KR101337096B1 - Method for manufacturing of polyelectrolyte multilayer coated inorganic filler and paper using thereof - Google Patents

Abstract

The present invention relates to a method for producing an inorganic filler for papermaking and paper produced through the same. According to the present invention, dispersing the packing particles into distilled water in the reaction tank, electrostatically adsorbing the cationic polymer material on the surface of the packing by introducing a cationic polymer material into the reaction tank, and non-adsorption with distilled water in the reaction tank. Discharging the cationic polymer material and then re-injecting distilled water to redistribute the packing material; and adding anionic polymer material to the reaction tank to electrostatically adsorb the anionic polymer material on the surface of the cationic polymer material; Discharging the anionic polymer material and the non-adsorbed anionic polymer material in the reaction tank, and then re-dispersing the packing material by re-injecting the distilled water, and adding a cationic polymer material into the reaction tank to electrostatically discharge the cationic polymer material on the surface of the anionic polymer material. Adsorption miraculously, and distilled water and It was discharged chakdoen cationic polymeric substance, and then the inorganic filler provides a papermaking method comprising the steps to re-supply of distilled water for re-dispersing the fillers.
According to the manufacturing method of the paper-making inorganic filler according to the present invention and the paper produced therefrom, by continuously adsorbing different ionic polymer material on the surface of the paper-making inorganic filler to form a multilayer polymer thin film on the filler particles, There is an advantage that can improve the strength of the paper to be manufactured and reduce the cost.

Description

Method for manufacturing inorganic filler coated with a polymer multilayer thin film and paper produced by the same {Method for manufacturing of polyelectrolyte multilayer coated inorganic filler and paper using

The present invention relates to a method for producing an inorganic filler for paper, and a paper produced through the same, and more particularly, to a method for manufacturing an inorganic filler for paper and a paper produced through the same, which can improve the strength of paper and reduce its cost. .

In general, inorganic fillers for paper making such as calcium carbonate, clay, etc. have advantages such as printability and optical property improvement, so that they are added in a proportion to pulp fibers during paper production. Background art of using calcium carbonate as a papermaking inorganic filler is disclosed in Korean Patent Publication No. 2006-0020655.

Since the inorganic filler for papermaking is cheaper than pulp, the higher the content of the filler in the paper, the lower the cost of paper manufacturing. However, the fillers have the disadvantage of impairing the bonds between the fibers and lowering the strength of the paper.

In general, as the content of the filler increases, the paper strength decreases because the hydrogen bonding between the fibers is interrupted by the filler and the contact between the filler-filler and the fiber-filler without chemical bonding force increases.

Therefore, in order to manufacture paper having excellent cost reduction and physical properties by increasing the content of the filler in the paper, it is urgently necessary to improve the retention of the filler and reduce the interference of the fillers between the fibers in the paper. For example, there is a method of adding a polymer material after adding the filler to the fiber suspension or adding a polymer material to the filler before adding the filler.

In the former case, a method conventionally used in the paper industry, the polymer can adsorb the filler on the surface of the fiber to improve the retention of the filler and can reduce the paper strength decrease in combination with the strength enhancer. However, this does not improve the fiber-fill linkages.

In the latter case, it is generally referred to as a preaggregation technique, which is a technique applied to paper manufacture after agglomerating the filler particles with a polymer material to form agglomerates of appropriate sizes. Increasing the particle size by agglomeration reduces the specific surface area of the filler particles, which can further preserve the bonds between fibers compared to when no preaggregation technique is applied, thereby increasing the strength of the paper relative to the same filler content.

This technique can reduce the interference between fibers when the filler is present in the paper to mitigate the strength degradation of the paper containing the filler, but there is a limit to the type of polymer used and the number of treatments. For example, in the case of preaggregation, only a relatively high molecular weight polymer should be selected to aggregate the filler particles. Moreover, this technique still has the limitation that it does not increase the binding force between the fiber-fill and the filler-fill. In addition, the filler agglomerate has a problem in that the optical properties such as the inherent opacity of the filler are slightly reduced.

The present invention is capable of improving the strength of paper and reducing the cost by forming a polymer multilayer thin film on the filler particles by continuously adsorbing different ionic polymer materials on the surface of the inorganic filler for papermaking. It is an object to provide a method for preparing an inorganic filler and a paper produced therefrom.

The present invention comprises the steps of (a) dispersing anionic filler particles in distilled water in a reaction tank, and (b) discharging the cationic polymer material on the surface of the filler by introducing a cationic polymer material into the reactor. Adsorbing miraculously, (c) discharging the distilled water and the unadsorbed cationic polymer material in the reactor, and then re-dispersing the packing material by re-injecting distilled water into the reactor, and (d) in the reactor. Electrostatically adsorbing the anionic polymer material on the surface of the cationic polymer material by adding an anionic polymer material, and (e) discharging distilled water and unadsorbed anionic polymer material in the reaction tank, Redispersing the packing material by re-injecting distilled water into the reactor, (f) adding a cationic polymer material into the reactor Electrostatically adsorbing the cationic polymer material on the surface of the anionic polymer material, and (g) discharging the distilled water and the unadsorbed cationic polymer material in the reactor, and then returning the distilled water to the reactor. It provides a papermaking inorganic filler manufacturing method comprising the step of re-dispersing the filler by the input.

The cationic polymer material may be added in a mass of 0.1 to 2.0% of the filler, and the anionic polymer material may be added in a mass of 0.1 to 2.0% of the filler.

In addition, the manufacturing method of the inorganic filler for papermaking, after performing the step (g), and further comprising repeating the steps (d) to (g) N (N is natural number) times, the An odd number of multilayer thin films in which the cationic polymer material and the anionic polymer material are alternately adsorbed may be formed on the surface of the filler.

In addition, the manufacturing method of the inorganic filler for papermaking, after performing the step (g) may further comprise the step of performing the step (d) and (e).

In addition, the manufacturing method of the inorganic filler for papermaking, after performing the step (g), and repeating the steps (d) to (g) N times (N is a natural number) and then the step (d) and The method may further include performing the step (e) to form an even number of multilayer thin films in which the cationic polymer material and the anionic polymer material are alternately adsorbed on the surface of the filler.

Here, the filler may include at least one of calcium carbonate, clay, talc, titanium dioxide, silica.

In addition, the cationic polymer material includes at least one of Poly-DADMAC (poly diallyldimethylammonium chloride), C-PAM (cationic polyacrylamide), PEI (polyethylenimine), PAH (poly allylamine), amphoteric starch, the anionic polymer material May include at least one of polyacrylic acid (PAA), poly sodium 4-styrene sulfonate (PSS), ationic polyacrylamide (A-PAM), and polyvinylalcohol (PVOH).

In addition, the present invention comprises the steps of (a) dispersing the cationic filler particles in distilled water in the reaction tank, and (b) injecting an anionic polymer material into the reactor to provide the anionic polymer material on the surface of the filler. Electrostatically adsorbing, (c) discharging the distilled water and the non-adsorbed anionic polymer material in the reactor, and then re-dispersing the packing material by re-injecting distilled water into the reactor, and (d) the reactor. Electrostatically adsorbing the cationic polymer material on the surface of the anionic polymer material by injecting a cationic polymer material therein, and (e) discharging distilled water and unadsorbed cationic polymer material in the reactor. Redispersing the packing material by re-injecting distilled water into the reactor, (f) anionic polymer material in the reactor Electrostatically adsorbing the anionic polymer material on the surface of the cationic polymer material, and (g) discharging the distilled water and the unadsorbed anionic polymer material in the reactor, and then distilled water into the reactor. It provides a papermaking inorganic filler manufacturing method comprising the step of re-dispersing the filler by re-feeding.

Here, the present invention may further include performing the step (g) and then performing the step (d) and the step (e).

In addition, the present invention after performing the step (g), and repeating the steps (d) to (g) N times (N is a natural number) and then the steps (d) and (e) The method may further include forming an even number of multilayer thin films in which the cationic polymer material and the anionic polymer material are alternately adsorbed on the surface of the filler.

In addition, the present invention provides a paper produced by containing the inorganic filler prepared by the method for producing an inorganic filler for papermaking.

According to the manufacturing method of the paper-making inorganic filler according to the present invention and the paper produced therefrom, by continuously adsorbing different ionic polymer material on the surface of the paper-making inorganic filler to form a multilayer polymer thin film on the filler particles, There is an advantage that can improve the strength of the paper to be manufactured and reduce the cost.

That is, the present invention can be prepared by adding filler particles formed by alternating polymer multilayer thin film to the pulp fibers to increase the chemical bond between the pulp fibers and the filler, and between the filler and the filler by the multilayer thin film and the strength of the paper Can improve. Furthermore, when the paper is manufactured, it is possible to lower the content of the pulp fibers by adding a filler having a lower cost than the pulp fibers, thereby reducing the manufacturing cost of the paper.

1 is a flowchart of a method for manufacturing an inorganic filler for papermaking according to an embodiment of the present invention.
2 is a flowchart corresponding to FIG. 1.
3 is a cross-sectional view of the inorganic filler particles produced by FIG. 1.
FIG. 4 shows a cross section of a paper made by adding the filler particles of FIG. 3 to pulp fibers. FIG.
5 shows the zeta potential of heavy calcium carbonate coated with a polymer multilayer thin film according to an embodiment of the present invention.
6 and 7 show particle size and particle size distribution of heavy calcium carbonate coated with a polymer multilayer thin film according to an embodiment of the present invention.
8 shows the reactivity of heavy calcium carbonate and pulp fibers coated with a polymer multilayer thin film according to an embodiment of the present invention.
Figure 9 shows the results of evaluating the binding capacity of the heavy calcium carbonate and pulp fibers coated with a polymer multilayer thin film according to an embodiment of the present invention.
FIG. 10 shows the ash content in paper during paper production by adding heavy calcium carbonate coated with a polymer multilayer thin film to pulp fibers according to an embodiment of the present invention.
11 is a result of comparing the tensile index of each layer in the same ash content 20% in the paper prepared corresponding to FIG.
FIG. 12 illustrates the relationship between ash content and tensile index of a paper according to a multilayer thin film layer in paper prepared by injecting heavy calcium carbonate having a polymer multilayer thin film formed into a pulp fiber according to an embodiment of the present invention.

DETAILED DESCRIPTION Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art may easily implement the present invention.

The present invention relates to a method for producing an inorganic filler for papermaking and paper produced through the same. This invention is intended for papermaking by alternately adsorbing a cationic polymer material and an anionic polymer material on the surface of a papermaking inorganic filler such as anionic (heavy) calcium carbonate, clay, talc, titanium dioxide, silica, and the like. The surface of the inorganic filler is nano-coated with a multilayer thin film.

Of course, when the paper-making inorganic filler is cationic, such as hard calcium carbonate, the anionic polymer material and the cationic polymer material are alternately adsorbed on the multilayer to make nano coating.

That is, when the polarity of the inorganic filler is anionic, the cationic polymer material of the opposite polarity is first adsorbed; on the contrary, when the polarity of the inorganic filler is cationic, the anionic polymeric material of the opposite polarity is 1 Adsorbed by car. Such thin film adsorption technology is to form a polymer multilayer thin film on the filler particles by continuously adsorbing different ionic polymer materials on the surface of the inorganic filler by the electrostatic attraction.

When paper is prepared by adding filler particles having a polymer multilayer thin film to the pulp fibers, the chemical bonding force between the pulp fibers and the filler and between the filler and the filler is increased by the multilayer thin film, thereby increasing the strength of the paper containing the filler. Can improve. In addition, when the paper is manufactured by adding a filler cheaper than the pulp fibers, the content of the pulp fibers can be lowered, thereby reducing the manufacturing cost of the paper.

Moreover, compared to the case of conventionally prepared by simply adding the inorganic filler to the pulp fibers, when using the present invention, it is possible to produce a paper of excellent strength compared to the same filler content, and also in contrast to the same strength It is possible to produce paper with a higher filling content.

Hereinafter will be described in detail with respect to the manufacturing method of the inorganic filler for papermaking according to an embodiment of the present invention. For convenience of description, the following examples illustrate a case in which a cationic polymer material and an anionic polymer material are sequentially adsorbed onto a surface of an inorganic filler having anionic properties to form a multilayer thin film.

1 is a flowchart of a method for manufacturing an inorganic filler for papermaking according to an embodiment of the present invention. 2 is a flowchart corresponding to FIG. 1.

First, the filler particles having an anion in the reaction tank are dispersed with distilled water to form a filler slurry (S110). At this time, the filler slurry is diluted in distilled water so as to have a concentration of 1% to 60%, for example, the concentration of the filler relative to the total mass is adjusted to about 30%.

In addition, the filler used may include at least one of calcium carbonate, clay, talc, titanium dioxide, and silica. Hereinafter, the case of using ground calcium carbonate (GCC) as a filler is taken as an example.

Since the heavy calcium carbonate is anionic, it primarily adsorbs the cationic polymer material by electrostatic attraction. That is, after the step S110, by adding a cationic polymer material in the reaction tank and stirred for 1 minute, the cationic polymer material is electrostatically adsorbed on the surface of the anionic filler (S120).

Here, the cationic polymer material may include at least one of Poly-DADMAC (poly diallyldimethylammonium chloride), C-PAM (cationic polyacrylamide), PEI (polyethylenimine), PAH (poly allylamine), and cationic starch.

According to the adsorption of step S120, a cationic polymer thin film is formed on the surface of the filler particles, and thus the surface of the filler particles is modified to be cationic. In the step S120, the cationic polymer material is added at a mass of 0.1 to 2.0% of the total charge. For example, 0.3-0.4% C-PAM is added to the total calcium carbonate in the heavy calcium carbonate slurry.

Thereafter, the distilled water and the non-adsorbed cationic polymer material in the reaction tank are discharged, and then distilled water is re-injected into the reaction tank to redistribute the packing material in which the cationic polymer thin film is formed (S130).

An embodiment of the step S130 refers to steps S130a to S130c of FIG. 2. Centrifugation of the reactor through step S120 causes the cationic polymer material to be adsorbed and the modified filler particles (modifier particles) sink down and the cationic polymer material that is not adsorbed on the filler material is in the supernatant due to the difference in specific gravity with the filler material. It will exist. The supernatant in the reactor is removed (S130a), distilled water is re-injected into the reactor again (S130b), and the mixture is stirred for a predetermined time to redistribute the modified filler particles (S130c). At this time, the redispersed filler particles are also adjusted to 30% of the total mass.

The previous method used a method of removing supernatant in which unadsorbed polymer material is present after centrifugation. In addition, a filter that does not pass filler particles is used to filter the filler particles and filtrate (unadsorbed cationic polymer material). Middle water containing) may be used.

According to the step S120, the surface of the heavy calcium carbonate was modified to be cationic, and then to adsorb the anionic material by electrostatic attraction. That is, after the step S120, the anionic polymer material is added to the reaction tank and stirred for 1 minute, thereby electrostatically adsorbing the anionic polymer material on the surface of the cationic polymer material (S140).

Here, the anionic polymer material may include at least one of polyacrylic acid (PAA), poly sodium 4-styrene sulfonate (PSS), ationic polyacrylamide (A-PAM), and polyvinylalcohol (PVOH).

According to the adsorption of step S130, while the anionic polymer thin film is formed on the surface of the cationic-modified filler particles, the surface of the filler particles are again modified to anionic. During the step S130, the anionic polymer material is added in a mass of 0.1 to 2.0% of the total charge. For example, 0.4 or 0.5% PSS relative to the total dry calcium carbonate is added.

Subsequently, the distilled water and the non-adsorbed anionic polymer material in the reaction tank are discharged, and then distilled water is re-injected into the reaction tank to redistribute the filling in which the anionic polymer thin film is formed (S150).

An embodiment of the step S150 refers to steps S150a to S150c of FIG. 2. This is the same principle as the steps S130a ~ S130c above, so a detailed description thereof will be omitted. This step S150 may also use a method using a filter that does not pass through the filler particles as in step S130. The filler particles redispersed through the step S150c are also adjusted back to a concentration of 30% of the total mass.

According to the step S150, since the surface of the heavy calcium carbonate has been modified to anionic so that the cationic material is again adsorbed by the electrostatic attraction. That is, after the step S150, by adding a cationic polymer material into the reaction tank and stirred for 1 minute, the cationic polymer material is electrostatically adsorbed on the surface of the anionic polymer material (S160).

According to the adsorption of step S160, while the cationic polymer thin film is formed on the surface of the anionically modified filler particles, the surface of the filler particles is modified to be cationic again. In this step S160, the cationic polymer material is added in a mass of 0.1 to 2.0% of the total charge. For example, 0.3 or 0.4% of C-PAM is added to the total dry calcium carbonate.

Thereafter, the distilled water and the non-adsorbed cationic polymer material in the reactor are discharged, and the distilled water is re-injected into the reactor to redistribute the packing material (S170). This step S170 refers to the principle of step S130 or step S150 above.

When performing the steps S110 ~ S170, a total of three layers are formed on the surface of the filler particles. 3 is a cross-sectional view of the inorganic filler particles produced by FIG. 1.

That is, as a result of performing the above steps, a total layer of the cationic polymer material 20, the anionic polymer material 30, and the cationic polymer material 20 is repeated on the surface of the filler particle 10. Three layers are formed. In order to form a multilayer thin film of a total of 5 layers, steps S130 to S170 may be further performed after the step S160.

That is, when repeating the steps S140 ~ S170 after the step S160, the odd number of exchanging the cationic polymer material and the anionic polymer material on the surface of the filler (ex, five, seven, nine The polymer thin film layer.

In addition to performing the steps S140 to S150 after the step S170, or after performing the steps S140 to S170 after the step S170 and then repeating the steps S140 to S150 again, on the surface of the filler The cationic polymer material and the anionic polymer material may alternately form four or six polymer thin film layers.

The summary is as follows. According to the present invention, first, as shown in FIG. 3, three multilayer thin films are formed on the surface of the filler 10 according to the steps S110 to S170.

If the three multilayer thin films are formed, repeating steps S140 to S170 N times (N is a natural number), the cationic polymer material 20 and the anionic polymer are formed on the surface of the filler 10. The material 30 alternately adsorbs to form five or more odd multilayer thin films. That is, if N = 1, a total of five multilayer thin films, and if N = 2, a total of seven multilayer thin films may be formed.

On the contrary, in the state where the above three multilayer thin films are formed, when the steps S140 to S150 are performed once, the cationic polymer material 20 and the anionic polymer material 30 are alternately adsorbed on the surface of the filler 10. A total of four even multilayer thin films are formed.

In addition, in the state in which the above three multilayer thin films are formed, repeating steps S140 to S170 N times (N is a natural number) and then performing steps S140 to S150 once again, the surface of the filler 10 is The cationic polymer material 20 and the anionic polymer material 30 may alternately form six or more even-numbered multilayer thin films. Here, if N = 1, a total of 6 multilayer thin films, and if N = 2, a total of 8 multilayer thin films are formed.

As described above, according to the present invention, the surface of the filler particle 10 is formed of a polymer multilayer thin film by polymer thin films formed by electrostatic attraction. In the case of the previous embodiment, the case where the filler particles are anionic, if the cationic, such as hard calcium carbonate to form an anionic polymer thin film, a cationic polymer thin film, and again an anionic polymer thin film Repeatedly three layers as well as more layers are possible. In this case, when even-numbered multi-layer thin films such as four or six layers are formed, the outermost layer of hard calcium carbonate will be formed of a cationic thin film.

The present invention is coated with a multilayer thin film on the surface of the filler particles, in order to control the ionicity of the outermost layer, the reaction may be terminated when the desired cationic or anionic thin film is formed.

In the present invention, the anionic or cationic high-molecular materials are used separately, but the present invention is not limited thereto and may be implemented using a high-molecular amphoteric material.

FIG. 4 shows a cross section of a paper made by adding the filler particles of FIG. 3 to pulp fibers. FIG. That is, Figure 4 shows a paper produced using the filler particles coated with a multi-layer polymer thin film, the filler particles increase the bonding force between the pulp fibers and the filler to increase the contact surface area.

That is, when the filler modified with polymer thin films is applied to papermaking, chemical bonding such as hydrogen bonds, ionic bonds, and covalent bonds occurs between the filler and the fiber and between the filler and the filler, thereby greatly increasing the bonding strength. Therefore, the paper containing the filler whose surface is modified into a multilayer thin film as in the present invention increases the strength of the paper compared to the same batch amount as compared to the conventional paper containing the untreated filler with the polymer thin film. This can further increase the content of the filling in the paper, and can reduce the amount of expensive pulp fibers added during paper manufacturing can reduce the cost. In addition, the present invention can also improve the retention of the filler during paper production by modifying the surface of the filler.

The previous embodiment is a configuration for forming a multilayer thin film on the packing having anionic. Forming a multilayer thin film for the cationic filling material also proceeds on the same principle as before, and its configuration is as follows.

First, cationic filler particles are dispersed in distilled water in the reactor (a). Thereafter, an anionic polymer material is introduced into the reaction tank to electrostatically adsorb the anionic polymer material on the surface of the packing material (b), and the distilled water and the non-adsorbed anionic polymer material in the reactor are discharged. Distilled water is re-injected into the reactor to redistribute the charge (c).

Thereafter, a cationic polymer material is introduced into the reaction tank to electrostatically adsorb the cationic polymer material on the surface of the anionic polymer material (d) and discharge distilled water and unadsorbed cationic polymer material in the reaction tank. Then, the distilled water is re-injected into the reactor to redistribute the charge (e).

In addition, an anionic polymer material is introduced into the reactor to electrostatically adsorb the anionic polymer material on the surface of the cationic polymer material (f), and discharge distilled water and unadsorbed anionic polymer material in the reactor. Then, distilled water is re-injected into the reactor to redispers the packing (g).

Thus, when performing steps (a) to (g), a total of three layers of multilayer thin films are formed on the surface of the packing. In the state in which the three multilayer thin films are formed, a total of four even multilayer thin films are formed on the surface of the filler when the steps (d) to (e) are performed.

In addition, in the state in which the above three multilayer thin films are formed, repeating steps (d) to (g) N times (N is a natural number) and then performing steps (d) to (e), S140 to S170. Repeating the step N (N is a natural number) and then performing the step S140 ~ S150 once, it is possible to form six or more even multi-layer thin film on the surface of the filling. Here, if N = 1, a total of 6 multilayer thin films, and if N = 2, a total of 8 multilayer thin films are formed.

Hereinafter, the properties of heavy calcium carbonate coated with a polymer multilayer thin film using an embodiment of the present invention will be described.

First, Figure 5 shows the zeta potential of heavy calcium carbonate coated with a polymer multilayer thin film according to an embodiment of the present invention. This is an example in which the cationic high molecular material uses C-PAM and the anionic high molecular material uses PSS.

According to the results of FIG. 5, the zeta potential value of each layer is determined by the ionicity of the polymer present in the outermost layer of the polymer multilayer thin film. Here, the negative value of the zeta potential corresponds to the case where the outermost layer is an even layer (ex, 2,4,6,8,10 layer) coated with an anionic polymer material. The positive case represents a case where the outermost layer is an odd layer (ex, 1,3,5,7,9 layer) coated with a cationic polymer material.

For example, the zeta potential of the heavy calcium carbonate coated with the polymer multilayer thin film through the continuous treatment using the cationic polymer C-PAM and the anionic PSS is compared with that of the anionic heavy calcium carbonate. One layer of heavy calcium carbonate in which the cationic C-PAM is at the outermost layer was cationic, and the two layers of heavy calcium carbonate coated with anionic PSS were again anionic. Subsequently, the C-PAM-treated odd layer calcium carbonate is cationic, and the PSS-treated even layer heavy calcium carbonate is anionic. It can be seen that the ionicity of the polymer present in the outermost layer of the coated heavy calcium carbonate particles is represented by zeta potential.

6 and 7 show particle size and particle size distribution of heavy calcium carbonate coated with a polymer multilayer thin film according to an embodiment of the present invention. The polymer material used in FIGS. 6 and 7 corresponds to the polymer material used in FIG. 5.

First, the particle size of heavy calcium carbonate for each layer can be seen through FIG. 6. Here, if the particle size of the heavy calcium carbonate is similar to the particle size of the 0 layer before coating the polymer thin film for each layer, the heavy calcium carbonate particles are not agglomerated with each other by the polymer material, but rather on the surface of the heavy calcium carbonate particles. It means that the adsorption of the polymer material is well maintained to maintain the dispersibility by the repulsive force between the particles.

On the other hand, when the particle size is changed in a larger direction than before the coating of the polymer thin film, the particles of the heavy calcium carbonate, which are the filler particles, are bonded to each other and the particles are aggregated to increase the particle size. In FIG. 6, no agglomeration of particles occurs, and the results of the particle size distribution of each layer of FIG. 7 are similar to those of the 0 layer. In other words, it can be seen that the polymer multilayer thin film is continuously formed on the surface of the heavy calcium carbonate through the change of zeta potential for each layer and no aggregation phenomenon between particles.

As described above, it can be seen that the present invention can control the surface ionicity while maintaining the particle size of the filler particles. In conclusion, it can be seen from the results of FIGS. 5 to 7 that it is possible to determine whether the polymer electrolyte is coated on the heavy calcium carbonate and the degree of coating.

Papermaking fillers containing heavy calcium carbonate are generally anionic and are significantly less reactive with the same anionic pulp fibers. On the other hand, the filler particles coated with a cationic multilayer thin film (multilayer thin film with odd layers) are easily adsorbed by the electrostatic attraction to the anionic fibers, and thus can exhibit excellent reactivity with the pulp fibers.

8 shows the reactivity of heavy calcium carbonate and pulp fibers coated with a polymer multilayer thin film according to an embodiment of the present invention. The cationic polymer used here is C-PAM, and the anionic polymer is PSS.

8 is obtained by reacting heavy calcium carbonate particles coated with a polymer multilayer thin film on such an aqueous solution with pulp fibers, and then filtering unreacted particles using a 200 mesh wire to evaluate the concentration of particles in the filtrate as turbidity. To calculate the amount of unheld particles, and then to calculate the retention of the charge.

Compared to the untreated heavy calcium carbonate (0 layer), the polymer multi-layer thin film coated heavy calcium carbonate (3, 5, 7 layer) can be seen that the reactivity with the fiber increased by about 7 times or more. Also, the retention rate increases as the number of layers increases. However, since the increase is not large, it can be seen that even if only three layers of the multilayer thin film are formed on the filler, the reactivity and retention with the fibers are excellent.

Figure 9 shows the results of evaluating the binding capacity of the heavy calcium carbonate and pulp fibers coated with a polymer multilayer thin film according to an embodiment of the present invention. This was evaluated by measuring the peel strength of the paper produced by forming a heavy calcium carbonate particle layer formed with a polymer multilayer thin film on a paper layer composed only of pulp fibers.

From the results of FIG. 9, when the particle weight of the heavy calcium carbonate coated with the polymer multilayer thin film is the same, the bond between the fiber and the fiber and the bond between the fiber and the heavy calcium carbonate particles are constant, and the measured strength (vertical axis value) is Higher means higher binding force between the fiber and the heavy calcium carbonate particles.

In the case of heavy calcium carbonate coated with 3,5,7 layers of polymer multilayer thin film by C-PAM / PSS combination, the three-layer coating of polymer multilayer thin film was untreated heavy calcium carbonate ( It can be seen that the peel strength is generally increased compared to 0 layer), which means that the heavy calcium carbonate coated with the polymer multilayer thin film has an increased binding force with fibers.

In addition, it can be seen that as the layer of the polymer multilayer thin film increases, the bonding strength with the fiber is higher. Through this, as the number of layer treatments on the heavy calcium carbonate increases, the bonding strength with the pulp fiber is more excellent.

FIG. 10 shows the ash content in paper during paper production by adding heavy calcium carbonate coated with a polymer multilayer thin film to pulp fibers according to an embodiment of the present invention. The cationic polymers used were Poly-DADMAC and C-PAM having molecular weights of Mw 150,000 and Mw 450,000, respectively, and PSS was used for all anionic polymers. FIG. 10 shows the ash content in the paper prepared by adding 60% of the heavy calcium carbonate coated with a total of three layers of polymer multilayer thin films to each of the polymer combinations compared to the dried pulp fibers. The result is the application of heavy calcium carbonate.

From the results of FIG. 10, it can be seen that a paper having a higher filler content can be produced when the heavy calcium carbonate coated with the polymer multilayer thin film is applied as compared with the untreated heavy calcium carbonate. This means that the heavy calcium carbonate coated with the polymer multilayer thin film has a higher retention than the untreated heavy calcium carbonate. For reference, if the sum of the amount of pulp fibers and fillers is constant for the same mass of paper, the amount of pulp fibers will decrease as the amount of filler increases. In other words, the higher the filler content, the more costly pulp fibers can be saved in paper manufacturing.

11 is a result of comparing the tensile index of each layer in the same ash content 20% in the paper prepared corresponding to FIG.

It can be seen that the strength of the paper (3, 5, 7 layer) is superior to that of the heavy calcium carbonate coated with the polymer multilayer thin film (3, 5, 7 layer) compared with the control of the untreated heavy calcium carbonate. . In addition, it can be seen that the strength of the paper (tensile strength) increases as the layer increases with respect to the same ash content regardless of the combination of the polymer materials.

FIG. 12 illustrates the relationship between ash content and tensile index of a paper according to a multilayer thin film layer in paper prepared by injecting heavy calcium carbonate having a polymer multilayer thin film formed into a pulp fiber according to an embodiment of the present invention.

Figure 12 shows the strength characteristics of the paper prepared by applying a heavy calcium carbonate coated with a poly-DADMAC (Mw 150,000) / PSS combination, the multilayer adsorption treatment 1 to 10 times each of the multilayer of 1 to 10 layers Heavy calcium carbonate coated with a thin film was applied to paper production. In the figures, each number represents a layer of a multilayer thin film. With respect to the ash content of the paper with a 17 to 18% interval, the strength of the paper increased as the layer of the multilayer thin film increased. In other words, it can be seen that when the heavy calcium carbonate coated by LbL treatment is applied to paper, a paper having high retention ratio and excellent strength characteristics can be produced.

The present invention as described above provides a method of coating the surface of the filler through the sequential adsorption reaction treatment of the cationic polymer material and the anionic polymer material, and when the multi-layer thin film-treated filler in this method is used for paper manufacturing, Increasing the reactivity and binding strength between the pulp fibers can improve retention and ash content of the fillers in the paper. Here, the retention rate is greatly improved compared to the untreated heavy calcium carbonate in the 3 layer, and there is no significant increase in the subsequent layer.

In addition, as the layer increases, the bonding strength between the filler and the fiber increases, and when the filler coated with the polymer multilayer thin film is used for paper making, the paper strength can be continuously increased as the layer of the multilayer thin film increases. However, since the number of polymer treatments cannot be increased indefinitely in consideration of cost and time, it can be seen that the characteristics of the 5 to 7 layers in which the strength increase of the paper starts to show a distinct difference are most suitable based on the result of this embodiment.

In conclusion, according to the manufacturing method of the paper-making inorganic filler according to the present invention and the paper produced therefrom, a polymer multilayer thin film is formed on the filler particles by continuously adsorbing different ionic polymers on the surface of the paper-making inorganic filler. As a result, it is possible to improve the strength of the paper to be produced, thereby reducing the paper manufacturing cost.

While the present invention has been described with reference to exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims. Accordingly, the true scope of the present invention should be determined by the technical idea of the appended claims.

10: filler 20: cationic polymer
30: anionic polymer

Claims (11)

(a) dispersing anionic filler particles in distilled water in a reactor;
(b) injecting a cationic polymer material into the reactor to electrostatically adsorb the cationic polymer material on the surface of the packing material;
(c) discharging the distilled water and the non-adsorbed cationic polymer in the reactor, and then re-dispersing the packing material by re-injecting distilled water into the reactor;
(d) injecting an anionic polymer material into the reactor to electrostatically adsorb the anionic polymer material on the surface of the cationic polymer material;
(e) discharging the distilled water and the non-adsorbed anionic polymer material in the reactor, and then re-dispersing the packing material by re-injecting distilled water into the reactor;
(f) injecting a cationic polymer material into the reactor to electrostatically adsorb the cationic polymer material on the surface of the anionic polymer material; And
(g) discharging the distilled water and the non-adsorbed cationic polymer in the reactor, and then re-dispersing the packing material by re-injecting distilled water into the reactor. The method according to claim 1,
The cationic polymer material is added to the mass of 0.1 to 2.0% relative to the filler, the anionic polymer material is introduced to the mass of 0.1 to 2.0% relative to the filler papermaking inorganic filler manufacturing method. The method according to claim 1,
After performing step (g) above,
Further comprising repeating the steps (d) to (g) N (N is a natural number) times,
And forming an odd number of multilayer thin films in which the cationic polymer material and the anionic polymer material are alternately adsorbed on the surface of the filler. The method according to claim 1,
After performing step (g) above,
The method for producing an inorganic filler for papermaking further comprising the step of (d) and (e). The method according to claim 1,
After performing step (g) above,
Further performing the steps (d) to (g) N times (N is a natural number) and then performing the steps (d) and (e),
A method for producing an inorganic filler for paper making an even number of multi-layered thin films in which the cationic polymer material and the anionic polymer material are alternately adsorbed on the surface of the filler. The method according to claim 1,
The filler comprises a calcium carbonate, clay, talc, titanium dioxide, silica. The method according to claim 1,
The cationic high molecular material includes at least one of poly-diDMAL (poly diallyldimethylammonium chloride), C-PAM (cationic polyacrylamide), PEI (polyethylenimine), PAH (poly allylamine), amphoteric starch,
The anionic polymer material may include at least one of polyacrylic acid (PAA), poly sodium 4-styrene sulfonate (PSS), ationic polyacrylamide (A-PAM), and polyvinylalcohol (PVOH). (a) dispersing cationic filler particles in distilled water in a reactor;
(b) injecting an anionic polymer material into the reactor to electrostatically adsorb the anionic polymer material on the surface of the filler;
(c) discharging the distilled water and the non-adsorbed anionic polymer material in the reactor, and then re-dispersing the packing material by re-injecting distilled water into the reactor;
(d) injecting a cationic polymer material into the reactor to electrostatically adsorb the cationic polymer material on the surface of the anionic polymer material;
(e) discharging the distilled water and the non-adsorbed cationic polymer in the reactor, and then re-dispersing the packing material by re-injecting distilled water into the reactor;
(f) injecting an anionic polymer material into the reactor to electrostatically adsorb the anionic polymer material on the surface of the cationic polymer material; And
(g) discharging the distilled water and the non-adsorbed anionic polymer material in the reaction tank, and then re-dispersing the packing material by re-injecting distilled water into the reaction tank. The method according to claim 8,
After performing step (g) above,
The method for producing an inorganic filler for papermaking further comprising the step of (d) and (e). The method according to claim 8,
After performing step (g) above,
Further performing the steps (d) to (g) N times (N is a natural number) and then performing the steps (d) and (e),
A method for producing an inorganic filler for paper making an even number of multi-layered thin films in which the cationic polymer material and the anionic polymer material are alternately adsorbed on the surface of the filler. A paper produced by containing an inorganic filler produced by the method according to any one of claims 1 to 10.

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