acid amine salt and cationic surfactant as active ingredients. The preservative for wood according to claim 1, wherein the amine of sulfamic acid amine salt is ammonium, guanidine, guanyl urea or aliphatic amine, alicyclic amine, heterocyclic amine. The preservative for wood according to claim 1, wherein the cationic surfactant is a long chain alkyl quaternary ammonium salt or a long chain alkyl amine salt having 8 to 22 carbon atoms. The wood preservative of claim 1, wherein the weight ratio of the sulfamic acid amine salt to the cationic surfactant is 1: 0.01 to 1.0. The wood preservative according to any one of claims 1 to 4, which is used for preservation treatment of wooden cultural assets. The wood preservative according to any one of claims 1 to 4, which is a one-component type.