CN111270559A - Nano-cellulose/nano-zinc oxide multifunctional protective solution, preparation method thereof and method for protecting paper documents - Google Patents
Nano-cellulose/nano-zinc oxide multifunctional protective solution, preparation method thereof and method for protecting paper documents Download PDFInfo
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- 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
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- 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
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
- D21H17/24—Polysaccharides
- D21H17/25—Cellulose
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- 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
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
- D21H17/675—Oxides, hydroxides or carbonates
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Abstract
The invention provides a multifunctional nano-cellulose/nano-zinc oxide protective solution, a preparation method thereof and a method for protecting paper documents. The protective solution comprises nano zinc oxide, nano cellulose and water, wherein the concentration of the nano cellulose is 0.4-0.6wt%, and the concentration of the nano zinc oxide is 0.5-2.5 wt%. The method combines the advantages of nano-cellulose, nano-zinc oxide and a screen printing process, wherein the nano-zinc oxide provides high specific surface area and self-alkalinity, can deacidify the paper and endows the paper with super-hydrophobicity; the mechanical strength of the protected paper ink writing is obviously improved without being affected, particularly the tensile index and the folding endurance are obviously improved, the hydrophobicity of the paper is also improved, the paper is further protected from being corroded by moisture in humid air, the long-term storage of the paper is facilitated, and the paper literature is protected.
Description
Technical Field
The invention relates to a preparation method of a multifunctional protective solution and a method for deacidifying and enhancing paper documents by using the multifunctional protective solution, in particular to a nano-cellulose/nano-zinc oxide multifunctional protective solution, a preparation method of the multifunctional protective solution and a method for protecting paper documents.
Background
The paper literature is a precious data of research history and social civilization, but due to the influences of factors such as war disorder, mildew, storage environment and the like, the damage of the paper literature is extremely serious, and the paper itself is subjected to continuous chemical degradation reaction, although the degradation is slow, the phenomenon is caused by the fact that the phenomenon is yellow and brittle after the long-term passage of years, and the phenomenon is caused by the degradation of cellulose macromolecules due to the acidification of the paper. Therefore, deacidification is the primary problem to be solved, and how to improve the strength of damaged paper is the difficulty of ancient preservation at present.
For deacidification of Paper, liquid phase deacidification and gas phase deacidification are the commonly used deacidification methods, and Clelia Isca et al (Paper preservation with polyamides: a preliminary study [ J ]. Cellulose,2016,23(2): 1415-. Seki et al (A New Technique for Strength whitening BookPapers with Cellulose Derivatives part 2: Effect of Cellulose Derivatives on Difference Types of Paper [ J ]. Restaurator,2010,31(2): 126-. Although the method can achieve the deacidification effect, the liquid-phase deacidification method can cause some writing, dyes and pigments of the paper to be halated, the paper can also have the phenomena of vinasse, wrinkle, deformation and the like after being soaked, the organic solvent can also damage artworks with water-sensitive printing ink and dyes, and diethyl zinc has high toxicity and has potential safety hazards of flammability and explosiveness.
At present, some new specific properties of nanoparticles arouse the interest of researchers, wherein nano zinc oxide forms microscopic roughness on the surface of an object to have a certain hydrophobic effect, and the nano zinc oxide is usually applied to the surface of cotton fabric and has no hydrophobic effect. The scholars of Qigao et al (super-hydrophobic and antibacterial performance [ J ] of zinc oxide nano-rod modified polyester silk, inorganic salt industry, 2010,42(04):58-59, 62) generate an oriented zinc oxide nano-rod array on the surface, so that the polyester silk surface has super-hydrophobic performance. Huxiangyu et al (Huxiangyu, arm, etc.. super-hydrophobic cotton fabric based on nano ZnO. printing and dyeing auxiliary agent, 2013,30(06):43-46) adopt chemical bath deposition method to make synthesis of nano ZnO and loading of ZnO on the fabric complete in one step, then padding Stearic Acid (SA) to form stearic acid self-assembled monomolecular layer on the surface of the fabric to prepare the anti-ultraviolet super-hydrophobic cotton fabric, and the water contact angle is increased from initial 0 degree to 143 degrees along with the increase of zinc ion concentration. The super-hydrophobic property of the nano zinc oxide is applied to the protection of paper documents, and is not reported at present.
The nano zinc oxide has small particle size, high specific surface area and high reaction activity, can be used as a filler, a coating and the like in the paper industry, is used as an alkaline substance and is coated on the surface layer of paper which can permeate the paper and neutralize the acidity of the damaged paper, so that the paper has certain acid resistance so as to prolong the service life of the paper, and the like (the microwave hydrothermal method is used for preparing nano ZnO applied to paper deacidification and reinforcement, J. chemical novel materials, 2011,39(08): 109) prepares a zinc acetate/hexamethylenetetramine aqueous solution according to a ratio of 1:5, and the nano zinc oxide is generated on the paper by the microwave hydrothermal method so that the pH value of the paper reaches 7.02, thereby proving that the nano zinc oxide has certain deacidification effect. Hanson et al (Paper deacidification and UV protection ZnO atomic layer deposition [ J ]. Journal of Vacuum Science & Technology a,2012) used atomic layer deposition of ZnO to form a UV protection on the surface of Paper documents with deacidification, increasing the pH of the Paper from 3.5-4 to > 7.0. Maryam (preceding protection of paper substrates using nano composite coating of zinc oxide [ J ]. Journal of basic Transmission 25(2017) 142-148) et al prepared that the nano ZnO particle/hydroxypropyl cellulose suspension was sprayed on paper as a protective coating, and the tensile strength of the paper was increased by 17.73%. Although the above reports confirm the deacidification effect of nano ZnO, the repair method adopted is unfavorable for the paper strength, for example, the microwave hydrothermal method is adopted to generate nano ZnO on paper to deacidify the paper, and the hydrothermal reaction of damaged paper under microwave causes further reduction of the paper strength. While the Maryam study can improve the tensile strength of paper, the improvement is very limited.
The nano-cellulose is a cellulose material with the diameter less than 100 nanometers, has high crystallinity, high specific surface area, high tensile strength and easy film forming capability on the basis of keeping the property of natural cellulose, and has huge application potential in the fields of papermaking, medicine, composite materials, food and the like. The nano-cellulose can form tightly combined hydrogen bonds with fibers in paper, and can be used for paper repair and reinforcement. The patent CN108252155A does not disperse the nanocellulose in the organic solvent to paper, the maximum tensile strength of the paper after the nanocellulose is not dispersed is 88.07%, the pH value is increased from 6.84 to 7.22, however, the patent does not exist the organic solvent, and the ink writing of the paper is damaged. Dawn et al (reinforcement performance study of two nanocelluloses on aged literature paper [ J ]. cellulose science and technology, 2017,25(03):8-13, 19) reinforced three simulated aged literature papers with two nanocelluloses of cotton nanocellulose whisker (CNC-C) and cotton cellulose nanofibril (CNF-C) and a complex thereof, and the results showed that: the compound of the two types of nano-cellulose has very obvious reinforcing effect on aged paper, the tensile strength is enhanced by 103 percent at most, the folding times are improved by 9.8 times at most, and the tearing strength is improved by 81 percent at most. However, the method only enhances the paper literature, does not deacidify the paper and is not beneficial to long-term preservation of the paper.
In summary, the prior deacidification and enhancement of ancient books are mainly applied to single component and single action. For example, the deacidification effect of nano zinc oxide in paper restoration has been verified, and the current research and patent mostly stay in the application of the deacidification effect, but the strengthening effect on paper is not obvious. The application of the hydrophobic effect on the nano zinc oxide in ancient book repair is not reported. Nanocellulose has a strengthening effect on paper, but does not have a deacidification effect. Although some research reports exist in the aspect of multi-component and multifunctional integrated application of various components, particularly novel nano materials, the application of the novel nano materials in ancient book repair and paper protection is not reported, so that the ancient book protection solution with deacidification, reinforcement and super-hydrophobic functions is urgently required to be developed.
Secondly, the paper using the deacidification strengthening protective solution is simple and easy to operate without means, and at present, the paper without means is dipped, sprayed, coated and the like. The dipping method causes waste of solution, has high cost and can blur ink writing on paper; the spraying method is difficult to uniformly distribute the solution on the paper, and the researchers of Cao Hua (paper coating technique discussion [ J ] printing technique, 2009(19):22-23) in the research on the coating technique, mention is made that the doctor blade coating technique is advantageous for improving the smoothness of the paper, the coating surface is complete and can be coated with high solid content, the coating speed is high but the coating surface is easy to form scratches. Scholars such as Huangbeiqing (influence of coating process on thick film coating performance [ J ] packaging engineering, 2008,29(10):118-120) prove that the screen printing coating can well obtain a flat coating surface, and meanwhile, the thickness of a coating film can be controlled through the mesh number of a screen.
CN108659266A adopts in-situ method to synthesize repair liquid, namely dissolving nano-cellulose in Zn (NO)3)2·6H2Adding aqueous alkali into the O aqueous solution to make the value of the aqueous alkali reach 8.0-11.0, stirring the mixture for 6-30 hours at the temperature of 30-55 ℃ to prepare the zinc oxide/cellulose nanocrystalline composite material, and protecting the paper cultural relics by adopting a spraying mode. The tensile strength of the unfired paper increased from 0.67kN/m to 1.25kN/m at the maximum, which was 86.57%. However, the process of preparing the composite material by the method is complicated and takes long time, and the spraying method is adopted without paper, so that the solution cannot be uniformly distributed on the whole surface of the paper.
Disclosure of Invention
The invention aims to solve the problems that the common deacidification agent can only achieve the aim of deacidifying paper documents and can not effectively improve the strength of the paper documents and the subsequent paper hydrophobic protection, and provides a nano-cellulose/nano-zinc oxide multifunctional protective solution, a preparation method thereof and a method for protecting the paper documents. In addition, the protective solution is coated on paper documents by adopting a screen printing coating method to protect damaged paper, the advantages of simplicity and convenience, low cost, uniform distribution of the coating, no damage to the paper and the like of the screen printing method are fully utilized, and the function of the multifunctional protective solution can be better exerted.
The purpose of the invention is realized by at least one of the following technical solutions.
The nano-cellulose/nano-zinc oxide multifunctional protective solution comprises nano-zinc oxide, nano-cellulose and water, wherein the concentration of the nano-cellulose is 0.4-0.6wt%, and the concentration of the nano-zinc oxide is 0.5-2.5 wt%. The paper protection solution takes nano zinc oxide as a deacidification and hydrophobic component and takes nano cellulose as a paper reinforcing component.
The preparation method of the multifunctional nano-cellulose/nano-zinc oxide protective solution specifically comprises the following steps:
(1) adding nano zinc oxide into water, and obtaining nano zinc oxide dispersion liquid through ultrasonic treatment without dispersion;
(2) and adding the nano zinc oxide dispersion liquid into the nano cellulose water suspension, and passing through a high-speed disperser without uniformly mixing to obtain the nano cellulose/nano zinc oxide multifunctional protective liquid.
Further, in the step (1), the nano zinc oxide dispersion liquid is obtained by dispersing deionized water serving as a dispersing agent through ultrasonic waves, and the particle size of the nano zinc oxide is smaller than 100 nm.
Further, in the step (1), the ultrasonic wave has not been carried out for 5-10 min.
Further, the nano-cellulose in the step (2) is cellulose nano-fibrils which are not prepared through combination of a neutral TEMPO oxidation method and high-pressure homogenization, the diameter is 3-20nm, the length is more than 400nm, and the carboxyl content is more than or equal to 0.8mmol/g (calculated on the absolute dry matter of the nano-cellulose).
Further, in the step (2), the rotation speed of the high-speed disperser is 1800-.
The method for protecting the paper documents by the multifunctional nano-cellulose/nano-zinc oxide protective solution comprises the following steps:
(1) uniformly coating the multifunctional nano-cellulose/nano-zinc oxide protective solution on paper documents to be protected in a screen printing manner;
(2) and (3) placing the paper which is not subjected to the step (1), namely finishing the protection of the paper documents.
Further, the mesh of the screen printing plate in the step (1) is 200-350 meshes.
Further, in the step (2), the mixture is placed for 64 to 76 hours.
Further, the paper not obtained in step (2) is placed in a constant temperature and humidity environment, such as at 20-25 deg.C and relative humidity of 60-65%.
The invention combines the advantages of nano-cellulose, nano-zinc oxide and a silk-screen printing process, wherein the nano-zinc oxide provides high specific surface area and self-alkalinity, can deacidify paper and endows the paper with super-hydrophobicity; the nano-cellulose provides high strength, high transparency and good film forming property, can enhance the mechanical strength of paper, and does not influence the appearance of original ink marks; the nano-cellulose also plays a role of a printing ink binder, the nano-zinc oxide particles are fixed on paper, the protective solution is more uniformly distributed through screen printing, and meanwhile, the nano-zinc oxide particles are convenient to form a super-hydrophobic micro-nano rough surface structure, so that multiple functions of deacidification, reinforcement and super-hydrophobicity can be better embodied. The screen printing and coating process can ensure that the protective solution is uniformly coated, and can better play the role of the multifunctional protective solution. The method is simple and convenient to operate, small in damage to paper, and good in deacidification effect on acidified and damaged paper, the mechanical strength of the protected paper is obviously improved without influencing the ink writing, particularly the tensile index and the folding endurance are obviously improved, the hydrophobicity of the paper is also improved, the paper is further protected from being corroded by moisture in humid air, the long-term storage of the paper is facilitated, and the paper literature is protected.
Compared with the prior art, the invention has the following advantages:
(1) the invention utilizes the fact that the nano zinc oxide has large specific surface area, self alkalinity, nano effect and micro roughness formed on the surface of paper, not only can deacidify the paper, but also can make the paper without acid have certain hydrophobicity, further protect the paper from being corroded by moisture in humid air, and is beneficial to long-term storage of the paper;
(2) the invention utilizes the high specific surface area and good film forming property of the nano-cellulose to act on the surface of the paper document and the inside of the fiber together with the nano-zinc oxide, so that the paper fiber and the nano-cellulose are tightly combined, and the mechanical strength of the paper document is improved while the paper document is effectively deacidified.
(3) The invention adopts the screen printing method to protect the paper documents, not only can lead the protective solution to be evenly coated and better play the role of the multifunctional protective solution, but also has simple process, easy operation, small damage to the paper and no influence on the ink writing of the protected paper.
Drawings
FIG. 1 is a graph showing the tensile index of the nanocellulose matrix to damaged paper in examples 4-8;
FIG. 2 is a graph showing the effect of nanocellulose quality on fold endurance in examples 4-8;
FIG. 3 is a graph showing the change in contact angle between 0s and 10s for the sheets of examples 1-3, which were not before.
Detailed Description
The invention is described in detail below with reference to the drawings and examples, but the embodiments and the scope of the invention are not limited thereto.
Example 1
Slowly adding the nano zinc oxide into deionized water, continuously stirring by using a glass rod in the adding process, carrying out ultrasonic treatment for 5min, and obtaining nano zinc oxide dispersion liquid by carrying out ultrasonic treatment without dispersing the nano zinc oxide dispersion liquid. And adding the nano zinc oxide dispersion liquid into the nano cellulose water suspension, dispersing for 8min by using a high-speed disperser at the rotating speed of 1800rpm, and uniformly mixing to obtain the nano cellulose/nano zinc oxide multifunctional protective liquid. Preparing multifunctional protective solution with the corresponding mass fractions of 0.5 wt% and 0.4 wt% of nano zinc oxide and nano cellulose (the total mass fraction of nano zinc oxide and nano cellulose is 0.9 wt%), uniformly coating the multifunctional protective solution on the surface of a paper document by using a 250-mesh silk screen printing plate, and then placing the paper document for 64 hours at the temperature of 20 ℃ and the relative humidity of 65%.
The paper documents which are not subjected to the treatment in the embodiment are characterized, the results are shown in table 1, and the paper which is not subjected to the multifunctional protective solution is compared with the raw paper which is not subjected to the treatment: the pH is increased from 4.99 to 7.15; the tensile index is improved to 47.1 N.m/g from 14.1 N.m/g which is not yet left, and is increased by 234.04 percent; the tear index is increased from the unseen 3.36mN m2The ratio of the concentration of the active carbon to the concentration of the active carbon is increased to 4.24 mN.m2The per gram is increased by 26.19 percent; the burst index is 1.28kPa · m2The/g is increased to 1.81kPa · m2The surface contact angle of the paper at 0s is increased from 90.1 degrees of the untreated raw paper to 92.5 degrees, as shown in figure 1, the surface contact angle is increased by 2.4 degrees and 10s is increased from 75.2 degrees to 90 degrees of the untreated raw paper, the angle is increased by 14.8 degrees, and the color difference △ E before and after treatment is 2.49 degrees (the untreated raw paper used in the table 1 and the paper without the protective solution in the examples 1-3 are the same batch of paper)
Example 2
Slowly adding the nano zinc oxide into deionized water, continuously stirring by using a glass rod in the adding process, then carrying out ultrasonic treatment for 8min, and obtaining nano zinc oxide dispersion liquid by carrying out ultrasonic treatment without dispersing the nano zinc oxide dispersion liquid. And adding the nano zinc oxide dispersion liquid into the nano cellulose water suspension, dispersing for 10min by using a high-speed disperser at the rotating speed of 2000rpm, and uniformly mixing to obtain the nano cellulose/nano zinc oxide multifunctional protective liquid. Preparing multifunctional protective solution with the quality fractions of nano zinc oxide and nano cellulose of 2.0 wt% and 0.4 wt%, respectively (the total quality fraction of nano zinc oxide and nano cellulose is 2.4 wt%), uniformly coating the multifunctional protective solution on the surface of a paper document by using a 250-mesh silk screen printing plate, and then placing the paper document for 72 hours at the temperature of 25 ℃ and the relative humidity of 65%.
The paper documents which are not subjected to the treatment in the embodiment are characterized, the results are shown in table 1, and the paper which is not subjected to the multifunctional protective solution is compared with the raw paper which is not subjected to the treatment: the pH is increased from 4.99 to 7.30; the tensile index is improved to 41.1 N.m/g from 14.1 N.m/g which is not yet left, and is increased by 191.49 percent; the tear index is increased from the unseen 3.36mN m2The ratio of the concentration of the active carbon to the concentration of the active carbon is increased to 4.50 mN.m2The per gram is increased by 33.93 percent; the burst index is 1.28kPa · m2The/g is increased to 1.61kPa · m2The per gram is increased by 25.78 percent, the folding endurance is increased from 1 time to 9 times and is increased by 8 times, the contact angle of the paper surface is increased from 90.1 degrees of the untreated raw paper to 113.1 degrees, as shown in figure 1, the surface contact angle of 10s is increased from 75.2 degrees to 108.6 degrees of the untreated raw paper, and the color difference △ E before and after the treatment is 4.18.
Example 3
The preparation conditions are protected, and are modified as follows: slowly adding the nano zinc oxide into deionized water, continuously stirring by using a glass rod in the adding process, then carrying out ultrasonic treatment for 15min, and obtaining nano zinc oxide dispersion liquid by carrying out ultrasonic treatment without dispersing the nano zinc oxide dispersion liquid. And adding the nano zinc oxide dispersion liquid into the nano cellulose water suspension, dispersing for 15min by using a high-speed disperser at the rotating speed of 2000rpm, and uniformly mixing to obtain the nano cellulose/nano zinc oxide multifunctional protective liquid. Preparing multifunctional protective solution with the quality fractions of nano zinc oxide and nano cellulose of 2.5wt% and 0.4 wt%, respectively (the total quality fraction of nano zinc oxide and nano cellulose is 2.9 wt%), uniformly coating the multifunctional protective solution on the surface of a paper document by using a 250-mesh silk screen printing plate, and then placing the multifunctional protective solution for 76 hours at the temperature of 25 ℃ and the relative humidity of 65%.
The paper documents which are not subjected to the treatment in the embodiment are characterized, the results are shown in table 1, and the paper which is not subjected to the multifunctional protective solution is compared with the raw paper which is not subjected to the treatment: the pH is increased from 4.99 to 7.30; the tensile index is formed byThe 14.1 N.m/g which is not yet left is improved to 41.5 N.m/g, and the increase is 194.33 percent; the tear index is increased from the unseen 3.36mN m2The ratio of the concentration of the active carbon to the concentration of the active carbon is increased to 4.05 mN.m2The per gram is increased by 20.54 percent; the burst index is 1.28kPa · m2The/g is increased to 1.56kPa · m2The folding endurance is increased by 21.88 percent from 1 time to 10 times and is increased by 9 times, the contact angle of the paper surface at 0s is increased to 115.5 degrees from 90.1 degrees of the untreated raw paper, as shown in figure 1, the contact angle of the paper surface at 25.4 s is increased, the contact angle of the paper surface at 10s is increased to 108.4 degrees from 75.2 degrees of the untreated raw paper, the contact angle is increased to 33.2 degrees, and the color difference △ E before and after treatment is 3.87.
TABLE 1 comparison of the Performance indices of the non-virgin patterns of examples 1-3 with those of the non-virgin patterns
Example 4
Referring to example 2, multifunctional protective solution with nano zinc oxide and nano cellulose quality fractions of 2.0 wt% and 0.4 wt%, respectively (the total quality fraction of nano zinc oxide and nano cellulose is 2.4 wt%) is prepared, and is uniformly coated on the surface of paper documents by using a 250-mesh screen plate, and then is placed at 25 ℃ and a relative humidity of 65% for 72 hours.
The paper documents which are not subjected to the treatment in the invention are characterized, the results are shown in table 2, and the paper which is not subjected to the treatment by the multifunctional protective solution is compared with the raw paper which is not subjected to the treatment: the pH is increased from 5.00 to 7.30; the tensile index is improved to 37.3 N.m/g from 14.4 N.m/g which is not yet left, and is increased by 159.03 percent; the tear index is increased from the unseen 3.46mN m2The ratio of the concentration of the active carbon to the concentration of the active carbon is increased to 3.90 mN.m2The per gram is increased by 12.72 percent; the burst index is 1.33kPa · m2The/g is increased to 1.60kPa · m2The increase in folding strength was 20.30% for the virgin paper, 10 times for the virgin paper, from 1 to 11 times, and the color difference △ E was 3.84 before and after the virgin paper was used (the virgin base paper used in Table 2 was the same as the virgin base paper of examples 4 to 8).
Example 5
Referring to example 2, multifunctional protective solution with nano zinc oxide and nano cellulose quality fractions of 2.0 wt% and 0.45 wt%, respectively (the total quality fraction of nano zinc oxide and nano cellulose is 2.45 wt%), which is prepared, uniformly coated on the surface of paper documents by using a 250-mesh screen plate, and then placed at 25 ℃ and 65% relative humidity for 72 hours.
The paper documents which are not subjected to the treatment in the embodiment are characterized, the results are shown in table 2, and the paper which is not subjected to the treatment by the multifunctional protective solution is compared with the base paper: the pH is increased from 5.00 to 7.38; the tensile index is improved to 48.7 N.m/g from 14.4 N.m/g which is not yet left, and is increased by 238.19 percent; the tear index is increased from the unseen 3.46mN m2The ratio of the concentration of the active carbon to the concentration of the active carbon is increased to 4.86 mN.m2The per gram, increased 40.46%; the burst index is 1.33kPa · m2The/g is increased to 1.77kPa · m2The percent folding strength is increased by 33.08 percent from 1 time to 15 times, the percent folding strength is increased by 14 times, and the color difference △ E before and after failure is 2.96.
Example 6
Slowly adding the nano zinc oxide into deionized water, continuously stirring by using a glass rod in the adding process, then carrying out ultrasonic treatment for 10min, and obtaining nano zinc oxide dispersion liquid by carrying out ultrasonic treatment without dispersing the nano zinc oxide dispersion liquid. And adding the nano zinc oxide dispersion liquid into the nano cellulose water suspension, dispersing for 10min by using a high-speed disperser at the rotating speed of 2200rpm, and uniformly mixing to obtain the nano cellulose/nano zinc oxide multifunctional protective liquid. Preparing multifunctional protective solution with the quality fractions of nano zinc oxide and nano cellulose of 2.0 wt% and 0.5 wt%, respectively (the total quality fraction of nano zinc oxide and nano cellulose is 2.5 wt%), uniformly coating the multifunctional protective solution on the surface of a paper document by using a 250-mesh silk screen printing plate, and then placing the paper document for 64 hours at the temperature of 25 ℃ and the relative humidity of 65%.
The paper documents which are not subjected to the treatment in the embodiment are characterized, the results are shown in table 2, and the paper which is not subjected to the treatment by the multifunctional protective solution is compared with the base paper: the pH is increased from 5.00 to 7.35; the tensile index is improved from 14.4 N.m/g to 51.2 N.m/g, and is increased by 255.56 percent; the tear index is increased from the unseen 3.46mN m2The concentration of the active carbon is increased to 4.57 mN.m2The per gram is increased by 32.08 percent; the burst index is 1.33kPa · m2The/g is increased to 1.63kPa · m2The folding endurance is improved from 1 time to 16 times by 15 times, and the color difference △ E before and after failure is 2.40.
Example 7
Slowly adding the nano zinc oxide into deionized water, continuously stirring by using a glass rod in the adding process, then carrying out ultrasonic treatment for 10min, and dispersing the nano zinc oxide through ultrasonic pretreatment to obtain a nano zinc oxide dispersion liquid. And adding the nano zinc oxide dispersion liquid into nano cellulose water suspension, dispersing for 15min by using a high-speed disperser at the rotating speed of 2200rpm, and uniformly mixing to obtain the nano cellulose/nano zinc oxide multifunctional protective liquid. The mass fraction ratio of the prepared nano zinc oxide to the nano cellulose is 2.0 wt%: 0.55 wt% (the total mass fraction of nano zinc oxide and nano cellulose is 2.55 wt%) of multifunctional protective liquid, which is uniformly coated on the surface of paper documents by using a 250-mesh screen plate, and then is placed at 25 ℃ and a relative humidity of 65% for 7264 hours.
The paper documents which are not subjected to the treatment in the embodiment are characterized, the results are shown in table 2, and the paper which is not subjected to the treatment by the multifunctional protective solution is compared with the base paper: the pH is increased from 5.00 to 7.42; the tensile index is improved to 57.1 N.m/g from 14.4 N.m/g which is not yet left, and is increased by 296.53 percent; the tear index is increased from the unseen 3.46mN m2The ratio of the concentration of the active carbon to the concentration of the active carbon is increased to 5.68mN · m2The per gram, increased 64.16%; the burst index is 1.33kPa · m2The/g is increased to 1.78kPa · m2The increase of the folding endurance is 33.83 percent, the increase of the folding endurance is 15 times from 1 time to 16 times, and the color difference △ E before and after failure is 3.36.
Example 8
Referring to example 7, the preparation process of the multifunctional nano-cellulose/nano-zinc oxide protective solution is prepared such that the mass fraction ratio of the nano-zinc oxide to the nano-cellulose is 2.0 wt%: 0.60 wt% (the total mass fraction of nano zinc oxide and nano cellulose is 2.6 wt%) of multifunctional protective solution, which is uniformly coated on the surface of paper literature by using a 250-mesh screen plate, and then is placed for 72 hours at 25 ℃ and a relative humidity of 65%.
The paper documents which are not subjected to the treatment in the embodiment are characterized, the results are shown in table 2, and the paper which is not subjected to the treatment by the multifunctional protective solution is compared with the base paper: the pH is increased from 5.00 to 7.41; the tensile index is improved to 56.2 N.m/g from 14.4 N.m/g which is not yet left, and is increased by 290.28%; the tear index is increased from the unseen 3.46mN m2The ratio of the total amount of the acid to the total amount of the acid is increased to 5.13mN · m2The per gram, increased 48.27%; the burst index is 1.33kPa · m2The/g is increased to 1.86kPa · m2Increase 39.85% for per gram, increase 13 times for folding endurance from 1 time to 14 times, and color difference △ E is 2.19.
Table 2 comparison of the performance indexes of the non-after pattern of examples 4 to 8 with those of the non-before pattern
Example 9
Referring to example 7, the preparation process of the multifunctional nano-cellulose/nano-zinc oxide protective solution is prepared such that the mass fraction ratio of the nano-zinc oxide to the nano-cellulose is 2.0 wt%: 0.55 wt% (the total mass fraction of nano zinc oxide and nano cellulose is 2.55 wt%) of multifunctional protective solution, which is uniformly coated on the surface of paper literature by using a 200-mesh screen plate, and then is placed for 72 hours at 25 ℃ and a relative humidity of 65%.
The paper documents which are not subjected to the treatment in the embodiment are characterized, the results are shown in table 3, and the paper which is not subjected to the treatment by the multifunctional protective solution is compared with the base paper: the pH is increased from 5.00 to 7.81; the tensile index is improved to 51.1 N.m/g from 14.8 N.m/g which is not yet left, and is increased by 245.27 percent; the tear index is increased from the unseen 3.56mN m2The concentration of the active carbon is increased to 4.51 mN.m2The per gram is increased by 26.69 percent; the burst index is 1.34kPa · m2The/g is increased to 1.57kPa · m2Increase in percent by 17.16% for the raw paper/g, increase in fold strength by 14 times from 1 to 15, and color difference △ E before and after failure of 4.13 (the virgin base paper used in Table 3 and the protective liquid in examples 9-11)The unprecedented paper is the same batch of paper).
Example 10
Referring to example 7, the preparation process of the multifunctional nano-cellulose/nano-zinc oxide protective solution is prepared such that the mass fraction ratio of the nano-zinc oxide to the nano-cellulose is 2.0 wt%: 0.55 wt% (the total mass fraction of nano zinc oxide and nano cellulose is 2.55 wt%) of multifunctional protective solution, which is uniformly coated on the surface of paper literature by using a 250-mesh screen plate, and then is placed for 72 hours at 25 ℃ and a relative humidity of 65%.
The paper documents which are not subjected to the treatment in the embodiment are characterized, the results are shown in table 3, and the paper which is not subjected to the treatment by the multifunctional protective solution is compared with the base paper: the pH is increased from 5.00 to 7.27; the tensile index is improved to 44.3 N.m/g from 14.8 N.m/g which is not yet left, and is increased by 199.32 percent; the tear index is increased from the unseen 3.56mN m2The ratio of the total amount of the acid to the total amount of the acid is increased to 4.09 mN.m2The per gram is increased by 14.89%; the burst index is 1.34kPa · m2The/g is increased to 1.64kPa · m2The folding endurance is increased by 22.39 percent from 1 time to 12 times, and is increased by 11 times, and the color difference △ E before and after failure is 2.90.
Example 11
Referring to example 7, the preparation process of the multifunctional nano-cellulose/nano-zinc oxide protective solution is prepared such that the mass fraction ratio of the nano-zinc oxide to the nano-cellulose is 2.0 wt%: 0.55 wt% (the total mass fraction of nano zinc oxide and nano cellulose is 2.55 wt%) of multifunctional protective solution, which is uniformly coated on the surface of paper literature by using a 350-mesh screen printing plate, and then is placed for 72 hours at 20 ℃ and 60% of relative humidity.
The paper documents which are not subjected to the treatment in the embodiment are characterized, the results are shown in table 3, and the paper which is not subjected to the treatment by the multifunctional protective solution is compared with the base paper: the pH is increased from 5.00 to 7.02; the tensile index is improved to 42.9 N.m/g from 14.8 N.m/g which is not yet left, and is increased by 189.86 percent; the tear index is not greatly changed, and the tear index is changed from the original 3.56mN m2Perg liter to 3.60 mN.m2The per gram is increased by 1.12 percent; the burst index is 1.34kPa · m2The/g is increased to 1.44kPa · m2The per gram is increased by 7.46 percent; durableThe folding degree is improved from 1 time to 6 times, the folding degree is increased by 5 times, although the tearing index change is not large (1.12%), the mechanical property of the paper is greatly increased as a whole, and the color difference △ E before and after the paper is not changed is 2.47.
TABLE 3 comparison of the Performance indices of the non-virgin patterns of examples 9-11 with those of the non-virgin patterns
Example 12
The aging resistance of the paper was evaluated by dry heat aging of the untreated paper sample and the untreated paper sample (examples 7 and 9) subjected to the multifunctional protective solution in an oven at 105 ℃ for 72 hours (see Table 4 for the results).
The pH value is reduced from 5.00 to 4.74 by 5.20 percent after the paper sample is not subjected to dry heat aging; the tensile index is reduced to 12.6 N.m/g from 14.1 N.m/g, and is reduced by 10.64 percent; the tear index is 3.46 mN.m2The ratio of the concentration of the acid to the concentration of the acid is reduced to 2.29mN · m2The reduction in the ratio of/g is 33.82%; the burst index is 1.34 kPa.m2The/g is reduced to 1.28kPa · m2The percent reduction is 4.48 percent in terms of/g, the folding endurance is reduced from 1 time to 0 time, the reduction rate is 100.00 percent, and the color difference △ E before and after aging is 3.52.
The paper sample which is not protected is not aged by dry heat, and the pH value is reduced to 7.31 from 7.42 and is only reduced by 1.48 percent after the dry heat of the example 7 is aged; the tensile index is reduced to 56.8 N.m/g from 57.1 N.m/g, and the reduction rate is only 0.53 percent; the tear index is 5.68 mN.m2The ratio of the acid to the acid is reduced to 3.79 mN.m2(ii)/g, the rate of decrease was 33.27%; the burst index is 1.78 kPa.m2The/g is reduced to 1.73kPa · m2The percent reduction is 2.81 percent per gram, the folding endurance is reduced from 16 times to 9 times, the percent reduction is 43.75 percent, the color difference △ E before and after aging is 1.29, the pH value is reduced from 7.81 to 7.68 and reduced by 1.66 percent after the dry heat aging of example 9 is not finished, the tensile index is reduced from 51.1 Nm/g to 47.5 Nm/g, the percent reduction is 7.05 percent, and the tear index is reduced from4.51mN·m2The/g is reduced to 3.73 mN.m2The yield is 17.29 percent, the burst index is not changed, the folding times are reduced from 15 times to 9 times, the yield is 40.00 percent, the color difference △ E before and after aging is 2.57, compared with the paper samples without the paper samples, the paper samples without the paper samples are protected, the pH value is still kept above 7 after dry heat aging, the pH stability is improved, the reduction range of the tensile index, the tearing index and the burst index is lower than that of the paper samples without the paper samples, and the mechanical property is still obviously higher than that of the paper samples without the paper samples.
Table 4 No influence of the nanocellulose/nano-zinc oxide multifunctional protective solution on the aging performance of paper
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any equivalent alterations, modifications or improvements made by those skilled in the art to the above-described embodiments using the technical solutions of the present invention are still within the scope of the technical solutions of the present invention.
Claims (10)
1. The multifunctional nano-cellulose/nano-zinc oxide protective solution is characterized by comprising nano-zinc oxide, nano-cellulose and water, wherein the concentration of the nano-cellulose is 0.4-0.6wt%, and the concentration of the nano-zinc oxide is 0.5-2.5 wt%.
2. The preparation method of the multifunctional nano-cellulose/nano-zinc oxide protective solution as claimed in claim 1, characterized by comprising the following steps:
(1) adding nano zinc oxide into water, and obtaining nano zinc oxide dispersion liquid through ultrasonic treatment without dispersion;
(2) and adding the nano zinc oxide dispersion liquid into the nano cellulose water suspension, and passing through a high-speed disperser without uniformly mixing to obtain the nano cellulose/nano zinc oxide multifunctional protective liquid.
3. The preparation method according to claim 2, wherein in the step (1), the nano zinc oxide has a particle size of less than 100 nm.
4. The method according to claim 2, wherein the ultrasonic sound has not been applied for 5 to 10min in the step (1).
5. The method of claim 2, wherein the nanocellulose of step (2) is cellulose nanofibrils that have been subjected to neutral TEMPO oxidation in combination with high pressure homogenization, which have a diameter of 3-20nm and a length of >400nm, and have a carboxyl content of 0.8mmol/g or more in terms of the absolutely dry mass of the nanocellulose.
6. The preparation method as claimed in claim 1, wherein in the step (2), the rotation speed of the high speed disperser is 1800-2200rpm, and the stirring time is 8-15 min.
7. The method for protecting paper documents by the multifunctional nano-cellulose/nano-zinc oxide protective solution as recited in claim 1, is characterized by comprising the following steps:
(1) uniformly coating the multifunctional nano-cellulose/nano-zinc oxide protective solution on paper documents to be protected in a screen printing manner;
(2) and (3) placing the paper which is not subjected to the step (1), namely finishing the protection of the paper documents.
8. The method for preparing the multifunctional nano-cellulose/nano-zinc oxide protective solution and protecting paper documents by using the multifunctional nano-cellulose/nano-zinc oxide protective solution as claimed in claim 7, is characterized in that: in the step (2), the placement is carried out under the conditions of constant temperature and constant humidity of 20-25 ℃ and relative humidity of 60-65%.
9. The method for preparing the multifunctional nano-cellulose/nano-zinc oxide protective solution and protecting paper documents by using the multifunctional nano-cellulose/nano-zinc oxide protective solution as claimed in claim 7, is characterized in that: in the step (2), the mixture is placed for 64-76 h.
10. The method for preparing the multifunctional nano-cellulose/nano-zinc oxide protective solution and protecting paper documents by using the multifunctional nano-cellulose/nano-zinc oxide protective solution as claimed in claim 7, is characterized in that: the mesh of the silk screen printing plate in the step (1) is 200-350 meshes.
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