CN112030602B - Deacidifying method for sizing paper - Google Patents
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- CN112030602B CN112030602B CN202010934998.8A CN202010934998A CN112030602B CN 112030602 B CN112030602 B CN 112030602B CN 202010934998 A CN202010934998 A CN 202010934998A CN 112030602 B CN112030602 B CN 112030602B
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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
Abstract
The application provides a deacidification method of sized paper, which comprises the following steps: 1) treating the sized paper to be deacidified in plasma; 2) deacidifying the treated sizing paper by using a deacidification solution, and standing until the surface sizing layer of the sizing paper is recovered. After deacidifying the sized paper by using the method, the sizing layer of the paper can gradually return to the state before plasma treatment. The method overcomes the limitation of the prior deacidification technology for the sized paper, can complete the deacidification of the sized paper under the condition of not damaging the paper surface sizing layer and the paper body, and has the advantages of low cost in the deacidification process, simple operation and obvious deacidification effect.
Description
Technical Field
The application relates to the field of paper deacidification, in particular to a deacidification method for sized paper.
Background
The paper fiber mainly comprises cellulose, hydrophilic groups such as hydroxyl and the like are arranged on a cellulose molecular chain, if the surface of the paper is not treated, the surface of the paper has strong hydrophilicity, ink can be diffused on the surface of the paper due to the existence of water molecules, the writing performance of the paper is affected, the mechanical strength of the paper is greatly reduced, and even the fiber is degraded and deteriorated. In order to solve these problems, the surface of the paper is generally sized in the paper making process, i.e. a certain amount of sizing material is uniformly coated on the surface of the paper to form a hydrophobic layer on the surface of the paper, thereby improving the performance of the paper. Besides, the waterproof and moisture-proof performance of the paper is improved, the surface sizing of the paper can reduce the penetration and diffusion of the printing ink, so that the printing ink is easy to wipe off, the wear resistance of the paper surface is improved, the folding resistance, the durability, the tensile strength and the like of the paper can be improved, the difference and the deformation of two surfaces of the paper are improved, and the flatness of the paper is improved.
As with ordinary paper, the sized paper also can generate acidification phenomenon along with the increase of the service time, and the deacidification effect of the aqueous deacidification agent is poor due to the existence of the colloid hydrophobic layer on the surface of the paper. The current common Bookkeeper deacidification technology adopts nonaqueous dispersion deacidification, uses alkaline oxide suspended in organic solvent to neutralize acid components in paper, but for sizing paper, the alkaline oxide components in organic solution can not pass through a sizing layer on the surface to reach the interior of the paper, so that the problem of acidification in the paper can not be solved.
In the deacidification process of the sized paper, a method indicates that a sizing layer on the surface of the paper is removed through special treatment, then deacidification of the paper is carried out, and the paper is sized again after deacidification is finished.
Disclosure of Invention
Based on this, it is necessary to provide a deacidification method for sized paper aiming at the problem of how to complete deacidification of the sized paper without damaging the surface sizing layer and the paper body of the sized paper.
A method of deacidifying sized paper comprising the steps of:
1) treating the sized paper to be deacidified in plasma;
2) deacidifying the treated sizing paper by using a deacidification solution, and standing until the surface sizing layer of the sizing paper is recovered.
Among the above-mentioned technical scheme, adopt plasma to handle the gluey paper, certain looseness can appear in the gluey layer on surface to hydrophilicity can temporarily improve, can accomplish the deacidification to the gluey paper under the condition of not destroying paper surface gluey layer and paper body, and deacidification process cost is lower, easy operation, and the deacidification effect is obvious.
Several alternatives are provided below, but not as an additional limitation to the above general solution, but merely as a further addition or preference, each alternative being combinable individually for the above general solution or among several alternatives without technical or logical contradictions.
Optionally, the sized paper comprises sized paper obtained by both internal sizing and surface sizing.
Optionally, the plasma is a cold plasma generated by gas discharge. Because the temperature of the ions in the cold plasma treatment process is lower, the temperature of the environment in the reaction process can be maintained in a lower range, and the influence of the thermal effect on paper is avoided. The cold plasma in the treatment process is mainly generated by gas discharge, and different conditions and environments in the discharge process can also influence the composition and performance of the finally generated cold plasma.
Optionally, the gas discharge mode includes glow discharge, capacitive coupling discharge under ac discharge, inductive coupling discharge under ac discharge, dielectric barrier discharge under ac discharge, or corona discharge under dc discharge. Further preferably, a dielectric barrier discharge method under ac discharge is adopted, that is, a specific dielectric material is attached to a discharge electrode to cause gas between the electrodes to break down and complete discharge, and the method is suitable for large-scale industrial application.
Optionally, the time for treating the sized paper in the plasma is 20-80 s. Since cold plasma is a non-equilibrium plasma in which the temperature of electrons is much higher than that of ions, the long-term plasma treatment causes permanent damage to the size layer and the bulk of the paper, and the plasma treatment time is strictly controlled. Further preferably, the treatment time of the sized paper in the plasma is 30-50 s.
Optionally, the input power of the sizing paper treated in the plasma is 20-30W. Too low an input power may result in a reduced activation of the paper size layer by the plasma. Too high a power input may damage the surface size layer of the paper and the internal structure of the paper.
Optionally, the deacidification in the step 2) needs to be performed within 0-24 hours after the step 1) is completed. After the plasma treatment is carried out on the sized paper in the step 1), the surface sizing layer is loosened to some extent, and the hydrophilicity is temporarily improved, but after a certain period of time, the surface sizing layer of the paper is restored to the original state and continues to present hydrophobicity, which is called relaxation phenomenon, so that after the step 1) is finished, the paper deacidification process in the step 2) needs to be finished as soon as possible.
Optionally, the deacidification solution is selected from an aqueous alkaline solution deacidification solution, an alkaline organic solution deacidification solution or a non-aqueous dispersion deacidification solution.
Optionally, the standing time is 10-15 days. And standing to ensure that the sized paper can relax, colloid pore channels in the surface sizing layer are closed, and the state is recovered to the state before plasma treatment.
The invention has the following beneficial effects:
(1) the method provided by the invention can be used for completing deacidification of the paper on the premise of not damaging the sizing layer on the surface of the sized paper.
(2) The invention adopts plasma treatment, has low requirements on equipment and environment, has little influence on the sizing paper body, and can loosen the sizing layer on the surface of the sizing paper in a short time.
(3) The method provided by the invention has the advantages of simple process, easy operation, obvious deacidification effect and suitability for large-scale operation.
Drawings
FIG. 1 is a graph comparing the wettability of sized and unsized paper in example 1;
FIG. 2 is a graph of the degree of wetting of the ink droplets on the surface of a sized paper sheet in example 1;
FIG. 3 is a graph comparing the wetting of the sized paper after cold plasma treatment in example 1 at various times.
Detailed Description
The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the embodiments of the present application and the accompanying drawings, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein in the description of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application.
Example 1
Putting the sizing paper into a cold plasma reaction chamber, wherein the cold plasma is generated by air discharge, the discharge mode is dielectric barrier discharge, a power supply is turned on, the voltage is adjusted to be 80V, the current is 0.3A, the input power is 24W, when the air in the reaction chamber is ionized, timing is started when the plasma flow with a specific color is shot on the surface of the sizing paper, the time is 40s, after the cold plasma treatment is finished, the power supply is turned off, and the sizing paper is taken out for standby.
And (3) performance testing:
(1) the same kind of sized paper (double-sided offset paper) as in example 1 and unsized paper (double-circled qualitative filter paper, Votmann Co.) were used for wettability comparison. As shown in fig. 1, the left side is unsized paper, which is known to be completely penetrated in aqueous solution; on the right is the sized paper, which may float in the aqueous solution and is not permeable to the aqueous solution.
(2) The same kind of sized paper as in example 1 was taken for the wetting degree test, fig. 2 is the wetting degree of the ink solution on the surface of the sized paper, and it can be seen that the contact angle of the ink drop on the surface of the sized paper is larger than 0 °, i.e. the aqueous solution cannot completely wet the sized paper.
(3) The sized paper after cold plasma treatment in example 1 was tested as follows: the first, third, sixth and tenth day after cold plasma treatment of the sized papers were tested for the degree of wetting of the ink solutions on these sized papers, respectively, for the end of observation point, 3s and 10s conditions, and the test results are shown in fig. 3.
On the first day after cold plasma treatment, the ink droplets can completely wet the sized paper and spread very fast. On the third day after treatment, the wettability of the ink droplets on the surface of the sized paper decreased and the diffusion rate also slowed down. On the sixth day after treatment, the wettability of the ink droplets on the surface of the sized paper continued to decrease, as did the diffusion rate. On the tenth day after treatment, the ink droplets were substantially unable to wet the sized paper and the ink droplets were substantially unable to spread, approaching the state of the sized paper prior to cold plasma treatment.
Example 2
The time for cold plasma treatment of the sized paper in example 1 was adjusted to 20s, and the procedure was otherwise the same as in example 1. In example 2, the plasma treatment time is short, and the pore channels in the sizing layer on the surface of the paper cannot be completely opened, so that the subsequent deacidification effect of the paper is slightly reduced.
Example 3
The time for cold plasma treatment of the sized paper in example 1 was adjusted to 80s, and the procedure was otherwise the same as in example 1. The longer plasma treatment time in example 3 resulted in some effect on the size coat on the surface of the sized paper.
Example 4
The sizing paper is placed into a cold plasma reaction chamber, the cold plasma is generated by air discharge, the discharge mode is dielectric barrier discharge, a power supply is turned on, the voltage is adjusted to be 100V, the current is 0.3A, the input power is 30W, when the air in the reaction chamber is ionized, timing is started when the plasma flow with specific color is shot on the surface of the sizing paper, the time is 40s, after the cold plasma treatment is completed, the power supply is turned off, and the sizing paper is taken out for standby. Under the condition, the cold plasma treatment can completely open the pore channels inside the sizing layer on the surface of the paper.
Example 5
Putting the sizing paper into a cold plasma reaction chamber, wherein the cold plasma is generated by air discharge, the discharge mode is dielectric barrier discharge, a power supply is turned on, the voltage is adjusted to be 75V, the current is 0.4A, the input power is 30W, when the air in the reaction chamber is ionized, timing is started when the plasma flow with a specific color is shot on the surface of the sizing paper, the time is 40s, after the cold plasma treatment is finished, the power supply is turned off, and the sizing paper is taken out for standby. Under the condition, the cold plasma treatment can completely open the pore channels inside the sizing layer on the surface of the paper.
Example 6
Putting the sizing paper into a cold plasma reaction chamber, wherein the cold plasma is generated by air discharge, the discharge mode is glow discharge, a power supply is turned on, the voltage is adjusted to be 80V, the current is 0.3A, the input power is 24W, when the air in the reaction chamber is ionized, the timing is started when the plasma flow with specific color is shot on the surface of the sizing paper, the time is 40s, after the cold plasma treatment is finished, the power supply is turned off, and the sizing paper is taken out for standby. Under the condition, the cold plasma treatment can completely open the pore channels inside the sizing layer on the surface of the paper.
Example 7
Putting the acidified sizing paper into a cold plasma reaction chamber, wherein the cold plasma is generated by air discharge, the discharge mode is dielectric barrier discharge, a power supply is turned on, the voltage is adjusted to be 80V, the current is 0.3A, the input power is 24W, when the air in the reaction chamber is ionized, the timing is started when the plasma flow with a specific color is shot on the surface of the sizing paper, the time is 40s, after the cold plasma treatment is finished, the power supply is turned off, and the sizing paper is taken out for standby.
Taking out the sizing paper treated by the plasma, deacidifying the paper in an aqueous deacidifying agent (magnesium bicarbonate solution) within 24 hours from the end of the plasma treatment, measuring the pH value of the paper after deacidification by using a pH pen after the deacidification process is finished, and comparing the pH value with the pH value of the paper before deacidification.
And standing the sized paper in the air for ten days after deacidification treatment is completed, and completing deacidification of the sized paper after a glue applying layer on the surface of the paper is recovered after a relaxation phenomenon occurs.
And (3) performance testing:
(1) taking the sized paper without the cold plasma treatment in example 7, performing deacidification treatment directly, and recording the pH value after deacidification and the original pH value of the paper, as shown in table 1 below, it can be seen from the table that the deacidification effect of the paper is not obvious after the sized paper is deacidified by using the aqueous deacidification solution directly, and the sized paper is neutral or weakly acidic after deacidification, which easily causes the paper to be acidified again in a short time.
Table 1: pH value before and after acidification and sizing paper is directly deacidified
(2) Table 2 shows that the sized paper is treated according to the steps of example 7, that is, deacidified after being subjected to the cold plasma treatment, and it can be seen from the table that the sized paper is significantly acidic before the plasma treatment, and the pH value of the paper surface does not significantly change after the paper is subjected to the plasma treatment, and after deacidifying the paper subjected to the cold plasma treatment with the aqueous deacidifying solution, the pH value of the paper surface is significantly increased, and the deacidifying effect is more significant than that of direct deacidification of the paper, and the paper surface is weakly alkaline after deacidification, so that the paper can be continuously protected.
Table 2: pH value before and after deacidification of acidified sized paper after plasma treatment
| Number of measurements | Original | After plasma treatment | After |
| 1 | 5.9 | 5.7 | 7.9 |
| 2 | 5.7 | 6.0 | 8.1 |
| 3 | 6.0 | 6.1 | 8.3 |
| Average | 5.9 | 5.9 | 8.1 |
Example 8
The type of deacidification solution used for deacidification of the sized paper in example 7 was adjusted to an alkaline organic solution deacidification solution (dibutoxy diethoxy magnesium carbonate heptane), and the procedure was the same as in example 7.
And (3) performance testing:
table 3 shows that the sized paper is treated according to the steps of embodiment 8, that is, after the cold plasma treatment, deacidification is performed on the sized paper, before the plasma treatment, the sized paper is significantly acidic, after the plasma treatment is performed on the paper, the pH value of the surface of the paper does not significantly change, after deacidification is performed on the cold plasma-treated paper by using an alkaline organic solution deacidification solution, the pH value of the surface of the paper is significantly increased, the deacidification effect is more significant than that of direct deacidification of the paper, and the surface of the paper is weakly alkaline after deacidification, so that the paper can be continuously protected.
Table 3: pH value before and after deacidification of acidified sized paper after plasma treatment
| Number of measurements | Original | After plasma treatment | After |
| 1 | 5.9 | 5.7 | 7.4 |
| 2 | 5.7 | 6.0 | 7.5 |
| 3 | 6.0 | 6.1 | 7.3 |
| Average | 5.9 | 5.9 | 7.4 |
Example 9
The type of deacidification solution used for deacidification of the sized paper in example 7 was adjusted to a nonaqueous dispersion deacidification solution (a perfluorocarbon solution of nano-magnesia), and the procedure was the same as that of example 7.
And (3) performance testing:
table 4 shows that the sized paper is treated according to the steps of example 9, that is, after the cold plasma treatment, deacidification is performed on the sized paper, before the plasma treatment, the sized paper is significantly acidic, after the plasma treatment is performed on the paper, the pH value of the paper surface does not significantly change, after deacidification is performed on the cold plasma-treated paper by using a non-aqueous dispersion system deacidification solution, the pH value of the paper surface is significantly increased, the deacidification effect is more significant than that of direct deacidification of the paper, and the paper surface is weakly alkaline after deacidification, so that the paper can be continuously protected.
Table 4: pH value before and after deacidification of acidified sized paper after plasma treatment
| Number of measurements | Original | After plasma treatment | After |
| 1 | 5.9 | 5.7 | 7.3 |
| 2 | 5.7 | 6.0 | 7.7 |
| 3 | 6.0 | 6.1 | 7.8 |
| Average | 5.9 | 5.9 | 7.6 |
Examples 7-9 deacidify the plasma-treated sized paper using different types of deacidification solutions, and the final deacidification treatment result shows that the aqueous deacidification solution is more suitable for deacidification of the plasma-treated sized paper.
The above-mentioned embodiments only express several embodiments of the present application, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the concept of the present application, which falls within the scope of protection of the present application. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (2)
1. A method of deacidifying sized paper, comprising the steps of:
1) treating the sized paper to be deacidified in plasma; the plasma is cold plasma generated by gas discharge; the gas discharge mode is dielectric barrier discharge under alternating current discharge; the sizing paper is treated in the plasma for 20-80 s; the input power of the sizing paper for processing in the plasma is 20-30W;
2) deacidifying the treated sizing paper by using a deacidification solution, and standing until the surface sizing layer of the sizing paper is recovered; the deacidification in the step 2) needs to be carried out within 0-24 h after the step 1) is finished; the standing time is 10-15 days.
2. A process for deacidifying sized paper as claimed in claim 1, wherein said deacidifying liquid is selected from an aqueous alkaline solution deacidifying liquid, an alkaline organic solution deacidifying liquid or a non-aqueous dispersion deacidifying liquid.
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| FI113791B (en) * | 1998-06-22 | 2004-06-15 | Metso Paper Inc | Method and apparatus for surface treatment of a web |
| AU2003234058A1 (en) * | 2003-05-13 | 2004-12-03 | Stazione Sperimentale Carta Cartoni E Paste Per Carte | Method for plasma treating paper and cardboards |
| CN102242530B (en) * | 2011-07-06 | 2012-11-14 | 浙江大学 | Deacidifying method for paper cultural relics |
| CN102644218A (en) * | 2012-04-17 | 2012-08-22 | 浙江大学 | Arc discharge paper deacidification device and method |
| CN105064132B (en) * | 2015-07-02 | 2017-08-01 | 浙江大学 | A kind of acid stripping method and deacidifying device |
| CN107460774B (en) * | 2017-09-15 | 2018-04-20 | 杭州众材科技有限公司 | A kind of paper guard method and equipment |
| CN108060612B (en) * | 2017-12-13 | 2020-03-31 | 中国科学技术大学 | Method for deacidifying paper by electrolytic process |
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