WO2017012458A1

WO2017012458A1 - Cultural relic fumigating method

Info

Publication number: WO2017012458A1
Application number: PCT/CN2016/087994
Authority: WO
Inventors: 姜标; 张琛; 陶黎明; 周新光; 吴来明
Original assignee: 中国科学院上海有机化学研究所; 华东理工大学; 上海博物馆
Priority date: 2015-07-19
Filing date: 2016-06-30
Publication date: 2017-01-26
Also published as: CN106693014A

Abstract

A cultural relic fumigating method comprises the following steps: placing a fumigant and a cultural relic into a fumigating box; fumigating the cultural relic for 1 to 36 hours at the temperature of 25 to 45°C, and extracting air under reduced pressure for 1 to 3 hours; and opening the fumigating box, and removing the cultural relic, the fumigant being a mixture of thiosulfinates compounds and thiosulfonates compounds. The method is obvious in effect, simple in operation, and wide in application range.

Description

Method for fumigation of cultural relics

Technical field

The invention relates to a method for fumigation of cultural relics, belonging to the technical field of cultural relics preservation.

Background technique

As a kind of item with special social value, cultural relics can reflect the cultural, scientific and technological level and production status at that time, as well as the life preferences, habits and conditions of people at all levels of society at that time, and have the inheritance of human civilization. There is no substitute for a major role. Therefore, the protection of cultural relics is of great significance.

Because a large part of the cultural relics in the collection are organic materials of various materials, such as silk, bamboo, cotton, paper, fur, lacquer wood, etc., the organic matter in the cultural relics can provide a lot of activities for the growth and physiological metabolism of microorganisms and pests. The nutrients and nutrients, therefore, the degree of damage caused by microorganisms and pests to cultural relics is extremely serious. Therefore, the anti-insect and anti-mildew treatment of cultural relics has become an important part of the protection of cultural relics.

However, due to the non-reproducibility, non-renewability and uniqueness of the cultural relics, it is decided that the cultural relics workers cannot protect them by conventional methods of pest control and mildew prevention. Because, once the cultural relics are damaged, it will cause irreparable huge losses. The protection effect of cultural relics will directly affect the life and value of cultural relics.

At present, the insecticidal sterilization methods widely used for disinfection of cultural relics mainly include physical insecticidal methods such as aeration (carbon dioxide, nitrogen) deoxidation and chemical control methods using fumigants such as ethylene oxide, methyl bromide and sulfuryl fluoride. Although the existing methods can achieve the effect of insecticidal sterilization to some extent, each has its own shortcomings, for example: nitrogen insecticidal time is long, and the tolerance of different insects to high-purity nitrogen is significantly different. Carbon dioxide is weakly acidic and has an effect on the material to be treated under high humidity conditions. In particular, a material containing lead oxide forms carbonate in a short time; ethylene oxide is an explosive substance and has a lure Degeneration; the bactericidal ability of methyl bromide is poor, and since the ninth "Convention of the Meeting of the Parties to the Montreal Protocol" in 1997, developed countries have agreed to phase out the use of methyl bromide from 2005, and according to the Montreal Protocol, by 2015, China It is forbidden to use methyl bromide; sulfuryl fluoride is difficult to penetrate into the watery eggs due to its hydrophobicity, so the ability to kill eggs is poor, and the deposition of fluoride is dangerous to human bones. In addition, the greenhouse effect of sulfuryl fluoride is significant, and the greenhouse effect caused by sulfuryl fluoride emissions is about 5,000 times that of the same amount of carbon dioxide! Therefore, research and development of a safe and environmentally-friendly method of preserving cultural relics that can effectively prevent insects and mildew without affecting the material and human health of the cultural relics, and not pollute the environment, is an urgent need to solve in front of cultural relics protection workers all over the world. problem.

Although the fumigation method of cultural relics disclosed in Chinese patent CN201310403788.6 uses the active ingredients in plants instead of fumigants such as cyclochloroethane and methyl bromide to solve the explosive, environmentally destructive and safe and harmless human body, The method requires the plant fumigant and the cultural relics to be placed in the fumigation box, and the amount of the plant essential oil for fumigation is also large, and high-purity nitrogen gas is also required, and the specific humidity needs to be selected for different types of mold diseases and cultural relic materials. Conditions and fumigation time, for example: for paper, bone, ivory materials, the humidity needs to be adjusted at 50-55%; for textile, wood, leather materials, the need to adjust the humidity is 50-60%; generally for black Aspergillus, Aspergillus and other molds need to be fumigated for 20-24 hours; therefore, this patented technology is not only cumbersome to operate, but also can not achieve one-time fumigation treatment of various materials and various bacterial molds under the same environment. The key is that The patented technology does not inform the cultural relics after being treated by the fumigation method, and then placed in the cultural relics collection environment to regenerate the mold.

Summary of the invention

In view of the above problems and needs in the prior art, the object of the present invention is to provide a green, safe and effective method for fumigation of cultural relics, which not only achieves safe and effective sterilization, but also does not affect the material and human health of the cultural relics, and does not pollute the environment. It can realize the one-time fumigation treatment of various materials and various bacterial molds under the same environment, and after fumigation treatment, it can be placed in the cultural relics collection environment for at least half a year without regenerating the bacterial mold.

In order to achieve the above object, the present invention adopts the following technical solutions;

A method for fumigation of cultural relics includes the following operations: placing the fumigant and the cultural relics into a fumigation box, fumigation at 25 to 45 ° C for 1 to 36 hours, evacuating under reduced pressure for 1 to 3 hours, opening the fumigation box, and removing the cultural relics. The fumigant is a compound of a thiosulfinate compound and a thiosulfonate compound.

Preferably, the fumigant is supported on a carrier material having an adsorption effect, and the carrier material may be filter paper, silica gel, filter membrane, cotton, sponge or cloth, or the like.

Preferably, the carrier material loaded with the fumigant is placed in a hollow device having an outwardly diffusing port or mesh surface, and the hollow device may be a box structure, a box structure, a cage structure, a bag, or the like. .

As a further preferred solution, the hollow device has a fan and a speed control function.

As a further preferred embodiment, the hollow device has a self-heating and temperature regulating function.

Preferably, the fumigant is a compound having a volume ratio of 1:1 to 1:5 by a thiosulfinate compound and a thiosulfonate compound.

Preferably, the thiosulfinate compound has the following structural formula:

a compound wherein: R ¹ and R ^{2 are the} same or different and are each selected from a C ₁ -C ₄ alkane group (for example, methyl, ethyl, propyl, butyl) or a C ₂ -C ₄ alkene group. (Example: allyl).

As a further preferred embodiment, R ¹ is the same as R ² .

Preferably, the thiosulfonate compound has the following structural formula:

a compound wherein: R ³ and R ^{4 are the} same or different and are each selected from a C ₁ -C ₄ alkane group (for example, methyl, ethyl, propyl, butyl) or a C ₂ -C ₄ alkene group. (Example: allyl).

As a further preferred embodiment, R ³ is the same as R ⁴ .

Compared with the prior art, the present invention has the following beneficial effects:

The invention adopts a compound of a thiosulfinate compound and a thiosulfonate compound as a fumigant, which not only realizes safe and effective sterilization and disinfection of cultural relics, but also has the lowest environmental pollution and no fumigant residue. The problem does not affect the material material and human health, and has the advantages of green environmental protection; in particular, the invention can realize the one-time treatment of various materials and various bacterial molds in the same fumigation environment, and is subjected to fumigation treatment according to the present invention. After the cultural relics can be placed in the cultural relics collection environment for at least half a year, no more regenerative bacterial molds; in addition, the method of the invention has the advantages of simple operation, low cost, wide applicable range of materials and bacterial molds, and long-term preservation of cultural relics. Has important value and far-reaching significance.

detailed description

The technical solution of the present invention will be further described in detail below by way of examples.

Example 1: Preparation of fumigant

1. A mixture of methyl methyl sulfinic acid sulfonate and ethyl ethyl thiosulfonate:

Methyl methylthiosulfinate and ethyl ethylthiosulfonate were stirred and mixed uniformly at room temperature according to a volume ratio of 1:3; abbreviated as fumigant A; determination of oral LD ₅₀ >500 mg/Kg in mice It belongs to low toxicity.

2. Compound of ethyl ethyl sulfinic acid sulfonate and methyl methyl thiosulfonate:

Ethyl ethyl thiosulfinate and methyl methyl sulfonate were stirred and mixed uniformly at room temperature according to a volume ratio of 1:2; abbreviated as fumigant B; determination of oral LD ₅₀ >500 mg/Kg in mice It belongs to low toxicity.

3. Compound of ethyl thiosulfinate and ethyl thiosulfonate:

Ethyl ethyl thiosulfinate and ethyl thiosulfonate were stirred and mixed uniformly at room temperature according to a volume ratio of 1:1; abbreviated as fumigant C; determination of oral LD ₅₀ >500 mg/Kg in mice It belongs to low toxicity.

4. Compound of methyl thiosulfinate and methyl methyl sulfonate:

Methyl methylthiosulfinate and methyl methyl sulfonate were stirred and mixed uniformly at room temperature according to a volume ratio of 1:1.5; abbreviated as fumigant D; the oral LD ₅₀ of the mouse was determined to be >500 mg/Kg. It belongs to low toxicity.

5. A mixture of propyl thiosulfinate and ethyl thiosulfonate:

The propyl thiosulfinate sulfonate and ethyl ethylthiosulfonate were stirred and mixed uniformly at room temperature according to a volume ratio of 1:2.5; abbreviated as fumigant E; the oral LD ₅₀ of the mouse was determined to be >500 mg/Kg. It belongs to low toxicity.

6. Compound of propyl thiosulfinate sulfonate and allyl thiosulfonic acid allyl ester:

The propyl thiosulfinate propyl ester and allyl thiosulfonic acid allyl ester were stirred and mixed uniformly at room temperature according to a volume ratio of 1:4; abbreviated as fumigant F; the oral LD ₅₀ >500 mg of the mouse was determined. /Kg, which is low in toxicity.

7. A mixture of ethyl ethyl thiosulfinate and butyl butyl sulfonate:

Ethyl ethyl thiosulfinate and butyl butyl sulfonate were stirred and mixed uniformly at a volume ratio of 1:5 at room temperature; abbreviated as fumigant G; determination of oral LD ₅₀ >500 mg/Kg in mice It belongs to low toxicity.

8. A mixture of methyl thiosulfinate and methyl thiosulfonate:

Ethyl methylthiosulfinate and methyl thiosulfonate were stirred and mixed uniformly at room temperature according to a volume ratio of 1:3; abbreviated as fumigant H; determination of oral LD ₅₀ >500 mg/Kg in mice It belongs to low toxicity.

9. A combination of allyl thiosulfinate and allyl methylthiosulfonate:

Allyl allysulfinyl sulfinate and allyl methylthiosulfonate were stirred and mixed uniformly at room temperature according to a volume ratio of 1:2.5; abbreviated as fumigant I; determination of oral LD ₅₀ of mice > 500mg/Kg, which is low in toxicity.

Example 2: Cultural relics fumigation experiment

Cultural relic material: paper

Diseases: Aspergillus and Penicillium

Fumigant: Fumigant A

Fumigation method:

The fumigant and the cultural relic sample are placed in a fumigation box, the fumigation box is closed, the temperature in the fumigation box is controlled at 25 ° C, fumigation is carried out for 36 hours, and the pressure is evacuated for 2 hours, the fumigation box is opened, and the cultural relic sample is removed;

It was found by microscopic examination that there was no mold growth on the cultural relic samples after the above fumigation treatment;

And by gas chromatography and mass spectrometry (GC-Ms) detection and analysis, it was found that there was no fumigant residue on the cultural relic samples after the above fumigation treatment.

The samples of the cultural relics subjected to the fumigation treatment in this embodiment are placed in the cultural relics collection room, and the mold tracking test is performed regularly. The test results are shown in the following table:

存放时间Storage time	0个月0 months	1个月1 month	3个月3 months	6个月6 months
霉菌生长情况Mold growth	无任何霉菌No mold	无任何霉菌No mold	无任何霉菌No mold	无任何霉菌No mold

In addition, the color of the paper sample after the fumigation treatment was not significantly changed by the color difference meter, and the paper strength of the cultural relic sample after the fumigation treatment was not significantly changed by the tensile test. The paper folding resistance test showed that the paper folding resistance of the cultural relic samples after the above fumigation treatment did not change significantly.

Example 3-1: Cultural relics fumigation experiment

Cultural relic material: silk material

Diseases: Aspergillus and Penicillium

Fumigant: Fumigant C

The fumigant and the cultural relic sample are placed in a fumigation box, the fumigation box is closed, the temperature in the fumigation box is controlled at 25 ° C, fumigation is carried out for 24 hours, and the pressure is evacuated for 2 hours, the fumigation box is opened, and the cultural relic sample is removed;

And by gas chromatography and mass spectrometry (GC-Ms) detection and analysis, there is no fumigant residue on the cultural relic samples after the above fumigation treatment;

In addition, it was observed by the color difference meter that the silk color of the cultural relic sample subjected to the above fumigation treatment did not change significantly, and the tensile strength of the silk fabric sample subjected to the above fumigation treatment did not change significantly by the tensile test.

Example 3-2: Cultural fumigation experiment

Cultural relic material: silk material

Diseases: Aspergillus and Penicillium

Fumigant: Fumigant C

First, the fumigant is loaded on the filter paper, and then placed in the fumigation box. After setting the fumigation box temperature to 35 ° C, the fumigation box is placed in the fumigation box together with the cultural relics sample, the fumigation box is closed, and the fumigation box is controlled. The temperature was 25 ° C, after fumigation for 18 hours, the air was depressurized for 2 hours, the fumigation box was opened, and the cultural relic samples were removed;

Example 3-3: Cultural fumigation experiment

Cultural relic material: silk material

Diseases: Aspergillus and Penicillium

Fumigant: Fumigant C

First, the fumigant is loaded on the filter paper, and then placed in the fumigation box. After setting the fumigation box wind level 2 (middle), the fumigating box and the cultural relic sample are placed in the fumigation box, the fumigation box is closed, and the fumigation box is controlled. The temperature is 25 ° C, after fumigation for 16 hours, vacuuming for 2 hours, opening the fumigation box, removing the cultural relic samples;

Example 3-4: Cultural fumigation experiment

Cultural relic material: silk material

Diseases: Aspergillus and Penicillium

Fumigant: Fumigant C

The fumigant and the cultural relic sample are placed in a fumigation box, the fumigation box is closed, the temperature in the fumigation box is controlled to be 35° C., after fumigation for 20 hours, the vacuum is evacuated for 2 hours, the fumigation box is opened, and the cultural relic sample is removed;

The samples of the cultural relics subjected to the fumigation treatment in this embodiment are placed in the cultural relics collection room, and the mold tracking test is performed regularly. The test results are shown in the table below:

However, it was observed by the color difference meter that the silk color of the cultural relic samples subjected to the above fumigation treatment would slightly turn yellow and the silk strength would be slightly deteriorated.

It can be seen by comparing Examples 3-1 and 3-2 that the same fumigating effect can be achieved in a shorter fumigation time by first loading the fumigant on the filter paper sheet, then putting it into the fumigation box, and allowing the fumigation box to have a heating function. And it will not cause any harm to the material of the cultural relics.

By comparing Examples 3-1 and 3-3, it can be seen that the same fumigating effect can be achieved in a shorter fumigation time by first loading the fumigant on the filter paper sheet, then placing it in the fumigation box, and allowing the fumigation box to have a fan function. And it will not cause any harm to the material of the cultural relics.

By comparing Examples 3-1 and 3-4, it can be seen that under the same conditions, although directly adjusting the temperature in the fumigation box has no effect on the fumigation effect, the increase in temperature will affect the color of the cultural material placed in the fumigation box and Other properties have a certain impact.

Example 4: Cultural relics fumigation experiment

Cultural relic material: bamboo

Diseases: Aspergillus and Penicillium

Fumigant: Fumigant F

Fumigation method:

The fumigant and the cultural relic sample are placed in a fumigation box, the fumigation box is closed, the temperature in the fumigation box is controlled at 45 ° C, fumigation is performed for 1 hour, and the vacuum is evacuated for 2 hours, the fumigation box is opened, and the cultural relic sample is removed;

In addition, the color of the bamboo and wood samples of the cultural relics treated by the above-mentioned fumigation treatment did not change significantly by the color difference meter, and the strength of the bamboo and wood samples subjected to the above fumigation treatment did not change significantly by the tensile test.

Example 5: Cultural relics fumigation experiment

Cultural relic material: cotton fabric

Diseases: Mycobacterium sphaeroides, Rhizopus and Trichoderma

Fumigant: fumigant G

Fumigation method:

The fumigant and the cultural relic sample are placed in a fumigation box, the fumigation box is closed, the temperature in the fumigation box is controlled to 30 ° C, fumigation is carried out for 4 hours, and the pressure is evacuated for 2 hours, the fumigation box is opened, and the cultural relic sample is removed;

In addition, the color of the cultural relic samples subjected to the above fumigation treatment was not significantly changed by the color difference meter, and the strength of the cultural relic samples subjected to the above fumigation treatment did not change significantly by the tensile test.

Example 6: Cultural relics fumigation experiment

Cultural relics: leather and bone products

Diseases: Chaetomium and Trichoderma

Fumigant: Fumigant H

Fumigation method:

Storage time

0 months

1 month

3 months

6 months

Mold growth

No mold

In addition, the color of the cultural relic samples subjected to the above fumigation treatment was not significantly changed by the color difference meter, and the fiber structure of the leather and bone products after the above-mentioned fumigation treatment was not significantly changed by scanning electron microscopic observation.

Example 7-1: Cultural relics fumigation experiment

Cultural relic material: hemp fabric

Diseases: Staphylococcus aureus, Escherichia coli, Bacillus megaterium, Bacillus subtilis, Pseudomonas fluorescens, etc.

Fumigant: Fumigant B

Fumigation method:

The fumigant and the cultural relic sample are placed in a fumigation box, the fumigation box is closed, the temperature in the fumigation box is controlled at 25 ° C, fumigation is carried out for 30 hours, and the pressure is evacuated for 2 hours, the fumigation box is opened, and the cultural relic sample is removed;

It was found by microscopic examination that there was no bacterial growth on the cultural relic samples after the above fumigation treatment;

The samples of the cultural relics subjected to the fumigation treatment of the present embodiment are placed in the cultural relics collection room, and the bacteria tracking test is performed regularly. The test results are shown in the following table:

存放时间Storage time	0个月0 months	1个月1 month	3个月3 months	6个月6 months
细菌生长情况Bacterial growth	无任何细菌No bacteria	无任何细菌No bacteria	无任何细菌No bacteria	无任何细菌No bacteria

In addition, it was observed by the color difference meter that the color of the cultural relic sample subjected to the above fumigation treatment did not change significantly, and the strength of the hemp fabric after the above fumigation treatment did not change significantly by the tensile test.

Example 7-2: Cultural fumigation experiment

Cultural relic material: hemp fabric

Fumigant: Fumigant B

Fumigation method:

First, the fumigant is loaded on the cotton wool sheet, and then placed in the fumigation box. After setting the fumigation box temperature to 45 ° C, the fumigation box and the cultural relic sample are placed in the fumigation box, the fumigation box is closed, and the fumigation box is controlled. The temperature was 25 ° C, after fumigation for 8 hours, the air was depressurized for 2 hours, the fumigation box was opened, and the cultural relic samples were removed;

And by gas chromatography and mass spectrometry (GC-Ms) detection and analysis, the cultural relic samples after the above fumigation treatment There is no fumigant residue on it;

Example 7-3: Cultural fumigation experiment

Cultural relic material: hemp fabric

Fumigant: Fumigant B

Fumigation method:

First, the fumigant is loaded on the cotton wool sheet, and then placed in the fumigation box. After setting the fumigation box wind level 3 (strong), the fumigating box and the cultural relic sample are placed in the fumigation box, the fumigation box is closed, and the fumigation box is controlled. The temperature was 25 ° C, after fumigation for 10 hours, the pressure was evacuated for 2 hours, the fumigation box was opened, and the cultural relic samples were removed;

Example 8-1: Cultured fumigation experiment

Cultural relics: paper, silk, linen, bamboo, leather and bone products, etc.

Diseases: Aspergillus, Penicillium, Trichoderma, Staphylococcus aureus, Escherichia coli, Bacillus megaterium, Bacillus subtilis, Pseudomonas fluorescens, etc.

Fumigant: Fumigant C

Fumigation method:

It was found by microscopic examination that there was no mold and bacteria growth on the samples of the cultural relics treated by the above fumigation;

It is indicated that the method of the invention can realize one-time treatment of various materials and various bacterial molds in the same fumigation environment.

In addition, the color, the silk, the linen, the bamboo, the leather, the bone and the bone products of the cultural relic samples after the above-mentioned fumigation treatment were not changed significantly by the color difference meter, and the sample of the cultural relics after the fumigation treatment was obtained by the tensile test. The paper, silk, linen, bamboo and other strengths did not change significantly. The paper folding resistance test showed that the paper folding resistance of the above-mentioned fumigation samples did not change significantly, and the scanning electron microscope was used. It was observed that the fibrous tissue arrangement of the leather and bone products after the above fumigation treatment did not change significantly.

Example 8-2: Cultural fumigation experiment

Cultural relics: paper, silk, linen, bamboo, leather and bone products, etc.

Fumigant: Fumigant A

Fumigation method:

Example 8-3: Cultured fumigation experiment

Cultural relics: paper, silk, linen, bamboo, leather and bone products, etc.

Fumigant: Fumigant B

Fumigation method:

Example 8-4: Cultural fumigation experiment

Cultural relics: paper, silk, linen, bamboo, leather and bone products, etc.

Fumigant: Fumigant D

Fumigation method:

Example 8-5: Artifact fumigation experiment

Cultural relics: paper, silk, linen, bamboo, leather and bone products, etc.

Fumigant: Fumigant E

Fumigation method:

Example 8-6: Cultural relics fumigation experiment

Cultural relics: paper, silk, linen, bamboo, leather and bone products, etc.

Fumigant: Fumigant F

Fumigation method:

Example 8-7: Cultural fumigation experiment

Cultural relics: paper, silk, linen, bamboo, leather and bone products, etc.

Fumigant: fumigant G

Fumigation method:

Example 8-8: Cultural fumigation experiment

Cultural relics: paper, silk, linen, bamboo, leather and bone products, etc.

Fumigant: Fumigant H

Fumigation method:

The fumigant and the cultural relic sample are placed in a fumigation box, the fumigation box is closed, and the temperature in the fumigation box is controlled at 25 ° C. After fumigation for 24 hours, evacuate under reduced pressure for 2 hours, open the fumigation box, and remove the cultural relic samples;

Example 8-9: Artifact fumigation experiment

Cultural relics: paper, silk, linen, bamboo, leather and bone products, etc.

Fumigant: Fumigant I

Fumigation method:

It is to be understood that the above description is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any technical person skilled in the art can disclose the technical scope disclosed by the present invention. Variations or substitutions that are conceivable within the scope of the invention are intended to be included within the scope of the invention.

Claims

A method for fumigation of cultural relics, comprising the steps of: putting a fumigant and a cultural relic into a fumigation box, fumigation at 25 to 45 ° C for 1 to 36 hours, and then evacuating for 1 to 3 hours under vacuum to open the fumigation. a box, the cultural relics are removed; the fumigant is a compound of a thiosulfinate compound and a thiosulfonate compound.
The method of fumigation of a cultural relic according to claim 1, wherein the fumigant is supported on a carrier material having an adsorption effect.
The method of fumigation of a cultural relic according to claim 2, wherein the carrier material loaded with the fumigant is placed in a hollow device having an outwardly diffusing port or mesh face.
The method for fumigation of cultural relics according to claim 3, wherein the hollow device has a fan and a speed control function.
The method for fumigation of cultural relics according to claim 3 or 4, characterized in that the hollow device has a self-heating and temperature-regulating function.
The fumigation method of the cultural relics according to claim 1 or 2, wherein the fumigant is a 1:1 to 1:5 by volume ratio of the thiosulfinate compound to the thiosulfonate compound. The compound.
The method for fumigation of cultural relics according to claim 6, wherein the thiosulfinate compound has the following structural formula:
A compound wherein R 1 and R 2 are the same or different and are each selected from a C 1 -C 4 alkane group or a C 2 -C 4 alkene group.
The method of fumigation of cultural relics according to claim 7, wherein R 1 is the same as R 2 .
The method for fumigation of cultural relics according to claim 6, wherein the thiosulfonate compound has the following structural formula:
A compound wherein: R 3 is the same as or different from R 4 and is each selected from a C 1 -C 4 alkane group or a C 2 -C 4 alkene group.
The method of fumigation of cultural relics according to claim 9, wherein R 3 is the same as R 4 .