KR100433059B1 - Manufacturing method of the washing agent for stone made cultural heritage - Google Patents

Abstract

The present invention relates to a method for producing a stone cultural property cleaning agent, characterized by the following method for the purpose of preparing a cleaning agent for cleaning used in the stone cultural property preservation process.

H ₂ O ₂ (30%): _{2.0 to} 5.0%, HF (40%): 2.0 to 5.0%, nonionic surfactant (Polyethylene Alkyl Phenyl ether: R- (Phenyl) -O- (CH ₂ -CH _2- O) _n- H, R: C number 9-14, n: 6-16): 0.05 to 0.30%, H ₂ O: characterized by having a composition of 90.0 to 95.0%, there is no risk of secondary pollution A method for producing a composite cleaner for stone cultural properties, characterized by having a cleaning power, an oxidizing power, and a corrosion power at the same time.

Description

MANUFACTURING METHOD OF THE WASHING AGENT FOR STONE MADE CULTURAL HERITAGE}

The present invention relates to a method for producing a stone cultural property cleaning agent suitable as a cleaning agent for preserving and treating stone cultural property of Korea by investigating the cleaning effect and corrosion rate by dirt and detergents present in the stone cultural property by a scientific method. In addition, there are about 1470 stone cultural properties designated as treasures. In particular, the stone pagoda accounts for the largest proportion of Korean cultural properties, with about 53.8% of all national treasures, 42.7% of treasures, and 38.9% of important cultural properties. They are mainly made of granite, and most of them are very large and are located outdoors. Therefore, physical factors caused by rain and wind and freezing and thawing, biological factors such as moss and microorganisms, chemical development due to acid rain and environmental pollution, etc. The damage to stone cultural assets is accelerating to a great extent due to factors, and therefore, scientific preservation treatment is more urgent than any cultural assets.

In the process of preservation of the cultural property, the washing must be performed, and the washing should not only be a perfect cleaning but also secondary pollution or damage.

Therefore, the present invention investigated the cleaning effect and corrosion by the dirt and detergents present in the stone cultural properties by scientific methods, and developed a stone cultural property cleaning agent suitable as a cleaning agent for stone cultural property preservation treatment of our country.

Most of the stone cultural properties in Korea vary in degree, but the surface of the stone is covered with various contaminants such as black, white and brown and microorganisms such as bacteria, moss and algae. These contaminants and microorganisms not only greatly damage the appearance of the stone itself, but also promote the weathering of the cultural property by secondary chemical and physical actions, so it is necessary to wash the stone cultural property at the appropriate time for permanent preservation of the stone cultural property. . In addition, washing is an important process that must be carried out in advance in preservation treatment for stopping the weathering process such as consolidation and waterproofing of the masonry itself.

However, the cleaning of the stone cultural property should be carried out in such a way that the stone itself should not be damaged, nor should the secondary damage caused by the washing occur.

Currently, chemicals that are mainly used to remove cyanobacteria and lichens that occur in stone or wooden cultural properties include AC322, AB57, K101, K201, but most of them use some additives for general detergents, but moderately weak and weak bases are used. It is just a mixture. In advanced countries, algaeicides, antibiotics, and other gas or infrared (UV) irradiation methods have been tried to protect or preserve stone buildings, sculptures, murals, and other materials made of mineral compounds.

The stone cultural properties of Korea are mainly composed of granite, granite and gneiss, and most of them are exposed to the outdoors where weather changes are inevitable.

The breakdown of stone cultural properties can be divided into chemical, biological and physical factors.

Chemical and mineral weathering of rocks is mainly caused by dissolution, hydration, hydrolysis, oxidation and reduction, carbonation and chelate, and feldspar and colored minerals that react well with water in rocks are weathered. Light gray · Changes from pink to white.

In particular, in recent years, SO _x , NO _x , and CO _{2, which} are the main causes of air pollution, form acid rain, which promotes the elution of various ions from stone cultural properties, and accelerates the damage of cultural properties, as well as K ⁺ , Na ^+. , Ca ^2+, Mg ²⁺ to the reaction as a white precipitate _{(Na 2 SO 4, K 2} SO 4, CaSO 4, MgSO 4, Na 2 CO 3, K 2 CO 3, CaCO 3, MgCO 3 , etc.) a stone cultural properties Precipitates on the surface and greatly damages the appearance. That is, when sulphates, such as gypsum, are crystallized in the micropores of the masonry, crusts are formed on the surface of the masonry due to the clarification pressure, resulting in dulling. And gypsum combines with dust to form black crust on the surface of marble masonry, but in granite crust and grayish brown and white crust are formed around black.

These phenomena are more severe in rocks with relatively high CaCO ₃ content such as marble, limestone and cement concrete.

Common organisms in exterior stone buildings include algae, bacteria, fungi, and moss. Normally, the root pressure applied by plant roots to soil or rock promotes mechanical weathering of the rock at about 10-15 kg / cm 2. In addition, the roots of plants release CO ₂ into the soil by respiration, and organic harmful substances in the soil are decomposed to form organic acids, so the water in the biologically active soil is lowered to pH 4.5. Therefore, it is known that biological weathering effect causes two to three times higher effects than simple physical and chemical weathering rates. Therefore, it is necessary to remove the bacteria and lichens living in the stone cultural property to suppress the damage of the stone cultural property.

However, when using cleaning agents, disinfectants, and herbicides to preserve or prevent damage to cultural property, be sure to carefully examine the characteristics of the chemicals in advance to ensure that there is no risk of secondary pollution by long-term reaction with rainwater or rocks. It is very important to use the medicine carefully.

The detergent most commonly used as a detergent is a kind of anionic surfactant whose main component is sulfonate group (-SO ₃ Na) or carboxylate group (-COONa). Should be made. However, if the solution is alkaline, there is a fear that secondary precipitates will form in the stone during washing. Recently, detergent builders such as tripolyphospate (TPP), carbonates, silicates, sulfates, etc. have been used in the detergents to reinforce the detergent's cleaning ability, but they also have the risk of forming inorganic salt deposits on the stone surface. Detergents cannot be used for cleaning. In particular, the phosphate remains in the masonry, causing a secondary pollution, such as more proliferation of red tide organisms after a certain period of time after the washing treatment. In addition, since soap is used as a main ingredient, stearic acid is a main component, white colloidal precipitates are formed on the surface of the stone culture material after use unless hot water is used during washing.

In addition, the cleaning process for the preservation process of the stone cultural property is generally used to first clean the dust, dirt, oil and organic components using a cleaner, and then completely remove the peroxide to remove contaminants or other residues that are stuck deep in the pores. (Oxidize organic materials) by treating with oxidizing agents such as H ₂ O ₂ or chlorine oxide (NaClO ₄ etc.), and use acid solution such as HCl · H ₂ SO ₄ · HF to corrode part of rock Completely remove contaminants

In general, however, a lot of chlorine ions in an acid or oxidizing agent aqueous solution used (Cl ^-) in it containing the sulfate ion (SO ₄ ^-) to generate a secondary contamination of the tan reacts with the acid component of the rock containing rock It reacts with various cations contained in it to form sulfate, which is a secondary pollutant, and precipitates on the surface of stone cultural properties. In addition, HCl, H ₂ SO ₄ and the like dissolve almost all the components constituting the rock is not suitable for use as a stone cultural property cleaning agent.

Therefore, in the present invention, the microorganisms and soils parasitic in domestic stone cultural properties are collected as samples, and the chemical functional groups of the stone soils are identified through FT-IR analysis, and the elution characteristics by various solvent treatments are investigated. Its purpose is to provide a new complex cleaning agent for masonry cultural properties that has no risk of rust and has both cleaning, oxidizing and corrosive properties.

The present invention is characterized in that the oxidizing agent / preservatives / nonionic surfactant, characterized in that there is no risk of secondary pollution, and having a cleaning power, oxidizing power, and corrosion power at the same time, the composite detergent used for washing stone cultural property Although it varies greatly depending on the location of the stone cultural property, it is generally judged that the stone cultural property located in the country in the country is almost free from contamination by organic materials. Microorganisms having functional groups such as OH, -CH ₂ or -CH-,> C = 0, -CH ₂ -NH ₂ or> CH-NH ₂ , -COC, aromatic rings and the like were identified as main components.

Therefore, for the preservation treatment of the stone cultural property, a complex cleaner mainly containing an oxidant-surfactant-acid, which is effective in removing microorganisms and other sediments that are parasitic in the stone, is preferable to using a general detergent for removing oil components. It was decided to do.

The oxidizing agent used in the complex cleaning agent includes perchlorate, but the oxidizing agent containing chlorine ions (Cl ⁻ ) cannot be used as a stone cultural property cleaning agent because it reacts with the rock components to produce yellowish brown secondary contaminants. On the other hand, hydrogen peroxide (H ₂ O ₂ ) is relatively stable under acidic conditions and relatively strong oxidizing power {E _o = 1.77V (18 ~ 25 ℃)} has a large decomposition and decolorization effect of the organic material parasitic in stone water, In the neutral or alkaline conditions that are easily formed when the stone is wet, there is an advantage that is decomposed and stabilized as shown in the following chemical reaction equation. Therefore, 3% H ₂ O ₂ was used as the oxidizing agent for the development of the complex detergent.

2 H ₂ O _{2 (aq)} → 2 H ₂ O (l) + O _{2 (g)}

The rinsing of stone cultural property wastes is carried out by decomposing and decolorizing the remaining color organic matter using an oxidizing agent, and by etching the sediments using an aqueous acid solution such as HF and HCl.

However, in general, the chloride ion (Cl ^-) in acid solution is commonly used as it is, which contains a sulfate ion (SO ₄ ^-) to generate a secondary contamination of the tan reacts with the acid component of the rock containing rock contained in the It reacts with various cations to form sulfate, which is a secondary pollutant, and precipitates on the surface of stone cultural properties. And HCl, H ₂ SO ₄ and the like has the property of dissolving almost all the components constituting the rock.

On the other hand, HF aqueous solution is an acid having a weak ionization constant (Ka) of about 2.4 × ₁₀ ⁻⁴ at 25 ° C., and only SiO ₂ and CaSiO ₃ components are known to react with HF.

As described above, the hydrofluoric acid aqueous solution has a severe erosion effect on rocks mainly composed of SiO ₂ , such as sandstone, and is therefore prohibited from being used for cleaning cultural property in Europe.

However, most of Korean stone cultural properties are made of granite, so the erosion by hydrofluoric acid solution is not very serious, and there is no risk of secondary pollution by HF use. In order to obtain the perfect cleaning effect, some rocks are inevitably eroded. In the present invention, the corrosion rate of the granite stone according to the concentration of HF aqueous solution and the treatment time was investigated, and an appropriate concentration of HF aqueous solution was used as the cleaning agent. .

In addition, when the dirt attached to the stone cultural property is a microorganism or a material showing hydrophobicity such as hydrocarbon, the use of low concentration of H ₂ O ₂ or HF solution alone does not attack the carbon layer, so the cleaning effect cannot be greatly expected. . Therefore, surfactants are needed to enhance the corrosion effect of HF and the oxidation power of H ₂ O ₂ , and to enhance the penetration, dispersion, and washing power in masonry.

In general, the most commonly used anionic surfactants may react with secondary acidic detergents (H ₂ O ₂ or HF) which exhibit acidity, resulting in the loss of the cleaning effect, and may not be used because of the possibility of various secondary contaminations. Therefore, the nonionic surfactant (Polyethylene Alkyl Phenyl ether), which is mainly used for cleaning of cultural cultural stones, is mainly used in polyethylene oxide (-CH ₂ CH ₂ O-), and has excellent cleaning power and low price. : R- (Phenyl) -O- (CH ₂ -CH ₂ -O) _n -H, R: C number 9-14, n: 6-16) are most suitable.

<Example>

Using an oxidizing agent (H ₂ O ₂ ) / preservatives (HF) / nonionic surfactant (Polyethylene Alkyl Phenyl ether: NP-10), a cleaner for stone culture material having the following composition was developed.

H ₂ O ₂ (30%): 3.0%, HF (40%): 2.5%, NP-10: 0.1%, H ₂ O: 94.5%

Using the composite cleaner for the stone cultural property presented in the above embodiment, the granite system contaminated with microorganisms and soils around Gapsa stone cultural property in Gongju-si, Chungcheongnam-do was tested as follows.

Claims (2)

H ₂ O ₂ (30%): _{2.0 to} 5.0%, HF (40%): 2.0 to 5.0%, nonionic surfactant (Polyethylene Alkyl Phenyl ether: R- (Phenyl) -O- (CH ₂ -CH _2- O) _n- H, R: C number 9-14, n: 6-16): 0.05 to 0.30%, H ₂ O: characterized by having a composition of 90.0 to 95.0%, there is no risk of secondary pollution A method for producing a composite cleaner for stone cultural properties, characterized by having a cleaning power, an oxidizing power, and a corrosion power at the same time. delete