CN109518527B - Multifunctional ancient book repairing liquid and treatment method thereof - Google Patents
Multifunctional ancient book repairing liquid and treatment method thereof Download PDFInfo
- Publication number
- CN109518527B CN109518527B CN201811175317.3A CN201811175317A CN109518527B CN 109518527 B CN109518527 B CN 109518527B CN 201811175317 A CN201811175317 A CN 201811175317A CN 109518527 B CN109518527 B CN 109518527B
- Authority
- CN
- China
- Prior art keywords
- treatment
- ancient
- quaternary ammonium
- ammonium salt
- paper
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H25/00—After-treatment of paper not provided for in groups D21H17/00 - D21H23/00
- D21H25/18—After-treatment of paper not provided for in groups D21H17/00 - D21H23/00 of old paper as in books, documents, e.g. restoring
Landscapes
- Paper (AREA)
Abstract
The invention discloses a multifunctional ancient book repairing liquid and a treatment method thereof, and belongs to the technical field of ancient book protection. The ancient book repairing liquid consists of an alkaline mixed sol and an alcohol aqueous solution, wherein the alkaline mixed sol is formed by dispersing metal oxide nano particles and a surfactant in an inert solvent, and the alcohol aqueous solution contains quaternary ammonium salt. The ancient book processing method comprises the following steps: the ancient book is soaked in alkaline mixed sol with uniform dispersion after being subjected to impurity cleaning, constant temperature and humidity and drying treatment, taken out, ventilated and dried, and then placed in sealed deacidification equipment, then a quaternary ammonium salt alcohol aqueous solution is introduced after being subjected to atomization treatment, the ancient book paper is subjected to spray treatment, then dried and placed in a ventilating way at an ambient temperature, and the treatment is completed. The ancient book treatment liquid and the method have the multifunctional treatment effects of deacidification, reinforcement, antibiosis, ageing resistance and the like on the ancient books.
Description
Technical Field
The invention belongs to the technical field of ancient book protection, and particularly relates to a multifunctional ancient book repairing liquid and a treatment method thereof.
Background
The history of China is long, ancient books and cultural relics are numerous, and according to statistics, the total number of the ancient books in China exceeds 3000 ten thousand books, and the listed good basis is more than 250 ten thousand books. The ancient book cultural relics have the equivalent attributes of historical cultural relics, academic data, artistic representativeness and the like. In the process of circulation, a large amount of ancient cultural relics are inevitably aged, damaged and the like due to poor storage conditions or artificial damage. Therefore, the protection work of ancient cultural relics is very important. However, ancient book protection is also a worldwide problem, and the traditional paper deacidification enhancement method has more or less problems, such as single function, complex process, long treatment period, poor treatment effect and the like, which affect the effective protection of ancient books. Therefore, a multifunctional ancient book treatment fluid and a simple and efficient treatment process are urgently needed to be found.
Paper aging is mainly manifested by paper acidification, reduced physical strength and yellowing of the color. The paper acidification factor is many, the lignin is unstable in chemical property and is easy to be coatedOxidation and hydrolysis to form acidic species; the trace chloride residue in the bleaching process accelerates the deterioration of alum on paper, and finally leads to the acidification of the paper; in the pulping and papermaking process, acidic chemicals such as acidic alum, acidic rosin, alum water sizing material and the like are added, so that the acidification condition of paper is increased; during printing, the acid or oxide-containing ink and pigment used are also one of the factors for enhancing the acidity of paper; in addition, the paper is subjected to atmospheric acidic gases (e.g., SO) during storage2、H2S、NOXEtc.) and attack by microorganisms (metabolically produced organic acids). In summary, there are many reasons for acidification of paper, and all factors do not act independently, but rather interact and promote each other. After the paper is acidified, cellulose acid catalytic hydrolysis reaction can be carried out under the condition of normal temperature, so that the cellulose macromolecular chain is shortened, the polymerization degree is reduced, and the physical strength of the paper is reduced. In addition, the paper can be oxidized in humid air or under ultraviolet light to generate a plurality of colored groups, so that the color of the paper is deepened, and the yellowing of the paper is more obvious particularly in the presence of lignin.
The deacidification research in foreign countries is earlier, and the research work of large-scale deacidification is always dedicated, and the methods which are mainly used in ancient books are Wei T' o method, Bookkeeper method, Batttle method, Book Saver method and the like, but have certain problems after treatment, such as powder deposition, ink blurring, other side effects and the like (Cellulose,2015,22(5): 2859-. With the development of technology, after 2000, Giorgi et al began to propose nanotechnology for ancient book protection (Langmuir,2002,18(21): 8198-. Giorgi et al teach the preparation of Mg (OH) in a homogeneous precipitation reaction using magnesium salts with NaOH2Nanoparticles of Mg (OH) to be prepared2The nanoparticles are uniformly dispersed in a mixture of isopropanol or fluoroalkane for deacidification. The results show that Mg (OH)2The nano-particles can simply permeate into paper fibers, the deacidification effect is better, and compared with the Wei T' o method, the nano-Mg (OH)2The deacidification efficiency is higher, and the deacidified paper has better anti-aging effect (Langmuir,2005,21(18): 8495-. Taglieri et al proposeA novel, simple and mass-preparable Mg (OH)2The synthesis route of nano-particles, which is based on ion exchange, prepares magnesium hydroxide nano-particles in aqueous suspension, the particle size can reach dozens of nanometers, and the magnesium hydroxide nano-particles are used for ancient book protection, and experiments show that the deacidification and alkali storage effect is good (Journal of Nanoparticle Research,2015,17(10): 411). Poggi et al propose a Ca (OH)2A method for synthesizing nanoparticles is used for inhibiting the oxidation and acid degradation processes of paper fibers. The results of the study show that the method is effective in inhibiting acid degradation of cellulose in aged paper for a long period of time (Journal of Current Reimage, 2016,18: 250-.
The domestic research on ancient book deacidification is gradually increased in recent years, and some preliminary progress is achieved. Zhangli et al have proposed that a deacidification solution containing zinc salt and magnesium salt in one body is used for deacidification of paper, and zinc acetate, Hexamethyltetramine (HTM) and Mg (HCO) are used3)2The compound deacidification agent is prepared according to a certain proportion, after treatment, the deacidification effect is obvious, the pH value of a paper sample is increased to 8.06, and a certain color fixing effect is also achieved (Nanjing university of Industrial science (own edition), 2011,33(2): 51-54). The research of applying nano magnesium oxide to deacidification of paper cultural relics is carried out on the WangHuyun, and experiments show that the WangHuyun has better deacidification effect and also has the effect of inhibiting Cu2+、Fe3+The effect of ions on the catalytic oxidation of cellulose (Chinese paper, 2012,31(3): 36-38). The Wangxiang et al have conducted research on the use of one-dimensional magnesium oxide in deacidification of ancient books, and the prepared nano-scale magnesium oxide has a good deacidification effect, and the pH value after treatment is increased from 4.18 to 8.82, but has a slight influence on the chroma of a paper sample (Redandan journal (Nature science edition), 2016,55(6):698 + 701).
Multifunctional deacidification agents are also the hot spots of research in the ancient book protection field in recent years. The invention discloses a treatment liquid for protecting paper cultural relics, a preparation method and an application patent (CN 105887566A). The treatment liquid takes deionized water as a solvent and polyethyleneimine as a deacidification substance and is prepared into the treatment liquid according to a certain proportion. Zhang jin Nu et al also invent a multifunctional sodium for paper cultural relic protectionThe rice composite treating fluid is compounded with nanometer magnesia, hydroxyethyl cellulose, polyoxyethylene and nanometer titania in certain proportion, and has also excellent deacidifying, strengthening, antiseptic and other effects. The method is characterized in that the deacidification liquid consists of a certain amount of magnesium-aluminum double hydroxides and roasting products thereof, a surfactant, a paper reinforcing agent and high-purity halogenated hydrocarbon, is mild in property, safe and environment-friendly, can be recycled, and has a pH value lower than 12 after treatment, has a certain reinforcing effect while deacidifying, and does not fade. The Rejunli et al also invented a multifunctional ancient book treatment liquor and treatment method, the ancient book repairing liquor mainly is made up by using NaOH/Ca (OH)2The MgO alkaline mixed solution and the quaternary ammonium salt-containing aqueous solution are formed, the effects of deacidifying, storing alkali and enhancing the antibacterial property can be simultaneously achieved after treatment, meanwhile, the generated color difference is less, and the writing ink is not obviously influenced (CN 108316054A).
At present, ancient book protection methods at home and abroad mainly focus on deacidification, but multifunctional ancient book treatment methods are rare, most of the ancient book treatment methods are complex, most of the ancient book treatment methods are impregnation treatment, and large-scale treatment is difficult to realize.
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art, the invention mainly aims to provide a multifunctional ancient book repairing liquid.
Another object of the present invention is to provide a simple and efficient ancient book processing method based on the ancient book processing liquid.
The purpose of the invention is realized by the following technical scheme.
The multifunctional ancient book repairing liquid consists of an alkaline mixed solution and an alcohol-water mixed solution, wherein the alkaline mixed solution is formed by dispersing metal oxide nanoparticles and a surfactant in an inert solvent, and the alcohol-water mixed solution contains quaternary ammonium salt.
Preferably, the metal oxide nanoparticles are nano MgO, nano CaO, nano ZnO and nanoTiO2At least two of; the surfactant is at least one of carboxymethyl cellulose (CMC), cetyl trimethyl ammonium bromide (CTMAB), sodium dodecyl benzene sulfonate (SDDS) and perfluoropolyether derivatives; the inert solvent is one of fluoro alkane, heptane and Hexamethyldisiloxane (HMDO); the quaternary ammonium salt is alkyl quaternary ammonium salt or organosilicon quaternary ammonium salt; the alcohol is one of ethanol, propanol, isopropanol and n-butanol.
Preferably, the mass concentration of the alkaline mixed sol is 0.5 g/L-8 g/L; the addition amount of the surfactant is 0.01-1% of the mass of the alkaline mixed sol; the mass ratio of the nano MgO to the nano CaO is 8: 1-0: 1; the concentration of the quaternary ammonium salt in the alcohol-water mixed solution containing the quaternary ammonium salt is 0.1-4 mol/L; the volume ratio of the alcohol to the water in the alcohol-water mixed solution containing the quaternary ammonium salt is 9: 1-0: 10.
The application of the multifunctional ancient book repairing liquid in ancient book treatment comprises the following steps:
(1) pre-treating ancient books: cleaning impurities on the surface of the ancient books, and putting the ancient books into vacuum drying equipment for treatment after constant temperature and humidity treatment;
(2) preparation of alkaline mixed sol: adding metal oxide nano particles into an inert solvent, then adding a surfactant, stirring, and then carrying out ultrasonic dispersion treatment;
(3) preparing alcohol-water mixed solution containing quaternary ammonium salt: dissolving quaternary ammonium salt in an alcohol-water mixed solvent, and shaking up;
(4) coating or dipping the ancient book pretreated in the step (1) in the alkaline mixed sol prepared in the step (2), drying, transferring into a closed device, atomizing the alcohol-water mixed solution containing quaternary ammonium salt, and introducing into the closed device to treat the ancient book;
(5) and (5) uniformly and flatly placing the ancient books treated in the step (4) between the wools, placing the ancient books together in vacuum drying equipment for drying treatment, taking out the ancient books, and placing the ancient books in an environment temperature for balancing moisture to finish the treatment.
Preferably, the vacuum drying device in the step (1) is used for treating for 12-48 h under the conditions that the temperature is 30-80 ℃ and the vacuum degree is 0.05-0.1013 MPa, and more preferably, the temperature is 40 ℃ and the vacuum degree is 0.1013MPa for 12-48 h.
Preferably, the moisture content of the paper treated in step (1) is 1-4 wt.%, more preferably 2 wt.%.
Preferably, the rotating speed of the stirring in the step (2) is 100-1000 r/min, and the stirring time is 10-50 min; the ultrasonic frequency is 10 KHz-200 KHz, and the ultrasonic time is 10-60 min;
preferably, the number of times of coating treatment on the ancient books by the alkaline mixed sol in the step (4) is 1-4, and the treatment time of dipping is 10-60 s; the time for processing the ancient books by the alcohol-water mixed solution containing the quaternary ammonium salt is 60-180 min.
Preferably, the time interval between the treatment of the ancient books by the alkaline mixed sol and the alcohol-water mixed solution containing the quaternary ammonium salt in the step (4) is 0-60 min, and more preferably 60 min.
Preferably, the drying treatment in the step (5) is carried out under the conditions of a vacuum degree of 0.05-0.1013 MPa and a temperature of 40-80 ℃ for 12-48 h, and more preferably under the conditions of a vacuum degree of 0.1013MPa and a temperature of 60 ℃ for 12-48 h.
After the multifunctional deacidification enhancer and the treatment process are utilized, the pH value of paper is 7.0-9.5, and the alkali residual amount is 100-300 mmol/Kg, so that a better deacidification and alkali storage effect can be achieved; the tensile strength of the paper sheet is improved by 5 to 50 percent, and the bursting strength is improved by 1 to 100 percent; the brightness (R457, D65) is slightly improved, the color difference delta E fluctuates between 1 and 3, the surface of a paper sheet is clean and flat after treatment, and the ink of the handwriting has no obvious change. In addition, the product also has certain antibacterial and anti-aging effects.
The invention mainly utilizes that alkaline metal oxide nano particles are easy to permeate into paper, thus easily achieving the purpose of deacidifying and storing alkali; the quaternary ammonium salt compound and cellulose in paper sheets are subjected to in-situ chemical reaction under an alkaline condition, so that part of cellulose fibers are provided with cations and can generate electrostatic attraction with the cellulose with negative electricity, and the aim of reinforcement is fulfilled; furthermore, outsideAdded nanoparticles, e.g. nano TiO2Has the functions of absorbing ultraviolet and inhibiting photoaging, and simultaneously the nano TiO2And quaternary ammonium cations also have bacteriostatic effects.
In the treatment process, acid groups of the paper are neutralized, and finally, the ancient book paper is recovered to be neutral and weakly alkaline, and the inert solvent which is easy to volatilize is added to uniformly disperse the nano particles on the surface of the paper without obviously influencing the ancient book paper; meanwhile, in the treatment process, the quaternary ammonium salt compound and the polymer in the paper undergo in-situ chemical reaction, the strength of the paper is enhanced, meanwhile, the paper is endowed with a good antibacterial effect, the propagation of microorganisms is prevented, the damage of the microorganisms to ancient book documents is reduced, the ancient book preservation time is prolonged, and in addition, the nano TiO compound and the polymer in the paper undergo an in-situ chemical reaction, so that the paper is endowed with a good antibacterial effect, the propagation of the microorganisms is prevented, the damage of the microorganisms to the ancient book documents is reduced, and the ancient book preservation time is prolonged2The addition of the compound not only has the function of inhibiting photoaging, but also has the bacteriostatic effect. The alcohol is added to reduce the amount of water added, to reduce the effect on the reaction efficiency, and to improve the atomization effect. In addition, the spraying method has the advantages of uniform liquid medicine dispersion, short treatment time, less liquid medicine consumption, less influence on paper and the like, and is also suitable for large-scale treatment, so the method has better application value in ancient book protection.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the ancient book repairing liquid has the multifunctional treatment effects of deacidification, reinforcement, bacteriostasis, ageing resistance and the like on the ancient books.
(2) The treatment method simplifies four-stage treatment of paper deacidification, paper strengthening, paper antibiosis and paper ageing resistance into two-stage treatment, and the two-stage treatment has a synergistic effect, obviously shortens the treatment flow, reduces the treatment operation, reduces the treatment period and improves the treatment efficiency.
Drawings
FIG. 1 is a bar graph of the change in the strength properties of a sample of paper treated with 2, 3-epoxypropyltrimethylammonium chloride (ETA) in aqueous alcohol in varying alcohol to water ratios as in example 2.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.
Example 1
The ancient book treatment liquid integrating deacidification, enhancement, bacteriostasis and anti-aging functions and the ancient book treatment method provided by the embodiment comprise the following specific steps:
(1) preprocessing a paper pattern: cleaning impurities on the surface of ancient books, then placing the ancient books in a standard constant temperature and humidity chamber (T23 ℃ and RH 50%) for 24h, taking out the ancient books, placing the ancient books into a vacuum drying device with the vacuum degree of 0.1013MPa, and drying the ancient books at 40 ℃ for 24h to ensure that the water content of the ancient books is 2.0 wt.%.
(2) Preparation of a liquid medicine: respectively preparing MgO/CaO/HMDO alkaline mixed sol with the mass concentration of 4g/L (the mass ratio of MgO to CaO is 4:1, the addition amount of CTMAB serving as a surfactant is 0.5 percent (based on the mass of the alkaline mixed sol), the stirring speed is 500r/min, the stirring time is 30min, the ultrasonic frequency is 100KHz, and the ultrasonic time is 30min) and ETA/isopropanol/water solution with the molar concentration of 2mol/L (isopropanol: water is 6:4, and the volume ratio).
(3) Treatment of the liquid medicine: and (3) coating the paper sample pretreated in the step (1) with the alkaline mixed sol prepared in the step (2), airing and then drying in vacuum, wherein the drying condition is that the vacuum degree is 0.1013MPa, and the drying is carried out for 60min at 60 ℃.
(4) Atomizing: and (3) placing the paper sample treated in the step (3) in a self-made cuboid sealed treatment device with the length, width and height of 50cm multiplied by 40cm multiplied by 30cm, atomizing the ETA/isopropanol/water solution in the step (2) by an atomizing device with the power of 130VA, and introducing into the sealed treatment device for treatment for 60 min.
(5) Paper drying treatment: and (3) uniformly and flatly placing the paper pattern treated in the step (4) between the wools, putting the paper pattern and the wools together in a vacuum drying device with the vacuum degree of 0.1013MPa, and drying for 24 hours at the temperature of 60 ℃. After being taken out, the paper is placed in a standard constant temperature and humidity chamber (T is 23 ℃, RH is 50%) for 24h to balance moisture, and then the paper performance test is carried out.
The brightness (R457, D65), color difference (. DELTA.E), tensile strength, folding strength, pH and residual alkali content of the sample treated in this example were measured. The detection result shows that the pH of the treated paper sample is greatly increased from 5.10 to 8.86, the deacidification requirement is met, and the residual alkali amount is 180 mmol/Kg; the tensile strength is greatly increased from 801N/m to 1020N/m, and the increase is 27.34 percent; the folding resistance is improved from 29 times to 36 times (double-page folding resistance test), after treatment, the surface of the paper is smooth and neat, the handwriting is clear, the ink is not obviously affected, the brightness (R457, D65) is slightly improved, the brightness is increased from 29.82 to 30.09, the generated color difference is small, and the Delta E is 2.03.
Example 2
The ancient book treatment liquid integrating deacidification, enhancement, bacteriostasis and anti-aging functions and the ancient book treatment method provided by the embodiment comprise the following specific steps:
(1) preprocessing a paper pattern: cleaning impurities on the surface of ancient books, then placing the ancient books in a standard constant temperature and humidity chamber (T23 ℃ and RH 50%) for 24h, taking out the ancient books, placing the ancient books into a vacuum drying device with the vacuum degree of 0.1013MPa, and drying the ancient books at 40 ℃ for 24h to ensure that the water content of the ancient books is 2.0 wt.%.
(2) Preparation of a liquid medicine: preparing MgO/CaO/HMDO alkaline mixed sol with the mass concentration of 4g/L (the mass ratio of MgO to CaO is 4:1, the addition amount of the surfactant CTMAB is 0.5 percent (based on the mass of the alkaline mixed sol), stirring at the rotating speed of 100r/min for 10min, the ultrasonic frequency of 100KHz and the ultrasonic time of 60min), and preparing a series of ETA/isopropanol/water solutions with the molar concentration of 2mol/L (the volume ratios of the isopropanol to the water are 8:2, 7:3, 6:4, 5:5, 3:7 and 0:10 respectively).
(3) Treatment of the liquid medicine: and (3) coating the paper sample pretreated in the step (1) with the alkaline mixed sol prepared in the step (2), coating the front side and the back side of the paper sample for 2 times respectively, airing and drying in vacuum under the conditions that the vacuum degree is 0.1013MPa and the drying is carried out for 60min at 60 ℃.
(4) Atomizing: and (3) placing the paper sample treated in the step (3) in a self-made cuboid sealed treatment device with the length, width and height of 50cm multiplied by 40cm multiplied by 30cm, atomizing the ETA alcohol aqueous solution in the step (2) by an atomizing device with the power of 130VA, and introducing into the sealed treatment device for treatment for 120 min.
(5) Paper drying treatment: and (3) uniformly and flatly placing the paper pattern treated in the step (4) between the wools, putting the paper pattern and the wools together in a vacuum drying device with the vacuum degree of 0.1013MPa, and drying for 24 hours at the temperature of 60 ℃. After being taken out, the paper is placed in a standard constant temperature and humidity chamber (T is 23 ℃, RH is 50%) for 24h to balance moisture, and then the paper performance test is carried out.
This example examines the effect of different volume ratios of isopropyl alcohol to water on the tensile strength properties of the sample as shown in Table 1 and is shown in FIG. 1.
TABLE 1
As can be seen from the results in Table 1, the brightness (R457, D65), color difference (. DELTA.E), tensile strength, folding strength, pH and residual alkali content of the sample treated in this example were measured. Along with the continuous reduction of the volume ratio of isopropanol to water in the quaternary ammonium salt alcohol aqueous solution, detection results show that the pH value of the treated paper sample can reach 7.5-9.0, the residual alkali content is over 160mmol/Kg, and a better deacidification and alkali storage effect is achieved; the brightness (R457, D65) of the paper does not change obviously, the fluctuation is within +/-2%, the generated color difference is small, and the Delta E is within 2; the variation trends of the tensile strength and the folding endurance are shown in figure 1, the treatment effect is better when the volume ratio of isopropanol/water is 6:4 and 0:10, the improvement amplitudes of the tensile strength are respectively 18.44% and 27.27%, and the folding endurance is slightly improved; in summary, when the volume ratio of isopropanol to water is 6:4, the treatment effect is relatively best; after treatment, the surfaces of all the paper sheets are smooth and tidy, the handwriting is clear, and the ink is not obviously influenced.
Example 3
The ancient book treatment liquid integrating deacidification, enhancement, bacteriostasis and anti-aging functions and the ancient book treatment method provided by the embodiment comprise the following specific steps:
(1) preprocessing a paper pattern: cleaning impurities on the surface of ancient books, then placing the ancient books in a standard constant temperature and humidity chamber (T23 ℃ and RH 50%) for 24h, taking out the ancient books, placing the ancient books into a vacuum drying device with the vacuum degree of 0.1013MPa, and drying the ancient books at 40 ℃ for 24h to ensure that the water content of the ancient books is 2.0 wt.%.
(2) Preparation of a liquid medicine: preparing MgO/CaO/TiO with the mass concentration of 4g/L2Basic mixed sol of/HMDO (MgO/CaO/TiO)2In a mass ratio of 4:1: 1(1 part of CaO), and 0.5% of CTMAB as a surfactant (based on the mass of the alkaline mixed sol); stirring at a rotation speed of 500r/min for 30 min; ultrasonic frequency is 100KHz, ultrasonic time is 30min), and ETA/isopropanol/water solution with molar concentration of 2mol/L (isopropanol-water volume ratio is 6:4) is prepared.
(3) Treatment of the liquid medicine: and (3) coating the paper sample pretreated in the step (1) with the alkaline mixed sol prepared in the step (2), coating the front side and the back side of the paper sample for 2 times respectively, airing and drying in vacuum under the conditions that the vacuum degree is 0.1013MPa and the drying is carried out for 60min at 40 ℃.
(4) Atomizing: and (3) placing the paper sample treated in the step (3) in a self-made cuboid sealed treatment device with the length, width and height of 50cm multiplied by 40cm multiplied by 30cm, atomizing the ETA alcohol aqueous solution in the step (2) by an atomizing device with the power of 130VA, and introducing into the sealed treatment device for treatment for 120 min.
(5) Paper drying treatment: and (3) uniformly and flatly placing the paper pattern treated in the step (4) between the wools, putting the paper pattern and the wools together in a vacuum drying device with the vacuum degree of 0.1013MPa, and drying for 24 hours at the temperature of 60 ℃. After being taken out, the paper is placed in a standard constant temperature and humidity chamber (T is 23 ℃, RH is 50%) for 24h to balance moisture, and then the paper performance test is carried out.
The brightness (R457, D65), color difference (. DELTA.E), tensile strength, folding strength, pH and residual alkali content of the sample treated in this example were measured. The detection result shows that the pH of the treated paper sample is greatly increased from 5.27 to 9.44, the residual alkali amount is 200mmol/Kg, and the requirement of deacidification and alkali storage is met; the tensile strength is greatly increased from 768N/m to 962N/m, and the increase is 25.26 percent; the folding endurance is improved from 17 times to 31 times (double-page folding endurance test), after treatment, the surface of the paper is smooth and neat, the handwriting is clear, the ink is not obviously affected, the brightness (R457, D65) is slightly improved and is increased from 28.07 to 28.70, the generated color difference is small, and the Delta E is 0.97.
The antibacterial performance of the paper treated by the method is detected as follows:
the paper sample treated in example 3 was used for the antibacterial effect test. The antibacterial test experiment is completed by the detection center of microorganisms in Guangdong province, the detection basis and the method are JISL1902:2015 quantitative tests, the selected test strain is common Aspergillus niger, and the test results are shown in Table 2. Wherein the bactericidal activity value L ═ Ma-Mc(ii) a Bacteriostatic activity value of S ═ Mb-Ma)-(Mc-Mo)。
TABLE 2
As can be seen from the results of the analytical tests, 4g/L of MgO/CaO/TiO was used2Antibacterial detection is carried out on paper sheets treated by alkaline mixed sol of/HMDO and 2mol/L ETA/isopropanol/water solution (the volume ratio of isopropanol to water is 6:4), no bactericidal effect is found, only bacteriostatic effect is achieved, and the bacteriostatic activity value is 0.57.
The anti-aging performance of the paper treated by the method is detected as follows:
the untreated paper sample, the paper sample treated in example 1 and the paper sample treated in example 3 were subjected to an anti-aging effect test. The three paper patterns are separated and put into an ultraviolet aging test box, and the illumination intensity of ultraviolet light is 1.0w/m2The wavelength is 260nm, and the irradiation time is 72 h. The brightness (R457, D65), color difference (. DELTA.E), tensile strength, folding strength, pH and residual alkali content of the treated pattern were measured again and compared with those before the UV aging treatment, and the results are shown in Table 3. The samples treated in examples 1 and 3, after artificially accelerated aging, exhibited a relatively small color difference, although the reduction in brightness was slightly greater, and the tensile strength and folding endurance of the paper were comparable to those of the reference samplesThe magnitude of the number reduction is small, wherein the magnitude of the reduction of the treated paper pattern in example 3 after aging is the smallest, and is 14.91% and 51.08% respectively; after aging, the paper is still alkalescent with the pH value of 7.0-8.0, so that the paper has a good anti-aging effect.
TABLE 3
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (8)
1. The multifunctional ancient book repairing liquid is characterized by comprising an alkaline mixed solution and an alcohol-water mixed solution, wherein the alkaline mixed solution is prepared by dispersing metal oxide nanoparticles and a surfactant in an inert solvent;
the metal oxide nanoparticles are nano MgO, nano CaO, nano ZnO and nano TiO2At least two of; the surfactant is at least one of carboxymethyl cellulose, cetyl trimethyl ammonium bromide, sodium dodecyl benzene sulfonate and perfluoropolyether derivatives; the inert solvent is one of fluoro alkane, heptane and hexamethyldisiloxane; the quaternary ammonium salt is alkyl quaternary ammonium salt or organosilicon quaternary ammonium salt; the alcohol is one of ethanol, propanol, isopropanol and n-butanol;
the mass concentration of the alkaline mixed sol is 0.5-8 g/L; the addition amount of the surfactant is 0.01-1% of the mass of the alkaline mixed sol; the concentration of the alcohol-water mixed solution containing the quaternary ammonium salt is 0.1-4 mol/L; the volume ratio of the alcohol to the water in the alcohol-water mixed solution containing the quaternary ammonium salt is 9: 1-3: 7.
2. The method for processing ancient books of claim 1, wherein the method comprises the following steps:
(1) pre-treating ancient books: cleaning impurities on the surface of the ancient books, and putting the ancient books into vacuum drying equipment for treatment after constant temperature and humidity treatment;
(2) preparation of alkaline mixed sol: adding metal oxide nano particles into an inert solvent, then adding a surfactant, stirring, and then carrying out ultrasonic dispersion treatment;
(3) preparing alcohol-water mixed solution containing quaternary ammonium salt: dissolving quaternary ammonium salt in an alcohol-water mixed solvent, and shaking up;
(4) coating or dipping the ancient book pretreated in the step (1) in the alkaline mixed sol prepared in the step (2), drying, transferring into a closed device, atomizing the alcohol-water mixed solution containing quaternary ammonium salt, and introducing into the closed device to treat the ancient book;
(5) and (5) uniformly and flatly placing the ancient books treated in the step (4) between the wools, placing the ancient books together in vacuum drying equipment for drying treatment, taking out the ancient books, and placing the ancient books in an environment temperature for balancing moisture to finish the treatment.
3. The method according to claim 2, wherein the treatment in the vacuum drying equipment in the step (1) is carried out at a temperature of 30 to 80 ℃ and a vacuum degree of 0.05 to 0.1013MPa for 12 to 48 hours.
4. The method according to claim 2, wherein the moisture content of the paper after the treatment in step (1) is 1-4 wt.%.
5. The method according to claim 2, wherein the stirring in the step (2) is performed at a rotation speed of 100-1000 r/min for 10-50 min; the frequency of the ultrasonic wave is 10 KHz-200 KHz, and the time of the ultrasonic wave is 10-60 min.
6. The method according to claim 2, wherein the number of times of coating treatment of the ancient books by the alkaline mixed sol in the step (4) is 1-4, and the treatment time of the immersion is 10-60 s; the time for processing the ancient books by the alcohol-water mixed solution containing the quaternary ammonium salt is 60-180 min.
7. The method as claimed in claim 2, wherein the time interval between the treatment of the ancient books with the alkaline mixed sol and the mixed alcohol-water solution containing the quaternary ammonium salt in the step (4) is 0-60 min.
8. The method according to claim 2, wherein the drying treatment in the step (5) is carried out under a vacuum degree of 0.05 to 0.1013MPa and at a temperature of 40 to 80 ℃ for 12 to 48 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811175317.3A CN109518527B (en) | 2018-10-10 | 2018-10-10 | Multifunctional ancient book repairing liquid and treatment method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811175317.3A CN109518527B (en) | 2018-10-10 | 2018-10-10 | Multifunctional ancient book repairing liquid and treatment method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109518527A CN109518527A (en) | 2019-03-26 |
| CN109518527B true CN109518527B (en) | 2021-11-23 |
Family
ID=65770276
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811175317.3A Active CN109518527B (en) | 2018-10-10 | 2018-10-10 | Multifunctional ancient book repairing liquid and treatment method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109518527B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110331621B (en) * | 2019-06-15 | 2021-08-03 | 湖北泰德安信信息技术有限公司 | Deacidification agent based on sodium dodecyl benzene sulfonate modified nano magnesium oxide and preparation method thereof |
| CN110172862B (en) * | 2019-06-15 | 2021-08-03 | 湖北泰德安信信息技术有限公司 | Deacidification agent based on sodium phytate modified nano magnesium oxide and preparation method thereof |
| CN112626917B (en) * | 2020-12-18 | 2023-04-07 | 山东纳美欣生物科技有限公司 | Ancient book reinforcing nanofiber liquid and preparation method and application thereof |
| CN112663392B (en) * | 2020-12-22 | 2023-05-02 | 山东纳美欣生物科技有限公司 | Device and method for reinforcing fiber-coated ancient books |
| CN115874485B (en) * | 2021-09-28 | 2024-04-26 | 华南理工大学 | Organic phase deacidification enhancement repair liquid and preparation method and application thereof |
| CN114703697B (en) * | 2022-04-28 | 2023-05-09 | 杭州众材科技股份有限公司 | Paper deacidification method adopting two-component water-based deacidification agent |
| CN115787350B (en) * | 2022-11-04 | 2024-05-31 | 国家图书馆 | Fluorine-containing deacidification liquid for paper |
| CN115748295B (en) * | 2022-11-22 | 2023-08-29 | 复旦大学 | Carbon dot-magnesium hydroxide composite paper deacidification agent and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103276627A (en) * | 2013-05-28 | 2013-09-04 | 南京博物院 | Multifunctional nano compound treating fluid for protecting paper cultural relics and preparation method thereof |
| CN105887566A (en) * | 2016-04-11 | 2016-08-24 | 南京工业大学 | Treating fluid for preservation of paper cultural relics, preparation method and application |
| CN107012736A (en) * | 2017-05-03 | 2017-08-04 | 清华大学 | A kind of depickling liquid for having strengthening for paper effect concurrently and preparation method thereof |
| CN108316054A (en) * | 2018-01-25 | 2018-07-24 | 华南理工大学 | A kind of ancient books treatment fluid and ancient books processing method |
-
2018
- 2018-10-10 CN CN201811175317.3A patent/CN109518527B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103276627A (en) * | 2013-05-28 | 2013-09-04 | 南京博物院 | Multifunctional nano compound treating fluid for protecting paper cultural relics and preparation method thereof |
| CN105887566A (en) * | 2016-04-11 | 2016-08-24 | 南京工业大学 | Treating fluid for preservation of paper cultural relics, preparation method and application |
| CN107012736A (en) * | 2017-05-03 | 2017-08-04 | 清华大学 | A kind of depickling liquid for having strengthening for paper effect concurrently and preparation method thereof |
| CN108316054A (en) * | 2018-01-25 | 2018-07-24 | 华南理工大学 | A kind of ancient books treatment fluid and ancient books processing method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109518527A (en) | 2019-03-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109518527B (en) | Multifunctional ancient book repairing liquid and treatment method thereof | |
| CN109695182B (en) | Deacidification enhancement treatment liquid and method for treating aged paper | |
| CN108316054B (en) | Ancient book treatment liquid and ancient book treatment method | |
| Parthasarathi et al. | Synthesis and characterization of zinc oxide nanopartilce and its application on fabrics for microbe resistant defence clothing | |
| Montazer et al. | Functionality of nano titanium dioxide on textiles with future aspects: Focus on wool | |
| CN107326742A (en) | A kind of depickling of paper fibre and reinforcement guard method | |
| CN104260169B (en) | Wood substrate composite material of a kind of hydrophobic, anti-ultraviolet aging and preparation method thereof | |
| Zhou et al. | Facile fabrication of hybrid PA6-decorated TiO 2 fabrics with excellent photocatalytic, anti-bacterial, UV light-shielding, and super hydrophobic properties | |
| CN105646923A (en) | Preparation method of nano-silver particle supported nanocellulose antibacterial film | |
| CN109529775A (en) | A kind of synthetic method and absorption property of graphene oxide-lanthanum hydroxide composite material | |
| CN103113762A (en) | Method for preparing high-light-resistance decorative laminated paper titanium pigment | |
| Zanatta et al. | The effect of titanium dioxide nanoparticles obtained by microwave-assisted hydrothermal method on the color and decay resistance of pinewood | |
| Wang et al. | Multifunctional nanocomposites for paper conservation | |
| Shupe et al. | The termiticidal properties of superhydrophobic wood surfaces treated with ZnO nanorods | |
| Nemoykina et al. | Restoration and conservation of old low-quality book paper using aqueous colloids of magnesium oxyhydroxide obtained by pulsed laser ablation | |
| CN111270559A (en) | Nano-cellulose/nano-zinc oxide multifunctional protective solution, preparation method thereof and method for protecting paper documents | |
| Prorokova et al. | Antimicrobial properties of polyester fabric modified by nanosized titanium dioxide | |
| Aminloo et al. | Clean sono-synthesis of ZnO on cotton/nylon fabric using dopamine: Photocatalytic, hydrophilic, antibacterial features | |
| Aggrawal et al. | Immobilization of Bi2O3 nanoparticles on the cellulose fibers of paper matrices and investigation of its antibacterial activity against E. coli in visible light | |
| US20150225531A1 (en) | Surface-treated titanium dioxide pigments | |
| CN115874485B (en) | Organic phase deacidification enhancement repair liquid and preparation method and application thereof | |
| Zhao et al. | Nanocomposites composed of modified natural polymer and inorganic nanomaterial for safe, high-efficiency, multifunctional protection of paper-based relics | |
| Li et al. | Conservation of aged paper using reduced cellulose nanofibrils/aminopropyltriethoxysilane modified CaCO3 particles coating | |
| CN109550508A (en) | A kind of preparation method and application of the bismuth oxygen bromine nano material of modification | |
| Touhid et al. | TiO2/Cu composite NPs coated polyester fabric for the enhancement of antibacterial durability |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |