KR100917665B1 - The method of preparing anti-flame compositions for preserving wooden cultural asset - Google Patents

Abstract

A fireproof composition for the conservation of wood cultural properties, and its preparation method are provided to improve fireproofing property, rotproofing property and insect control effect, reduce air contact and to prevent the absorption of moisture. A method for preparing a fireproof composition for the conservation of wood cultural properties comprises the steps of adding 8~12 wt% of guanidinophosphate to 86~90 wt% of distilled water and stirring it at 84~90 °C for 30 min; adding 0.5~2 wt% of formalin to the mixed one and reacting it at 80~83 °C and at 2 atm for 1~2 hours in a closed vessel; cooling the resultant to a room temperature to obtain a solution; and adding 0.2~0.5 wt% of a penetration accelerant, 0.1~0.5 wt% of a wood preservative, 0.1~0.3 wt% of an anticorrosive and 0.05~0.2 wt% of a silane coupling agent to the solution, homogenizing the mixture, and filtering the homogenized one.

Description

Flame-retardant composition for preserving wooden cultural properties and its manufacturing method {THE METHOD OF PREPARING ANTI-FLAME COMPOSITIONS FOR PRESERVING WOODEN CULTURAL ASSET}

The present invention relates to a flame retardant composition for preserving wooden cultural properties and a method of manufacturing the flame retardant as a flame retardant composition containing guarine phosphate as a main component and formarin, a surfactant, a wood preservative, an anticorrosive agent, a silane capping agent, and water. The present invention relates to a flame retardant composition suitable for the preservation of a cultural property and a method of manufacturing the same, which are excellent for preservation, insect repellent effect, prevent discoloration and fall of monochromium, and moreover, prevent the corrosion of the metal material constituted with the wooden cultural property.

Structures such as palaces, temples, seowon, and old houses, which make up a large part of the cultural assets, are mainly made of wood, which has two major weaknesses in terms of cultural heritage preservation.

First of all, most of the materials that make up the wooden cultural properties of Korea are vulnerable to fire because they are inherently combustible, and secondly, compared to inorganic materials such as stone, wood is more resistant to weathering and bacteria, mold, insects, etc. This is due to the fact that the wooden cultural property is relatively short in life due to its low resistance.

Flame retardant treatment of wooden cultural properties should satisfy the demanding conditions that should not cause deterioration of wood itself or discoloration of monochromatic, but in reality, flame retardant treatment is not only the most effective for preventing fire of wooden cultural properties, but also has insect repellent and antiseptic effect. In view of the fact that the life span of the cultural property can be extended, it is very important for the nation to develop and disperse excellent wood flame retardant compositions.

Conventionally, wood-based flame retardant treatment methods using ammonium phosphate, sodium phosphate, sulfate, borax, etc., mainly using water-soluble inorganic salts, are inorganic flame retardants as time passes after flame retardant treatments due to the hygroscopic properties of these water-soluble inorganic salts. There is a problem that the salt is precipitated on the surface of the wood, so that the flame retardant effect is lowered. Also, when the surface of the cultural property is coated with monochromatic or the like, there is a problem that whitening, discoloration, and deterioration of the monochromatic are caused.

In order to solve these drawbacks, a method of thermally infiltrating a flame retardant in the form of a thermosetting resin into wood has been proposed, but this method has a problem in that it cannot be applied to large wood structures that are difficult to heat-treat.

Meanwhile, in the conventional method of treating cultural properties, the insecticide and the antiseptic effect have been mainly used for heavy metals or strong toxic substances, but it also has the problem of causing the discoloration of monochromatic as well as harmful to the human body.

In short, as a conventional flame retardant composition and treatment method known in the wood can be expected flame retardant itself, there is a problem that can not prevent discoloration and deterioration such as bleaching of white, deterioration, etc., conventional insect repellent and antiseptic treatment method human body In addition, there is a need for improvement as there is a problem that causes harmful deterioration and monochromatic deterioration. For example, the report of Sungnyemun Flame Retardant, which is included in the National Audit Policy Data Sheet of 2008, contains Daimpox III, which has been used as a wood preservative since 1984 (Dimefox Ⅲ). ) Is a preservative that has the problem of damaging the main wooden cultural property because of the discoloration of the color of the monochromatic to appear whitening phenomenon, the occurrence of the monochromatic falling and absorbing moisture.

In recent years, most of the compositions focusing only on the fire prevention and preservation of wooden cultural properties, such as metal doors, iron ornaments, hinges, etc., which are composed of parts of wooden cultural properties by infiltrating or coating them during construction. The corrosion of the external metal parts is severe and is a situation that is emerging as a big problem.

As a recent example of the above problems, the fall of the column (Historic No. 157) column surface, Mihwangsa Daeungjeon (Treasure No. 947) have been severely damaged by moisture, and the door ring iron ornaments have been corroded and Yongjusa (National Treasure No. 120) Due to the continuous damage cases such as the damage of iron and steel plants in Korea, there is a need for preservatives that have no problem in flame retardant performance as well as whitening, peeling, absorption and corrosion of iron fences.

The present invention is a flame retardant composition for preserving and improving the wooden cultural properties to improve the problems of the prior art, and excellent flame retardant, antiseptic and insect repellent effect, to prevent the discoloration and fall of monochromatic and to prevent corrosion of the metal parts constituted together in the wooden cultural properties The present invention provides a flame retardant composition for preserving wooden cultural properties and a method of manufacturing the same.

In order to achieve the above object, the present invention provides a method for preparing a composition consisting of guanadine phosphate, formarin, a surfactant (polyoxy ethylen nonyl phenol), wood preservatives, anti-corrosion metals, water, and a composition according to the present invention. Could.

In the present invention, the flame retardant composition for preserving wooden cultural properties has excellent flame retardancy, antiseptic property, and insect repellent effect, preventing discoloration, peeling and staining of the single layer, and easy construction, and the addition of the silane capping agent improves the effect of falling off and preventing the single layer. It is a flame retardant composition for the preservation of wooden cultural properties, which can expect the synergistic effect of wooden cultural properties along with the antiseptic function of wood preservatives by reducing the contact of air and preventing the absorption of moisture due to the compactness of the coating structure.

Flame retardant composition of wooden cultural properties according to the present invention is 8 to 12 wt% phosphate guanadine salt, 0.5 to 2 wt% formalin, 0.2 to 0.5 wt% penetration accelerator, 0.1 to 0.5 wt% wood preservative, 0.1 to 0.3 wt% anticorrosive, silane capping It can be referred to as a cultural property flame retardant composition of 0.05 ~ 0.2wt%, 86 ~ 90wt% of distilled water.

After adding guanadine phosphate 8-12 wt% to the composition content and stirring it for 30 minutes with a stirrer while maintaining the temperature in the range of 84-90 ° C., adding 0.5-2 wt% of formalin at 2 atm, 80 After maintaining at ~ 83 ℃ and reacted for 1 to 2 hours and then cooled to room temperature 0.2 ~ 0.5wt% penetration promoter, 0.1 ~ 0.5wt% wood preservative, 0.1 ~ 0.3wt% anticorrosive agent, 0.05 ~ 0.2wt It is a manufacturing method of flame retardant composition of wooden cultural property obtained by adding and stirring% to homogenize.

In the above method, heating the primary guanadine salt is sufficiently dissolved in water, and in the second heating, the amount of formalin evaporates if it is not heated in an airtight container.

In addition, when various additives are added, the sealed container is cooled to room temperature to lower the vapor pressure, thereby preventing the amount of evaporation of formarin.

The guanadine phosphate salt tends to cause whitening when an active ingredient having excellent flame retardancy or formalin is not added or a small amount is added. Formarin also has excellent miscibility with guanidine phosphate, which inhibits evaporation of formarin and provides excellent insect repelling effect. Have In addition, the penetration promoter may include at least one penetration promoter selected from polyoxyethylene nonylphenol, ethoxy lated nonyl phenol, ethoxylated octylphenol, ethoxylated sorbitan laurate, sodium ethoxylated and ethoxylated sulfate. use. Indeed, the penetration promoter also has the function of a dispersant or a surfactant, so that it can more easily penetrate deep into the wood tissue and obtain a homogeneous composition.

As a wood preservative, one or more wood preservatives selected from sodium fluoride, sodium silicate, and acid fluoride ammonium organic compound (tributyl oxite) are used. By inhibiting the fungal activity of the wood to prevent the degradation of cellulose and lignin of the wood.

The anticorrosive is to use one or more anticorrosive selected from the group consisting of a dicyclohexyl ammonium carbamate, a higher fatty acid salt of ammonium fluoride amine, sodium mercapto-benzodia, a polymer amine compound (cationic active agent), and an organic sulfur compound. Their action is to adsorb on the surface of the metal or chemically combine with the metal to form a thin film on the surface to have a corrosion protection function and to prevent severe corrosion of the metal parts in the wood cultural properties that are a problem recently. Will have

In addition, in the composition relationship of the flame retardant composition, the water composition is controlled to some extent, so that the concentrated liquid can be used if the corrosion condition is severe. However, the composition ratio of the phosphate guanadine salt and the formalin is extremely important. The specific mechanism is unknown, but whitening occurs in the monolayer when no formalin is added or a small amount is used.

If a large amount of dispersant, preservative, anticorrosive, etc. is used, some inorganic salts may precipitate out of the composition that penetrates between the wood and the monolayer, causing the color of the monolayer to deteriorate, which may cause environmental pollution. The possibility cannot be ruled out.

Based on the embodiment according to the present invention will be described a clear technical configuration and effect of the flame retardant composition.

Example (1) Add 11 kg of guanadine phosphate to 87 kg of distilled water to maintain a temperature of 85 to 88 ° C., stir for 30 minutes with a stirrer to dissolve completely, transfer the guanadine phosphate solution to a closed tank, add 1 kg of formalin, and pressurize to 2 After adjusting to atmospheric pressure and keeping the temperature at 80 ~ 83 ℃ for 1 hour, the sealed container was cooled to room temperature and stirred by adding 0.4kg of penetration accelerator, 0.3kg of wood preservative, 0.2kg of anticorrosive, and 0.1kg of silane capping agent. After homogenization by filtration to prepare a flame retardant composition of the present invention through filtration to evaluate the performance of the flame retardant composition.

1. Flame resistance test (KOFEIS 0201)

The specimens were made of flawless wood without domestic pine knots with a total specific gravity of 0.44 (± 0.44), and three (1, 2, 3) specimens of 100 mm tangential width, 290 mm fiber length and 5 mm radial thickness were made.

Each test piece was leaning against the wall at 45 ° and the flame retardant formulated was sprayed secondly after 48 hours after the first spraying. The test results are listed in Table 1 below.

Table (1)

Test Items standard Test result Remarks One 2 3 Afterglow time Within 10 seconds 2 One One Remaining time Within 30 seconds 7 8 5 Ammunition Within 50㎠ 20.2 20.5 18.3 Carbonization length Within 20cm 6.3 6.2 5.9

2. Weather resistance test and color difference measurement

The test pieces were made of 5 (1, 2, 3, 4, 5) test pieces of tangential width of 70 mm, fiber length of 150 mm and radial thickness of 5 mm or less.

Apply mono pigments (such as brain green, lime wine, dark blue, scarlet and black ink) that meet the pigment mixing criteria on the specimen surface.

48 hours after the first spraying of the flame retardant composed of each test specimen, the second spray was applied, and after 7 days of natural drying vertically to avoid direct sunlight, the surface of the test specimen was visually examined after 25 repetitive tests using the accelerated weather resistance tester of KS M 5982. Observations of whitening, peeling, staining, etc. of the monochromatic and examined in Table 2 are listed.

Table (2)

Test piece Mono Pigment test results One Brain rock No whitening, peeling, or staining occurred on the specimen. 2 Evening No whitening, peeling, or staining occurred on the specimen. 3 County Office No whitening, peeling, or staining occurred on the specimen. 4 scarlet No whitening, peeling, or staining occurred on the specimen. 5 Indian ink No whitening, peeling, or staining occurred on the specimen.

3. Corrosiveness of flame retardant

As can be seen from the experiments of the above examples, the flame retardant of the present invention is not only flame retardant, but also has no abnormality in monochromatic whitening, peeling, staining, and the like.

In addition, in order to compare the effect on the content of formarin, a flame retardant composition was prepared in the same manner as in Example (1) with a composition as shown in Table 3 below.

Table (3) Composition ratio that varied formarin consumption

Composition (1) Composition ratio (wt%) Composition (2) Composition ratio (wt%) Distilled water 98.5 Distilled water 99 Formalin 0.3 Formalin 0 Penetration accelerator 0.5 Penetration accelerator 0.5 Wood preservative 0.3 Wood preservative 0.3 Anticorrosive 0.2 Anticorrosive 0.2 system 100wt% 100wt%

1. Flame retardancy test (KOFEIS 0201)

In the flame retardancy evaluation test (KOFEIS 0201), the composition showed almost the same results as the flame retardancy evaluation test of Example (1).

2. Weather resistance, evaluation test and color difference measurement

Weather resistance evaluation tests and color difference measurement results for the compositions (1) and (2) are shown in Tables (4) and (5). The measuring method is the same as that of Example (1).

Table (4) Composition (1)

Test piece Mono Pigment test results One Brain rock No whitening, peeling, or staining occurred on the specimen. 2 Evening No whitening, peeling, or staining occurred on the specimen. 3 County Office No whitening, peeling, or staining occurred on the specimen. 4 scarlet No whitening, peeling, or staining occurred on the specimen. 5 Indian ink Minor stains occurred on the test piece.

Table (5) Composition

Test piece Mono Pigment test results One Brain rock No whitening, peeling, or staining occurred on the specimen. 2 Evening No whitening, peeling, or staining occurred on the specimen. 3 County Office No whitening, peeling, or staining occurred on the specimen. 4 scarlet Some bleaching and staining occurred. 5 Indian ink Severe bleaching and staining occurred.

As shown in the weather resistance test and the color difference side, the flame retardant composition (1) used formarin less than the formalin minimum value of 0.5 of the composition of the present invention, and the flame retardant composition (2) was a test result that did not use formarin as a test result for evaluation of weatherability and color. The monopigmental pigment with whitening and staining on the side of the tea is found to be found in Kuncheong, which is an organic monochromate, mainly in the ink side.

In the above test, the flame retardant composition according to the present invention had no abnormality in flame retardancy, monochromatic whitening, peeling, staining, or the like, and had no abnormality in corrosion of the iron decoration. In addition, the determination of the corrosion of wood takes a long time, so it cannot be known from the results of the experiment. It is expected to have corrosion protection.

In particular, since the silane-based capping agent is added to the flame retardant composition, the silane having functional groups such as amino group, epoxy group, and double bond has strong adhesion between organic compound and inorganic compound, organic compound and organic compound, and the capping agent penetrated into wood Of course, it can be expected to have excellent anti-falling effect by having strong binding strength with organic and inorganic substances added to the composition and inorganic or organic monolayer, and by densifying the structure of the membrane to prevent moisture penetration or air contact. In addition, excellent corrosion protection can be expected.

In addition, the method of use (construction method) of the flame retardant composition of the present invention is not particularly limited, and a method of applying or spraying with a brush or the like is also possible.

Conventionally, a flame retardant solution and a layer of anticorrosion, antiseptic, and other functional materials are prepared separately, and the flame retardant solution is first coated with a cultural material and dried, and then a solution of a functional material having insect repellent and antiseptic and other functions thereon. Peeling occurs due to lack of bonding strength between the two layers to which the two solutions are applied by using a re-applied method, but the present flame retardant composition is applied by the same composition, so it can be said to be efficient.

Claims (5)

Guanadine phosphate 8-12 wt% was added to 86-90 wt% of distilled water and stirred for 30 minutes with a stirrer while maintaining the temperature in the range of 84-90 ℃, followed by adding 0.5-2 wt% of formalin at 2 atmospheres in a closed container. After maintaining at 80 ~ 83 ℃ and reacting for 1 ~ 2 hours, 0.2 ~ 0.5wt% of penetration accelerator, 0.1 ~ 0.5wt% of wood preservative, 0.1 ~ 0.3wt% of anticorrosive, 0.05 ~ 0.2 in solution cooled to room temperature A method for producing a flame retardant composition of wooden cultural properties, characterized by filtering by homogenization by adding wt%. Guanadine phosphate 8 ~ 12wt%, formalin 0.5 ~ 2wt%, penetration accelerator 0.2 ~ 0.5wt%, wood preservative 0.1 ~ 0.5wt%, anticorrosive 0.1 ~ 0.3wt%, silane capping agent 0.05 ~ 0.2wt%, distilled water 86 Flame retardant composition made of wooden cultural properties at ~ 90wt%. The method of claim 2, wherein the penetration accelerator is at least one of the penetration promoter selected from polyoxyethylene nonylphenol, ethoxylated nonylphenol, ethoxylated octylphenol, ethoxylated sorbitan laurate, sodium ethoxylated, ethoxylated sulfate Flame retardant composition made of wooden cultural properties. The method of claim 2, wherein the wood preservative is a wooden cultural property flame retardant composition characterized in that at least one wood preservative selected from fluoride fluoride, fluoride fluoride, acidic ammonium fluoride organic compounds. The anticorrosive composition according to claim 2, wherein the anticorrosive agent is at least one anticorrosive agent selected from nucleus ammonium carbamate, higher fatty acid salt of ammonium fluoride, amine compound of high molecular weight, and organic sulfur.