A kind of paper and bamboo cultural relics ink color reinforcing agent and its preparation method and application

Abstract

The present application relates to the technical field of cultural relic protection, and particularly relates to a kind of bamboo and wooden slips cultural relic ink color developing reinforcing agent and its preparation method and application, the bamboo and wooden slips cultural relic ink color developing reinforcing agent, by weight parts, including the following raw materials: ionic liquid composition 20-40 parts, modified silk fibroin 0.02-0.05 parts, solvent III 2-4 parts.The bamboo and wooden slips cultural relic ink color developing reinforcing agent prepared by the present application has good stability, long storage period, good color developing and fixing effect and can reinforce bamboo and wooden slips cultural relics.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of cultural relic protection, and particularly relates to a kind of bamboo and wooden slips cultural relic ink color development reinforcing agent and its preparation method and application. BACKGROUND

[0002] As an important carrier of Chinese ancient characters, bamboo and wooden slips cultural relics carry rich historical and cultural information, and are the first-hand materials for studying ancient society, economy and culture. In recent years, with the continuous increase of archaeological discoveries, a large number of bamboo and wooden slips cultural relics have been unearthed, among which the most representative are the Han Dynasty bamboo slips in Wuwei, Gansu, the Qin Dynasty bamboo slips in Yuncheng, Hubei, and the Qin Dynasty bamboo slips in Lijie, Hunan. However, these precious cultural relics, which have been buried underground for more than 2,000 years, are generally facing serious problems such as ink fading and wood matrix degradation. According to the 2022 census data of the State Administration of Cultural Heritage, about 63% of the bamboo and wooden slips in China's collection have blurred characters, and 27% have serious fading, which is a very serious situation for cultural relic protection.

[0003] The main component of bamboo and wooden slips ink is pine soot ink, and its stability is influenced by various environmental factors. Existing research shows that the ink degradation process involves complex physical and chemical changes. On the physical level, the repeated expansion and contraction of the wood matrix caused by temperature and humidity fluctuations is the main reason for the separation of the ink layer. Experimental data shows that when the relative humidity changes more than ± 15%, the surface of the bamboo and wooden slips will produce about 0.3-0.5% strain, and this periodic stress directly leads to the separation of the ink and the matrix interface. In addition, mechanical friction during post-excavation processing can also cause surface wear and accelerate the disappearance of the ink. Currently, the protection of bamboo and wooden slips ink mainly adopts physical reinforcement and chemical reinforcement methods. In the physical reinforcement method, polyvinyl butyral film covering is a common means, although this method can effectively fix the ink, but the film layer will seriously hinder the direct observation and scientific research of the cultural relics. The chemical reinforcement method mainly uses acrylic resin as the reinforcing material. However, there is a significant difference in the thermal expansion coefficient between this material and the wood matrix (about 3-5 times), which will generate interfacial stress when the environmental temperature fluctuates, and thus accelerate the deterioration of the cultural relics. Moreover, most of the systems only focus on single function of reinforcement or color development and lack systematic research on the special material and preservation state of bamboo and wooden slips cultural relics.

[0004] Patent CN101736352A discloses a bronze cultural relic repair liquid and its repair method, the weight percentage of each component in the repair liquid is: imidazole ionic liquid 32-35%, copper oxide powder 9-11%, titanium cyanide green 1-2%, phosphoric acid 15-20%, water 38-41%. The repair liquid has strong penetration ability and reactivity, can remove copper rust and convert it into a high-strength material under the condition of small acid ratio (10-12%) and low temperature, significantly improves the strength of bronze ware, and enhances the compression resistance, tearing degree, breaking degree and tensile strength of bronze ware. The repair liquid of the invention can effectively repair the rusted and mineralized bronze cultural relics and restore them to their original shape. However, the solubility of imidazole ionic liquid in water is poor, which leads to poor stability of the cultural relic repair liquid.

[0005] Patent CN108148450B discloses a faded cultural relic color developing repair agent and its use method, leather scrap hydrolysate is obtained by hydrolyzing chromium-containing leather scrap, the color developing repair agent is composed of 1-butyl-3-methylimidazolium hexafluorophosphate and acetone solution according to a certain proportion, its composition and use are simple and easy to operate, the introduction of the cultural relic system does not damage the original organization of the cultural relic, and it can be prepared on demand; the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate is dissolved in acetone with acetone as the solvent, the filling of 1-butyl-3-methylimidazolium hexafluorophosphate to the cultural relic pigment layer is realized by using the volatility of acetone, the light scattering of the pigment layer of the faded cultural relic is reduced, acetone is an environmentally friendly reagent with high boiling point, the color of the faded cultural relic can be developed, and the developing operation has reversibility and stable developing effect. However, the color developing and fixing mechanism of 1-butyl-3-methylimidazolium hexafluorophosphate is relatively single and the reinforcement effect on the cultural relic is poor.

[0006] Therefore, there is an urgent need in the market for a color developing and reinforcing agent for ink color development and reinforcement of bamboo and wooden slips. SUMMARY

[0007] In view of the problems in the prior art, the purpose of the present application is to obtain a bamboo and wooden slip cultural relic ink color developing and reinforcing agent with good stability, long storage period, excellent color developing and fixing effect and reinforcement effect.

[0008] In order to achieve the above-mentioned purpose, the technical scheme adopted by the present application is as follows:

[0009] In one aspect, the present application provides a bamboo and wooden slip cultural relic ink color developing and reinforcing agent, which comprises the following raw materials in parts by weight: ionic liquid composition 20-40 parts, modified silk fibroin 0.02-0.05 parts, and solvent III 2-4 parts.

[0010] The application can realize ink color enhancement and structure stabilization by adding the modified silk fibroin and solvent III into the ion liquid composition, thereby effectively prolonging the preservation life of the simple and ancient document and improving the scientific research value thereof. The color reinforcing agent has simple composition, stable system, environmental protection, strong operability, does not damage the body structure of the simple and ancient document, and can realize the color reinforcement of the ink of the simple and ancient document.

[0011] In some embodiments, the ion liquid composition comprises the following raw materials in parts by weight: ion liquid 7-11 parts, modified carboxymethyl cellulose 0.5-1 part, and solvent 18-30 parts.

[0012] In some embodiments, the ion liquid is a combination of 1-butyl-3-methyl imidazole hexafluorophosphate and 1-ethyl-3-methyl imidazole tetrafluoroborate, and the mass ratio of the two is 1:(0.2-0.4).

[0013] In some embodiments, the preparation method of the modified carboxymethyl cellulose comprises the following steps:

[0014] A1, adding sodium carboxymethyl cellulose, fatty acid chloride, and tetrabutylammonium bromide into solvent I, stirring at 80-90°C for 6-8h, taking the lower liquid and rinsing with n-heptane for 2-4 times, and drying at 50-60°C to obtain hydrophobic modified sodium carboxymethyl cellulose;

[0015] A2, adding the hydrophobic modified sodium carboxymethyl cellulose obtained in step A1 and benzyl bromide into solvent II, adding sodium hydroxide, and reacting at 60-85°C for 4-6h, and then dialyzing to remove impurities to obtain modified carboxymethyl cellulose.

[0016] In some embodiments, the mass ratio of the sodium carboxymethyl cellulose and the fatty acid chloride is 1:(0.4-0.8).

[0017] In some embodiments, the ratio of the sodium carboxymethyl cellulose and solvent I is 1g:(10-15)ml.

[0018] In some embodiments, the solvent I is a combination of n-heptane and DMF, and the volume ratio of the two is 1:(0.05-0.1).

[0019] In some embodiments, the ratio of the hydrophobic modified sodium carboxymethyl cellulose and benzyl bromide in step A2 is 1g:(0.1-0.5)ml.

[0020] In some embodiments, the mass ratio of the hydrophobic modified sodium carboxymethyl cellulose and sodium hydroxide in step A2 is 1:(0.08-0.16).

[0021] In some embodiments, the solvent II is DMF or DMSO.

[0022] In some embodiments, the solvent is a combination of acetone and deionized water, the mass ratio of which is 1:(0.15-0.25).

[0023] In some embodiments, the preparation method of the color-developing and fixing ionic liquid composition comprises the following steps: adding an ionic liquid and modified carboxymethyl cellulose into a solvent and mixing uniformly, thereby obtaining the color-developing and fixing ionic liquid composition.

[0024] In some embodiments, the preparation method of the modified silk fibroin comprises the following steps:

[0025] B1, adding nano tungsten oxide into deionized water, ultrasonic treatment for 10-25 min, and then stirring at room temperature for 30-60 min to form a nano tungsten oxide dispersion liquid;

[0026] B2, adding silk fibroin into 1-ethyl-3-methyl imidazole chloride, stirring at 95-105°C for 30-60 min to obtain a silk fibroin solution;

[0027] B3, mixing the silk fibroin solution obtained in step B2 with the nano tungsten oxide dispersion liquid obtained in step B1, stirring at room temperature for 1-3 h, adding ethanol, taking out the precipitate, and drying to obtain the modified silk fibroin.

[0028] After the ink color-developing and fixing agent is coated on the bamboo and wooden slips, a part of the modified silk fibroin and the modified carboxymethyl cellulose form a uniform film on the surface of the cultural relics through hydrogen bond interaction, which reduces light scattering and improves the color-developing effect of the color-developing and fixing agent. Another part of the modified silk fibroin penetrates into the fiber gap of the wood, solidifies to form a β-sheet crystal structure, and constructs a three-dimensional reinforcing network. In addition, the polar amino acids in the modified silk fibroin can adsorb / release water, buffer the expansion and contraction of the cultural relics caused by sudden changes in humidity, thereby enhancing the bending strength of the bamboo and wooden slips. Moreover, the tyrosine residues in the modified silk fibroin absorb ultraviolet rays, reducing the photo-degradation of the cultural relics, and further improving the color-developing and fixing effect of the ionic liquid composition.

[0029] In the present application, the silk fibroin is added into 1-ethyl-3-methyl imidazole chloride, which can destroy the hydrogen bonds in the silk fibroin molecules and improve the dispersibility of the silk fibroin in the ionic liquid composition.

[0030] In the present application, the light-sensitive nanomaterials are used to modify the silk fibroin, which can absorb specific wavelengths of light, reduce light scattering, and enhance the light reflection and refraction effects of the fiber surface, thereby improving the color-developing effect of the ink.

[0031] In some embodiments, the particle size of the nano tungsten oxide is 2-10 nm.

[0032] The present application can make the color development and fixation agent for ancient documents and relics have better stability and further improved color development and fixation effect by limiting the particle size of nano tungsten oxide, which may be because the nano tungsten oxide with smaller particle size has larger specific surface area and stronger surface activity, can more effectively absorb and scatter light, thereby enhancing the depth and saturation of color, and the nano tungsten oxide with smaller particle size contains more active groups, has stronger interaction force with silk fibroin and ionic liquid composition, thereby making the modified silk fibroin have better dispersibility in the system, can be more uniformly distributed, thereby improving the uniformity of color.

[0033] In some embodiments, the mass ratio of the silk fibroin and the nano tungsten oxide is 1:(0.05-0.15).

[0034] The present application can make the color development and fixation agent for ancient documents and relics have better stability and further improved color development and fixation effect by limiting the mass ratio of silk fibroin and nano tungsten oxide, which may be because the nano tungsten oxide has better dispersibility and makes the color more uniform at this ratio.

[0035] In some embodiments, the mass ratio of the silk fibroin and 1-ethyl-3-methylimidazole chloride is 1:(6-9).

[0036] The present application can make the color development and fixation agent for ancient documents and relics have better stability, reinforcement effect and color development and fixation effect by limiting the mass ratio of silk fibroin and 1-ethyl-3-methylimidazole chloride, which may be because the silk fibroin has good dispersibility and retains the strength of the internal β-sheet structure at this ratio, thereby better enhancing the internal strength of ancient documents and relics.

[0037] In some embodiments, the molecular weight of the silk fibroin is less than 50kDa.

[0038] The present application can make the color development and fixation agent for ancient documents and relics have better stability, reinforcement effect and color development and fixation effect by limiting the molecular weight of silk fibroin, which may be because the silk fibroin with this molecular weight has better dispersibility and is easy to penetrate into ancient documents and relics and is not easy to remain.

[0039] In some embodiments, the solvent III is ethanol or methanol.

[0040] The second aspect of the present application discloses a preparation method of a color development and fixation agent for ancient documents and relics, comprising the following steps: adding modified silk fibroin into an ionic liquid composition, stirring at 70-80°C for 20-40min, cooling to room temperature, adding solvent III, stirring for 30-50min, and obtaining.

[0041] Preferably, the solvent III is anhydrous ethanol.

[0042] The third aspect of the present application provides an application of the ink color development and reinforcement agent for ancient documents, and the coating method of the ink color development and reinforcement agent is pen coating.

[0043] In the present application, the ink color development and reinforcement agent for ancient documents is coated on the relics by spraying, dropping and pen coating. When the spraying method is used, it is found that the color development and reinforcement agent is not easy to control and diffuses to the surrounding of the font when spraying, which affects the original appearance of the sample. In addition, the spray pen is easy to be blocked when the liquid output is small, so this coating method is not suitable for the ink color development and reinforcement agent for ancient documents. When the dropping method is used, it is found that the color development and reinforcement agent diffuses to the outside of the ink of the font, which affects the original appearance of the sample, and the operation time of this method is relatively long, and the color development and reinforcement efficiency is low for large-area ancient documents. When the pen coating method is used, it is found that this coating method has high precision and is very suitable for processing small or complex text patterns on ancient documents. By accurately controlling the pen force and touch, it can ensure that the reinforcement agent is uniformly and accurately covered on the surface of the text, while avoiding unnecessary blurring or damage to the text. The pen coating method not only is suitable for local fine processing, but also can effectively improve the overall effect of color development and reinforcement under the premise of maintaining the clarity of the text.

[0044] Compared with the prior art, the present application has the following beneficial effects:

[0045] (1) The ink color development and reinforcement agent for ancient documents obtained by uniformly mixing modified silk fibroin and solvent III into the ionic liquid composition can simultaneously realize ink color development enhancement and structure stability, thereby effectively prolonging the preservation life of ancient documents and improving the scientific research value thereof. The composition ratio of the color development and reinforcement agent is simple, the system is stable, it is environmentally friendly, the operation is strong, the coating on the surface of the sample does not damage the body structure of the ancient document, and the color development and reinforcement of the ink of the ancient document can be realized. In addition, the coating method of the reinforcement agent is selected, and the pen coating method has the best application effect.

[0046] (2) After the ionic liquid composition in the ink color development and reinforcement agent for ancient documents prepared by the present application penetrates into the fiber gap of the wood of the paper, the silk fibroin and the modified carboxymethyl cellulose form a uniform film on the surface of the relic through hydrogen bonding, which can reduce light scattering and improve the color development effect of the color development and reinforcement agent. It can also penetrate into the fiber gap of the wood and form a beta-folded crystal structure after solidification, construct a three-dimensional reinforcing network, and the polar amino acids of silk fibroin can absorb / release moisture, buffer the expansion and contraction of the relic caused by sudden changes in humidity, thereby improving the tensile strength of the paper. The tyrosine residues in silk fibroin absorb ultraviolet rays, reducing the photodegradation of the relic body, and further improving the color fixing effect of the ionic liquid composition.

[0047] (3) The application improves the color development effect of ink marks by using photosensitive nanomaterials to modify silk fibroin and introducing photosensitive nanomaterials into the color development reinforcing agent, which can absorb light of specific wavelengths, reduce light scattering, and enhance the light reflection and refraction effects of the fiber surface, thereby improving the color development effect of ink marks. BRIEF DESCRIPTION OF DRAWINGS

[0048] Figure 1 The prepared bamboo and wooden slips simulation sample photos;

[0049] Figure 2 The sample surface photos after spraying coating;

[0050] Figure 3 The sample surface photos after drop coating;

[0051] Figure 4 The sample surface photos after pen coating;

[0052] Figure 5 The sample surface photos after coating the color development reinforcing agent;

[0053] Figure 6 The surface SEM photos of the sample after being placed for 1 year before coating the color development reinforcing agent;

[0054] Figure 7 The surface SEM photos of the sample after being placed for 1 year after coating the color development reinforcing agent;

[0055] Figure 8 The surface Mapping photos of the sample after being placed for 1 year before coating the color development reinforcing agent;

[0056] Figure 9 The surface Mapping photos of the sample after being placed for 1 year after coating the color development reinforcing agent. DETAILED DESCRIPTION

[0057] The application will be described below in conjunction with specific embodiments. It should be noted that the following examples are examples of the application and are only used to illustrate the application, but not to limit the application. Other combinations and various modifications within the concept of the application can be made without departing from the spirit or scope of the application.

[0058] In the following examples and comparative examples, the remaining compounds and related reagents used, except for the modified carboxymethyl cellulose and modified silk fibroin, can be purchased from the market, wherein the molecular weight of sodium carboxymethyl cellulose is 30000-50000 g / mol; the molecular weight of silk fibroin-1 is 20-35 kDa, and the molecular weight of silk fibroin-2 is 70-100 kDa, which are purchased from Shanghai Yeyuan Technology Co., Ltd.; the particle size of nano tungsten oxide-1 is 2-10 nm; and the average particle size of nano tungsten oxide-2 is 50 nm.

[0059] Preparation Example 1

[0060] The preparation method of the modified carboxymethyl cellulose comprises the following steps:

[0061] A1, 10 g of sodium carboxymethyl cellulose, 6 g of octadecanoyl chloride, and 0.1 g of tetrabutylammonium bromide are added to 120 ml of solvent I, stirred at 85°C for 7 h, the supernatant is rinsed with n-heptane for 3 times, and dried at 55°C to obtain hydrophobic modified sodium carboxymethyl cellulose;

[0062] A2, 10 g of the hydrophobic modified sodium carboxymethyl cellulose obtained in step A1 and 3.5 ml of benzyl bromide are added to 50 g of DMSO, 1.2 g of sodium hydroxide is added, and reacted at 75°C for 5 h, and then impurities are removed by dialysis to obtain modified carboxymethyl cellulose.

[0063] The solvent I is a combination of n-heptane and DMF, and the volume ratio of the two is 1:0.07.

[0064] Preparation Example 2

[0065] The preparation method of the ionic liquid composition comprises the following steps: 9 parts of ionic liquid and 0.7 parts of modified carboxymethyl cellulose are added to 25 parts of solvent and mixed uniformly at room temperature.

[0066] The ionic liquid is a combination of 1-butyl-3-methylimidazolium hexafluorophosphate and 1-ethyl-3-methylimidazolium tetrafluoroborate, and the mass ratio of the two is 1:0.3.

[0067] The solvent is a combination of acetone and deionized water, and the mass ratio of the two is 1:0.2.

[0068] Preparation Example 3

[0069] The preparation method of the modified silk fibroin-1 comprises the following steps:

[0070] B1, 0.1 g of nano tungsten oxide-1 is added to 5 g of deionized water, ultrasonic treated for 15 min, and then stirred at room temperature for 45 min to form a nano tungsten oxide dispersion liquid;

[0071] B2, 1 g of silk fibroin-1 is added to 7.5 g of 1-ethyl-3-methylimidazolium chloride, and stirred at 100°C for 45 min to obtain a silk fibroin solution;

[0072] B3, the silk fibroin solution obtained in step B2 is mixed with the nano tungsten oxide dispersion liquid obtained in step B1, stirred at room temperature for 2 h, anhydrous ethanol is added, the precipitate is removed, and dried to obtain modified silk fibroin-1.

[0073] Preparation Example 4

[0074] The preparation method of modified silk fibroin-2 is the same as that of Preparation Example 3, except that the nano tungsten oxide-1 is replaced by an equal amount of nano tungsten oxide-2.

[0075] Preparation Example 5

[0076] The preparation method of modified silk fibroin-3 is the same as that of Preparation Example 3, except that the addition amount of nano tungsten oxide-1 is 0.25 g.

[0077] Preparation Example 6

[0078] The preparation method of modified silk fibroin-4 is the same as that of Preparation Example 3, except that the addition amount of 1-ethyl-3-methylimidazole chloride salt is 11 g.

[0079] Preparation Example 7

[0080] The preparation method of modified silk fibroin-5 is the same as that of Preparation Example 3, except that the silk fibroin-1 is replaced by an equal amount of silk fibroin-2.

[0081] Example 1

[0082] A simple document cultural relic ink color developing reinforcing agent, by weight parts, comprising the following raw materials: ionic liquid composition 30 parts, modified silk fibroin-1 0.035 parts, anhydrous ethanol 3 parts.

[0083] The preparation method of the simple document cultural relic ink color developing reinforcing agent of the embodiment comprises the following steps: adding modified silk fibroin-1 into ionic liquid composition, stirring at 75°C for 30 min, cooling to room temperature, adding anhydrous ethanol, stirring for 40 min, and then obtaining.

[0084] Example 2

[0085] A simple document cultural relic ink color developing reinforcing agent, by weight parts, comprising the following raw materials: ionic liquid composition 20 parts, modified silk fibroin-1 0.02 parts, anhydrous ethanol 2 parts.

[0086] The preparation method of the simple document cultural relic ink color developing reinforcing agent of the embodiment comprises the following steps: adding modified silk fibroin-1 into ionic liquid composition, stirring at 70°C for 40 min, cooling to room temperature, adding anhydrous ethanol, stirring for 50 min, and then obtaining.

[0087] Example 3

[0088] A simple document cultural relic ink color developing reinforcing agent, by weight parts, comprising the following raw materials: ionic liquid composition 40 parts, modified silk fibroin-1 0.05 parts, anhydrous ethanol 4 parts.

[0089] The preparation method of the simple document cultural relic ink color developing reinforcing agent comprises the following steps: adding modified silk fibroin-1 into an ionic liquid composition, stirring at 80℃ for 20min, cooling to room temperature, adding anhydrous ethanol, and stirring for 30min.

[0090] Example 4

[0091] A preparation method of a simple document cultural relic ink color developing reinforcing agent, the specific implementation manner is the same as that in Example 1, and the difference lies in that the modified silk fibroin-1 is replaced by an equal amount of modified silk fibroin-2.

[0092] Example 5

[0093] A preparation method of a simple document cultural relic ink color developing reinforcing agent, the specific implementation manner is the same as that in Example 1, and the difference lies in that the modified silk fibroin-1 is replaced by an equal amount of modified silk fibroin-3.

[0094] Example 6

[0095] A preparation method of a simple document cultural relic ink color developing reinforcing agent, the specific implementation manner is the same as that in Example 1, and the difference lies in that the modified silk fibroin-1 is replaced by an equal amount of modified silk fibroin-4.

[0096] Example 7

[0097] A preparation method of a simple document cultural relic ink color developing reinforcing agent, the specific implementation manner is the same as that in Example 1, and the difference lies in that the modified silk fibroin-1 is replaced by an equal amount of modified silk fibroin-5.

[0098] Comparative Example 1

[0099] A preparation method of a simple document cultural relic ink color developing reinforcing agent, the specific implementation manner is the same as that in Example 1, and the difference lies in that the modified silk fibroin-1 is replaced by an equal amount of silk fibroin.

[0100] Performance test

[0101] The simple document cultural relic ink color developing reinforcing agents obtained in the above examples and comparative examples are tested in the following performances:

[0102] 1. Color developing and reinforcing experiment

[0103] 1.1 Preparation of simple document cultural relic simulation sample

[0104] The simple document simulation sample is prepared by taking the Wuwei Hanjian as an example, and the cedar wood placed for 80 years is selected as the carrier, the wood is stable, the texture is similar to that of the ancient simple document, and the characteristics of the real cultural relics can be better simulated, therefore, the natural aging simulation link is not performed. Figure 1 The specific steps of the prepared simple document cultural relic simulation sample are as follows:

[0105] (1) First, cut the 80-year-old cypress according to the size of the original bamboo slips, ensuring that the length and width of each piece of the simulation sample are consistent with the Wuwei Han Dynasty bamboo slips (such as the "Yi Li" bamboo slip, about 56 cm long and 0.7 cm wide);

[0106] (2) After cutting, the wood pieces are polished carefully with fine sandpaper, and the edges are polished to remove burrs and unevenness on the surface, making it smooth and delicate. During polishing, special attention is paid to preserving the natural texture of the wood to enhance the authenticity of the simulation sample;

[0107] (3) After polishing, use the writing method of Han Dynasty clerical script to mimic the original text with a brush dipped in pine smoke ink, striving to match the font, strokes, and layout with the original bamboo slips, while preserving the traces of scratching and changing characters to restore ancient writing habits;

[0108] (4) Finally, refer to the "Wuwei Han Dynasty Bamboo Slips" (published by Zhonghua Book Company) and "Wuwei Han Dynasty Bamboo Slips Collection" (published by Gansu Culture Publishing House) and other materials to check the details of the bamboo slips, such as size, line, and handwriting, to ensure that the bamboo slip artifact simulation sample is close to the real product in terms of material, ink, and weathering effect, while labeling the number and avoiding the use of modern chemical adhesives.

[0109] 1.2 Experiment of color development and reinforcement technology for bamboo slip artifact simulation sample

[0110] Apply the bamboo slip artifact ink color development and reinforcement agent obtained in Example 1 to the surface of the bamboo slip artifact simulation sample, use a soft brush to remove dust, and perform surface cleaning. Use spraying, dripping, and pen coating methods to apply the color development and reinforcement agent to the bamboo slip artifact.

[0111] 1) Spraying: Use a 0.3 mm diameter spray pen to dilute the color development and reinforcement agent with deionized water to a concentration of 17 wt%, maintain a spraying distance of 30 cm, and perform cross-spraying at a pressure of 0.1 MPa. Figure 2 The surface photo of the sample after spraying shows that the color development and reinforcement agent is not easy to control and spreads to the surrounding of the font, affecting the original appearance of the sample.

[0112] 2) Dripping: Use a micro-syringe to suck the color development and reinforcement agent, control the position and dose under a microscope, and ensure that the color development and reinforcement agent can evenly cover the surface of the bamboo slip without affecting the clarity of the characters. After dripping, the agent needs to be left to fully penetrate and solidify, and then the next dripping operation is performed. Figure 3 The surface photo of the sample after dripping shows that the color development and reinforcement agent will spread to the outside of the font ink after dripping and standing, affecting the original appearance of the simulation sample.

[0113] 3) Use a soft brush to remove dust and clean the surface, and use a brush dipped in bamboo slip artifact ink color development and reinforcement agent to depict the characters on the bamboo slip simulation sample, Figure 4The surface of the sample after being coated by the pen coating method was photographed. It can be seen that the color development and fixation effect of the pen coating method is better and is not easy to spread to the outside of the ink mark.

[0114] 1.3 Color development and reinforcement effect of the ancient document simulation sample

[0115] The ancient document ink color development and reinforcement agent obtained in Example 1 was dipped with a marking pen and coated on the surface of the ancient document simulation sample. After standing at room temperature for 24 h, the sample after color development and reinforcement was obtained. Figure 5 The surface of the sample after being coated by the color development and reinforcement agent was photographed. The font in the red dashed box is the font after being coated by the color development and reinforcement agent. After comparison with other fonts that are not coated, it is found that the color of the coated font is brighter, the lines of the font are more full, and the overall visual effect is significantly improved. The uncoated font appears dim, and some lines of the font are blurred or broken. The comparison result shows that the application effect of the color development and reinforcement agent in the ancient document simulation sample is significant. Not only is the reinforcement agent not observed to damage the body structure of the ancient document simulation sample, but also the ancient document is effectively protected, and the color development effect of the font is effectively improved.

[0116] The ancient document ink color development and reinforcement agents obtained in each example and the comparative example were coated on the ancient document simulation sample by the pen coating method. The front and back color difference values (ΔE) of each sample were tested by using a portable color difference meter. The ΔE value determines the degree of color difference. The larger the ΔE value, the more significant the color change. Generally, 0<ΔE≤0.5 is a slight difference, 0.5<ΔE≤1.5 is a very small difference, 1.5<ΔE≤3.0 is a significant difference, 3.0<ΔE<6.0 is a clear difference, 6.0<ΔE≤12.0 is a very large difference, and ΔE>12.0 is a huge difference.

[0117] The test results are shown in Table 1.

[0118] 1.4 Mechanical properties of ancient documents

[0119] The ancient document ink color development and reinforcement agents obtained in each example and the comparative example were coated on the cypress that had been stored for 80 years to obtain each sample. After drying, the compressive strength of each sample was tested according to GB / T 1935-2009.

[0120] The test results are shown in Table 1.

[0121] Table 1

[0122] Group ΔΕ Compressive strength MPa Example 1 2.34 18.5 Example 2 2.25 18.3 Example 3 2.28 18.1 Example 4 2.13 17.6 Example 5 2.15 17.8 Example 6 2.05 17.2 Example 7 1.99 16.9 Comparative Example 1 1.91 16.4

[0123] From the data in Table 1, it can be seen that the ink color developing and reinforcing agent for ancient bamboo and wooden slips in the embodiments 1-3 has excellent color developing and fixing effect and reinforcing effect; from the comparison between the embodiment 4 and the embodiment 1, it can be seen that changing the particle size of the nano tungsten oxide affects the dispersibility of the modified silk fibroin in the system, so that the color developing and fixing effect and the reinforcing effect of the ink color developing and reinforcing agent for ancient bamboo and wooden slips are reduced; from the comparison between the embodiment 5 and the embodiment 1, it can be seen that changing the ratio of the silk fibroin and the nano tungsten oxide affects the dispersibility of the nano tungsten oxide, so that the color developing and fixing effect and the reinforcing effect of the ink color developing and reinforcing agent for ancient bamboo and wooden slips are reduced; from the comparison between the embodiment 6 and the embodiment 1, it can be seen that changing the ratio of the silk fibroin and the 1-ethyl-3-methyl imidazole chloride affects the crystalline structure formed after the modified silk fibroin is solidified, so that the color developing and fixing effect and the reinforcing effect of the ink color developing and reinforcing agent for ancient bamboo and wooden slips are reduced; from the comparison between the embodiment 7 and the embodiment 1, it can be seen that changing the molecular weight of the silk fibroin affects its dispersibility and permeability, so that the color developing and fixing effect and the reinforcing effect of the ink color developing and reinforcing agent for ancient bamboo and wooden slips are reduced; from the comparison between the comparative example 1 and the embodiment 1, it can be seen that when the unmodified silk fibroin is used, the color developing and fixing effect and the reinforcing effect of the ink color developing and reinforcing agent for ancient bamboo and wooden slips are poor.

[0124] 2. Stability of the ancient bamboo and wooden slips simulation sample

[0125] The ancient bamboo and wooden slips simulation sample after the ink color developing and reinforcing by the ink color developing and reinforcing agent for ancient bamboo and wooden slips obtained in the embodiment 1 is placed in a dry and closed environment for 1 year. By comparing the scanning electron microscope analysis, Figure 6 The SEM picture of the sample surface before the color developing and reinforcing agent is applied is shown in the figure, and there are obvious cracks and wear marks on the surface of the sample, the edges of the font ink are blurred, and part of the ink even appears to fall off. Figure 7 The SEM picture of the sample surface after the color developing and reinforcing agent is applied is shown in the figure, and the surface of the sample becomes smooth, the cracks and wear are effectively repaired, the edges of the font ink are clear, the boundary between the reinforcing agent layer and the wood matrix is blurred, the ink is firmly attached to the surface of the sample, and there is no falling off. This comparison result fully proves that the reinforcing agent has effectively penetrated into the wood, and a firm bonding layer is formed. This not only enhances the adhesion of the ink, but also improves the overall stability of the ancient bamboo and wooden slips. After one year of placement test, the ancient bamboo and wooden slips simulation sample after the color developing and reinforcing still maintains good state, which further verifies its excellent stability.

[0126] In addition, the ionic liquid composition contains F element, and the mapping picture of F element can reflect the distribution of the color developing and reinforcing agent on the surface of the simulation sample. By comparing the mapping picture of F element on the surface of the sample after the color developing and reinforcing agent is applied for 1 year Figure 8 The surface mapping picture of the sample after being placed for 1 year before the color developing and reinforcing agent is applied is compared with Figure 9The surface mapping photo of the sample after 1 year of placing after applying the color developing consolidant can clearly observe the distribution change of F element on the surface of the simulation sample. In Figure 8 , F element almost does not exist, while in Figure 9 , F element is uniformly distributed on the surface of the simulation sample, which shows that the color developing consolidant for ancient Chinese writing ink has successfully penetrated into the simulation sample and formed a uniform cover layer on the surface thereof. This result not only verifies the effective penetration of the color developing consolidant, but further proves the excellent stability and uniformity thereof.

[0127] The above embodiments are only for illustrating the technical concept and characteristics of the present application, and the purpose is to enable those skilled in the art to understand the content of the present application and implement it, and cannot limit the protection scope of the present application. Any equivalent changes or modifications made according to the spirit and essence of the present application shall be covered within the protection scope of the present application.

Claims

1. A kind of bamboo and wooden slips cultural relics ink color reinforcement agent, characterized by, The ion liquid composition comprises the following raw materials in parts by weight: 20-40 parts of ion liquid composition, 0.02-0.05 parts of modified silk fibroin, and 2-4 parts of solvent III; The ion liquid composition comprises the following raw materials in parts by weight: 7-11 parts of ion liquid, 0.5-1 parts of modified carboxymethyl cellulose, and 18-30 parts of solvent III; The preparation method of the modified silk fibroin comprises the following steps: B1, adding nano tungsten oxide into deionized water, ultrasonic treatment for 10-25 min, and then stirring at room temperature for 30-60 min to form a nano tungsten oxide dispersion liquid; B2, adding silk fibroin into 1-ethyl-3-methyl imidazole chloride, stirring at 95-105 ℃ for 30-60 min to obtain a silk fibroin solution; B3, mixing the silk fibroin solution obtained in step B2 with the nano tungsten oxide dispersion liquid obtained in step B1, stirring at room temperature for 1-3 h, adding ethanol, taking out the precipitate, and drying to obtain the modified silk fibroin; The mass ratio of the silk fibroin and the nano tungsten oxide is 1: (0.05-0.15) ; The solvent III is ethanol or methanol.

2. The ink color development and reinforcement agent for ancient documents and relics according to claim 1, characterized by, The particle size of the nano tungsten oxide is 2-10 nm.

3. The ink color development and reinforcement agent for ancient documents and relics according to claim 1, characterized by, The mass ratio of the silk fibroin and 1-ethyl-3-methyl imidazole chloride is 1: (6-9).

4. The ink color development and reinforcement agent for ancient documents and relics according to claim 1, characterized by, The molecular weight of the silk fibroin is less than 50 kDa.

5. A method for preparing the ink color developing and reinforcing agent for ancient documents and relics according to any one of claims 1 to 4, characterized in that, The method comprises the following steps: adding the modified silk fibroin into the ion liquid composition, stirring at 70-80 ℃ for 20-40 min, cooling to room temperature, adding the solvent III, and stirring for 30-50 min.

6. A method for using the ink color developing and reinforcing agent for ancient documents and cultural relics according to any one of claims 1 to 4 or the ink color developing and reinforcing agent for ancient documents and cultural relics obtained by the preparation method of claim 5, characterized in that, The coating method of the calligraphy and document cultural relics ink color development and reinforcement agent is pen coating.

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