CN116356087B - Environment-friendly leather cultural relic reinforcing and protecting method - Google Patents
Environment-friendly leather cultural relic reinforcing and protecting method Download PDFInfo
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- CN116356087B CN116356087B CN202310253662.9A CN202310253662A CN116356087B CN 116356087 B CN116356087 B CN 116356087B CN 202310253662 A CN202310253662 A CN 202310253662A CN 116356087 B CN116356087 B CN 116356087B
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Classifications
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- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C11/00—Surface finishing of leather
- C14C11/003—Surface finishing of leather using macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J189/00—Adhesives based on proteins; Adhesives based on derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J189/00—Adhesives based on proteins; Adhesives based on derivatives thereof
- C09J189/04—Products derived from waste materials, e.g. horn, hoof or hair
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
- D06M15/03—Polysaccharides or derivatives thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/10—Animal fibres
- D06M2101/12—Keratin fibres or silk
Abstract
The invention relates to the technical field of reinforcement and protection of leather cultural relics, and discloses a green and environment-friendly reinforcement and protection method of leather cultural relics, which comprises the following steps: (1) Adding the single silk fiber treated by chitosan into a collagen peptide solution, and heating for reaction to obtain a reinforced mixed solution A; (2) taking genipin solution as reinforcing mixed solution B; (3) Coating a reinforcing mixed solution A on the interface of the broken or decayed leather cultural relics, and standing for not more than 5min; and then the reinforcing mixed liquid B is smeared at the same position, and is spliced and fixed according to the shape before the leather cultural relics are broken or decayed, and the leather cultural relics are kept stand for not less than 1h, so that the reinforcing protection of the leather cultural relics is finished. The invention improves the bonding strength of leather cultural relic interfaces through cross-linking polymerization, and improves the softness and bending strength of bonding parts; after reinforcement, the color difference at the connecting interface of fracture and decay is unchanged, secondary damage to cultural relics is avoided, and the cultural relics can be stored and displayed for a long time.
Description
Technical Field
The invention relates to the technical field of reinforcement and protection of leather cultural relics, in particular to a green and environment-friendly reinforcement and protection method of leather cultural relics.
Background
The leather cultural relics are the physical evidence of witnessed world clothing culture and civilization, and from a large number of leather cultural relics which are unearthed and inherited in China, china is one of the earliest countries using animal leather tanning materials, and the historical value and the skill of the leather cultural relics are enough to reflect the excellent traditional culture of China. At present, most of leather cultural relics such as leather clothing, leather tools, armatures and the like which are unearthed are broken, rotten, incomplete, hardened and other diseases due to the influence of the embedded environment, and repair protection is urgently needed, so that the leather cultural relics can be stored and displayed for a long time.
The protection and repair of leather cultural relics are studied at home and abroad, modern chemical products such as glutaraldehyde and epoxy resin are adopted as a cross-linking agent to reinforce the leather cultural relics, and the risk brought by the reinforcing agent is that the reinforcing agent has potential collagen modification influence on the leather cultural relics, and the effect is irreversible and easy to cause secondary damage. And natural materials such as leather glue are used as a reinforcing agent, but the reinforcing adhesive strength is not high, so that the flexibility of the reinforced relics is reduced, and the precious leather relics cannot be protected for a long time.
Therefore, the existing reinforcing and repairing methods for leather cultural relics have defects, a large number of leather cultural relics are still unearthed every year in China, and a green and environment-friendly reinforcing method is urgently needed for repairing and protecting the cultural relics, so that the cultural relics can be preserved and displayed for a long time on the premise of not causing secondary damage to the cultural relics, and the cognition of masses to the history culture of the long-term leather cultural relics is enriched.
Disclosure of Invention
In order to solve the technical problems, the invention provides a green and environment-friendly leather cultural relic reinforcing and protecting method, which adopts natural biological cross-linking agents, small molecular peptides with good permeability, functional finishing silk fibers and other materials, and enables the broken and decayed parts of the leather cultural relic to be bonded and repaired through a reinforcing process, so that the interface bonding strength is high, secondary damage to the cultural relic is avoided, and the material and the process are green and environment-friendly, and are very suitable for reinforcing and protecting the leather cultural relic.
The specific technical scheme of the invention is as follows: the invention provides a green and environment-friendly leather cultural relic reinforcing and protecting method, which comprises the following steps:
(1) Adding the single silk fiber treated by chitosan into a collagen peptide solution, and heating for reaction to obtain a reinforced mixed solution A;
(2) Taking genipin solution as a strengthening mixed solution B;
(3) Coating a reinforcing mixed solution A on the interface of the broken or decayed leather cultural relics, and standing for not more than 5min; and then the reinforcing mixed liquid B is smeared at the same position, and is spliced and fixed according to the shape before the leather cultural relics are broken or decayed, and the leather cultural relics are kept stand for not less than 1h, so that the reinforcing protection of the leather cultural relics is finished.
The reinforcement method of the invention adopts the principle that the bonding strength of the interface is improved by adopting the crosslinked polymer obtained by the reaction of the natural crosslinking agent and the micromolecular collagen peptide, and simultaneously the flexibility and the bending strength of the bonding part are improved by utilizing the tensile toughness of silk fibers.
The reinforced mixed solution A adopts collagen peptide solution with the range of 3000-6000 daltons, and is attached to and permeated into the surface layer of leather by utilizing the characteristic of small molecular weight. After the single silk fiber is treated by chitosan, the crosslinking strength, the antibacterial property and the toughness are all improved, and the crosslinking reinforcement is facilitated. The single silk fiber adopted in the invention refers to a single silk fiber which is not subjected to twisting treatment, and the silk is in single independent fibrous dispersion. The reinforcing mixed solution B adopts a natural cross-linking agent genipin, is a natural biological agent, and can effectively carry out cross-linking reinforcing reaction.
After the leather cultural relics are broken, the whole cultural relics are decomposed into more than 2 incomplete residues; after the leather cultural relics are decayed, the cultural relics are completely preserved, but the breaking strength is extremely reduced, and the cultural relics are extremely easy to break. The connecting interface of the broken or decayed leather cultural relics needs to be firstly attached to and permeated into the surface layer of the leather, the time is controlled within 5 minutes, the time is too long, after the moisture in the solution permeates into the collagen of the leather, the fluidity of the collagen peptide remained at the interface is greatly reduced, the uniformity of the crosslinking reaction of the reinforcing part is influenced, and the local strength cannot be obviously improved. The cross-linking reinforcement reaction of the reinforcement mixture A and the reinforcement mixture B takes 1 hour or more, and the interface can obtain the best adhesive strength. In addition, after the leather cultural relics are reinforced by the reagent proportioning and reinforcing process, the color difference at the connecting interface where the leather cultural relics are broken and decayed is unchanged, secondary damage to the cultural relics is avoided, and the leather cultural relics can be stored and displayed for a long time.
Preferably, the molecular weight of the collagen peptide is 3000-6000 daltons.
Preferably, the length of the single silk fiber treated by the chitosan is 1-10 mm.
The length of the single silk fiber added into the collagen peptide solution is controlled within the range of 1-10 mm, if the length of the single silk fiber is less than 1mm, when the cross-linked matter is stretched, the cross-linked matter has almost no function of enhancing the stretching strength force of the cross-linked matter due to the too short length of the silk fiber, and the breaking strength is detected, so that the breaking strength of the single silk fiber which is less than 1mm is almost the same as that of the single silk fiber which is not added. If the length of a single silk fiber is greater than 10mm, the dispersion uniformity of the silk fiber in a collagen peptide solution is mainly affected, the uniformity of fracture strength promotion at different positions after reinforcement is further affected, meanwhile, the silk fiber is overlong and is easy to form winding among fibers, but not one is dispersed into the solution, the silk fiber winding can directly lead to more and more silk fiber winding and aggregation in the solution to form silk fiber clew or yarn, but not single fiber shape, the effect of promoting the fracture strength after reinforcement can not be achieved, the bonding property at an interface is affected, and more obvious trace and color difference can appear at the reinforced connection interface to affect the integrity of leather cultural relics.
Preferably, the genipin solution uses absolute ethyl alcohol as a solvent, and the genipin concentration is 0.25-0.5 g/mL.
The adoption of ethanol for dissolution can achieve the risks of quick crosslinking and reinforcement reaction, quick water volatilization of reinforcement solution and difficult swelling of leather cultural relics.
Preferably, the mass volume ratio of the collagen peptide solution to the chitosan-treated single silk fiber is 3mL: 0.05-0.1 g, and the mass concentration of the collagen peptide in the collagen peptide solution is not less than 30%.
The chitosan-treated single silk fiber is added into a collagen peptide solution, and the chitosan-treated single silk fiber is mainly used for enhancing flexibility and improving exercise strength of a crosslinked product after the collagen and the genipin are subjected to chemical reaction, and meanwhile, the chitosan is also reacted with the genipin, so that the bonding degree of the silk fiber and the crosslinked product is higher, the reinforced leather cultural relics are ensured to be broken and the rotten connecting interface is ensured to have no obvious trace, and the consistency and the integrity of the cultural relics are ensured.
However, the mass-volume ratio of the collagen peptide solution to the chitosan-treated single silk fiber is lower than 3mL: when 0.05g, the addition amount of silk fiber is too small, the effect of enhancing the breaking strength of single silk fiber is not obvious, and the mass-volume ratio is higher than 3mL: at 0.1g, the amount of silk fiber added is too large, resulting in too small amount of crosslinked product, which is after all the main reason for improving the breaking strength after reinforcement. In addition, experiments prove that after the concentration of the collagen peptide is lower than 30%, the generation amount of the cross-linking substance is insufficient to remarkably improve the breaking strength after reinforcement.
Preferably, the heating reaction is carried out by stirring for 1-2 hours at 40-60 ℃.
Preferably, the collagen peptide solution is obtained by extracting fish scales with keratinase and trypsin.
Preferably, the method for extracting the collagen peptide solution comprises the following steps: adding fish scales, keratinase and trypsin into water, adjusting the pH value to 7.5-8.5, and reacting for 2-5 hours at 55 ℃; heating to 90 ℃ for reaction for 10-15 min, cooling the solution, filling into a dialysis bag with a cut-off molecular weight of 3000 daltons, placing into 100ml of sucrose solution with a mass concentration of 80%, and placing for 72h at 10-20 ℃; and then loading the solution in the dialysis bag into a centrifugal ultrafiltration tube with a molecular weight of 3000-6000 daltons, adopting a rotor with a fixed angle of 35 DEG on a centrifugal machine, setting a centrifugal force of 3000, centrifuging until the concentrated solution of the ultrafiltration tube is 3ml, and obtaining the collagen peptide solution with a molecular weight of 3000-6000 daltons on an outer centrifugal tube.
The collagen content in the fish scales is higher than that of other mammal skin collagens, and compared with collagen peptides extracted from other mammal skin collagens, the collagen peptides extracted from the fish scales have better thermal stability and biocompatibility and high extraction rate. The collagen peptide solution with the range of 3000-6000 daltons is adopted, and mainly because the chain length of the collagen peptide is too short when the molecular weight of the collagen peptide is less than 3000 daltons, the cross-linked substance generated by the reaction has a certain effect of enhancing the breaking strength, but is not obviously improved, and the reinforced leather cultural relics are not sufficiently preserved for a long time. When the molecular weight of the collagen peptide is more than 6000 daltons, macromolecular collagen is formed, the solubility is rapidly reduced, meanwhile, the reactivity of the macromolecular collagen is reduced, the reaction sites with genipin are reduced, the production of a cross-linked product is influenced, and the binding property at a connecting interface is further influenced.
Preferably, the mass-volume ratio of the fish scales to the keratinase to the trypsin to the water is 10g: 0.2-0.5 g: 0.2-0.5 g:50mL.
Preferably, the preparation method of the chitosan-treated single silk fiber comprises the following steps: and mixing chitosan, glacial acetic acid and water, heating and stirring to obtain a mixed solution, adding the single silk fiber, soaking for 3-6 hours, and adjusting the pH of the solution to 7 to obtain the single silk fiber treated by the chitosan.
Preferably, the mass volume ratio of the silk fiber to the single chitosan to the glacial acetic acid to the water is 0.1-0.5 g:10g: 1-2 mL: 40-60 mL.
The purpose of the chitosan treatment silk fiber is to enhance the stiffness and breaking strength of the silk fiber, and change the property that the silk fiber is not easy to react with genipin. In addition, the chitosan is loaded and wrapped on the surface of the silk fiber, and the silk fiber is easy to uniformly distribute in the collagen solution after having a certain stiffness, but the dosage of the chitosan needs to be controlled in a reasonable range, the content of the chitosan is too low, the chitosan loading amount of the silk fiber is insufficient, and the effect of finishing the silk fiber cannot be achieved; the chitosan content is too high, the chitosan can be adhered to itself, so that silk fibers are aggregated to form silk fiber bundles, instead of single independent silk fibers, the silk fiber bundles cannot be uniformly dispersed in collagen peptide solution, and the reinforcing effect is extremely reduced.
Preferably, the heating and stirring are carried out at 40-60 ℃ for 1-2 hours.
Compared with the prior art, the invention has the beneficial effects that:
(1) The bonding strength of the interface is improved by adopting a crosslinked polymer obtained by the reaction of a natural crosslinking agent and small molecular collagen peptide, and meanwhile, the flexibility and the bending strength of the bonding part are improved by utilizing the tensile toughness of silk fibers;
(2) The collagen peptide solution with the molecular weight of 3000-6000 daltons is adopted, and the collagen peptide solution is attached to and permeated into the surface layer of leather by utilizing the characteristic of small molecular weight;
(3) After the single silk fiber is treated by chitosan, the crosslinking strength, the antibacterial property and the toughness are improved, and the crosslinking reinforcement is facilitated;
(4) After the leather cultural relics are reinforced by the selected reagent proportion and the reinforcing process, the color difference at the connecting interface where the leather cultural relics are broken and decayed is unchanged, secondary damage to the cultural relics is avoided, and the leather cultural relics can be stored and displayed for a long time.
Drawings
FIG. 1 is a graph showing the comparison of breaking strength after strengthening the leather cultural relics simulation sample in example 1 and comparative examples 1-3;
FIG. 2 is an infrared spectrum of the collagen peptide, genipin and post-reinforcement cross-linked product of example 1;
FIG. 3 is a cross-sectional image of a simulated leather cultural relic sample reinforced in example 1;
FIG. 4 is a graph comparing breaking strength before and after reinforcement of a simulated sample of a decayed leather cultural relic in example 2;
fig. 5 is a graph showing comparison of breaking strength of simulated leather cultural relics reinforced by different collagen peptide solutions in example 3.
Detailed Description
The invention is further described below with reference to examples.
Example 1
An environment-friendly leather cultural relic reinforcing and protecting method comprises the following steps:
(1) Adding 10g of fish scales, 0.4g of keratinase and 0.3g of trypsin into 50ml of deionized water, adjusting the pH value to 8.5, and reacting for 5 hours at 55 ℃; heating to 90 ℃ for reaction for 10min, cooling the solution, filling into a dialysis bag with a cut-off molecular weight of 3000 daltons, placing into 100ml of sucrose solution with a mass concentration of 80%, and placing at 20 ℃ for 72h; then the solution in the dialysis bag is put into a centrifugal ultrafiltration tube with the molecular weight of 4000 daltons and 15ml, a rotor with a fixed angle of 35 degrees is adopted on a centrifuge, the centrifugal force of 3000 is set, the centrifugation is carried out until the concentrated solution of the ultrafiltration tube is 3ml, and the collagen peptide solution with the molecular weight of 3000-4000 daltons is obtained on an outer tube of the centrifugation.
(2) Mixing and stirring 10g of chitosan powder, 2ml of glacial acetic acid and 50ml of deionized water at 60 ℃ for 2 hours, putting 0.3g of single silk fiber into the mixed solution, soaking for 5 hours, and adding sodium hydroxide to adjust the pH of the solution to 7 to obtain the single silk fiber treated by the chitosan.
(3) 0.05g of chitosan-treated single silk fiber with the length of 2mm is added into 3mL of collagen peptide solution with the molecular weight of 3000-4000 daltons, and stirred for 2h at 40 ℃ to obtain a reinforced mixed solution A.
(4) 0.5g of genipin powder is added into 2ml of absolute ethanol, and stirred at room temperature until the genipin powder is completely dissolved and turns into colorless transparent liquid, thus obtaining reinforced mixed liquid B.
(5) And uniformly smearing the reinforcing mixed solution A on the interface of the fracture of the leather-made cultural relic simulation sample for 4 minutes, uniformly smearing the reinforcing mixed solution B on the same position, and then splicing and fixing according to the shape of the leather-made cultural relic simulation sample before fracture, so that the interface is bonded for 4 hours, thereby finishing the reinforcing protection of the leather-made cultural relic simulation sample (the reinforcing sample is named as reinforcing mixed solution A-1).
Comparative example 1
The difference from example 1 is that: and a single silk fiber treated by chitosan is not added into the strengthening mixed solution A.
The method comprises the following steps:
(1) Adding 10g of fish scales, 0.4g of keratinase and 0.3g of trypsin into 50ml of deionized water, adjusting the pH value to 8.5, and reacting for 5 hours at 55 ℃; heating to 90 ℃ for reaction for 10min, cooling the solution, filling into a dialysis bag with a cut-off molecular weight of 3000 daltons, placing into 100ml of sucrose solution with a mass concentration of 80%, and placing at 20 ℃ for 72h; then the solution in the dialysis bag is put into a centrifugal ultrafiltration tube with the molecular weight of 4000 daltons and 15ml, a rotor with a fixed angle of 35 degrees is adopted on a centrifuge, the centrifugal force of 3000 is set, the centrifugation is carried out until the concentrated solution of the ultrafiltration tube is 3ml, and the collagen peptide solution with the molecular weight of 3000-4000 daltons is obtained on an outer tube of the centrifugation.
(2) 3mL of collagen peptide solution with molecular weight in the range of 3000-4000 daltons was used as the reinforcement mix A.
(4) 0.5g of genipin powder is added into 2ml of absolute ethanol, and stirred at room temperature until the genipin powder is completely dissolved and turns into colorless transparent liquid, thus obtaining reinforced mixed liquid B.
(5) And uniformly smearing the reinforcing mixed solution A on the interface of the fracture of the leather-made cultural relic simulation sample for 4 minutes, uniformly smearing the reinforcing mixed solution B on the same position, and then splicing and fixing according to the shape of the leather-made cultural relic simulation sample before fracture, so that the interface is bonded for 4 hours, thereby finishing the reinforcing protection of the leather-made cultural relic simulation sample (the reinforcing sample is named as reinforcing mixed solution A-2).
Comparative example 2
The difference from example 1 is that: the individual silk fibers were not chitosan treated.
An environment-friendly leather cultural relic reinforcing and protecting method comprises the following steps:
(1) Adding 10g of fish scales, 0.4g of keratinase and 0.3g of trypsin into 50ml of deionized water, adjusting the pH value to 8.5, and reacting for 5 hours at 55 ℃; heating to 90 ℃ for reaction for 10min, cooling the solution, filling into a dialysis bag with a cut-off molecular weight of 3000 daltons, placing into 100ml of sucrose solution with a mass concentration of 80%, and placing at 20 ℃ for 72h; then the solution in the dialysis bag is put into a centrifugal ultrafiltration tube with the molecular weight of 4000 daltons and 15ml, a rotor with a fixed angle of 35 degrees is adopted on a centrifuge, the centrifugal force of 3000 is set, the centrifugation is carried out until the concentrated solution of the ultrafiltration tube is 3ml, and the collagen peptide solution with the molecular weight of 3000-4000 daltons is obtained on an outer tube of the centrifugation.
(2) 0.05g of single silk fiber with the length of 2mm is taken and added into 3mL of collagen peptide solution with the molecular weight of 3000-4000 daltons, and the mixture is stirred for 2 hours at 40 ℃ to obtain reinforced mixed solution A.
(3) 0.5g of genipin powder is added into 2ml of absolute ethanol, and stirred at room temperature until the genipin powder is completely dissolved and turns into colorless transparent liquid, thus obtaining reinforced mixed liquid B.
(4) And uniformly smearing the reinforcing mixed solution A on the interface of the fracture of the leather-made cultural relic simulation sample for 4 minutes, uniformly smearing the reinforcing mixed solution B on the same position, and then splicing and fixing according to the shape of the leather-made cultural relic simulation sample before fracture, so that the interface is bonded for 4 hours, thereby finishing the reinforcing protection of the leather-made cultural relic simulation sample (the reinforcing sample is named as reinforcing mixed solution A-3).
Comparative example 3
The difference from example 1 is that: and uniformly coating the reinforcing mixed solution A at the interface of the leather cultural relics simulated sample where the fracture occurs, and uniformly coating the reinforcing mixed solution B at the same position after 6 minutes (more than 5 minutes).
An environment-friendly leather cultural relic reinforcing and protecting method comprises the following steps:
(1) Adding 10g of fish scales, 0.4g of keratinase and 0.3g of trypsin into 50ml of deionized water, adjusting the pH value to 8.5, and reacting for 5 hours at 55 ℃; heating to 90 ℃ for reaction for 10min, cooling the solution, filling into a dialysis bag with a cut-off molecular weight of 3000 daltons, placing into 100ml of sucrose solution with a mass concentration of 80%, and placing at 20 ℃ for 72h; then the solution in the dialysis bag is put into a centrifugal ultrafiltration tube with the molecular weight of 4000 daltons and 15ml, a rotor with a fixed angle of 35 degrees is adopted on a centrifuge, the centrifugal force of 3000 is set, the centrifugation is carried out until the concentrated solution of the ultrafiltration tube is 3ml, and the collagen peptide solution with the molecular weight of 3000-4000 daltons is obtained on an outer tube of the centrifugation.
(2) 0.05g of single silk fiber with the length of 2mm is taken and added into 3mL of collagen peptide solution with the molecular weight of 3000-4000 daltons, and the mixture is stirred for 2 hours at 40 ℃ to obtain reinforced mixed solution A.
(3) 0.5g of genipin powder is added into 2ml of absolute ethanol, and stirred at room temperature until the genipin powder is completely dissolved and turns into colorless transparent liquid, thus obtaining reinforced mixed liquid B.
(4) And uniformly smearing the reinforcing mixed solution A on the interface of the fracture of the leather-made cultural relic simulation sample for 6 minutes, uniformly smearing the reinforcing mixed solution B on the same position, and then splicing and fixing according to the shape of the leather-made cultural relic simulation sample before fracture, so that the interface is bonded for 4 hours, thereby finishing the reinforcing protection of the leather-made cultural relic simulation sample (the reinforcing sample is named as reinforcing mixed solution A-4).
Example 2
An environment-friendly leather cultural relic reinforcing and protecting method comprises the following steps:
(1) Adding 10g of fish scales, 0.2g of keratinase and 0.5g of trypsin into 50ml of deionized water, adjusting the pH value to 7.5, and reacting for 5 hours at 55 ℃; heating to 90 ℃ for reaction for 10min, cooling the solution, filling into a dialysis bag with a cut-off molecular weight of 3000 daltons, placing into 100ml of sucrose solution with a mass concentration of 80%, and placing at 20 ℃ for 72h; then the solution in the dialysis bag is put into a centrifugal ultrafiltration tube with the molecular weight of 6000 daltons and 15ml, a rotor with a fixed angle of 35 degrees is adopted on a centrifuge, the centrifugal force of 3000 is set, the centrifugation is carried out until the concentrated solution of the ultrafiltration tube is 3ml, and the collagen peptide solution with the molecular weight of 3000-6000 daltons is obtained on the outer tube of the centrifugation.
(2) Mixing and stirring 10g of chitosan powder, 1ml of glacial acetic acid and 60ml of deionized water at 60 ℃ for 2 hours, putting 0.2g of single silk fiber into the mixed solution, soaking for 4 hours, and adding sodium hydroxide to adjust the pH of the solution to 7 to obtain the single silk fiber treated by the chitosan.
(3) And adding 0.05g of chitosan-treated single silk fiber with the length of 8mm into 3mL of collagen peptide solution with the molecular weight of 3000-6000 daltons, and stirring at 60 ℃ for 2 hours to obtain a reinforced mixed solution A.
(4) 0.5g of genipin powder is added into 1ml of absolute ethanol, and stirred at room temperature until the genipin powder is completely dissolved and turns into colorless transparent liquid, thus obtaining reinforced mixed liquid B.
(5) And uniformly smearing the reinforcing mixed solution A on the interface of the leather cultural relic simulation sample (before the sample is reinforced) where the groove is decayed, uniformly smearing the reinforcing mixed solution B on the same position after 3 minutes, and then splicing and fixing the leather cultural relic simulation sample according to the shape of the leather cultural relic simulation sample before the groove is decayed, so that the interface is bonded for 5 hours, and the reinforcing protection (after the sample is reinforced) of the leather cultural relic simulation sample is completed.
Example 3
An environment-friendly leather cultural relic reinforcing and protecting method comprises the following steps:
(1) Adding 10g of fish scales, 0.4g of keratinase and 0.3g of trypsin into 50ml of deionized water, adjusting the pH value to 8.5, and reacting for 5 hours at 55 ℃; heating to 90 ℃ for reaction for 10min, cooling the solution, filling into a dialysis bag with a cut-off molecular weight of 3000 daltons, placing into 100ml of sucrose solution with a mass concentration of 80%, and placing at 20 ℃ for 72h; then the solution in the dialysis bag is put into a centrifugal ultrafiltration tube with the molecular weight of 5000 daltons and 15ml, a rotor with a fixed angle of 35 degrees is adopted on a centrifuge, the centrifugal force of 3000 is set, the centrifugation is carried out until the concentrated solution of the ultrafiltration tube is 3ml, and the collagen peptide solution with the molecular weight of 3000-5000 daltons is obtained on the outer tube of the centrifugation.
(2) Mixing and stirring 10g of chitosan powder, 2ml of glacial acetic acid and 40ml of deionized water at 60 ℃ for 2 hours, putting 0.2g of single silk fiber into the mixed solution, soaking for 6 hours, and adding sodium hydroxide to adjust the pH of the solution to 7 to obtain the single silk fiber treated by the chitosan.
(3) 0.07g of chitosan-treated single silk fiber with the length of 1mm is added into 3mL of collagen peptide solution with the molecular weight of 3000-5000 daltons, and stirred for 2 hours at 60 ℃ to obtain a reinforced mixed solution A.
(4) 0.5g of genipin powder is added into 1ml of absolute ethanol, and stirred at room temperature until the genipin powder is completely dissolved and turns into colorless transparent liquid, thus obtaining reinforced mixed liquid B.
(5) And uniformly smearing the reinforcing mixed solution A on the interface of the fracture of the leather-made cultural relic simulation sample for 4 minutes, uniformly smearing the reinforcing mixed solution B on the same position, and then splicing and fixing according to the shape of the leather-made cultural relic simulation sample before fracture, so that the interface is bonded for 3 hours, thereby finishing the reinforcing protection of the leather-made cultural relic simulation sample (the reinforcing sample is named as collagen solution A-2).
Comparative example 3
The difference from example 3 is that: the collagen peptide solution was not subjected to molecular weight cut-off dialysis and ultrafiltration.
The method comprises the following steps:
(1) Adding 10g of fish scales, 0.4g of keratinase and 0.3g of trypsin into 50ml of deionized water, adjusting the pH value to 8.5, reacting for 5 hours at 55 ℃, then raising the temperature of the solution to 90 ℃ for reacting for 10 minutes, and cooling the solution to obtain the collagen peptide solution.
(2) Mixing and stirring 10g of chitosan powder, 2ml of glacial acetic acid and 40ml of deionized water at 60 ℃ for 2 hours, putting 0.2g of single silk fiber into the mixed solution, soaking for 6 hours, and adding sodium hydroxide to adjust the pH of the solution to 7 to obtain the single silk fiber treated by the chitosan.
(3) 0.07g of chitosan-treated single silk fiber with the length of 1mm is added into 3mL of collagen peptide solution, and stirred for 2h at 60 ℃ to obtain a reinforced mixed solution A.
(4) 0.5g of genipin powder is added into 1ml of absolute ethanol, and stirred at room temperature until the genipin powder is completely dissolved and turns into colorless transparent liquid, thus obtaining reinforced mixed liquid B.
(5) And uniformly smearing the reinforcing mixed solution A on the interface of the fracture of the leather-made cultural relic simulation sample for 4 minutes, uniformly smearing the reinforcing mixed solution B on the same position, and then splicing and fixing according to the shape of the leather-made cultural relic simulation sample before fracture, so that the interface is bonded for 3 hours, thereby finishing the reinforcing protection of the leather-made cultural relic simulation sample (the reinforcing sample is named as collagen solution A-1).
Because of the precious nature of leather cultural relics, a strength tester cannot be directly used for testing breaking strength of the cultural relics in the embodiment, and leather cultural relics simulation samples are selected to replace the cultural relics for reinforcement performance testing. Infrared spectrum test was performed using an infrared spectrometer (model Nicolet 6700, thermo-electric Nicolet corporation, usa) and breaking strength test was performed using an electronic strength tester (AG-1, SHIMAZU, japan).
As shown in fig. 1, the comparison result of breaking strength after the leather cultural relics are reinforced in the example 1 and the comparative examples 1-3 shows that the breaking strength of the leather cultural relics reinforced in the example 1 is highest and reaches 16.8N, which indicates that the breaking strength of the sample can be effectively improved by the single silk fiber treated by chitosan.
As shown in FIG. 2, from the infrared spectra of the collagen peptide, genipin and the post-reinforcement crosslinked product of example 1, it was found that the post-reinforcement crosslinked product was obtained at wavenumber 1050 cm as compared with the infrared spectra of genipin and collagen peptide -1 And 2947cm -1 The absorption vibration and the methyl saturated C-H stretching vibration of the ester group v C-O are respectively used for indicating that the collagen peptide and genipin undergo a crosslinking reaction on average, which is the main reason for the improvement of the breaking strength of the sample after the sample breaking interface is bonded.
As shown in fig. 3, as can be seen from the sectional image of the leather cultural relics simulated sample reinforced in example 1, the reinforced sample collagen fiber bundles are closely arranged, have no obvious difference from the peripheral collagen fiber bundles without fracture, have no change in color difference at the fracture and decay connecting interface, do not cause secondary damage to the cultural relics, and have good reinforcing effect.
As shown in fig. 4, the breaking strength of the leather-made cultural relic simulation sample in the final example 2 is improved from 4.6N to 13.5N before reinforcement, and the color difference at the connecting interface is unchanged.
As shown in fig. 5, the breaking strength of the simulated leather-made cultural relics reinforced with the different collagen peptide solutions of example 3 was compared with that of the simulated leather-made cultural relics reinforced with the collagen peptide solution having a molecular weight in the range of 3000-5000 daltons, because the breaking strength of the simulated leather-made cultural relics reinforced with the collagen peptide solution without the molecular weight cut-off dialysis and ultrafiltration treatment was higher than that of the simulated leather-made cultural relics reinforced with the collagen peptide solution without the molecular weight cut-off dialysis and ultrafiltration treatment, the content of collagen peptide outside the limited range was too high, which could affect the bondability at the junction interface.
The raw materials and equipment used in the invention are common raw materials and equipment in the field unless specified otherwise; the methods used in the present invention are conventional in the art unless otherwise specified.
The foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and any simple modification, variation and equivalent transformation of the above embodiment according to the technical substance of the present invention still fall within the scope of the technical solution of the present invention.
Claims (4)
1. The environment-friendly leather cultural relic reinforcing and protecting method is characterized by comprising the following steps of:
(1) Adding the single silk fiber treated by chitosan into a collagen peptide solution, and heating for reaction to obtain a reinforced mixed solution A; the length of the single silk fiber treated by the chitosan is 1-10 mm; the mass volume ratio of the collagen peptide solution to the chitosan-treated single silk fiber is 3mL: 0.05-0.1 g; the molecular weight of the collagen peptide is 3000-6000 daltons;
the preparation method of the chitosan-treated single silk fiber comprises the following steps: mixing chitosan, glacial acetic acid and water, heating and stirring to obtain a mixed solution, adding single silk fibers, soaking for 3-6 hours, and adjusting the pH of the solution to 7 to obtain the single silk fibers treated by the chitosan; the mass volume ratio of the single silk fiber to the chitosan to the glacial acetic acid to the water is 0.1-0.5 g:10g: 1-2 mL: 40-60 mL; the heating and stirring are carried out for 1-2 hours at the temperature of 40-60 ℃;
(2) Taking genipin solution as a strengthening mixed solution B; the concentration of the genipin solution is 0.25-0.5 g/mL;
(3) Coating a reinforcing mixed solution A on the interface of the broken or decayed leather cultural relics, and standing for not more than 5min; and then the reinforcing mixed liquid B is smeared at the same position, and is spliced and fixed according to the shape before the leather cultural relics are broken or decayed, and the leather cultural relics are kept stand for not less than 1h, so that the reinforcing protection of the leather cultural relics is finished.
2. The method for reinforcing and protecting leather cultural relics in environment protection according to claim 1, wherein the mass concentration of collagen peptide in the collagen peptide solution is not less than 30%.
3. The method for reinforcing and protecting leather cultural relics according to claim 1, wherein the heating reaction is carried out by stirring for 1-2 hours at 40-60 ℃.
4. The method for reinforcing and protecting leather cultural relics in environment protection according to claim 1, wherein the collagen peptide solution is obtained by extracting fish scales with keratinase and trypsin.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104450997A (en) * | 2014-12-31 | 2015-03-25 | 浙江理工大学 | Method for reinforcing dry and hard fragile leather historical relic |
| CN105220479A (en) * | 2015-09-21 | 2016-01-06 | 中国丝绸博物馆 | A kind of preparation method being applicable to the silk fiber of textiles historical relic's protection |
| CN112996961A (en) * | 2018-07-18 | 2021-06-18 | 自然进化公司 | Silk-coated leather and products and methods for making the same |
| CN114875670A (en) * | 2022-04-02 | 2022-08-09 | 陕西科技大学 | Preparation method and application of gelatin-based leather cultural relic protection material |
| CN115605547A (en) * | 2020-01-17 | 2023-01-13 | 自然进化公司（Us） | Silk-coated leather and products and methods for making the same |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104450997A (en) * | 2014-12-31 | 2015-03-25 | 浙江理工大学 | Method for reinforcing dry and hard fragile leather historical relic |
| CN105220479A (en) * | 2015-09-21 | 2016-01-06 | 中国丝绸博物馆 | A kind of preparation method being applicable to the silk fiber of textiles historical relic's protection |
| CN112996961A (en) * | 2018-07-18 | 2021-06-18 | 自然进化公司 | Silk-coated leather and products and methods for making the same |
| CN115605547A (en) * | 2020-01-17 | 2023-01-13 | 自然进化公司（Us） | Silk-coated leather and products and methods for making the same |
| CN114875670A (en) * | 2022-04-02 | 2022-08-09 | 陕西科技大学 | Preparation method and application of gelatin-based leather cultural relic protection material |
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