KR101245656B1 - Preservation method of Korean bronzeware - Google Patents

Abstract

The present invention relates to a preservation value organic storage method, which is used intermittently or periodically or exposed to the atmosphere in an unused state, and (1) isophorone diisocyanate as a reaction material in 1 kg of toluene as a solvent. IPDI) 290 to 300 g polyether glycol-400 (weight average molecular weight 400) 85 to 90 g, polyether glycol-1000 (weight average molecular weight 1000) 70 to 75 g 1,3-butylene glycol (1,3 40-45 g of -butylene glycol; 1,3-BG) was added to the reaction vessel, and heated up to 65 ± 2 ° C. at 5 ° C./10 min intervals, and maintained at this temperature for 8 hours to obtain NCO 5 ± 0.3%. A preservative preparation step of preparing a one-component preservative by synthesizing an isocyanate terminated prepolymer and diluting it to 35% concentration in acetone as a solvent; (2) a washing step of removing foreign substances such as rust, dust, water, etc. from the surface of the organic to be preserved; And (3) after drying the washed organic, the preservation treatment step of preserving the organic by coating and drying with a thickness of 5 to 7㎛ with the preservative.

Description

Preservation method of Korean bronzeware

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to organic preservation methods, and more particularly, to a preservation value organic preservation method that is used intermittently or periodically or exposed to the atmosphere in an unused state.

As a result of the analysis of pottery dishes (hereinafter called `` wares '') of palaces and museums, bronze and brass containing copper and tin or zinc are used as main materials. Among them, the appearance is beautiful, and it has a strong and beautiful luster, so it is highly cultural and artistic value and needs long-term preservation.

In Korea, organics have been used since the Bronze Age, and it is possible to guess the organic manufacturing techniques of those days from various bronze artifacts that are currently excavated. Korea's Bronze Age culture seems to have been influenced by the northern Orthodox Bronze culture associated with Siberia's Minusinsk-Scythian Bronze Culture. In the early days of the Bronze Age, non-wave-shaped bronze swords and Jomun-gyeong were produced. In the late stages, they were cast in their own form, forming the heyday. ), Drops, rituals and other tools were produced. Afterwards, the Bronze Age coexists with Iron for some time and then gradually disappears. It begins to develop again in the Three Kingdoms Period. In the case of Baekje, the smelting and craftsmanship was handed down to Japan in the “Writing Day of Japan”, and Geumdongje Daebal, excavated from the head of the Queen of King Muryeong (525), was made of bronze. It is a produced cow. In addition, according to the records of Samguk Sagi, Silla has been in charge of iron and oilstones before the King Gyeongdeok (742-765). As such, during the Three Kingdoms and the Unified Silla era, it was a time of revolutionary development in terms of materials and technologies. The excellent manufacturing technology of that time can be guessed through many Buddhist art items such as Baekryeoksa Pharmacist Statue, Sangwonsa Dongjong (725) and King Seongdeok Sinjong (771). During the Goryeo Dynasty, Korea produced `` Koryo-dong, '' which is beautiful in color, and traded with China. Production techniques have also been developed to produce various kinds of objects such as Buddha statues, various Buddhist utensils, living containers, children's shoes, and canvases at the end. Royal and nobility used thin and strong bronze bowls made by magnetic method as tableware. In the Joseon Dynasty, mining efforts were made in the country from the early days. According to the “Gyeongkuk Daejeon”, eight of the whey for making organic foods used in the country were coordinated with the Gyeonggi factory, a central craftsman. It has four members in the upper house, and there is a record of a large number of foreign factories that make organic materials for local governments. The Joseon Dynasty did not have many gold crafts with Buddhist colors under the influence of the Uncung-fu policy, while many household goods and folk crafts were produced in the form of simple and simple feelings such as cigarette box, brazier, incense burner, and anti-wounding. Although it was an era of using porcelain as a popular tableware, Yugi was used as a tableware in the upper class following the Goryeo Dynasty. At the end of modern times, almost all organics owned by each family were taken away in the name of organic release by Japan. After the liberation in 1945, Yuji began to flourish again, but after 6/25, the use of briquettes began to dissipate. Recently, various experiments have revealed the pathogen O-157 sterilization function, abscess component detection function, etc. are emerging, and is currently being produced as musical instruments, meat, tableware and various household goods.

In addition, organic is roughly classified into the organic oil (bang free organic), casting organic and semi-bang organic (half cloud jade method). Bangjagi uses a brass ball (go) made by melting copper and tin in a ratio of 78:22, and several people repeatedly hammer and thinly shape it. Bangjakgi is not bent or broken easily, and the characteristic of the mezzanine remains. Casting organics are also called 'bushback organic organs' because they are cast by pouring molten copper and tin together into a fixed mold. Foundry organics are free of alloys and can produce large quantities of products of the same size and shape, but cannot be forged. The quality and color of the metals are clearly distinguished, and various types of products can be produced. In addition, the half-banged organic oil is a manufacturing technique that is a compromise between the production method of the organic oil and the foundry organic oil. Use a tool to concave the ends of the organics.

These organics are corroded from the surface according to the usage time, the ambient air environment, and the moisture, and the surface corrosion is removed every year to remove the corrosion. Corrosion-removed bronze and brass filings are stored in the same storage area until the next use, which is observed to cause corrosion of surface corrosion from storage and reuse. In order to slow the progress of corrosion at present, it is treated with silicon oil and the like so that the contact with the corrosion atmosphere or moisture is kept low. However, in the case of this silicone oil-coated fissure, the surface gloss or color changes after contact with acidic foods, and the internal corrosion progresses and it is a significant problem to remove when mixed with the corroded condition of fissure. Appearing.

In this case, when the corrosion treatment is completed after the anticorrosive treatment is completed, the coating process is prevented, and thus the generation of re-corrosion is suppressed and the time until the reprocessing is increased. This is a very urgent situation.

The present invention was devised to solve the above problems of the prior art, and the present inventors apply various polymers to solve the above problems, color change, glossiness change, reversibility (property which can easily remove the coating agent) water repellency Urethane, which shows excellent results, was selected.

It is an object of the present invention to provide a preservation method of organically preserved value, which is used intermittently or periodically or exposed to the atmosphere in an unused state.

The organic preservation method according to the present invention is (1) 85 to 90 g of isophorone diisocyanate (IPDI) 290 to 300 g polyether glycol-400 (weight average molecular weight 400) as a reaction raw material in 1 kg of toluene as a solvent. , 70 to 75 g of polyether glycol-1000 (weight average molecular weight 1000) was added 40 to 45 g of 1,3-butylene glycol (1,3-BG) as a crosslinking agent in the reaction vessel, Warm up to 65 ± 2 ° C. at 5 ° C./10 min intervals and maintain this temperature for 8 hours to synthesize NCO 5 ± 0.3% isocyanate terminated prepolymer, 35% concentration in acetone as a solvent. Preservative preparation step of preparing a one-component preservative by diluting with; (2) a washing step of removing foreign substances such as rust, dust, water, etc. from the surface of the organic to be preserved; And (3) after drying the washed organic, the preservation treatment step of preserving the organic by coating and drying with a thickness of 5 to 7㎛ with the preservative.

The preservation method of the organic may further include a deconservation treatment step of peeling the coating by immersing the preserved organic in xylene after the preservation treatment step.

The preservation method of the organic may further include a re-preservation treatment step of preserving the organic by coating and drying the de-preserved organic to a thickness of 5 to 7㎛ with the preservative after the deconservation treatment step. .

According to the present invention, there is an effect of providing a preservation value organic preservation method, which is used intermittently or periodically or exposed to the atmosphere in an unused state.

1 is an infrared spectroscopy spectrum of a preservative used in the present invention.
Figure 2 is a photograph showing the contact angle to the organic surface of the preservative used in the present invention.
Figure 3 is a photograph of the surface of the organic non-coated with a preservative used in the present invention as a comparative example.
FIG. 4 is a photograph photographing the degree of corrosion of the organic surface of FIG. 3 after a corrosion test. FIG.
Figure 5 is a photograph of the surface of the organic coating with a preservative according to the invention.
FIG. 6 is a photograph photographing the degree of corrosion of the organic surface of FIG. 5 after a corrosion test. FIG.
7 is a surface photograph of a silicon coated organic used in the preservation of conventional organics.
FIG. 8 is a photograph of the surface after 48 hours of spraying acetic acid on the surface of the silicon-coated organic of FIG. 7.

Hereinafter, specific embodiments of the present invention will be described in detail with reference to the accompanying drawings.

The organic preservation method according to the present invention is (1) 85 to 90 g of isophorone diisocyanate (IPDI) 290 to 300 g polyether glycol-400 (weight average molecular weight 400) as a reaction raw material in 1 kg of toluene as a solvent. , 70 to 75 g of polyether glycol-1000 (weight average molecular weight 1000) was added 40 to 45 g of 1,3-butylene glycol (1,3-BG) as a crosslinking agent in the reaction vessel, The temperature was raised to 65 ± 2 ° C. at 5 ° C./10 min intervals, and this temperature was maintained for 8 hours to synthesize NCO 5 ± 0.3% of isocyanate terminal prepolymer, which was diluted to 35% concentration in acetone as a solvent to form a one-part form. Preservative preparation step of preparing a preservative; (2) a washing step of removing foreign substances such as rust, dust, water, etc. from the surface of the organic to be preserved; And (3) after drying the washed organic, the preservation treatment step of preserving the organic by coating and drying with a thickness of 5 to 7㎛ with the preservative.

The present inventors compared and tested urethanes of various compositions for the development of a preservative which is particularly suitable for organic preservation methods, and among them, one-component composition of the composition having excellent adhesion to bronze or brass and having internal and external separation and stability. This possible urethane was selected and applied to the organic preservation method.

The preparation of the preservative of (1) is a step of preparing a preservative having the characteristics as described above, isophorone diisocyanate (IPDI) 290 to 300 g polyether glycol-400 (reaction raw material in 1 kg of toluene as a solvent) Weight average molecular weight 400) 85 to 90 g, polyether glycol-1000 (weight average molecular weight 1000) 70 to 75 g 1,3-butylene glycol (1,3-butylene glycol; 1,3-BG) 40 to 45 g were placed in a reaction vessel, heated to 65 ± 2 ° C. at 5 ° C./10 min intervals, and maintained at this temperature for 8 hours to synthesize NCO 5 ± 0.3% isocyanate terminated prepolymer, which was acetone as a solvent. Dilution at 35% concentration to prepare a one-part preservative. The raw materials used in the reaction, namely, isophorone diisocyanate, polyether glycol, 1,3-butylene glycol, and toluene (for reaction) and acetone (for dilution) as solvents are all known to those skilled in the art. These are those that can be understood as known so that they can be purchased and used commercially from. The use range of the reaction raw materials as described above is the inventors of the urethane that can be composed as a one-component composition having excellent adhesion to bronze or brass, and internal and external separation and stability through repeated experiments by the inventors in a trial and error method. As determined experimentally for the manufacture, if the physical properties of the urethane is beyond the above-mentioned range, the adhesion of the urethane to the bronze or brass is excellent, and it is not suitable for the composition of the one-component type having the internal and external separability and stability. There may be a problem. The preservative obtained in the preservative preparation step as described above does not appear yellowing occurs when the application of the epoxy used for the conventional organic preservation treatment, has an excellent point that is easy to remove when reprocessing. This preservative can maintain the inherent glossiness of the organic, it is possible to express the intrinsic color of the parent material (organic) due to the preservative, it is prepared in a composition that is excellent in adhesion, but no adsorption to dust. In addition, it has excellent water repellency, has a barrier against moisture, and has a dense internal structure, thereby showing a result of preventing access from corrosive gas.

The washing step of (2) consists of removing foreign matters such as rust, dust, moisture, etc. from the surface of the organic to be preserved, and this washing step is to be understood as that of a person skilled in the art for the management of organic matter. It will be understood by those skilled in the art that any means capable of removing foreign matters such as rust, dust, moisture, and the like may be applied to perform the washing step.

The preservation step of (3) comprises drying the washed organic, and then coating the film with a preservative to a thickness of 5 to 7 μm and drying to preserve the organic. The coating is spray coating to spray a conventional preservative spray (spray coating), immersion coating immersed in the preservative and taken out, electrodeposition coating using a coating machine using a constant voltage, or coating by application using a conventional brush, etc. Although coating methods may be used, the present invention is not limited thereto, and any method of forming a coating layer of a preservative on an organic surface by applying a preservative to an organic surface may be understood. will be. By forming a coating layer of a preservative on the surface of the organic to be preserved by the above-described preservation treatment so that the surface of the metal organic is not exposed to the air, avoiding contact with moisture and oxygen, preventing the occurrence of rust, The gloss can be maintained by preventing deposition. If the thickness of the above coating is less than 5㎛, the ability to lower the corrosion may be reduced, on the contrary, if it exceeds 7㎛, it may reduce the inherent color or glossiness or cause problems in adhesion. .

The preservation method of the organic may further include a deconservation treatment step of peeling the coating by immersing the preserved organic in xylene after the preservation treatment step. The above-mentioned depreservation treatment functions to return the organic-coated state to the uncoated state, and in the present invention, by simply depositing the organic preserved with the preservative according to the present invention having the characteristics as described above in ethanol. The coating of the preservative can be easily removed to allow the organic to be used again for its intended use, or to remove debris from the surface of the coating and to apply a new preservative coating again. Since the above-mentioned deconservation treatment can be performed only by immersing the coated organic in ethanol, the physical stress for removing the coating is not applied, and thus the preservation and deconservation treatment are repeatedly performed without applying excessive force to the organic. This makes it possible to preserve the organic intact without damage.

The preservation method of the organic may further include a re-preservation treatment step of preserving the organic by coating and drying the de-preserved organic to a thickness of 5 to 7㎛ with the preservative after the deconservation treatment step. . The re-preservation treatment step may be the same as or similar to the above-described preservation treatment step, and may be repeatedly alternating in the order of preservation treatment, depreservation treatment, and re-preservation treatment to treat organics and thus preserve organic semipermanently.

Hereinafter, preferred embodiments and comparative examples of the present invention will be described.

The following examples are intended to illustrate the invention and should not be understood as limiting the scope of the invention.

Example

As the polyol, polyether glycol-400 and polyether glycol-1000, which were distinguished by the weight average molecular weights of Polyoriol Co., Ltd., were used. As isocyanate, BASF's isophorone diisocyanate (IPDI) was used and stored at room temperature. 1,3-butylene glycol was used by purchasing the product of Oxea (Oxea). Toluene was used as the solvent used for the reaction.

A 3-liter four-necked flask was equipped with a stirrer, a dropping funnel, a nitrogen injection tube, and a thermometer, and then, in a nitrogen atmosphere, liquid isophorone diisocyanate was added, and polyether glycol-1000 and polyether glycol- 400 was added. 1, 3- butylene glycol was put here as a crosslinking agent, and toluene was added in order as a solvent. The final compositions used for the synthesis were 296.13 g of isophorone diisocyanate (IPDI), 88.64 g of polyetherglycol-400, 73.87 g of polyetherglycol-1000, 41.37 g of 1,3-butylene glycol and 500 g of toluene. At this time, if the reagents are suddenly added or the reaction is performed at a high temperature, the side reaction proceeds and the coating agent of the desired physical property is not synthesized and the heterogeneous reaction proceeds. After the above materials were filled, the temperature was raised to 65 ± 2 ° C. at about 5 ° C./10 min intervals. This temperature was maintained for 8 hours, through which an NCO 5 ± 0.3% isocyanate terminated prepolymer was synthesized. After the reaction of the isocyanate terminated prepolymer terminated infrared spectroscopy spectrum (IR spectrum; Fig. 1) in the NCO group of about ^{2270㎝ -1 (NCO group; 2261.02㎝ -1} ) and the NH group of 3000㎝ vicinity ^-1 (NH group 2963.92 cm ^-1 , 2928.91 cm ^-1 ) confirmed the appearance of the isocyanate terminated prepolymer.

The isocyanate terminated prepolymer obtained above was prepared as a 35% solution in acetone and used as a preservative according to the present invention. All materials were measured by moisture before use, and when the moisture content was 0.05% or more, vacuum dehydration or simple distillation was used at 100 ° C.

Experimental Example  1: chromaticity measurement result

In the case of bronze having a chromaticity of (L: 50.66, a: -1.14 b: -1.14), after the coating of the preservative according to the present invention, (L: 50.18, a: -1.12, b: -1.06) shows a very small change. It could be confirmed that only indicates. The chromaticity change after ultraviolet irradiation measured using the UV tester manufactured according to KS M 5982 shows only a very small change of (L: 51.02, a: -1.27, b: -1.09) even after 12 hours. It was confirmed that the discoloration within the range.

L * a * b * ΔE * Bronze before coating 50.66 -1.14 -1.14 28.99 Bronze after coating 50.18 -1.12 -1.06 28.49 After UV exposure 51.02 -1.27 -1.09 29.33

Experimental Example  2: glossiness measurement result

Glossiness measurement was performed using a gloss meter (Gloss meter IG-320 manufactured by HORIBA) and in accordance with the provisions of KS L2405. Gloss Mteter Reading always As a standard, the glossiness of the glass mirror was set to 100. The measurement condition was a light emitting diode (LED) having a main light source of 880 nm. The measurement was performed up to 0.1 units at a scanning angle of 60 °, a light receiving angle of 60 °, and a cross-sectional area of 12 × 6 mm. It was.

The average change in the measured glossiness before and after treatment with the preservative according to the present invention was confirmed that the glossiness does not change significantly from 28.9 to 25.9.

Experimental Example  3: Coating film  Thickness measurement result

Coating film thickness measurement was measured using a magnetic induction film thickness measuring device Qnix (QNix 7500), was carried out in accordance with the experimental method of KS D8544. The distance between the electrode and the raw material was measured and converted into thickness by contacting the coated surface on the material and increasing the magnetic flux with the voltage in the second coil. It was confirmed that the thickness after the primary coating was 5 to 7 μm (up to 9.8 μm).

Experimental Example  4: coating adhesion measurement result

Coating adhesion measurements were measured using a coating adhesion tester (DeFelsko PosiTest AT-A Automatic) and in accordance with the provisions of KSM ISO 4624. On the coated specimen, a high-adhesion araldite rapid type was applied to the bottom of an uncoated stone (a metal specimen for adhesion or adhesion), and then bonded to the specimen. Cured for time. The test instrument was placed at right angles to the surface of the test specimen and then tensioned until the stone was separated to calculate the pressure (MPa) per unit area (cm 2) when the test specimen and the stone were separated. The average adhesive strength was found to be 3.5MPa / cm 2 (up to 4.1MPa / cm 2).

Experimental Example  5: Contact angle  Measurement result

The contact angle was quantified based on the provisions of KS L2110, and it could be confirmed that the average contact angle was 75 ° or more based on the 6.3 μm coating (FIG. 2).

Experimental Example  6: gas corrosion test results

Gas corrosion test was performed using a device (Suga test instruments, GS-4SOS) that can control the temperature and humidity inside the device, the corrosion gas using sulfur dioxide (SO ₂ ), nitrogen dioxide (NO ₂ ), hydrogen sulfide (H ₂ S) It was.

The chromaticity change (Table 2) and glossiness change (Table 3) after gas exposure are shown in Tables 2 and 3 below.

gas Sulfur dioxide
(SO ₂ ) Nitrogen dioxide
(NO ₂ ) Hydrogen sulfide
(H ₂ S) Color change of coating surface after gas exposure
(ΔE ^* ab)
1.7
1.3
2.6

gas Sulfur dioxide
(SO ₂ ) Nitrogen dioxide
(NO ₂ ) Hydrogen sulfide
(H ₂ S) Glossiness change of coating surface after gas exposure -0.7 -1.1 -1.5

In addition, the degree of corrosion of the uncoated surface (FIG. 3) and the uncoated surface (FIG. 4) with the preservative according to the present invention is described as the degree of corrosion of the coated surface (FIG. 5) and the coated surface (FIG. 6). The pictures are shown in comparison. As shown in the above photographs, the surface not coated with the preservative according to the present invention was severely corroded, whereas in the case of the organic coating with the preservative according to the present invention, it was confirmed that the corrosion did not proceed on the surface.

On the other hand, the surface photograph of the silicon coated organic (FIG. 7) used in the conventional organic preservation and the surface after 48 hours of spraying acetic acid on the surface of the silicon coated organic (FIG. 8) are shown as photographs. As shown in the above photographs, it was confirmed that the silicon coating used for the preservation of the conventional organic matter does not sufficiently preserve (protect) the acidic material.

The above experimental results are summarized as follows.

The preservative according to the present invention was found to be a one-component type in a stable form at 60% or less of atmospheric moisture, and thus did not show the result of self-expansion by room temperature moisture. After the deposition of the corrosive treatment was carried out in the preservative solution, the coating was completed by evaporation of the solvent by taking out and standing at room temperature. The thickness of the coating layer formed by drying after immersion in the preservative (concentration 35%) was 5 to 7㎛, the coating layer shows a strong adhesion to the organic cotton of 3.5MPa / ㎠ or more, the moisture contact angle is 75 ° or more It has been shown to have excellent water repellent properties.

In addition, the discoloration degree in the UV chamber also showed a change within the 0.2% error range so that there was no yellowing phenomenon, and it could be completely dissolved in xylene heated above 60 ° C. The removal of the coating did not appear to be a problem. In addition, when immersed in ethanol, peeling from the metal surface proceeded, and physical removal over time was also simple. The gas corrosion test shows that it is about 7 times more stable than silicone oil coating, which is 3 times more corrosion resistant than uncoated filings, which can extend the reprocessing time by about 20 times more than the minimum uncoated filings. It is expected that the manufacturing price is very low price of the stock solution before the 35% solution is manufactured.

The present invention can be used in the industry of handling and preserving valuable organics, which are used intermittently or periodically or exposed to the atmosphere in an unused state.

Although the present invention has been described in detail only with respect to the described embodiments, it will be apparent to those skilled in the art that various modifications and variations are possible within the technical scope of the present invention, and such modifications and modifications are within the scope of the appended claims.

Claims (4)

(1) Isophorone diisocyanate (IPDI) 290 to 300 g polyether glycol-400 (weight average molecular weight 400) 85 to 90 g, polyether glycol-1000 (weight average molecular weight) as a reaction raw material in 1 kg of toluene as a solvent 1000) 40 to 45 g of 1,3-butylene glycol (1,3-BG) as a 70 to 75 g crosslinking agent was added to the reaction vessel, and 65 ± 2 at 5 ° C./10 min intervals. The temperature was raised to ℃ and maintained for 8 hours to synthesize NCO 5 ± 0.3% isocyanate terminated prepolymer, which was diluted to 35% concentration in acetone as a solvent to prepare a one-component preservative Preservative preparation step;
(2) a washing step of removing foreign substances such as rust, dust, water, etc. from the surface of the organic to be preserved; And
(3) after drying the washed organic, the preservation step of preserving the organic coating and drying to a thickness of 5 to 7㎛ with the preservative;
Organic preservation method characterized in that it comprises a.
The method of claim 1,
The organic preservation method further comprises a preservation step of releasing the coating by immersing the pretreated organic in ethanol after the preservation step.
The method of claim 2,
The preservation method of the organic re-preservation treatment step of preserving the organic by coating and drying the deconserved organic to a thickness of 5 to 7㎛ with the preservative after the deconservation treatment step; Organic preservation method to use.
Isophorone diisocyanate (IPDI) 290 to 300 g polyether glycol-400 (weight average molecular weight 400) 85 to 90 g, polyether glycol-1000 (weight average molecular weight 1000) 70 in 1 kg of toluene as a solvent 40 to 45 g of 1,3-butylene glycol (1,3-BG) as a 75-g crosslinking agent was added to the reaction vessel, and the temperature was raised to 65 ± 2 ° C. at 5 ° C./10 min intervals. And maintaining this temperature for 8 hours to synthesize NCO 5 ± 0.3% isocyanate terminated prepolymer, which is prepared by diluting it to 35% concentration in acetone as a solvent. One part preservative used.

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