KR20070104181A - Manufacturing method of the metal noncorrosive acidic cleaning agent for buildings & stone made cultural heritages - Google Patents

Abstract

A method for preparing an acidic detergent for stone-made or architectural cultural assets is provided to obtain a detergent causing no secondary contamination, having excellent cleaning power to organic contaminants, and non-corrosive to iron, aluminum, bronze, titanium or zinc-made ornaments. A method for preparing an acidic detergent for stone-made or architectural cultural assets comprises a step of mixing: a nonionic surfactant as an agent for removing organic contaminants; hydrogen peroxide(H2O2) and hydrofluoric acid(HF) or hydrochloric acid(HCl) as an agent for cleaning whitening materials and microorganism contaminants; and side ingredients including an ethanolamine-based neutralizing agent, an ethylene glycol-based compatibilizer, a higher fatty acid amide condensate-based foam stabilizer, a methyl cellulose- or xanthane gum-based thickening agent, and a silicone-based defoaming agent.

Description

MANUFACTURING METHOD OF THE METAL NONCORROSIVE ACIDIC CLEANING AGENT FOR BUILDINGS & STONE MADE CULTURAL HERITAGES}

The present invention is a risk of secondary pollution and the cleaning work that must be performed in the maintenance and repair work and preservation process of concrete, brick building structure cultural properties and stone cultural properties damaged by various contaminants such as dust, soot, gum gum And it relates to a method for manufacturing cleaning detergents for buildings and stone cultural properties used to effectively without corrosion of copper ornaments.

The stone cultural properties designated by the state as national treasures and treasures are about 1470 points, and the stone pagoda is the largest proportion in Korea's cultural properties, with 53.8% of all national treasures, 42.7% of treasures, and 38.9% of important cultural properties. . In Korea, various stone, brick, and concrete buildings built in the 1900's have been registered as modern cultural properties, and their preservation and processing work has been actively carried out.

They are mainly composed of granite and cement concrete, and most of them are very large and are located outdoors. The damage is accelerating to a great extent due to factors, and therefore scientific preservation treatment is more urgent than any cultural property.

In the process of preservation of cultural property for stopping the weathering process such as maintenance, repair, consolidation and waterproofing of masonry and buildings, cleaning is one of the important processes that must be performed. In addition, unlike the general buildings and masonry, the washing of cultural properties requires not only perfect cleaning, but also essential conditions that the occurrence of secondary pollution or secondary damage should not occur absolutely.

However, while the maintenance and repair work of buildings and masonry registered as cultural property is actively underway in Korea, there is no proper cleaning agent for washing masonry or building cultural property, and general detergents that can cause secondary pollution or Since acidic detergents, such as hydrochloric acid and hydrofluoric acid, which are strongly corrosive to metals are used irresponsibly, they face the risk of damaging various ornaments that are decorated in serious cultural assets.

In recognition of the seriousness of these problems, the Cultural Heritage Administration announced and supplemented the "Standard Specification for Repair of Cultural Property Repair" in early 2005. However, in the Stone Conservation Treatment Specification (2030), the whitening material (calcium carbonate: CaCO ₃ ), which accounts for most of the pollution of stone and building cultural properties, is treated with only dilute hydrochloric acid (water: hydrochloric acid = 10: 1). In addition, there is a risk of causing serious corrosion when the cleaning liquid comes into contact with various metal decorations attached to the cultural property, and there are no concrete guides for removing organic pollutants. The situation is facing difficulties.

Therefore, in the present invention, as an acidic detergent that can be used to wash stone and building cultural properties, it effectively removes various contaminants such as dust, soot, gum, etc., and is not corrosive to various metal decorations attached to the cultural property, and secondary pollution. And to provide a method for producing a metal non-corrosive acid detergent for washing stone and building cultural properties, there is no risk of damage.

Korea's stone cultural properties are mainly composed of granite, granite, gneiss, and the buildings that are managed and protected by cultural properties are mainly composed of marble, granite, red brick, and concrete, and most of them are exposed to the outdoors where weather changes cannot be avoided. .

These exposed cultural assets are rapidly becoming unsightly and rapidly changed due to severe contamination of the surface by various volatile organic substances (VOCs) and dust such as automobile smoke and slippery.

In particular, in recent years, SOx, NOx, and CO _{2, which} are the main causes of air pollution, form acid rain, which promotes the dissolution of various ions from stone and building cultural properties, thereby accelerating the damage of cultural properties, as well as whitening materials (ettringite, thaumasite, etc.) on the surface of cultural properties. ) Greatly damages the cultural property. These phenomena are more severe in rocks with relatively high CaCO ₃ content, such as marble, limestone, granite and cement concrete.

In addition, the exposed stone and building cultural properties accumulate dust on the surface and maintain proper moisture, and microorganisms such as algae, bacteria, fungi, moss, etc. propagate, resulting in the living organisms on the surface of the cultural property. Promotes the mechanical weathering by producing a muscle pressure of 10 ~ 15 kg / cm ² , as well as the release of various organic acids from the root of the plant causes chemical erosion.

As a preservation treatment to prevent damage to the stone and building cultural property, the most basic and priority should be performed.

The cleaning agent for masonry and building cultural properties has not only a cleaning effect but also a precondition that there should be no risk of secondary contamination and damage. Therefore, the selection of the main and subsidiary materials of the cleaning agent becomes the core of the manufacturing technology.

Therefore, in [Method of manufacturing organic pollutant cleaning agent for stone and building cultural property (Korea Patent, Registration No .: 10-0570916], cleaning agent for cleaning organic pollutant such as dust, smoke, oil, and grease deposited on stone and building cultural property It has been proposed to use a neutral detergent containing phosphates, sulfates, ammonium salts, organic chloride compounds, and nonionic surfactants containing no anionic surfactant as a main ingredient.

The calcium carbonate (CaCO ₃ ) treatment method of the stone preservation treatment (2030) of [Cultural Property Standard Repair Specification] published by the Korean Cultural Heritage Administration in early 2005 was presented as follows.

A. Dilute hydrochloric acid (water: hydrochloric acid = 10: 1) on cotton wool, touch the calcium carbonate part for a while, and wipe off the dirt with dry cotton.

N. Repeat the work of 'a' four or five times, and then wipe several times with a cotton ball soaked in clean water.

C. The thick part is repeatedly wiped for about 20 to 50 times, and after the calcium carbonate is sufficiently removed, it is wiped off with more diluted hydrochloric acid (water: hydrochloric acid = 25: 1).

D. The last two to three times are wiped with about 2% aqueous ammonium chloride (NH ₃ Cl) solution and washed thoroughly with water to prevent chemicals from remaining.

In addition, in [Method for manufacturing stone cultural property cleaning agent (Korean Patent, Registration No .: 10-0433068)], H ₂ O ₂ (30 wt%): 2.0 to 5.0 wt%, HF (40 wt%): 2.0 to 5.0 wt% %, 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- 0.30% by weight, H ₂ O: 90.0 to 95.0% by weight composition, characterized in that there is no risk of secondary contamination, and having a cleaning power, oxidizing power and corrosion power at the same time characterized in that the composite cleaner for stone culture material Has developed a method for effectively removing white matter and microbial contaminants from cultural assets.

However, acidic detergents based on hydrochloric acid or hydrofluoric acid as mentioned above effectively remove white matters and microorganisms of stone and building cultural properties, but when the cleaning liquid comes into contact with various metal decorations attached to cultural properties, There is a problem to damage the decoration.

Therefore, in the present invention, while effectively removing white matters and microorganisms generated in stone and building cultural properties, it is possible to remove organic contaminants such as dust, soot and grease at the same time, without corroding various metallic decorations attached to the cultural properties. The purpose of the present invention is to provide a method for preparing metal non-corrosive acid detergent for masonry and building cultural property.

The present invention is characterized by an acidic detergent consisting mainly of acids such as hydrofluoric acid (HF) and hydrochloric acid (HCl), and nonionic surfactants and corrosion inhibitors, and there is no risk of secondary contamination during masonry and building cultural property cleaning. The present invention relates to a method for manufacturing metal non-corrosive acid detergent for masonry and building cultural properties, which has excellent cleaning power for organic pollutants and is not corrosive to iron, aluminum, bronze, titanium, and zinc ornaments. It is composed as follows.

In the present invention, the cleaning agent used for removing organic pollutants in stone and building cultural properties is ethylene oxide in polyoxyethylene alkylaryl ether nonionic surfactant or polyoxyethylene alkyl ether nonionic surfactant of polyethylene oxide condensed surfactant. It is characterized by comprising 0.1-10 weight% of nonionic surfactant which an addition mole number 7-10 and a cloud point 20-80 degreeC.HLB value fall into 12.0-13.3.

Chemicals for cleaning whitening and microbial contaminants of stone and building cultural properties include H ₂ O ₂ (30 wt%): 2.0 to 5.0 wt%, HF (40 wt%) or HCl (35 wt%): 2.0 to It is used as a 5.0% by weight composition.

As the minor components used in the present invention, ethanolamine-based neutralizing agent 0.02-0.10% by weight, ethylene glycol-based compatibilizer 0.3-0.8% by weight, higher fatty acid amide condensate foam stabilizer 0.02-0.10% by weight, methylcellulose-based or xanthan gum system It is characterized by consisting of 0.1 to 0.5 weight% of a thickener and 0.01 to 0.05 weight% of a silicone type antifoamer.

In the present invention, organic chemicals used as corrosion inhibitors for iron (Fe) materials include acetylene, unsaturated alcohols, saturated linear primary, secondary, tertiary amines and quaternary ammonium salts of n ≥ 6, saturated aliphatic cyclic amines, aromatic amines, Thioureas, aromatic aldehydes, furans, pyrroles, pyridines, quinolines, benzothiazoles, and the like are zinc hydroxide and zinc compounds.

The aluminum (Al) corrosion inhibitors used in this acidic detergent include saturated linear primary, secondary and tertiary amines, aromatic amines, thioureas and pyridines with n ≥ 6, and titanium (Ti) materials. Corrosion inhibitors include benzenes and quinolines. Zinc (Zn) corrosion inhibitors include saturated linear primary, secondary, tertiary amines and tetraphenyl with n ≥ 6, and copper (Cu) corrosion inhibitors. And halogen acetates, benzotriazoles (BTA), and aliphatic mercaptans with n ≧ 12.

The present invention is characterized in that the above-mentioned iron, aluminum, titanium, zinc, and copper corrosion inhibitors are added in a composition of 0.01 to 0.10% by weight of the total weight of the cleaning agent.

Metal non-corrosive acid detergent for washing stone and building cultural properties proposed in the present invention {polyoxyethylene alkyl ether nonionic surfactant (LE1020): 1.0% by weight, H ₂ O ₂ (30% by weight): 3.0% by weight, HCl (35 wt%): 3.5 wt%, cetyl ammonium chloride: 0.01 wt%, quinoline: 0.01 wt%, BTA: 0.01 wt%, zinc chloride: 0.02 wt%, water: 92.45 wt%) The corrosion and iron pollutants of iron, aluminum, titanium, zinc and copper were compared with 3.5 wt% solution of hydrochloric acid.

1) As a result of experiment of calcium carbonate dissolving power to evaluate the removal ability of white matter, the detergent consumption per 1g of calcium carbonate of the present invention is 15.679ml, which is 25% higher than the surface detergent consumption of 21.233ml using the same concentration of hydrochloric acid. It became.

2) 10 g of iron, copper, aluminum, zinc, and titanium pieces were immersed in 100 ml of the detergent of the present invention and visually observed after 5 hours, and the surface detergent using the same concentration of hydrochloric acid generated bubbles and corroded. No corrosion traces were observed in all samples used. After 14 days, in the corrosion rate test, the corrosion rate of iron was decreased by 47% by weight and 20-25% by weight of copper, aluminum, zinc, and titanium, respectively.

3) As a result of testing organic pollutant cleaning power by the KS M 2709 dish detergent cleaning power test method, the present invention was found to have a good cleaning power than the surface detergent.

Claims (1)

Nonionic surfactants are used to remove organic pollutants from masonry and building cultural properties. Hydrogen peroxide (H ₂ O ₂ ), hydrofluoric acid (HF), or hydrochloric acid (HCl) are used as chemicals for washing white matter and microbial contaminants. Ethanolamine-based neutralizer, ethylene glycol-based compatibilizer, advanced fatty acid amide condensate foam stabilizer, methylcellulose-based or xanthan gum thickener, silicone-based antifoaming agent, and iron, aluminum, titanium, zinc, There is no risk of secondary pollution when cleaning stone and building cultural properties by using copper corrosion inhibitor, and it has excellent cleaning power for organic pollutants, and it is suitable for iron, aluminum, copper, titanium, and zinc decoration. It is characterized by non-corrosiveness, non-corrosive metal for washing stone and building cultural property as follows: Method of preparing an acidic detergent. First, the cleaning agent used to remove organic pollutants in masonry and building cultural properties, the addition of ethylene oxide in polyoxyethylene alkylaryl ether nonionic surfactant or polyoxyethylene alkyl ether nonionic surfactant of polyethylene oxide condensed surfactant The number of moles is 7 to 10 and the cloud point is 20 to 80 ° C. The HLB value is characterized by constituting 0.1 to 1.0% by weight of the nonionic surfactant in the range of 12.0 to 13.3. Second, the chemicals for cleaning whitening and microbial contaminants of stone and building cultural properties include H ₂ O ₂ (30 wt%): _{2.0 to} 5.0 wt%, HF (40 wt%) or HCl (35 wt%): It is used in a composition of 2.0 to 5.0% by weight. Third, the minor components used in the present invention include 0.02 to 0.10% by weight of ethanolamine neutralizing agent, 0.3 to 0.8% by weight of ethylene glycol compatibilizer, 0.02 to 0.10% by weight of higher fatty acid amide condensate foam stabilizer, methylcellulose or xanthan It is characterized by consisting of 0.1-0.5 weight% of a gauge thickener and 0.01-0.05 weight% of a silicone type antifoamer. Fourth, organic chemicals used as corrosion inhibitors for iron (Fe) materials in the present invention are acetylene, unsaturated alcohols, saturated linear primary, secondary, tertiary amines of n ≥ 6 and quaternary ammonium salts, saturated aliphatic cyclic amines, aromatic Amines, thioureas, aromatic aldehydes, furans, pyrroles, pyridines, quinolines, benzothiazoles, and zinc compounds. The aluminum (Al) corrosion inhibitor used in this acidic detergent is characterized by saturated linear primary, secondary and tertiary amines, aromatic amines, thioureas and pyridines with n≥6. The corrosion inhibitors are characterized by benzenes and quinolines, and the zinc (Zn) corrosion inhibitors are characterized by saturated straight chain primary, secondary, tertiary amines and tetraphenyls with n ≥ 6 and copper (Cu The corrosion inhibitors are characterized by halogenacetic acid, benzotriazoles (BTA) and aliphatic mercaptans with n ≧ 12. The above-mentioned corrosion inhibitors for iron, aluminum, titanium, zinc, and copper may be used independently or in combination, and the appropriate amount of each type is composed of 0.01 to 0.10% by weight of the total detergent. It is done.