CN114350278B - Paste for repairing and mounting paper cultural relics and preparation method and application method thereof - Google Patents
Paste for repairing and mounting paper cultural relics and preparation method and application method thereof Download PDFInfo
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- CN114350278B CN114350278B CN202111612638.7A CN202111612638A CN114350278B CN 114350278 B CN114350278 B CN 114350278B CN 202111612638 A CN202111612638 A CN 202111612638A CN 114350278 B CN114350278 B CN 114350278B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
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Abstract
The invention discloses a paste material for repairing and mounting paper cultural relics, which is prepared by mixing and reacting the following components: starch, deionized water, polyethylene glycol, animal wax, berberine and silane coupling agent, and the appearance of the gel is uniform and transparent. The invention also discloses a preparation method of the paste material for repairing and mounting the paper cultural relics. The paste material for repairing and mounting the paper cultural relic disclosed by the invention can form a hydrophobic layer on the surface of the paper, so that the water absorption of the paper can be reduced, the growth and reproduction of microorganisms and the like on the surface of the paper are hindered, the damage of the microorganisms to the paper cultural relic is prevented, the corrosion of acid, pollutants and the like can be resisted to a certain extent, the tensile strength and the folding strength of the paper are improved, and the paper cultural relic body cannot be damaged. The preparation method is environment-friendly in process, simple to operate, easy to control and beneficial to expanding production, and does not cause any damage to the paper cultural relic body.
Description
Technical Field
The invention belongs to the technical field of paper cultural relic protection and repair materials and preparation and application thereof, and particularly relates to a paste material for repairing and mounting paper cultural relics and a preparation method and an application method thereof.
Background
Ancient books, calligraphy and painting paper cultural relics are mostly made of paper. Over time, these papers are highly susceptible to aging and decay. The paper, especially the painting and calligraphy cultural relics, which can be preserved to date, are mostly subjected to traditional mounting and repairing in the process of passing through the generations.
The most important material used in the mounting repair process is paste. As the binding material, the paste is prepared by heating starch and water under a certain temperature condition. The preparation and use of the paste occupy a very important position in mounting and repairing, and the paste is directly related to the flatness of the painting and calligraphy and the preservation condition of the paper cultural relics.
Since ancient times, the paste is used as a mounting and repairing material, and firstly, the paste is cheap, easy to obtain, nontoxic and harmless; secondly, the appearance of the paper cultural relics is basically not influenced, and the paper cultural relics can play a role in reinforcement while being used as a bonding material; thirdly, the operation is reversible, namely the cultural relics can be removed very conveniently when not needed, which completely accords with the basic principle of modern cultural relic protection. However, the traditional starch paste also has certain limitations, and because the starch paste is a natural polymer material formed by connecting glucose units through glycosidic bonds and is also a food source for bacteria, mold and the like, the damage of the mold to the paper cultural relics repaired by the traditional starch paste mounting is one of the reasons for damage of the paper cultural relics. In order to prevent the damage of microorganisms, some natural materials such as pepper, bletilla and the like are added in the paste making process by ancient people, so that certain sterilization and mildew prevention effects are achieved. However, the use of these additives usually brings about changes in the paste properties, for example, the increase in the acidity of the paste brings about acidification and embrittlement of the paper carrier after mounting and repairing, and causes irreparable loss of the painting and calligraphy cultural relics; the reversibility causes difficulty in remounting and the like when remounting.
Disclosure of Invention
The invention provides a novel paste material for repairing and mounting paper cultural relics, which aims at the problems of the existing traditional paste, and the bonding material is particularly suitable for mounting painting and calligraphy and can be used for large-scale industrial production.
The invention also aims to provide a preparation method of the paste material for repairing and mounting the paper cultural relics.
The invention also aims to provide an application method of the paste material for repairing and mounting the paper cultural relics.
The invention provides a novel paste material for repairing and mounting paper cultural relics, which comprises the following components in part by weight: the material is prepared by mixing and reacting the following components in parts by weight:
the appearance of the sol is uniform and transparent sol.
The average molecular weight of the polyethylene glycol in the material is 800-4000.
The animal wax in the above materials is any one of beeswax, insect wax or Chinese wax.
The berberine in the above materials is any one of Coptidis rhizoma, radix Berberidis Amurensis or radix Berberidis Virgetori natural plant extract.
The silane coupling agent in the material is any one of methoxy, ethoxy or methyl ethoxy silane coupling agents.
The invention provides a preparation method of the paste material for repairing and mounting paper cultural relics, which comprises the following process steps and conditions:
1) Firstly, 100 parts of starch is put into 500 to 1500 parts of deionized water, and after being uniformly stirred, the starch is kept stand and soaked for 0.5 to 5 hours at room temperature;
2) Adding 0.1-5 parts of polyethylene glycol and 0.01-0.5 part of berberine into the soaked starch aqueous solution, stirring and mixing uniformly, and then performing ultrasonic dispersion for 3-120 minutes at 20-30 ℃;
3) And (3) putting the dispersed starch solution into a constant-temperature water bath, adding 0.01-5 parts of animal wax and 0.01-5 parts of silane coupling agent, heating, keeping the temperature at 85-100 ℃, and stirring for 10-120 minutes to obtain the uniform and transparent gel paste material.
The parts of the materials are all parts by weight.
The average molecular weight of the polyethylene glycol PEG used in the method is 800-4000; the amount of addition is preferably 0.5 to 5 parts.
The animal wax used in the method is any one of beeswax, insect wax or Chinese wax, and the addition amount is preferably 0.1-2 parts.
The berberine used in the above method is any one of extracts of natural plants such as Coptidis rhizoma, radix Berberidis Amurensis or radix Berberidis, and the addition amount is preferably 0.05-0.5 parts.
The silane coupling agent used in the method is any one of methoxy, ethoxy or methyl ethoxy silane coupling agents; the amount of addition is preferably 0.1 to 2 parts.
The invention provides an application method of the paste material for repairing and mounting the paper cultural relics, which comprises the following specific steps and conditions:
1) The uniform and transparent gel paste material prepared by the method is mashed in a mortar, diluted by 0-5 times by deionized water, and then the surface of the painting and calligraphy/ancient book to be protected is brushed or sprayed, wherein the brushing and spraying times are not less than 2 times, and the interval time of every two times is not more than 15 minutes.
2) And (4) sucking the redundant paste materials at the edge of the paper after brushing or spraying, and then placing the paper in a natural environment for airing.
The dilution times by deionized water in the application method are preferably 1 to 5 times; the number of brushing and spraying is preferably 2 to 6, more preferably 2 to 3, and the interval time between two times is preferably 5 to 10 minutes.
Compared with the prior art, the invention has the following positive effects:
1. the polyethylene glycol and the animal wax added in the paste material for repairing and mounting the paper cultural relic can form a certain hydrophobic layer on the surface of the paper under the coupling action of the silane coupling agent, so that the water absorption of the paper is reduced, the growth and the propagation of microorganisms and the like on the surface of the paper can be hindered, the damage of the microorganisms to the paper cultural relic is prevented, and the damage to the body of the paper cultural relic is avoided.
2. The polyethylene glycol and the animal wax added into the paste material for repairing and mounting the paper cultural relic can form a continuous protective film on the surface of the porous paper under the coupling action of the silane coupling agent, so that the paper cultural relic to be protected can be resisted from the erosion of the external environment such as acid, pollutants and the like to a certain extent.
3. The tillerine of natural alkaloid is also added into the paste material for repairing and mounting the paper cultural relic, so that the antibacterial and mildewproof performance of the paper can be further improved, the color and the pH value of the paper can not be influenced, and the problem of acidification and embrittlement of a paper carrier after mounting and repairing caused by the fact that the acidity of the paste is increased by the additive used in the prior art is solved.
4. When the paste material for repairing and mounting paper cultural relics is used, the paste material can be uniformly distributed on the surface of the mounted paper cultural relics and is connected with paper fibers through hydrogen bonds, so that the tensile strength and the folding endurance of the paper are greatly improved after starch paste is applied to hand paper.
5. Because the compound in the paste material for repairing and mounting the paper cultural relic is connected with the paper fiber through the hydrogen bond, strong chemical bond can not be formed, so the reversibility of starch paste can not be changed, and the problem of difficult mounting during remounting can not be caused.
6. The preparation method of the paste material for repairing and mounting the paper cultural relic only adopts deionized water as a solvent, so that the process is green and environment-friendly, the operation is simple, the control is easy, and the expanded production is facilitated.
Drawings
FIG. 1 is a scanning electron microscope image of a gel obtained by drying the paste material for repairing and mounting the sol-like paper cultural relics prepared by the invention at room temperature. As can be seen from the figure, the composite material prepared by the whole system is very uniform.
FIG. 2 is a scanning electron micrograph of a cross-section of the protective material prepared in example 3 applied to a hand-made paper after brittle fracture in liquid nitrogen. As can be seen from the figure: the prepared starch paste protects the uniform distribution of the material on the surface of the paper, and the paste can form a continuous protective film on the surface of the porous paper. The microstructure can resist the erosion of external environment such as acid, pollutant and the like to the protected paper cultural relic to a certain extent, and can improve the strength of the paper cultural relic.
Detailed Description
The present invention is described in detail by the following examples and application examples, which should be pointed out here only for further illustration of the present invention and should not be construed as limiting the scope of the present invention, and those skilled in the art can make some insubstantial modifications and adaptations to the present invention based on the above-mentioned disclosure.
It is worth mentioning that: 1) The parts of the materials in the following examples, application examples and comparative examples are parts by weight. 2) The materials obtained in the following application examples and comparative application examples were tested in the following manner, and the test results are shown in the attached table:
(1) appearance color change test: the test is carried out by adopting a Japan Meinenda CM700D color difference meter and passing through a formula
To calculate the color change Δ E, 4 samples were taken for each application example in the experiment, and 20 points of 5 points were arbitrarily selected for each sample and averaged.
(2) Testing the tensile strength; the tensile properties of the paper were tested according to GB/T12914-2008 paper and board tensile strength using a TMI 84-56 horizontal tensile machine (Testing Machines, netherlands) and 10 bars were tested per group and the results averaged.
(3) And (3) testing the folding endurance: according to the determination of the folding endurance of the paper and the paperboard in GB/T457-2008, a U.S. TMI 31-23 folding endurance tester (Testing Machines company in America) is adopted to test the double folding times of the paper as the folding endurance value, 10 pieces of sample strips in each group are selected, and the average value is taken.
(4) And (3) testing antibacterial performance: common yellow mold, blue mold and trichoderma separated from paper are selected as antibacterial performance experiments, strains are inoculated on paper coated with paste materials, and the paper is cultured for ten days, wherein the growth conditions are shown in the attached table.
Example 1
Firstly, 100 parts of starch is put into 600 parts of deionized water, stirred uniformly and then stood and soaked for 1 hour at room temperature, then 1 part of polyethylene glycol with the average molecular weight of 1200 and 0.1 part of berberine extracted from coptis chinensis are added and stirred uniformly, and then ultrasonic dispersion is carried out for 30 minutes at the temperature of 30 ℃; and (3) putting the dispersed starch solution into a constant-temperature water bath, directly adding 0.01 part of beeswax and 0.2 part of tetramethoxysilane coupling agent, heating, keeping the temperature at 90 ℃, and stirring for 10 minutes to obtain a uniform and transparent gel paste material.
Example 2
Firstly, 100 parts of starch is put into 1500 parts of deionized water, stirred evenly and then kept stand and soaked for 5 hours at room temperature, then 2 parts of polyethylene glycol with the average molecular weight of 4000 and 0.5 part of berberine extracted from barberry root are added and stirred evenly, and then ultrasonic dispersion is carried out for 120 minutes at the temperature of 25 ℃; and (3) putting the dispersed starch solution into a constant-temperature water bath, directly adding 5 parts of beeswax and 5 parts of tetramethoxydivinyl siloxane coupling agent, heating, keeping the temperature at 100 ℃, and stirring for 120 minutes to obtain a uniform and transparent gel paste material.
Example 3
Firstly, 100 parts of starch is put into 500 parts of deionized water, stirred uniformly and then stood and soaked for 0.5 hour at room temperature, then 0.1 part of polyethylene glycol with the average molecular weight of 800 and 0.025 part of berberine extracted from berberis thunbergii are added and stirred uniformly, and then ultrasonic dispersion is carried out for 20 minutes at the temperature of 25 ℃; and (3) putting the starch solution obtained by dispersion into a constant-temperature water bath, directly adding 0.1 part of insect wax and 0.1 part of hexaethoxydisiloxane coupling agent, heating, keeping the temperature at 95 ℃, and stirring for 40 minutes to obtain the uniform and transparent gel paste material.
Example 4
Firstly, 100 parts of starch is put into 1000 parts of deionized water, stirred uniformly and then kept stand and soaked for 3 hours at room temperature, then 5 parts of polyethylene glycol with the average molecular weight of 2000 and 0.01 part of berberine extracted from coptis chinensis are added and stirred uniformly, and then ultrasonic dispersion is carried out for 40 minutes at the temperature of 20 ℃; and (3) putting the dispersed starch solution into a constant-temperature water bath, directly adding 2 parts of Chinese wax and 2 parts of tetraethoxy divinyl disiloxane coupling agent, heating, keeping the temperature at 85 ℃, and stirring for 80 minutes to obtain the uniform and transparent gel paste material.
Example 5
Firstly, 100 parts of starch is put into 800 parts of deionized water, stirred evenly and then kept stand and soaked for 1.5 hours at room temperature, then 0.5 part of polyethylene glycol with the average molecular weight of 1000 and 0.2 part of berberine extracted from berberis thunbergii are added and stirred evenly, and then ultrasonic dispersion is carried out for 60 minutes at the temperature of 28 ℃; and (3) putting the dispersed starch solution into a constant-temperature water bath, directly adding 0.5 part of beeswax and 0.01 part of diethoxy polydimethylsiloxane coupling agent, heating, keeping the temperature at 90 ℃, and stirring for 100 minutes to obtain a uniform and transparent gel paste material.
Comparative example 1
Firstly, 100 parts of starch is put into 500 parts of deionized water, stirred evenly and then kept stand and soaked for 0.5 hour at room temperature, and then ultrasonic dispersion is carried out for 20 minutes at 25 ℃; and (3) putting the starch solution obtained by dispersion into a constant-temperature water bath, heating and stirring for 40 minutes at 95 ℃ to obtain a uniform and transparent gel paste material.
Comparative example 2
Firstly, 100 parts of starch is put into 500 parts of deionized water, stirred evenly and then kept stand at room temperature for soaking for 0.5 hour, then 0.025 part of berberine extracted from berberis thunbergii is added and stirred evenly, and then ultrasonic dispersion is carried out for 20 minutes at 25 ℃; and (3) putting the starch solution obtained by dispersion into a constant-temperature water bath, heating and stirring for 40 minutes at 95 ℃ to obtain a uniform and transparent gel paste material.
Comparative example 3
Firstly, 100 parts of starch is put into 500 parts of deionized water, stirred uniformly and then stood and soaked for 0.5 hour at room temperature, then 0.1 part of polyethylene glycol with the average molecular weight of 800 is added and stirred and mixed uniformly, and then ultrasonic dispersion is carried out for 20 minutes at the temperature of 25 ℃; and (3) putting the starch solution obtained by dispersion into a constant-temperature water bath, heating and stirring for 40 minutes at 95 ℃ to obtain a uniform and transparent gel paste material.
Application example 1
The average gram weight of the mixture is 24.56g/m 2 Handsheets having an average thickness of 94 μm, which are constant at a temperature of 23. + -. 1 ℃ and a relative humidity of 50. + -. 2% for at least 24 hours. The paste sol obtained in example 1 was diluted 5 times and then applied to the surface of hand paper with a soft wool brush for 6 times with an interval of 5 minutes. After finishing, wiping the redundant paste around by using filter paper; drying in the air in natural environment.
And (3) testing various performances of the dried paper coated with the paste according to corresponding standards, wherein the measured performance results are shown in an attached table.
Application example 2
The average gram weight is 24.56g/m 2 Handsheets having an average thickness of 94 μm, which are constant at a temperature of 23. + -. 1 ℃ and a relative humidity of 50. + -. 2% for at least 24 hours. The sol obtained in example 2 was subjected toAfter being mashed, the mixture is sprayed on the surface of hand-made paper for 3 times, and the interval time between the two times is 8 minutes. Wiping the redundant paste around by using filter paper; drying in the air in natural environment.
And testing various performances of the dried paper coated with the paste according to corresponding standards, wherein the measured performance results are shown in an attached table.
Application example 3
The average gram weight of the mixture is 24.56g/m 2 Handsheets having an average thickness of 94 μm and being held constant at a temperature of 23. + -. 1 ℃ and a relative humidity of 50. + -. 2% for at least 24 hours. The paste sol obtained in example 3 was directly diluted 1-fold and then applied to the surface of handsheets with a soft wool brush 2 times with an interval of 10 minutes. Wiping the redundant paste around by using filter paper; drying in the air in natural environment.
And (4) testing various performances of the dried paper coated with the paste according to corresponding standards, wherein the performance results are shown in the attached table.
Application example 4
The average gram weight of the mixture is 24.56g/m 2 Handsheets having an average thickness of 94 μm and being held constant at a temperature of 23. + -. 1 ℃ and a relative humidity of 50. + -. 2% for at least 24 hours. The paste sol obtained in example 4 was diluted 3 times and sprayed on the surface of hand paper 4 times with an interval of 15 minutes. After finishing, wiping the redundant paste around by using filter paper; drying in the air in natural environment.
And testing various performances of the dried paper coated with the paste according to corresponding standards, wherein the measured performance results are shown in an attached table.
Application example 5
The average gram weight is 24.56g/m 2 Handsheets having an average thickness of 94 μm, which are constant at a temperature of 23. + -. 1 ℃ and a relative humidity of 50. + -. 2% for at least 24 hours. The sol obtained in example 5 was diluted 2 times and applied to the surface of handsheets with a soft wool brush 2 times with an interval of 12 minutes. Wiping the redundant paste around by using filter paper; drying in the air in natural environmentAnd (5) drying.
And (3) testing various performances of the dried paper coated with the paste according to corresponding standards, wherein the measured performance results are shown in an attached table.
Blank example
The average gram weight of the mixture is 24.56g/m 2 Handsheets having an average thickness of 94 μm and being held constant at a temperature of 23. + -. 1 ℃ and a relative humidity of 50. + -. 2% for at least 24 hours. And brushing deionized water on the surface of the hand paper by using a soft wool brush for 2 times, wherein the interval time between the two times is 10 minutes. And after the completion, drying the mixture in the natural environment.
And (3) testing various performances of the dried paper coated with the paste according to corresponding standards, wherein the measured performance results are shown in an attached table.
Comparative application
The average gram weight is 24.56g/m 2 Handsheets having an average thickness of 94 μm and being held constant at a temperature of 23. + -. 1 ℃ and a relative humidity of 50. + -. 2% for at least 24 hours. The paste sol obtained in comparative example 1 was diluted 5 times and then applied to the surface of hand sheets with a soft wool brush 3 times with an interval of 10 minutes. After finishing, wiping the redundant paste around by using filter paper; drying in the air in natural environment.
And (4) testing various performances of the dried paper coated with the paste according to corresponding standards, wherein the performance results are shown in the attached table.
Attached table: performance test results of application examples 1 to 5 and application comparative example
Note: "-" indicates a smaller amount of mold growth, "+" indicates a larger amount of mold growth, and "+" more indicates a larger amount of mold growth. "No" means no mold growth.
Claims (9)
1. The paste material for repairing and mounting the paper cultural relics is prepared by mixing and reacting the following components in parts by weight:
starch 100 parts
500 to 1500 portions of deionized water
0.1 to 5 portions of polyethylene glycol
0.01 to 5 portions of animal wax
0.01 to 0.5 portion of berberine
0.01 to 5 portions of silane coupling agent,
the appearance of the sol is uniform and transparent sol.
2. The paste material for repairing and mounting paper relics, which is prepared from the polyethylene glycol of claim 1, wherein the polyethylene glycol has an average molecular weight of 800-4000.
3. The paste material for repairing and mounting paper relics, which is prepared from the animal wax as one of beeswax and Chinese wax, according to claim 1 or 2.
4. The paper cultural relic repairing and mounting paste material as claimed in claim 1 or 2, wherein the berberine in the material is any one of coptis chinensis, berberis thunbergii or barberry natural plant extract.
5. The paste material for repairing and mounting paper relics, which is prepared from the material as claimed in claim 1 or 2, wherein the silane coupling agent is any one of methoxy, ethoxy or methyl ethoxy silane coupling agents.
6. A method for preparing the paste material for repairing and mounting the paper cultural relics as defined in any one of claims 1 to 5, which comprises the following process steps and conditions:
1) Firstly, 100 parts of starch is put into 500 to 1500 parts of deionized water, stirred evenly and then kept stand and soaked for 0.5 to 5 hours at room temperature;
2) Adding 0.1 to 5 parts of polyethylene glycol and 0.01 to 0.5 part of berberine into the soaked starch aqueous solution, stirring and mixing uniformly, and then performing ultrasonic dispersion for 3 to 120 minutes at the temperature of 20 to 30 ℃;
3) Putting the dispersed starch solution into a constant-temperature water bath, adding 0.01 to 5 parts of animal wax and 0.01 to 5 parts of silane coupling agent, heating, keeping the temperature at 85 to 100 ℃, stirring for 10 to 120 minutes to obtain a uniform and transparent gel paste material,
the parts of the materials are all parts by weight.
7. The preparation method of the paste material for repairing and mounting paper cultural relics, which is characterized in that the addition amount of the polyethylene glycol used in the method is 0.5 to 2 parts; the addition amount of the animal wax is 0.1 to 2 parts; the addition amount of the berberine is 0.05 to 0.5 parts; the addition amount of the silane coupling agent is 0.1 to 2 parts.
8. The application method of the paste material for repairing and mounting the paper relic, which is prepared by the method in claim 6, comprises the following specific steps and conditions:
1) The uniform and transparent gel paste material prepared by the method is mashed in a mortar, diluted by deionized water for 0 to 5 times, and then the surface of the painting and calligraphy/ancient book to be protected is brushed or sprayed for not less than 2 times, and the interval time of each time is not more than 15 minutes.
2) And (4) sucking the redundant paste materials at the edge of the paper after brushing or spraying, and then placing the paper in a natural environment for airing.
9. The application method of the paste material for repairing and mounting paper relics, which is characterized in that the dilution with deionized water is 1 to 5 times; brushing and spraying for 2 to 6 times; the interval time of every two times is 5-10 minutes.
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